Porous glasses as a matrix for incorporation of photonic materials. Pore determination by positron annihilation lifetime spectroscopy

NASA Astrophysics Data System (ADS)

Reisfeld, Pore determination by positron annihilation lifetime spectroscopy R.; Saraidarov, T.; Jasinska, B.

2004-07-01

Porous glasses prepared by the sol-gel technique have a variety of applications when incorporated by photonic materials: tunable lasers, sensors, luminescence solar concentrators, semiconductor quantum dots, biological markers. The known methods of pore size determinations, the nitrogen adsorption and mercury porosimetry allow to determine the sizes of open pores. Positron annihilation lifetime spectroscopy (PALS) allows to determine pore sizes also of closed pores. As an example we have performed measurements of non-doped zirconia-silica-polyurethane (ZSUR) ormocer glasses and the same glasses doped with lead sulfide quantum dots. The pore radii range between 0.25-0.38 nm, total surface area 15.5-23.8 m 2/g.

Nanostructured silver sulfide: synthesis of various forms and their application

NASA Astrophysics Data System (ADS)

Sadovnikov, S. I.; Rempel, A. A.; Gusev, A. I.

2018-04-01

The results of experimental studies on nanostructured silver sulfide are analyzed and generalized. The influence of small particle size on nonstoichiometry of silver sulfide is discussed. Methods for the synthesis of various forms of nanostructured Ag2S including nanopowders, stable colloidal solutions, quantum dots, core–shell nanoparticles and heteronanostructures are described. The advantages and drawbacks of different synthetic procedures are analyzed. Main fields of application of nanostructured silver sulfide are considered. The bibliography includes 184 references.

Biosynthesis of luminescent CdS quantum dots using plant hairy root culture

NASA Astrophysics Data System (ADS)

Borovaya, Mariya N.; Naumenko, Antonina P.; Matvieieva, Nadia A.; Blume, Yaroslav B.; Yemets, Alla I.

2014-12-01

CdS nanoparticles have a great potential for application in chemical research, bioscience and medicine. The aim of this study was to develop an efficient and environmentally-friendly method of plant-based biosynthesis of CdS quantum dots using hairy root culture of Linaria maroccana L. By incubating Linaria root extract with inorganic cadmium sulfate and sodium sulfide we synthesized stable luminescent CdS nanocrystals with absorption peaks for UV-visible spectrometry at 362 nm, 398 nm and 464 nm, and luminescent peaks at 425, 462, 500 nm. Transmission electron microscopy of produced quantum dots revealed their spherical shape with a size predominantly from 5 to 7 nm. Electron diffraction pattern confirmed the wurtzite crystalline structure of synthesized cadmium sulfide quantum dots. These results describe the first successful attempt of quantum dots synthesis using plant extract.

Defect-mediated photoluminescence up-conversion in cadmium sulfide nanobelts (Conference Presentation)

NASA Astrophysics Data System (ADS)

Morozov, Yurii; Kuno, Masaru K.

2017-02-01

The concept of optical cooling of solids has existed for nearly 90 years ever since Pringsheim proposed a way to cool solids through the annihilation of phonons via phonon-assisted photoluminescence (PL) up-conversion. In this process, energy is removed from the solid by the emission of photons with energies larger than those of incident photons. However, actually realizing optical cooling requires exacting parameters from the condensed phase medium such as near unity external quantum efficiencies as well as existence of a low background absorption. Until recently, laser cooling has only been successfully realized in rare earth doped solids. In semiconductors, optical cooling has very recently been demonstrated in cadmium sulfide (CdS) nanobelts as well as in hybrid lead halide perovskites. For the former, large internal quantum efficiencies, sub-wavelength thicknesses, which decrease light trapping, and low background absorption, all make near unity external quantum yields possible. Net cooling by as much as 40 K has therefore been possible with CdS nanobelts. In this study, we describe a detailed investigation of the nature of efficient anti-Stokes photoluminescence (ASPL) in CdS nanobelts. Temperature-dependent PL up-conversion and optical absorption studies on individual NBs together with frequency-dependent up-converted PL intensity spectroscopies suggest that ASPL in CdS nanobelts is defect-mediated through involvement of defect levels below the band gap.

Synthesis of Bi2S3 quantum dots for sensitized solar cells by reverse SILAR

NASA Astrophysics Data System (ADS)

Singh, Navjot; Sharma, J.; Tripathi, S. K.

2016-05-01

Quantum Dot Sensitized Solar cells (QDSSC) have great potential to replace silicon-based solar cells. Quantum dots of various materials and sizes could be used to convert most of the visible light into the electrical current. This paper put emphasis on the synthesis of Bismuth Sulphide quantum dots and selectivity of the anionic precursor by Successive Ionic Layer Adsorption Reaction (SILAR). Bismuth Sulfide (Bi2S3) (group V - Vi semiconductor) is strong contestant for cadmium free solar cells due to its optimum band gap for light harvesting. Optical, structural and electrical measurements are reported and discussed. Problem regarding the choice of precursor for anion extraction is discussed. Band gap of the synthesized quantum dots is 1.2 eV which does not match with the required energy band gap of bismuth sulfide that is 1.7eV.

Carbon nanotube/metal-sulfide composite flexible electrodes for high-performance quantum dot-sensitized solar cells and supercapacitors

NASA Astrophysics Data System (ADS)

Muralee Gopi, Chandu V. V.; Ravi, Seenu; Rao, S. Srinivasa; Eswar Reddy, Araveeti; Kim, Hee-Je

2017-04-01

Carbon nanotubes (CNT) and metal sulfides have attracted considerable attention owing to their outstanding properties and multiple application areas, such as electrochemical energy conversion and energy storage. Here we describes a cost-effective and facile solution approach to the preparation of metal sulfides (PbS, CuS, CoS, and NiS) grown directly on CNTs, such as CNT/PbS, CNT/CuS, CNT/CoS, and CNT/NiS flexible electrodes for quantum dot-sensitized solar cells (QDSSCs) and supercapacitors (SCs). X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy confirmed that the CNT network was covered with high-purity metal sulfide compounds. QDSSCs equipped with the CNT/NiS counter electrode (CE) showed an impressive energy conversion efficiency (η) of 6.41% and remarkable stability. Interestingly, the assembled symmetric CNT/NiS-based polysulfide SC device exhibited a maximal energy density of 35.39 W h kg-1 and superior cycling durability with 98.39% retention after 1,000 cycles compared to the other CNT/metal-sulfides. The elevated performance of the composites was attributed mainly to the good conductivity, high surface area with mesoporous structures and stability of the CNTs and the high electrocatalytic activity of the metal sulfides. Overall, the designed composite CNT/metal-sulfide electrodes offer an important guideline for the development of next level energy conversion and energy storage devices.

Carbon nanotube/metal-sulfide composite flexible electrodes for high-performance quantum dot-sensitized solar cells and supercapacitors.

PubMed

Muralee Gopi, Chandu V V; Ravi, Seenu; Rao, S Srinivasa; Eswar Reddy, Araveeti; Kim, Hee-Je

2017-04-19

Carbon nanotubes (CNT) and metal sulfides have attracted considerable attention owing to their outstanding properties and multiple application areas, such as electrochemical energy conversion and energy storage. Here we describes a cost-effective and facile solution approach to the preparation of metal sulfides (PbS, CuS, CoS, and NiS) grown directly on CNTs, such as CNT/PbS, CNT/CuS, CNT/CoS, and CNT/NiS flexible electrodes for quantum dot-sensitized solar cells (QDSSCs) and supercapacitors (SCs). X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy confirmed that the CNT network was covered with high-purity metal sulfide compounds. QDSSCs equipped with the CNT/NiS counter electrode (CE) showed an impressive energy conversion efficiency (η) of 6.41% and remarkable stability. Interestingly, the assembled symmetric CNT/NiS-based polysulfide SC device exhibited a maximal energy density of 35.39 W h kg -1 and superior cycling durability with 98.39% retention after 1,000 cycles compared to the other CNT/metal-sulfides. The elevated performance of the composites was attributed mainly to the good conductivity, high surface area with mesoporous structures and stability of the CNTs and the high electrocatalytic activity of the metal sulfides. Overall, the designed composite CNT/metal-sulfide electrodes offer an important guideline for the development of next level energy conversion and energy storage devices.

Plastic scintillator enhancement through Quantum Dot

NASA Astrophysics Data System (ADS)

Tam, Alan; Boyraz, Ozdal; Nilsson, Mikael

2017-08-01

Plastic scintillators such as Polyvinyl Toluene (PVT) are used for radiation detection but due to their poor performance they are not widely implemented. In order to circumnavigate this, dopants are added to enhance scintillation by energy transfer otherwise lost through non-radiative processes. In this work, we exploit the effects of energy transfer through the use of short wavelength emission Cadmium Sulfide Quantum Dots (QD) as the transfer stimulant. Scintillation enhancement was observed as Cadmium Sulfide QD with scintillating dyes are embedded in PVT polymer matrix for beta and gamma radiation. Energy transfer was observed between Quantum Dots, scintillating dye, and the host polymer. Different concentrations of QD and 2,5-diphenyloxazole (PPO) dye are investigated to characterize the energy transfer.

A novel method for improving cerussite sulfidization

NASA Astrophysics Data System (ADS)

Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

2016-06-01

Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

The role of surface ligands in determining the electronic properties of quantum dot solids and their impact on photovoltaic figure of merits.

PubMed

Goswami, Prasenjit N; Mandal, Debranjan; Rath, Arup K

2018-01-18

Surface chemistry plays a crucial role in determining the electronic properties of quantum dot solids and may well be the key to mitigate loss processes involved in quantum dot solar cells. Surface ligands help to maintain the shape and size of the individual dots in solid films, to preserve the clean energy band gap of the individual particles and to control charge carrier conduction across solid films, in turn regulating their performance in photovoltaic applications. In this report, we show that the changes in size, shape and functional groups of small chain organic ligands enable us to modulate mobility, dielectric constant and carrier doping density of lead sulfide quantum dot solids. Furthermore, we correlate these results with performance, stability and recombination processes in the respective photovoltaic devices. Our results highlight the critical role of surface chemistry in the electronic properties of quantum dots. The role of the size, functionality and the surface coverage of the ligands in determining charge transport properties and the stability of quantum dot solids have been discussed. Our findings, when applied in designing new ligands with higher mobility and improved passivation of quantum dot solids, can have important implications for the development of high-performance quantum dot solar cells.

Self-organized colloidal quantum dots and metal nanoparticles for plasmon-enhanced intermediate-band solar cells.

PubMed

Mendes, Manuel J; Hernández, Estela; López, Esther; García-Linares, Pablo; Ramiro, Iñigo; Artacho, Irene; Antolín, Elisa; Tobías, Ignacio; Martí, Antonio; Luque, Antonio

2013-08-30

A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude.In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance.The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

Carbon nanotube/metal-sulfide composite flexible electrodes for high-performance quantum dot-sensitized solar cells and supercapacitors

PubMed Central

Muralee Gopi, Chandu V. V.; Ravi, Seenu; Rao, S. Srinivasa; Eswar Reddy, Araveeti; Kim, Hee-Je

2017-01-01

Carbon nanotubes (CNT) and metal sulfides have attracted considerable attention owing to their outstanding properties and multiple application areas, such as electrochemical energy conversion and energy storage. Here we describes a cost-effective and facile solution approach to the preparation of metal sulfides (PbS, CuS, CoS, and NiS) grown directly on CNTs, such as CNT/PbS, CNT/CuS, CNT/CoS, and CNT/NiS flexible electrodes for quantum dot-sensitized solar cells (QDSSCs) and supercapacitors (SCs). X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy confirmed that the CNT network was covered with high-purity metal sulfide compounds. QDSSCs equipped with the CNT/NiS counter electrode (CE) showed an impressive energy conversion efficiency (η) of 6.41% and remarkable stability. Interestingly, the assembled symmetric CNT/NiS-based polysulfide SC device exhibited a maximal energy density of 35.39 W h kg−1 and superior cycling durability with 98.39% retention after 1,000 cycles compared to the other CNT/metal-sulfides. The elevated performance of the composites was attributed mainly to the good conductivity, high surface area with mesoporous structures and stability of the CNTs and the high electrocatalytic activity of the metal sulfides. Overall, the designed composite CNT/metal-sulfide electrodes offer an important guideline for the development of next level energy conversion and energy storage devices. PMID:28422182

Low temperature regulated growth of PbS quantum dots by wet chemical method

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

Kumar, Hitanshu, E-mail: hitanshuminhas@gmail.com; Barman, P. B.; Singh, Ragini Raj

2015-08-28

Narrow size distribution with regulated synthesis of lead sulfide (PbS) quantum dots (QDs) was achieved through wet chemical method. Different concentrations of 2-mercaptoethanol (capping agent) were used for tailoring the QDs size. Transmission electron microscopy and X-ray diffraction studies revealed that the QDs have mean diameters between 6 to 15 nm. The optical absorption spectra were compared to the predictions of a theoretical model for the electronic structure. The theory agrees well with experiment for QDs larger than 7 nm, but for smaller dots there is some deviation from the theoretical predictions. Consequently, the produced particles are having monodispersity, good water solubility,more » stability and may be good arguments to be biologically compatible due to the use of 2-mercaptoethanol.« less

Inorganic-ligand exchanging time effect in PbS quantum dot solar cell

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

Kim, Byung-Sung; Hong, John; Hou, Bo

2016-08-08

We investigate time-dependent inorganic ligand exchanging effect and photovoltaic performance of lead sulfide (PbS) nanocrystal films. With optimal processing time, volume shrinkage induced by residual oleic acid of the PbS colloidal quantum dot (CQD) was minimized and a crack-free film was obtained with improved flatness. Furthermore, sufficient surface passivation significantly increased the packing density by replacing from long oleic acid to a short iodide molecule. It thus facilities exciton dissociation via enhanced charge carrier transport in PbS CQD films, resulting in the improved power conversion efficiency from 3.39% to 6.62%. We also found that excess iodine ions on the PbSmore » surface rather hinder high photovoltaic performance of the CQD solar cell.« less

Extraction of lead from waste CRT funnel glass by generating lead sulfide - An approach for electronic waste management.

PubMed

Hu, Biao; Hui, Wenlong

2017-09-01

Waste cathode ray tube (CRT) funnel glass is the key and difficult points in waste electrical and electronic equipment (WEEE) disposal. In this paper, a novel and effective process for the detoxification and reutilization of waste CRT funnel glass was developed by generating lead sulfide precipitate via a high-temperature melting process. The central function in this process was the generation of lead sulfide, which gathered at the bottom of the crucible and was then separated from the slag. Sodium carbonate was used as a flux and reaction agent, and sodium sulfide was used as a precipitating agent. The experimental results revealed that the lead sulfide recovery rate initially increased with an increase in the amount of added sodium carbonate, the amount of sodium sulfide, the temperature, and the holding time and then reached an equilibrium value. The maximum lead sulfide recovery rate was approximately 93%, at the optimum sodium carbonate level, sodium sulfide level, temperature, and holding time of 25%, 8%, 1200°C, and 2h, respectively. The glass slag can be made into sodium and potassium silicate by hydrolysis in an environmental and economical process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Quantum cascade laser-based analyzer for hydrogen sulfide detection at sub-parts-per-million levels

NASA Astrophysics Data System (ADS)

Nikodem, Michal; Krzempek, Karol; Stachowiak, Dorota; Wysocki, Gerard

2018-01-01

Due to its high toxicity, monitoring of hydrogen sulfide (H2S) concentration is essential in many industrial sites (such as natural gas extraction sites, petroleum refineries, geothermal power plants, or waste water treatment facilities), which require sub-parts-per-million sensitivities. We report on a quantum cascade laser-based spectroscopic system for detection of H2S in the midinfrared at ˜7.2 μm. We present a sensor design utilizing Herriott multipass cell and a wavelength modulation spectroscopy to achieve a detection limit of 140 parts per billion for 1-s integration time.

Fluorescent Lead(IV) Sulfide Nanoparticles Synthesized by Idiomarina sp. Strain PR58-8 for Bioimaging Applications.

PubMed

Srivastava, Pallavee; Kowshik, Meenal

2017-04-01

The fabrication of nanoparticles by microorganisms presents a "green" method for generating biocompatible nanomaterials. We discovered the intracellular biosynthesis of fluorescent lead(IV) sulfide nanoparticles by the moderate halophile, Idiomarina sp. strain PR58-8. The bacterium tolerated up to 8 mM Pb(NO 3 ) 2 during growth. Non-protein thiols dose-dependently increased in response to metal exposure, which suggests they are involved in the growth of PbS 2 crystals and lead detoxification. Using X-ray diffraction, transmission electron microscopy (TEM), high-resolution TEM, and energy dispersive analysis of X-rays, the nanoparticles were characterized as spherical β-PbS 2 nanoparticles (PbS 2 NPs) with a tetragonal crystal lattice, a crystallite domain size of 2.38 nm, and an interplanar distance of 0.318 nm. A narrow symmetric emission spectrum with a Gaussian distribution and an emission maximum at 386 nm was obtained when the particles were excited at 570 nm. The PbS 2 NPs exhibited a large Stokes' shift (8,362 cm -1 ) and a relatively high quantum yield (67%). These properties, along with fluorescence that was maintained in various microenvironments and their biocompatibility, make these nanoparticles excellent candidates for bioimaging. The particles were internalized by HeLa cells and evenly distributed within the cytoplasm, exhibiting their potential for in situ bioimaging applications. The "as-synthesized" lead(IV) sulfide nanoparticles may provide expanded opportunities for targeted bioimaging via modifying the surface of the particles. IMPORTANCE This article reports the intracellular synthesis of fluorescent lead(IV) sulfide nanoparticles (PbS 2 NPs) by a microorganism. All previous reports on the microbial synthesis of lead-based nanoparticles are on lead(II) sulfide that exhibits near-infrared fluorescence, requiring expensive instrumentation for bioimaging. Bioimaging using PbS 2 NPs can be achieved using routine epifluorescence microscopes, as it fluoresces in the visible range. The research on PbS 2 nanoparticles to date is on their chemical synthesis employing toxic precursors, extreme pH, pressure, and temperature, resulting in cytotoxic products. In this context, the synthesis of PbS 2 nanoparticles by Idiomarina sp. strain PR58-8, described in this work, occurs at ambient temperature and pressure and results in the generation of biocompatible nanoparticles with no hazardous by-products. The excellent fluorescence properties that these particles exhibit, as well as their abilities to easily penetrate the cells and evenly distribute within the cytoplasm, make them exceptional candidates for bioimaging applications. This study demonstrated the synthesis and fluorescence bioimaging application of microbially synthesized PbS 2 nanoparticles. Copyright © 2017 American Society for Microbiology.

Photo-induced surface modification to improve the performance of lead sulfide quantum dot solar cell.

PubMed

Tulsani, Srikanth Reddy; Rath, Arup Kumar

2018-07-15

The solution-processed quantum dot (QD) solar cell technology has seen significant advancements in recent past to emerge as a potential contender for the next generation photovoltaic technology. In the development of high performance QD solar cell, the surface ligand chemistry has played the important role in controlling the doping type and doping density of QD solids. For instance, lead sulfide (PbS) QDs which is at the forefront of QD solar cell technology, can be made n-type or p-type respectively by using iodine or thiol as the surfactant. The advancements in surface ligand chemistry enable the formation of p-n homojunction of PbS QDs layers to attain high solar cell performances. It is shown here, however, that poor Fermi level alignment of thiol passivated p-type PbS QD hole transport layer with the n-type PbS QD light absorbing layer has rendered the photovoltaic devices from realizing their full potential. Here we develop a control surface oxidation technique using facile ultraviolet ozone treatment to increase the p-doping density in a controlled fashion for the thiol passivated PbS QD layer. This subtle surface modification tunes the Fermi energy level of the hole transport layer to deeper values to facilitate the carrier extraction and voltage generation in photovoltaic devices. In photovoltaic devices, the ultraviolet ozone treatment resulted in the average gain of 18% in the power conversion efficiency with the highest recorded efficiency of 8.98%. Copyright © 2018 Elsevier Inc. All rights reserved.

Achieving copper sulfide leaf like nanostructure electrode for high performance supercapacitor and quantum-dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Durga, Ikkurthi Kanaka; Rao, S. Srinivasa; Reddy, Araveeti Eswar; Gopi, Chandu V. V. M.; Kim, Hee-Je

2018-03-01

Copper sulfide is an important multifunctional semiconductor that has attracted considerable attention owing to its outstanding properties and multiple applications, such as energy storage and electrochemical energy conversion. This paper describes a cost-effective and simple low-temperature solution approach to the preparation of copper sulfide for supercapacitors (SCs) and quantum-dot sensitized solar cells (QDSSCs). X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy confirmed that the nickel foam with a coriander leaf like nanostructure had been coated successfully with copper sulfide. As an electrode material for SCs, the CC-3 h showed excellent specific capacitance (5029.28 at 4 A g-1), energy density (169.73 W h kg-1), and superior cycling durability with 107% retention after 2000 cycles. Interestingly, the QDSSCs equipped with CC-2 h and CC-3 h counter electrodes (CEs) exhibited a maximum power conversion efficiency of 2.52% and 3.48%, respectively. The improved performance of the CC-3 h electrode was attributed mainly to the large surface area (which could contribute sufficient electroactive species), good conductivity, and high electrocatalytic activity. Overall, this work delivers novel insights into the use of copper sulfide and offers an important guidelines for the fabrication of next level energy storage and conversion devices.

3D superstructures with an orthorhombic lattice assembled by colloidal PbS quantum dots.

PubMed

Ushakova, Elena V; Cherevkov, Sergei A; Litvin, Aleksandr P; Parfenov, Peter S; Kasatkin, Igor A; Fedorov, Anatoly V; Gun'ko, Yurii K; Baranov, Alexander V

2018-05-03

We report a new type of metamaterial comprising a highly ordered 3D network of 3-7 nm lead sulfide quantum dots self-assembled in an organic matrix formed by amphiphilic ligands (oleic acid molecules). The obtained 3D superstructures possess an orthorhombic lattice with the distance between the nanocrystals as large as 10-40 nm. Analysis of self-assembly and destruction of the superstructures in time performed by a SAXS technique shows that their morphology depends on the quantity of amphiphilic ligands and width of the quantum dot size and its distribution. Formation of the superstructures is discussed in terms of a model describing the lyotropic crystal formation by micelles from three-phase mixtures. The results show that the organic molecules possessing surfactant properties and capable of forming micelles with nanoparticles as a micelle core can be utilized as building blocks for the creation of novel metamaterials based on a highly ordered 3D network of semiconductors, metals or magnetic nanoparticles.

Low-Cost Flexible Nano-Sulfide/Carbon Composite Counter Electrode for Quantum-Dot-Sensitized Solar Cell

PubMed Central

2010-01-01

Cu2S nanocrystal particles were in situ deposited on graphite paper to prepare nano-sulfide/carbon composite counter electrode for CdS/CdSe quantum-dot-sensitized solar cell (QDSC). By optimization of deposition time, photovoltaic conversion efficiency up to 3.08% was obtained. In the meantime, this composite counter electrode was superior to the commonly used Pt, Au and carbon counter electrodes. Electrochemical impedance spectra further confirmed that low charge transfer resistance at counter electrode/electrolyte interface was responsible for this, implied the potential application of this composite counter electrode in high-efficiency QDSC. PMID:20672135

Synthesis and Optical Properties of MnS–ZnS and MnS–CdS Nanoparticles in Montmorillonite.

PubMed

Kabilaphat, Jirabhorn; Poosimma, Poonsuk; Khaorapapong, Nithima; Intachai, Sonchai; Ogawa, Makoto

2017-02-01

The incorporation of metal sulfide mixture, manganese sulfide and zinc sulfide (MnS–ZnS) or manganese sulfide and cadmium sulfide (MnS–CdS), in two types of montmorillonites (sodium montmorillonite and cetyltrimethylammonium modified montmorillonite) was investigated. The hybrids were characterized by powder X-ray diffraction, thermogravimetric-differential thermal analysis, transmission electron microscopy (TEM), and Raman, UV-visible and photoluminescence spectroscopies. The experimental evidences such as the expansion of the interlayer spaces and the presence of the absorption and photoluminescence due to MnS, ZnS and/or CdS revealed that the mixed metal sulfides formed in the interlayer space of montmorillonites. TEM images of the hybrids showed diskor plate-shaped nanoparticles with a mean diameter of ca. 2 nm. The increase of the luminescence intensities of the hybrids was assumed to be caused by quantum confinement effect in the interlayer space of montmorillonite.

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

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

Caldwell, Andrew H.; Ha, Don-Hyung; Ding, Xiaoyue

2014-10-28

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu 1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

NASA Astrophysics Data System (ADS)

Caldwell, Andrew H.; Ha, Don-Hyung; Ding, Xiaoyue; Robinson, Richard D.

2014-10-01

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ˜8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.

Thermo-optical characterization of cadmium selenide/zinc sulfide (CdSe/ZnS) quantum dots embedded in biocompatible materials.

PubMed

Pilla, Viviane; Alves, Leandro P; Iwazaki, Adalberto N; Andrade, Acácio A; Antunes, Andrea; Munin, Egberto

2013-09-01

Cadmium selenide/zinc sulfide (CdSe/ZnS) core-shell quantum dots (QDs) embedded in biocompatible materials were thermally and optically characterized with a thermal lens (TL) technique. Transient TL measurements were performed with a mode-mismatched, dual-beam (excitation and probe) configuration. A thermo-optical study of the CdSe/ZnS QDs was performed for different core diameters (3.5, 4.0, 5.2, and 6.6 nm) in aqueous solution and synthetic saliva, and three different core diameters (2.4, 2.9, and 4.1 nm) embedded in restorative dental resin (0.025% by mass). The thermal diffusivity results are characteristic of the biocompatible matrices. The radiative quantum efficiencies for aqueous solution and biofluid materials are dependent on the core size of the CdSe/ZnS core-shell QDs. The results obtained from the fluorescence spectral measurements for the biocompatible materials support the TL results.

Narrow Band Gap Lead Sulfide Hole Transport Layers for Quantum Dot Photovoltaics.

PubMed

Zhang, Nanlin; Neo, Darren C J; Tazawa, Yujiro; Li, Xiuting; Assender, Hazel E; Compton, Richard G; Watt, Andrew A R

2016-08-24

The band structure of colloidal quantum dot (CQD) bilayer heterojunction solar cells is optimized using a combination of ligand modification and QD band gap control. Solar cells with power conversion efficiencies of up to 9.33 ± 0.50% are demonstrated by aligning the absorber and hole transport layers (HTL). Key to achieving high efficiencies is optimizing the relative position of both the valence band and Fermi energy at the CQD bilayer interface. By comparing different band gap CQDs with different ligands, we find that a smaller band gap CQD HTL in combination with a more p-type-inducing CQD ligand is found to enhance hole extraction and hence device performance. We postulate that the efficiency improvements observed are largely due to the synergistic effects of narrower band gap QDs, causing an upshift of valence band position due to 1,2-ethanedithiol (EDT) ligands and a lowering of the Fermi level due to oxidation.

Electrochemical surface-enhanced Raman scattering measurement on ligand capped PbS quantum dots at gap of Au nanodimer

NASA Astrophysics Data System (ADS)

Li, Xiaowei; Minamimoto, Hiro; Murakoshi, Kei

2018-05-01

The vibrational characteristics of ligand-capped lead sulfide (PbS) quantum dots (QDs) were clarified via electrochemical surface-enhanced Raman spectroscopy (EC-SERS) using a hybridized system of gold (Au) nanodimers and PbS QDs under electrochemical potential control. Enhanced electromagnetic field caused by the coupling of QDs with plasmonic Au nanodimers allowed the characteristic behavior of the ligand oleic acid (OA) on the PbS QD surface to be detected under electrochemical potential control. Binding modes between the QDs and OA molecules were characterized using synchronous two-dimensional correlation spectra at distinct electrochemical potentials, confirming that the bidentate bridging mode was probably the most stable mode even under relatively negative potential polarization. Changes in binding modes and molecular orientations resulted in fluctuations in EC-SERS spectra. The present observations strongly recommend the validity of the QD-plasmonic nanostructure coupled system for sensitive molecular detection via EC-SERS.

Cobalt Sulfide Quantum Dot Embedded N/S-Doped Carbon Nanosheets with Superior Reversibility and Rate Capability for Sodium-Ion Batteries.

PubMed

Guo, Qiubo; Ma, Yifan; Chen, Tingting; Xia, Qiuying; Yang, Mei; Xia, Hui; Yu, Yan

2017-12-26

Metal sulfides are promising anode materials for sodium-ion batteries due to their large specific capacities. The practical applications of metal sulfides in sodium-ion batteries, however, are still limited due to their large volume expansion, poor cycling stability, and sluggish electrode kinetics. In this work, a two-dimensional heterostructure of CoS x (CoS and Co 9 S 8 ) quantum dots embedded N/S-doped carbon nanosheets (CoS x @NSC) is prepared by a sol-gel method. The CoS x quantum dots are in situ formed within ultrafine carbon nanosheets without further sulfidation, thus resulting in ultrafine CoS x particle size and embedded heterostructure. Meanwhile, enriched N and S codoping in the carbon nanosheets greatly enhances the electrical conductivity for the conductive matrix and creates more active sites for sodium storage. As a result, the hybrid CoS x @NSC electrode shows excellent rate capability (600 mAh g -1 at 0.2 A g -1 and 500 mAh g -1 at 10 A g -1 ) and outstanding cycling stability (87% capacity retention after 200 cycles at 1 A g -1 ), making it promising as an anode material for high-performance sodium-ion batteries. A CoS x @NSC//Na 0.44 MnO 2 full cell is demonstrated, and it can deliver a specific capacity of 414 mAh g -1 (based on the mass of CoS x @NSC) at a current density of 0.2 A g -1 .

Cadmium sulfide quantum dots induce oxidative stress and behavioral impairments in the marine clam Scrobicularia plana.

PubMed

Buffet, Pierre-Emmanuel; Zalouk-Vergnoux, Aurore; Poirier, Laurence; Lopes, Christelle; Risso-de-Faverney, Christine; Guibbolini, Marielle; Gilliland, Douglas; Perrein-Ettajani, Hanane; Valsami-Jones, Eugenia; Mouneyrac, Catherine

2015-07-01

Cadmium sulfide (CdS) quantum dots have a number of current applications in electronics and solar cells and significant future potential in medicine. The aim of the present study was to examine the toxic effects of CdS quantum dots on the marine clam Scrobicularia plana exposed for 14 d to these nanomaterials (10 µg Cd L(-1) ) in natural seawater and to compare them with soluble Cd. Measurement of labile Cd released from CdS quantum dots showed that 52% of CdS quantum dots remained in the nanoparticulate form. Clams accumulated the same levels of Cd regardless of the form in which it was delivered (soluble Cd vs CdS quantum dots). However, significant changes in biochemical responses were observed in clams exposed to CdS quantum dots compared with soluble Cd. Increased activities of catalase and glutathione-S-transferase were significantly higher in clams exposed in seawater to Cd as the nanoparticulate versus the soluble form, suggesting a specific nano effect. The behavior of S. plana in sediment showed impairments of foot movements only in the case of exposure to CdS quantum dots. The results show that oxidative stress and behavior biomarkers are sensitive predictors of CdS quantum dots toxicity in S. plana. Such responses, appearing well before changes might occur at the population level, demonstrate the usefulness of this model species and type of biomarker in the assessment of nanoparticle contamination in estuarine ecosystems. © 2015 SETAC.

Viability of pyrite pulled metabolism in the ‘iron-sulfur world’ theory: Quantum chemical assessment

NASA Astrophysics Data System (ADS)

Michalkova, Andrea; Kholod, Yana; Kosenkov, Dmytro; Gorb, Leonid; Leszczynski, Jerzy

2011-04-01

The viability of pyrite-pulled metabolism in the 'iron-sulfur world' theory was assessed using a simple model of iron-nickel sulfide (Fe-Ni-S) surface and data obtained from quantum chemical calculations. We have investigated how the individual reactions in the carbon fixation cycle (carboxylic acids formation) on an Fe-Ni-S surface could have operated to produce carboxylic acids from carbon oxide and water. The proposed model cycle reveals how the individual reactions might have functioned and provides the thermodynamics of each step of the proposed pathway. The feasibility of individual reactions, as well the whole cycle was considered. The reaction of acetic acid production from CH 3SH and CO on an Fe-Ni sulfide surface was revealed to be endergonic with a few partial steps having positive Gibbs free energy. On the other hand, the pyrite formation was found to be slightly exergonic. The significance of the catalytic activity of transition metal sulfides in generation of acetic acid was shown. The Gibbs free energy values indicate that the acetic acid synthesis is unfavorable to proceed on the studied Fe-Ni-S model under simulated conditions. The importance of these results in terms of a primordial chemistry on iron-nickel sulfide surfaces is discussed.

Zinc sulfide quantum dots for photocatalytic and sensing applications

NASA Astrophysics Data System (ADS)

Sergeev, Alexander A.; Leonov, Andrei A.; Zhuikova, Elena I.; Postnova, Irina V.; Voznesenskiy, Sergey S.

2017-09-01

Herein, we report the photocatalytic and sensing applications of pure and Mn-doped ZnS quantum dots. The quantum dots were prepared by a chemical precipitation in an aqueous solution in the presence of glutathione as a stabilizing agent. The synthesized quantum dots were used as effective photocatalyst for the degradation of methylene blue dye. Interestingly, fully degradation of methylene blue dye was achieved in 5 min using pure ZnS quantum dots. Further, the synthesized quantum dots were used as efficient sensing element for methane fluorescent sensor. Interfering studies confirmed that the developed sensor possesses very good sensitivity and selectivity towards methane.

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

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

Caldwell, Andrew H.; Ha, Don-Hyung; Robinson, Richard D., E-mail: rdr82@cornell.edu

2014-10-28

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu{sub 1.81}S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ∼8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less

Biomolecule-assisted hydrothermal synthesis of silver bismuth sulfide with nanostructures

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

Kaowphong, Sulawan, E-mail: sulawank@gmail.com; Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200

2012-05-15

Silver bismuth sulfide (AgBiS{sub 2}) nanostructures were successfully prepared via a simple biomolecule-assisted hydrothermal synthesis at 200 Degree-Sign C for 12-72 h. Silver nitrate, bismuth nitrate and L-cysteine were used as starting materials. Here, the biomolecule, L-cysteine, was served as the sulfide source and a complexing agent. The products, characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), were cubic AgBiS{sub 2} nanoparticles with a diameter range of about 20-75 nm. It was found that their crystallinity and particle size increased with increasing reaction time. The energy dispersive X-ray spectroscopy (EDX) and inductively coupledmore » plasma optical emission spectrophotometry (ICP-OES) analyses were used to confirm the stoichiometry of AgBiS{sub 2}. The optical band gap of the AgBiS{sub 2} nanoparticles, calculated from UV-vis spectra, was 3.0 eV which indicated a strong blue shift because of the quantum confinement effect. A possible formation mechanism of the AgBiS{sub 2} nanoparticles was also discussed. - Graphical abstract: The optical band gap of the as-prepared AgBiS{sub 2} nanoparticles displays a strong blue shift comparing to the 2.46 eV of bulk AgBiS{sub 2} caused by the quantum confinement effects. Highlights: Black-Right-Pointing-Pointer A simple biomolecule-assisted hydrothermal method is developed to prepare AgBiS{sub 2}. Black-Right-Pointing-Pointer L-Cysteine is served as the sulfide source and a complexing agent. Black-Right-Pointing-Pointer Increase in band gap of the AgBiS{sub 2} nanoparticles attributes to the quantum confinement effects.« less

Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

NASA Technical Reports Server (NTRS)

Zhao, Z.; Stickel, R. E.; Wine, P. H.

1995-01-01

Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well-known quantum yield for CO production from 248 nm photolysis of phosgene (Cl2CO2). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S((sup 3)P(sub J)) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S((sup 1)D(sub 2)) + OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N2 + N2O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought.

Selective Sulfidation of Lead Smelter Slag with Pyrite and Flotation Behavior of Synthetic ZnS

NASA Astrophysics Data System (ADS)

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

2016-08-01

The selective sulfidation of lead smelter slag with pyrite in the presence of carbon and Na salts, and the flotation behavior of synthetic ZnS were studied. The effects of temperature, time, pyrite dosage, Na salts, and carbon additions were investigated based on thermodynamic calculation, and correspondingly, the growth mechanism of ZnS particles was studied at high temperatures. The results indicated that the zinc in lead smelter slag was selectively converted into zinc sulfides by sulfidation roasting. The sulfidation degree of zinc was increased until the temperature, time, pyrite, and carbon dosages reached their optimum values, under which it was more than 95 pct. The growth of ZnS particles largely depended upon roasting temperature, and the ZnS grains were significantly increased above 1373 K (1100 °C) due to the formation of a liquid phase. After the roasting, the zinc sulfides generated had a good floatability, and 88.34 pct of zinc was recovered by conventional flotation.

A strategy to improve the energy conversion efficiency and stability of quantum dot-sensitized solar cells using manganese-doped cadmium sulfide quantum dots.

PubMed

Gopi, Chandu V V M; Venkata-Haritha, M; Kim, Soo-Kyoung; Kim, Hee-Je

2015-01-14

This article describes the effect of manganese (Mn) doping in CdS to improve the photovoltaic performance of quantum dot sensitized solar cells (QDSSCs). The performances of the QDSSCs are examined in detail using a polysulfide electrolyte with a copper sulfide (CuS) counter electrode. Under the illumination of one sun (AM 1.5 G, 100 mW cm(-2)), 10 molar% Mn-doped CdS QDSSCs exhibit a power conversion efficiency (η) of 2.85%, which is higher than the value of 2.11% obtained with bare CdS. The improved photovoltaic performance is due to the impurities from Mn(2+) doping of CdS, which have an impact on the structure of the host material and decrease the surface roughness. The surface roughness and morphology of Mn-doped CdS nanoparticles can be characterised from atomic force microscopy images. Furthermore, the cell device based on the Mn-CdS electrode shows superior stability in the sulfide/polysulfide electrolyte in a working state for over 10 h, resulting in a highly reproducible performance, which is a serious challenge for the Mn-doped solar cell. Our finding provides an effective method for the fabrication of Mn-doped CdS QDs, which can pave the way to further improve the efficiency of future QDSSCs.

Evaluation of feed COD/sulfate ratio as a control criterion for the biological hydrogen sulfide production and lead precipitation.

PubMed

Velasco, Antonio; Ramírez, Martha; Volke-Sepúlveda, Tania; González-Sánchez, Armando; Revah, Sergio

2008-03-01

The ability of sulfate-reducing bacteria to produce hydrogen sulfide and the high affinity of sulfide to react with divalent metallic cations represent an excellent option to remove heavy metals from wastewater. Different parameters have been proposed to control the hydrogen sulfide production by anaerobic bacteria, such as the organic and sulfate loading rates and the feed COD/SO4(2-) ratio. This work relates the feed COD/SO4(2-) ratio with the hydrogen sulfide production and dissolved lead precipitation, using ethanol as carbon and energy source in an up-flow anaerobic sludge blanket reactor. A maximum dissolved sulfide concentration of 470+/-7 mg S/L was obtained at a feed COD/SO4(2-) ratio of 2.5, with sulfate and ethanol conversions of approximately 94 and 87%, respectively. The lowest dissolved sulfide concentration (145+/-10 mg S/L) was observed with a feed COD/SO4(2-) ratio of 0.67. Substantial amounts of acetate (510-1730 mg/L) were produced and accumulated in the bioreactor from ethanol oxidation. Although only incomplete oxidation of ethanol to acetate was observed, the consortium was able to remove 99% of the dissolved lead (200 mg/L) with a feed COD/SO4(2-) ratio of 1.5. It was found that the feed COD/SO4(2-) ratio could be an adequate parameter to control the hydrogen sulfide production and the consequent precipitation of dissolved lead.

In Situ Passivation for Efficient PbS Quantum Dot Solar Cells by Precursor Engineering.

PubMed

Wang, Yongjie; Lu, Kunyuan; Han, Lu; Liu, Zeke; Shi, Guozheng; Fang, Honghua; Chen, Si; Wu, Tian; Yang, Fan; Gu, Mengfan; Zhou, Sijie; Ling, Xufeng; Tang, Xun; Zheng, Jiawei; Loi, Maria Antonietta; Ma, Wanli

2018-04-01

Current efforts on lead sulfide quantum dot (PbS QD) solar cells are mostly paid to the device architecture engineering and postsynthetic surface modification, while very rare work regarding the optimization of PbS synthesis is reported. Here, PbS QDs are successfully synthesized using PbO and PbAc 2  · 3H 2 O as the lead sources. QD solar cells based on PbAc-PbS have demonstrated a high power conversion efficiency (PCE) of 10.82% (and independently certificated values of 10.62%), which is significantly higher than the PCE of 9.39% for PbO-PbS QD based ones. For the first time, systematic investigations are carried out on the effect of lead precursor engineering on the device performance. It is revealed that acetate can act as an efficient capping ligands together with oleic acid, providing better surface coverage and replace some of the harmful hydroxyl (OH) ligands during the synthesis. Then the acetate on the surface can be exchanged by iodide and lead to desired passivation. This work demonstrates that the precursor engineering has great potential in performance improvement. It is also pointed out that the initial synthesis is an often neglected but critical stage and has abundant room for optimization to further improve the quality of the resultant QDs, leading to breakthrough efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of transport properties of ZnO/PbS heterojunction solar cells

NASA Astrophysics Data System (ADS)

Cheng, Yang; Whitaker, Michael D. C.; Whiteside, Vincent R.; Bumm, Lloyd A.; Sellers, Ian R.

Lead sulfide (PbS) and lead selenide (PbSe) colloidal quantum dots (CQDs) are considered as a potential candidate material for solar cell applications due to their large band gap tunability range (0.5 to 1.7 eV) and cost-effective solution based processing. A series of Glass/ITO/ZnO/PbS/MoO3/Au heterojunction solar cells were processed and analyzed. A stable (reproducible) 2% conversion efficiency under 1-sun is achieved based on the result of J - V measurements. Absorbance and external quantum efficiency (EQE) measurements clearly show photo-generated carrier extraction from PbS active layers in the solar cell. However, a non-ideal J - V behavior is observed in current-voltage measurements. This behavior may be attributed to a high density of trap states at the QD surface or defect states at the PbS/ZnO or ITO/ZnO interfaces. C-V and Impedance spectroscopy measurements are used to study this unusual behavior. These techniques could also help probe the transport properties and limitation of these heterojunction solar cells. This research is funded through NASA EPSCoR program Award # NNX13AN101A.

Hybrid zinc oxide/graphene electrodes for depleted heterojunction colloidal quantum-dot solar cells.

PubMed

Tavakoli, Mohammad Mahdi; Aashuri, Hossein; Simchi, Abdolreza; Fan, Zhiyong

2015-10-07

Recently, hybrid nanocomposites consisting of graphene/nanomaterial heterostructures have emerged as promising candidates for the fabrication of optoelectronic devices. In this work, we have employed a facile and in situ solution-based process to prepare zinc oxide/graphene quantum dots (ZnO/G QDs) in a hybrid structure. The prepared hybrid dots are composed of a ZnO core, with an average size of 5 nm, warped with graphene nanosheets. Spectroscopic studies show that the graphene shell quenches the photoluminescence intensity of the ZnO nanocrystals by about 72%, primarily due to charge transfer reactions and static quenching. A red shift in the absorption peak is also observed. Raman spectroscopy determines G-band splitting of the graphene shell into two separated sub-bands (G(+), G(-)) caused by the strain induced symmetry breaking. It is shown that the hybrid ZnO/G QDs can be used as a counter-electrode for heterojunction colloidal quantum-dot solar cells for efficient charge-carrier collection, as evidenced by the external quantum efficiency measurement. Under the solar simulated spectrum (AM 1.5G), we report enhanced power conversion efficiency (35%) with higher short current circuit (80%) for lead sulfide-based solar cells as compared to devices prepared by pristine ZnO nanocrystals.

Genesis of copper-lead mineralization in the regionally zoned Agnigundala Sulfide Belt, Cuddapah Basin, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Bhattacharya, H. N.; Bandyopadhyay, Sandip

2018-03-01

Shallow marine sandstone-shale-carbonate sedimentary rocks of the Paleoproterozoic northern Cuddapah basin host copper (Nallakonda deposit), copper-lead (Dhukonda deposit), and lead mineralization (Bandalamottu deposit) which together constitute the Agnigundala Sulfide Belt. The Cu sulfide mineralization in sandstone is both stratabound and disseminated, and Pb sulfide mineralization occurs as stratabound fracture filling veins and/or replacement veins within dolomite. Systematic mineralogical and sulfur, carbon, and oxygen isotope studies of the three deposits indicate a common ore-fluid that deposited copper at Nallakonda, copper-lead at Dhukonda, and lead at Bandalamottu under progressive cooling during migration through sediments. The ore-fluid was of low temperature (< 200 °C) and oxidized. Thermochemical reduction of basinal water sulfate produced sulfide for ore deposition. It is envisaged that basal red-bed and evaporite-bearing rift-related continental to shallow marine sediments might have acted as the source for the metals. Rift-related faults developed during sedimentation in the basin might have punctured the ore-fluid pool in the lower sedimentary succession and also acted as conduits for their upward migration. The ore-bearing horizons have participated in deformations during basin inversion without any recognizable remobilization.

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

DOE PAGES

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; ...

2017-05-16

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the bandmore » edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. As a result, we expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.« less

A filterless, visible-blind, narrow-band, and near-infrared photodetector with a gain

NASA Astrophysics Data System (ADS)

Shen, Liang; Zhang, Yang; Bai, Yang; Zheng, Xiaopeng; Wang, Qi; Huang, Jinsong

2016-06-01

In many applications of near-infrared (NIR) light detection, a band-pass filter is needed to exclude the noise caused by visible light. Here, we demonstrate a filterless, visible-blind, narrow-band NIR photodetector with a full-width at half-maximum of <50 nm for the response spectrum. These devices have a thick (>4 μm) nanocomposite absorbing layers made of polymer-fullerene:lead sulfide (PbS) quantum dots (QDs). The PbS QDs yield a photoconductive gain due to their hole-trapping effect, which effectively enhances both the responsivity and the visible rejection ratio of the external quantum efficiency by >10 fold compared to those without PbS QDs. Encouragingly, the inclusion of the PbS QDs does not increase the device noise. We directly measured a noise equivalent power (NEP) of 6.1 pW cm-2 at 890 nm, and a large linear dynamic range (LDR) over 11 orders of magnitude. The highly sensitive visible-blind NIR narrow-band photodetectors may find applications in biomedical engineering.

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

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

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the bandmore » edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. As a result, we expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.« less

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

PubMed Central

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; McNichols, Brett W.; Miller, Elisa M.; Gu, Jing; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

2017-01-01

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications. PMID:28508866

Quantum-Dot-Based Theranostic Micelles Conjugated with an Anti-EGFR Nanobody for Triple-Negative Breast Cancer Therapy.

PubMed

Wang, Yuyuan; Wang, Yidan; Chen, Guojun; Li, Yitong; Xu, Wei; Gong, Shaoqin

2017-09-13

A quantum-dot (QD)-based micelle conjugated with an anti-epidermal growth factor receptor (EGFR) nanobody (Nb) and loaded with an anticancer drug, aminoflavone (AF), has been engineered for EGFR-overexpressing cancer theranostics. The near-infrared (NIR) fluorescence of the indium phosphate core/zinc sulfide shell QDs (InP/ZnS QDs) allowed for in vivo nanoparticle biodistribution studies. The anti-EGFR nanobody 7D12 conjugation improved the cellular uptake and cytotoxicity of the QD-based micelles in EGFR-overexpressing MDA-MB-468 triple-negative breast cancer (TNBC) cells. In comparison with the AF-encapsulated nontargeted (i.e., without Nb conjugation) micelles, the AF-encapsulated Nb-conjugated (i.e., targeted) micelles accumulated in tumors at higher concentrations, leading to more effective tumor regression in an orthotopic triple-negative breast cancer xenograft mouse model. Furthermore, there was no systemic toxicity observed with the treatments. Thus, this QD-based Nb-conjugated micelle may serve as an effective theranostic nanoplatform for EGFR-overexpressing cancers such as TNBCs.

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

NASA Astrophysics Data System (ADS)

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; McNichols, Brett W.; Miller, Elisa M.; Gu, Jing; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

2017-05-01

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.

Graphene and PbS quantum dot hybrid vertical phototransistor

NASA Astrophysics Data System (ADS)

Song, Xiaoxian; Zhang, Yating; Zhang, Haiting; Yu, Yu; Cao, Mingxuan; Che, Yongli; Dai, Haitao; Yang, Junbo; Ding, Xin; Yao, Jianquan

2017-04-01

A field-effect phototransistor based on a graphene and lead sulfide quantum dot (PbS QD) hybrid in which PbS QDs are embedded in a graphene matrix has been fabricated with a vertical architecture through a solution process. The n-type Si/SiO2 substrate (gate), Au/Ag nanowire transparent source electrode, active layer and Au drain electrode are vertically stacked in the device, which has a downscaled channel length of 250 nm. Photoinduced electrons in the PbS QDs leap into the conduction band and fill in the trap states, while the photoinduced holes left in the valence band transfer to the graphene and form the photocurrent under biases from which the photoconductive gain is evaluated. The graphene/QD-based vertical phototransistor shows a photoresponsivity of 2 × 103 A W-1, and specific detectivity up to 7 × 1012 Jones under 808 nm laser illumination with a light irradiance of 12 mW cm-2. The solution-processed vertical phototransistor provides a new facile method for optoelectronic device applications.

Enhanced interfacial contact between PbS and TiO2 layers in quantum dot solar cells using 2D-arrayed TiO2 hemisphere nanostructures

NASA Astrophysics Data System (ADS)

Lee, Wonseok; Ryu, Ilhwan; Lee, Haein; Yim, Sanggyu

2018-02-01

Two-dimensionally (2D) arrayed hemispherical nanostructures of TiO2 thin films were successfully fabricated using a simple procedure of spin-coating or dip-coating TiO2 nanoparticles onto 2D close-packed polystyrene (PS) nanospheres, followed by PS extraction. The nanostructured TiO2 film was then used as an n-type layer in a lead sulfide (PbS) colloidal quantum dot solar cell. The TiO2 nanostructure could provide significantly increased contacts with subsequently deposited PbS quantum dot layer. In addition, the periodically arrayed nanostructure could enhance optical absorption of the cell by redirecting the path of the incident light and increasing the path length passing though the active layer. As a result, the power conversion efficiency (PCE) reached 5.13%, which is approximately a 1.7-fold increase over that of the control cell without nanostructuring, 3.02%. This PCE enhancement can mainly be attributed to the increase of the short-circuit current density from 19.6 mA/cm2 to 30.6 mA/cm2, whereas the open-circuit voltage and fill factor values did not vary significantly.

Millisecond-Timescale Monitoring of PbS Nanoparticle Nucleation and Growth Using Droplet-Based Microfluidics.

PubMed

Lignos, Ioannis; Stavrakis, Stavros; Kilaj, Ardita; deMello, Andrew J

2015-08-26

The early-time kinetics (<1 s) of lead sulfide (PbS) quantum dot formation are probed using a novel droplet-based microfluidic platform, which allows for high-throughput and real-time optical analysis of the reactive process with millisecond time resolution. The reaction platform enables the concurrent investigation of the emission characteristics of PbS quantum dots and a real-time estimation of their size and concentration during nucleation and growth. These investigations reveal a two-stage mechanism for PbS nanoparticle formation. The first stage corresponds to the fast conversion of precursor species to PbS crystals, followed by the growth of the formed particles. The growth kinetics of the PbS nanoparticles follow the Lifshitz-Slyozov-Wagner model for Ostwald ripening, allowing direct estimation of the rate constants for the process. In addition, the extraction of absorption spectra of ultrasmall quantum dots is demonstrated for first time in an online manner. The droplet-based microfluidic platform integrated with online spectroscopic analysis provides a new tool for the quantitative extraction of high temperature kinetics for systems with rapid nucleation and growth stages. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inhibitors of the serotonin transporter protein (SERT): the design and synthesis of biotinylated derivatives of 3-(1,2,3,6-tetrahydro-pyridin-4-yl)-1H-indoles. High-affinity serotonergic ligands for conjugation with quantum dots.

PubMed

Tomlinson, Ian D; Mason, John N; Blakely, Randy D; Rosenthal, Sandra J

2005-12-01

There is a growing demand for compounds with specificity for the serotonin transporter protein (SERT) that can be conjugated to cadmium selenide/zinc sulfide core shell nanocrystals. This letter describes the design and synthesis of two different biotinylated SERT antagonists that can be attached to streptavidin-coated cadmium selenide/zinc sulfide core shell nanocrystals.

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

Ruberu, T. Purnima A.; Albright, Haley R.; Callis, Brandon

We demonstrate molecular control of nanoscale composition, alloying, and morphology (aspect ratio) in CdS–CdSe nanocrystal dots and rods by modulating the chemical reactivity of phosphine–chalcogenide precursors. Specific molecular precursors studied were sulfides and selenides of triphenylphosphite (TPP), diphenylpropylphosphine (DPP), tributylphosphine (TBP), trioctylphosphine (TOP), and hexaethylphosphorustriamide (HPT). Computational (DFT), NMR (31P and 77Se), and high-temperature crossover studies unambiguously confirm a chemical bonding interaction between phosphorus and chalcogen atoms in all precursors. Phosphine–chalcogenide precursor reactivity increases in the order: TPPE < DPPE < TBPE < TOPE < HPTE (E = S, Se). For a given phosphine, the selenide is always more reactivemore » than the sulfide. CdS1–xSex quantum dots were synthesized via single injection of a R3PS–R3PSe mixture to cadmium oleate at 250 °C. X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV/Vis and PL optical spectroscopy reveal that relative R3PS and R3PSe reactivity dictates CdS1–xSex dot chalcogen content and the extent of radial alloying (alloys vs core/shells). CdS, CdSe, and CdS1–xSex quantum rods were synthesized by injection of a single R3PE (E = S or Se) precursor or a R3PS–R3PSe mixture to cadmium–phosphonate at 320 or 250 °C. XRD and TEM reveal that the length-to-diameter aspect ratio of CdS and CdSe nanorods is inversely proportional to R3PE precursor reactivity. Purposely matching or mismatching R3PS–R3PSe precursor reactivity leads to CdS1–xSex nanorods without or with axial composition gradients, respectively. We expect these observations will lead to scalable and highly predictable “bottom-up” programmed syntheses of finely heterostructured nanomaterials with well-defined architectures and properties that are tailored for precise applications.« less

Quantum dot bioconjugates for ultrasensitive nonisotopic detection.

PubMed

Chan, W C; Nie, S

1998-09-25

Highly luminescent semiconductor quantum dots (zinc sulfide-capped cadmium selenide) have been covalently coupled to biomolecules for use in ultrasensitive biological detection. In comparison with organic dyes such as rhodamine, this class of luminescent labels is 20 times as bright, 100 times as stable against photobleaching, and one-third as wide in spectral linewidth. These nanometer-sized conjugates are water-soluble and biocompatible. Quantum dots that were labeled with the protein transferrin underwent receptor-mediated endocytosis in cultured HeLa cells, and those dots that were labeled with immunomolecules recognized specific antibodies or antigens.

Lead isotopic compositions of soil and near-surface till profiles from a watershed containing arsenic-enriched groundwater in coastal Maine

USGS Publications Warehouse

Ayuso, Robert; Foley, Nora; Wandless, Gregory; Dillingham, Jeremy; Colvin, Anna

2005-01-01

Lead isotope compositions of soils and near-surface tills from an area of coastal Maine known to have groundwater with anomalously high arsenic contents were measured in order to determine the source of the lead and, by inference, possible sources of arsenic. Five soil and till sites were selected for detailed chemical and isotopic analysis. To construct profiles of the soil and till horizons, five samples were collected at 10-cm intervals from the surface to the base of each horizon. Total lead and arsenic concentrations and lead isotopic compositions were measured for 48 leaches and bulk residues. The soils and tills are underlain by sulfidic schists of the Penobscot Formation. Several generations of minerals containing arsenic and lead exist in the regional bedrock, including rock-forming silicates (feldspar and micas), sulfide minerals formed during diagenesis (for example, arsenic-rich pyrite), and sulfide and oxide minerals that formed as a result of Silurian metamorphic and igneous events (for example, arsenopyrite, galena, iron-oxides, and arsenic-sulfides). A young group of secondary minerals (for example, iron-hydroxides, arsenic-hydroxides, lead-sulfate, and arsenic-jarosite) formed from recent weathering and pedogenic processes.

Biological conversion of anglesite (PbSO(4)) and lead waste from spent car batteries to galena (PbS).

PubMed

Weijma, Jan; De Hoop, Klaas; Bosma, Wobby; Dijkman, Henk

2002-01-01

Lead paste, a solid mixture containing PbSO(4), PbO(2), PbO/Pb(OH)(2) precipitate, and elemental Pb, is one of the main waste fractions from spent car batteries. Biological sulfidation represents a new process for recovery of lead from this waste. In this process the lead salts in lead paste are converted to galena (PbS) by sulfate-reducing bacteria. This paper investigates a continuous process for sulfidation of anglesite (PbSO(4)), the main constituent of lead paste, and lead paste, consisting of a laboratory-scale gas-lift bioreactor to which a slurry of anglesite or lead paste was supplied. Sulfate or elemental sulfur was added as an additional sulfur source. Hydrogen gas served as an electron donor for the biological reduction of sulfate and elemental sulfur to sulfide by sulfate- and sulfur-reducing bacteria. Anglesite was almost completely converted to galena at a loading rate of 19 kg of PbSO(4) m(-)(3) day(-)(1), producing a sludge of which the crystalline lead phases consisted of >98% PbS (galena) and 1-2% elemental Pb. With lead paste, stable sulfidation rates of up to 17 kg of lead paste m(-)(3) day(-)(1) were demonstrated, producing a sludge of which the crystalline lead phases consisted of an estimated >96% PbS, 1-2% elemental Pb, and 1-2% PbO(2).

Luminescence in Sulfides: A Rich History and a Bright Future

PubMed Central

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

2010-01-01

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

A fluorescent sensor based on thioglycolic acid capped cadmium sulfide quantum dots for the determination of dopamine

NASA Astrophysics Data System (ADS)

Kulchat, Sirinan; Boonta, Wissuta; Todee, Apinya; Sianglam, Pradthana; Ngeontae, Wittaya

2018-05-01

A fluorescent sensor based on thioglycolic acid-capped cadmium sulfide quantum dots (TGA-CdS QDs) has been designed for the sensitive and selective detection of dopamine (DA). In the presence of dopamine (DA), the addition of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (NHS) activates the reaction between the carboxylic group of the TGA and the amino group of dopamine to form an amide bond, quenching the fluorescence of the QDs. The fluorescence intensity of TGA-CdS QDs can be used to sense the presence of dopamine with a limit of detection of 0.68 μM and a working linear range of 1.0-17.5 μM. This sensor system shows great potential application for dopamine detection in dopamine drug samples and for future easy-to-make analytical devices.

PEG-phospholipid-encapsulated bismuth sulfide and CdSe/ZnS quantum dot core-shell nanoparticle and its computed tomography/fluorescence performance

NASA Astrophysics Data System (ADS)

Chen, Jun; Yang, Xiao-Quan; Qin, Meng-Yao; Zhang, Xiao-Shuai; Xuan, Yang; Zhao, Yuan-Di

2015-11-01

In this paper, polyethylene glycol-phospholipid structure is used to synthesize hybrid cluster of 40-50 nm diameter that contains hydrophobic bismuth sulfide nanoparticles and CdSe/ZnS quantum dots. The composite probe's toxicity, CT imaging, and fluorescence imaging performance are also studied. Experimental results show that the nanocomposite hybrid cluster has obvious CT contrast enhancement and fluorescence imaging capability in vitro even after cellular uptake. It gives a CT number of 700 (Hounsfield units) at 15 mg/mL, higher than that of the current iobitridol CT contrast agent. 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide experiment reveals that it has low cytotoxicity at concentration up to of 3.14 mg/mL of Bi, indicating the composite probe has potential ability for CT and fluorescence bimodal imaging.

Optimization Photodetectors from Zinc Sulfide Deposited on Porous Silicon with Different Doping Metals

NASA Astrophysics Data System (ADS)

Nayef, Uday Muhsin; Khalaf, Haider Amer

In this work, the structural properties of the zinc sulfide (ZnS) films have been investigated using X-ray diffraction (XRD) analysis which show an enhancement in the crystallite degree after doping with copper (Cu). Good matching between the ZnS and porous silicon (PS) structure was noted from the atomic force microscope (AFM) results. The reflectivity gave a clear observation of anti-reflected coating improvement for PS layer and more enhancements after the ZnS deposition. The optical properties show a blue shift in the bandgap for the ZnS deposited with higher substrate temperature and a red shift after doped with different elements. For ZnS/PS heterojunction, the electrical resistivity has been increased after PS layer formed and changed with the variation of the pore size and it was much higher after ZnS deposited on the PS. However, use of ZnS:Cu/PS photodetector showed much higher output current at the ultraviolet (UV) region compared to ZnS/PS. The ZnS:Cu/PS photodetector showed higher output current value than that of the ZnS/PS leading to improvement in the quantum efficiency of 42%.

Synthesis, Optical and Structural Properties of Copper Sulfide Nanocrystals from Single Molecule Precursors

PubMed Central

Ajibade, Peter A.; Botha, Nandipha L.

2017-01-01

We report the synthesis and structural studies of copper sulfide nanocrystals from copper (II) dithiocarbamate single molecule precursors. The precursors were thermolysed in hexadecylamine (HDA) to prepare HDA-capped CuS nanocrystals. The optical properties of the nanocrystals studied using UV–visible and photoluminescence spectroscopy showed absorption band edges at 287 nm that are blue shifted, and the photoluminescence spectra show emission curves that are red-shifted with respect to the absorption band edges. These shifts are as a result of the small crystallite sizes of the nanoparticles leading to quantum size effects. The structural studies were carried out using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy. The XRD patterns indicates that the CuS nanocrystals are in hexagonal covellite crystalline phases with estimated particles sizes of 17.3–18.6 nm. The TEM images showed particles with almost spherical or rod shapes, with average crystallite sizes of 3–9.8 nm. SEM images showed morphology with ball-like microspheres on the surfaces, and EDS spectra confirmed the presence of CuS nanoparticles. PMID:28336865

Comparison of Hydrogen Sulfide Analysis Techniques

ERIC Educational Resources Information Center

Bethea, Robert M.

1973-01-01

A summary and critique of common methods of hydrogen sulfide analysis is presented. Procedures described are: reflectance from silver plates and lead acetate-coated tiles, lead acetate and mercuric chloride paper tapes, sodium nitroprusside and methylene blue wet chemical methods, infrared spectrophotometry, and gas chromatography. (BL)

Structural and optical studied of nano structured lead sulfide thin films prepared by the chemical bath deposition technique

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

Al Din, Nasser Saad, E-mail: nsaadaldin@yahoo.com; Hussain, Nabiha, E-mail: nabihahssin@yahoo.com; Jandow, Nidhal, E-mail: nidhaljandow@yahoo.com

2016-07-25

Lead (II) Sulfide PbS thin films were deposited on glass substrates at 25°C by chemical bath deposition (CBD) method. The structural properties of the films were studied as a function of the concentration of Thiourea (CS (NH{sub 2}){sub 2}) as Source of Sulfide and deposition time. The surface morphology of the films was characterized by X-ray diffraction and SEM. The obtained results showed that the as-deposited films Polycrystalline had cubic crystalline phase that belong to S.G: Fm3m. We found that they have preferred orientation [200]. Also the thickness of thin films decrease with deposition time after certain value and, itmore » observed free sulfide had orthorhombic phase. Optical properties showed that the thin films have high transmission at visible range and low transmission at UV, IR range. The films of PbS have direct band gap (I.68 - 2.32 ev) at 300 K the values of band energy decreases with increases thickness of the Lead (II) Sulfide films.« less

Acid Volatile Sulfides and Simultaneously Extracted Copper, Lead, and Zinc in Sediments of Sinclair Inlet, Washington

DTIC Science & Technology

1993-09-01

to Doug Vaught, J. Towell, and Eric Schlierman of Puget Sound Naval Shipyard for providing laboratory space, equipment, and logistical support for the...availability and mobility of toxic metal contamination in the sediments of Sinclair Inlet, Puget Sound , Washington, acid volatile sulfide (AVS) and... Puget Sound , Washington ........ 1 2. Apparatus used for measuring acid volatile sulfides ........................... 5 3. Sulfide electrode

Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

NASA Technical Reports Server (NTRS)

Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.

2008-01-01

Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

Efficiencies of Dye-Sensitized Solar Cells using Ferritin-Encapsulated Quantum Dots with Various Staining Methods

NASA Astrophysics Data System (ADS)

Perez, Luis

Dye-sensitized solar cells (DSSC) have the potential to replace traditional and cost-inefficient crystalline silicon or ruthenium solar cells. This can only be accomplished by optimizing DSSC's energy efficiency. One of the major components in a dye-sensitized solar cell is the porous layer of titanium dioxide. This layer is coated with a molecular dye that absorbs sunlight. The research conducted for this paper focuses on the different methods used to dye the porous TiO2 layer with ferritin-encapsulated quantum dots. Multiple anodes were dyed using a method known as SILAR which involves deposition through alternate immersion in two different solutions. The efficiencies of DSSCs with ferritin-encapsulated lead sulfide dye deposited using SILAR were subsequently compared against the efficiencies produced by cells using the traditional immersion method. It was concluded that both methods resulted in similar efficiencies (? .074%) however, the SILAR method dyed the TiO2 coating significantly faster than the immersion method. On a related note, our experiments concluded that conducting 2 SILAR cycles yields the highest possible efficiency for this particular binding method. National Science Foundation.

Optical Analysis of Iron-Doped Lead Sulfide Thin Films for Opto-Electronic Applications

NASA Astrophysics Data System (ADS)

Chidambara Kumar, K. N.; Khadeer Pasha, S. K.; Deshmukh, Kalim; Chidambaram, K.; Shakil Muhammad, G.

Iron-doped lead sulfide thin films were deposited on glass substrates using successive ionic layer adsorption and reaction method (SILAR) at room temperature. The X-ray diffraction pattern of the film shows a well formed crystalline thin film with face-centered cubic structure along the preferential orientation (1 1 1). The lattice constant is determined using Nelson Riley plots. Using X-ray broadening, the crystallite size is determined by Scherrer formula. Morphology of the thin film was studied using a scanning electron microscope. The optical properties of the film were investigated using a UV-vis spectrophotometer. We observed an increase in the optical band gap from 2.45 to 3.03eV after doping iron in the lead sulfide thin film. The cutoff wavelength lies in the visible region, and hence the grown thin films can be used for optoelectronic and sensor applications. The results from the photoluminescence study show the emission at 500-720nm. The vibrating sample magnetometer measurements confirmed that the lead sulfide thin film becomes weakly ferromagnetic material after doping with iron.

A pyrazolyl-based thiolato single-source precursor for the selective synthesis of isotropic copper-deficient copper(I) sulfide nanocrystals: synthesis, optical and photocatalytic activity

NASA Astrophysics Data System (ADS)

Mondal, Gopinath; Santra, Ananyakumari; Bera, Pradip; Acharjya, Moumita; Jana, Sumanta; Chattopadhyay, Dipankar; Mondal, Anup; Seok, Sang Il; Bera, Pulakesh

2016-10-01

Hexagonal copper-deficient copper(I) sulfide (Cu2- x S, x = 0.03, 0.2) nanocrystals (NCs) are synthesized from a newly prepared single-source precursor (SP), [Cu(bdpa)2][CuCl2], where bdpa is benzyl 3,5-dimethyl-pyrazole-1-carbodithioate. The SP is crystallized with space group Pī and possesses a distorted tetrahedron structure with a CuN2S2 chromophore where the central copper is in +1 oxidation state. Distortion in copper(I) structure and the low decomposition temperature of SP make it favorable for the low-temperature solvent-assisted selective growth of high-copper content sulfides. The nucleation and growth of Cu2- x S ( x = 0.03, 0.2) are effectively controlled by the SP and the solvent in the solvothermal decomposition process. During decomposition, fragment benzyl thiol (PhCH2SH) from SP effectively passivates the nucleus leading to spherical nanocrystals. Further, solvent plays an important role in the selective thermochemical transformation of CuI-complex to Cu2- x S ( x = 0.03, 0.2) NCs. The chelating binders (solvent) like ethylene diamine (EN) and ethylene glycol (EG) prefer to form spherical Cu1.97S nanoparticles (djurleite), whereas nonchelating hydrazine hydrate (HH) shows the tendency to furnish hexagonal platelets of copper-deficient Cu1.8S. The optical band gap values (2.25-2.50 eV) show quantum confinement effect in the structure. The synthesized NCs display excellent catalytic activity ( 87 %) toward photodegradation of organic dyes like Congo Red (CR) and Methylene Blue (MB).

Optical, electrical, and photovoltaic properties of PbS thin films by anionic and cationic dopants

NASA Astrophysics Data System (ADS)

Cheraghizade, Mohsen; Jamali-Sheini, Farid; Yousefi, Ramin

2017-06-01

Lead sulfide (PbS) thin films were deposited by CVD method to examine the effects of anionic and cationic dopants on optical and electrical properties for photovoltaic applications. XRD diffractograms verified the formation of cubic phase of multicrystalline PbS thin films. FESEM images showed surface morphologies in nano-dimensions (rods and flowers). UV-Vis-NIR spectrum revealed absorbance in the visible and NIR regions for all samples, in which dopants decreased the intensity of absorbance. Se as an anionic dopant for PbS thin films increased electrical resistance, acceptor concentrations, and crystallite defects, and decreased flat-band voltage and depletion width. Finally, photovoltaic measurements indicated that Zn-doped PbS thin film, as a photovoltaic cell, exhibited higher conversion efficiency and external quantum efficiency (EQE).

Chemical Bath Deposited Zinc Sulfide Buffer Layers for Copper Indium Gallium Sulfur-selenide Solar Cells and Device Analysis

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

Kundu, Sambhu N.; Olsen, Larry C.

2005-01-03

Cd free CIGSS thin film solar cell structures with a MgF2/TCO/CGD-ZnS/CIGSS/Mo/SLG structure have been fabricated using chemical bath deposited (CBD)-ZnS buffer layers and high quality CIGSS absorber layers supplied from Shell Solar Industries. The use of CBD-ZnS, which is a higher band gap materials than CdS, improved the quantum efficiency of fabricated cells at lower wavelengths, leading to an increase in short circuit current. The best cell to date yielded an active area (0.43 cm2) efficiency of 13.3%. This paper also presents a discussion of the issues relating to the use of the CBD-ZnS buffer materials for improving device performance.

Removal of metals from lead-zinc mine tailings using bioleaching and followed by sulfide precipitation.

PubMed

Ye, Maoyou; Li, Guojian; Yan, Pingfang; Ren, Jie; Zheng, Li; Han, Dajian; Sun, Shuiyu; Huang, Shaosong; Zhong, Yujian

2017-10-01

Mine tailings often contain significant amounts of metals and sulfide, many traditional operations used to minerals was not as good as those currently available. This study investigated metals removal from lead-zinc mine tailings using bioleaching and followed by sulfide precipitation. Metals were dissolved from the tailings by the bacteria in a bioleaching reactor. During a 10% pulp density bioleaching experiment, approximately 0.82% Pb, 97.38% Zn, and 71.37% Fe were extracted after 50 days. With the pulp density of 10% and 20%, the dissolution of metals followed shrinking core kinetic model. Metals (Pb, Zn, and Fe) present in the pregnant bioleaching leachate. Metals were next precipitated as a sulfide phase using sodium sulfide (Na 2 S). Metal precipitations were selectively and quantitatively produced from the bioleaching leachate by adding Na 2 S. More than 99% of the zinc and 75% of the iron was precipitated using 25 g/L Na 2 S in the bioleaching leachate. The results in the study were to provide useful information for recovering or removing metals from lead-zinc mine tailings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Remediation of arsenic and lead with nanocrystalline zinc sulfide.

PubMed

Piquette, Alan; Cannon, Cody; Apblett, Allen W

2012-07-27

Nanocrystalline (1.7 ± 0.3 nm) zinc sulfide with a specific surface area up to 360 m(2) g(-1) was prepared from the thermal decomposition of a single-source precursor, zinc ethylxanthate. Zinc ethylxanthate decomposes to cubic zinc sulfide upon exposure to temperatures greater than or equal to 125 °C. The resulting zinc sulfide was tested as a water impurity extractant. The target impurities used in this study were As(5+), As(3+), and Pb(2+). The reaction of the nanocrystalline ZnS with Pb(2+) proceeds as a replacement reaction where solid PbS is formed and Zn(2+) is released into the aqueous system. Removal of lead to a level of less than two parts per billion is achievable. The results of a detailed kinetics experiment between the ZnS and Pb(2+) are included in this study. Unlike the instance of lead, both As(5+) and As(3+) adsorb on the surface of the ZnS extractant as opposed to an ion-exchange process. An uptake capacity of > 25 mg g(-1) for the removal of As(5+) is possible. The uptake of As(3+) appears to proceed by a slower process than that of the As(5+) with a capacity of nearly 20 mg g(-1). The nanocrystalline zinc sulfide was extremely successful for the removal of arsenic and lead from simulated oil sand tailing pond water.

Mn-doped quantum dot sensitized solar cells: a strategy to boost efficiency over 5%.

PubMed

Santra, Pralay K; Kamat, Prashant V

2012-02-08

To make Quantum Dot Sensitized Solar Cells (QDSC) competitive, it is necessary to achieve power conversion efficiencies comparable to other emerging solar cell technologies. By employing Mn(2+) doping of CdS, we have now succeeded in significantly improving QDSC performance. QDSC constructed with Mn-doped-CdS/CdSe deposited on mesoscopic TiO(2) film as photoanode, Cu(2)S/Graphene Oxide composite electrode, and sulfide/polysulfide electrolyte deliver power conversion efficiency of 5.4%.

A strategy of combining SILAR with solvothermal process for In2S3 sensitized quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Yang, Peizhi; Tang, Qunwei; Ji, Chenming; Wang, Haobo

2015-12-01

Pursuit of an efficient strategy for quantum dot-sensitized photoanode has been a persistent objective for enhancing photovoltaic performances of quantum dot-sensitized solar cell (QDSC). We present here the fabrication of the indium sulfide (In2S3) quantum dot-sensitized titanium dioxide (TiO2) photoanode by combining successive ionic layer adsorption and reaction (SILAR) with solvothermal processes. The resultant QDSC consists of an In2S3 sensitized TiO2 photoanode, a liquid polysulfide electrolyte, and a Co0.85Se counter electrode. The optimized QDSC with photoanode prepared with the help of a SILAR method at 20 deposition cycles and solvothermal method yields a maximum power conversion efficiency of 1.39%.

Ag2S Quantum Dot-Sensitized Solar Cells by First Principles: The Effect of Capping Ligands and Linkers.

PubMed

Amaya Suárez, Javier; Plata, Jose J; Márquez, Antonio M; Fernández Sanz, Javier

2017-09-28

Quantum dots solar cells, QDSCs, are one of the candidates for being a reliable alternative to fossil fuels. However, the well-studied CdSe and CdTe-based QDSCs present a variety of issues for their use in consumer-goods applications. Silver sulfide, Ag 2 S, is a promising material, but poor efficiency has been reported for QDSCs based on this compound. The potential influence of each component of QDSCs is critical and key for the development of more efficient devices based on Ag 2 S. In this work, density functional theory calculations were performed to study the nature of the optoelectronic properties for an anatase-TiO 2 (101) surface sensitized with different silver sulfide nanoclusters. We demonstrated how it is possible to deeply tune of its electronic properties by modifying the capping ligands and linkers to the surface. Finally, an analysis of the electron injection mechanism for this system is presented.

Self-assembly and alignment of semiconductor nanoparticles on cellulose nanocrystals

Treesearch

Sonal Padalkar; Jeff R. Capadona; Stuart J. Rowan; Christoph Weder; Robert J. Moon; Lia A. Stanciu

2011-01-01

The synthesis of cadmium sulfide (CdS), zinc sulfide (ZnS), and lead sulfide (PbS) nanoparticle chains on cellulose nanocrystal (CNC) templates can be accomplished by the reaction of the precursor salts. The use of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), was critical for the synthesis of well-defined semiconductor nanoparticle chains on the...

Selective Sulfidation of Lead Smelter Slag with Sulfur

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Synergistic Effect of a Molecular Cocatalyst and a Heterojunction in a 1 D Semiconductor Photocatalyst for Robust and Highly Efficient Solar Hydrogen Production.

PubMed

Jiang, Daochuan; Irfan, Rana Muhammad; Sun, Zijun; Lu, Dapeng; Du, Pingwu

2016-11-09

Photocatalytic production of hydrogen by water splitting is a promising pathway for the conversion of solar energy into chemical energy. However, the photocatalytic conversion efficiency is often limited by the sluggish transfer of the photogenerated charge carriers, charge recombination, and subsequent slow catalytic reactions. Herein, we report a highly active noble-metal-free photocatalytic system for hydrogen production in water. The system contains a water-soluble nickel complex as a molecular cocatalyst and zinc sulfide on 1D cadmium sulfide as the heterojunction photocatalyst. The complex can efficiently transport photogenerated electrons and holes over a heterojunction photocatalyst to hamper charge recombination, leading to highly improved catalytic efficiency and durability of a heterojunction photocatalyst- molecular cocatalyst system. The results show that under optimal conditions, the average apparent quantum yield was approximately 58.3 % after 7 h of irradiation with monochromatic 420 nm light. In contrast, the value is only 16.8 % if the molecular cocatalyst is absent. Such a remarkable performance in a molecular cocatalyst-based photocatalytic system without any noble metal loading has, to the best of our knowledge, not been reported to date. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recurrence of Seagrass Mortality in Florida Bay: The Role of Climate Change and Implications for Carbon Sequestration

NASA Astrophysics Data System (ADS)

Yarbro, L.; Carlson, P. R., Jr.

2016-02-01

Catastrophic mortality of seagrass in Florida Bay (USA) from 1987 to 1991 resulted in the complete loss of thousands of hectares of dense Thalassia testudinum beds. At that time, acutely toxic levels of dissolved sulfide in sediments were determined to be the proximal cause of seagrass mortality, but the mechanisms responsible for sulfide accumulation in sediments were not demonstrated. With the recurrence of seagrass mortality in Florida Bay in summer 2015, we show that several processes create the conditions that lead to sulfide toxicity and catastrophic mortality of Thalassia. Regional drought and elevated water temperature lead to hypersalinity, particularly in the northern Bay. In addition, evaporation of seawater on mudbanks and microtidal flow patterns create stratified brine layers in basins adjacent to mudbanks. Because of very high seagrass shoot densities and limited tidal exchange, brine layers limit oxygen diffusion and prevent oxidation of sulfide in sediments and bottom water, exposing roots, rhizomes and lateral meristems of Thalassia to acutely toxic levels of sulfide, causing extensive mortality. Dead belowground tissues provide labile carbon sources to sulfate-reducing bacteria enhancing sulfide production and creating a positive feedback loop of increasing sulfide toxicity leading to further seagrass death. The carbon sequestration capacity of these dense seagrass communities is diminished three ways: 1) export of dead seagrass shoots and leaves as floating wrack, 2) in situ decomposition of roots, rhizomes, and some leaf material, and 3) reduced areal productivity of surviving seagrasses. Climate analyses show that, in the short term ( 50 years), higher water temperatures and evaporation rates might result in recurring seagrass mortality events. However, in the long term, sea level rise will increase tidal exchange and flushing in Florida Bay reducing the likelihood of seagrass mortality.

Speculation on quantum mechanics and the operation of life giving catalysts.

PubMed

Haydon, Nathan; McGlynn, Shawn E; Robus, Olin

2011-02-01

The origin of life necessitated the formation of catalytic functionalities in order to realize a number of those capable of supporting reactions that led to the proliferation of biologically accessible molecules and the formation of a proto-metabolic network. Here, the discussion of the significance of quantum behavior on biological systems is extended from recent hypotheses exploring brain function and DNA mutation to include origins of life considerations in light of the concept of quantum decoherence and the transition from the quantum to the classical. Current understandings of quantum systems indicate that in the context of catalysis, substrate-catalyst interaction may be considered as a quantum measurement problem. Exploration of catalytic functionality necessary for life's emergence may have been accommodated by quantum searches within metal sulfide compartments, where catalyst and substrate wave function interaction may allow for quantum based searches of catalytic phase space. Considering the degree of entanglement experienced by catalytic and non catalytic outcomes of superimposed states, quantum contributions are postulated to have played an important role in the operation of efficient catalysts that would provide for the kinetic basis for the emergence of life.

Lead recovery from waste CRT funnel glass by high-temperature melting process.

PubMed

Hu, Biao; Hui, Wenlong

2018-02-05

In this research, a novel and effective process for waste CRT funnel glass treatment was developed. The key to this process is removal of lead from the CRT funnel glass by high-temperature melting process. Sodium carbonate powder was used as a fusion agent, sodium sulfide serves as a catalytic agent and carbon powder acts as reducing agent. Experimental results showed that lead recovery rate increased with an increase in the amount of added sodium carbonate, sodium sulfide, carbonate, temperature and holding time initially, and then reached a stable value. The maximum lead recovery rate was approximately 94%, when the optimum adding amount of sodium carbonate, sodium sulfide, carbonate, temperature and holding time were 25%, 8%, 3.6%, 1200°C and 120min, respectively. In the high-temperature melting process, lead silicate in the funnel glass was firstly reduced, and then removed. The glass slag can be made into sodium and potassium silicate by hydrolysis process. This study proposed a practical and economical process for recovery of lead and utilization of waste glass slag. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of colloidal PbS quantum dot-based solar cells with near infrared emission.

PubMed

Lim, Sungoh; Kim, Yohan; Lee, Jeongno; Han, Chul Jong; Kang, Jungwon; Kim, Jiwan

2014-12-01

Colloidal quantum dots (QD)-based solar cells with near infrared (NIR) emission have been investigated. Lead sulfide (PbS) QDs, which have narrow band-gap and maximize the absorption of NIR spectrum, were chosen as active materials for efficient solar cells. The inverted structure of indium tin oxide/titanium dioxide/PbS QDs/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)/silver (ITO/TiO2/PbS QDs/ PSS/Ag) was applied for favorable electron and hole seperation from the PbS QD. Through the ligand exchange by 1,2-Ethanedithiol (EDT), the interparticle distance of the PbS QDs in thin film became closer and the performance of the PbS QD-based solar cells was improved. Our PbS QD-based inverted solar cells showed open circuit voltages (V(oc)) of 0.33 V, short circuit current density (J(sc)) of 10.89 mA/cm2, fill factor (FF) of 30%, and power conversion efficiency (PCE) of 1.11%. In our PbS QD-based multifunctional solar cell, the NIR light emission intensity was simply detected with photodiode system, which implies the potential of multi-functional diode device for various applications.

Thin-Film Quantum Dot Photodiode for Monolithic Infrared Image Sensors.

PubMed

Malinowski, Pawel E; Georgitzikis, Epimitheas; Maes, Jorick; Vamvaka, Ioanna; Frazzica, Fortunato; Van Olmen, Jan; De Moor, Piet; Heremans, Paul; Hens, Zeger; Cheyns, David

2017-12-10

Imaging in the infrared wavelength range has been fundamental in scientific, military and surveillance applications. Currently, it is a crucial enabler of new industries such as autonomous mobility (for obstacle detection), augmented reality (for eye tracking) and biometrics. Ubiquitous deployment of infrared cameras (on a scale similar to visible cameras) is however prevented by high manufacturing cost and low resolution related to the need of using image sensors based on flip-chip hybridization. One way to enable monolithic integration is by replacing expensive, small-scale III-V-based detector chips with narrow bandgap thin-films compatible with 8- and 12-inch full-wafer processing. This work describes a CMOS-compatible pixel stack based on lead sulfide quantum dots (PbS QD) with tunable absorption peak. Photodiode with a 150-nm thick absorber in an inverted architecture shows dark current of 10 -6 A/cm² at -2 V reverse bias and EQE above 20% at 1440 nm wavelength. Optical modeling for top illumination architecture can improve the contact transparency to 70%. Additional cooling (193 K) can improve the sensitivity to 60 dB. This stack can be integrated on a CMOS ROIC, enabling order-of-magnitude cost reduction for infrared sensors.

Lead sulfide - Silicon MOSFET infrared focal plane development

NASA Technical Reports Server (NTRS)

Barrett, J. R.; Jhabvala, M. D.

1983-01-01

A process for directly integrating photoconductive lead sulfide (PbS) infrared detector material with silicon MOS integrated circuits has been developed primarily for application in long (greater than 10,000 detector elements) linear arrays for pushbroom scanning applications. The processing technology is based on the conventional PMOS and CMOS technologies with a variation in the metallization. Results and measurements on a fully integrated eight-element multiplexer are shown.

Magnetic properties and phase transformations of iron sulfides synthesized under the hydrothermal method

NASA Astrophysics Data System (ADS)

Li, S. H.; Chen, Y. H.

2016-12-01

The iron sulfide nano-minerals possess advantages of high abundance, low cost, and low toxicity. These advantages make them be competitive in the magnetic, electronic, and photoelectric applications. Mackinawite can be used in soil or water remediations. Greigite is very important for paleomagnetic and geochemical environment studies and the anode materials for lithium ion batteries. Besides, greigite is also utilized for hyperthermia and biomedicine. Pyrrhotite can be applied as geothermometry. Due to the above-mentioned reasons, iron sulfide minerals have specific significances and they must be further investigated, like their phase transformations, magnetic properties, and etc. In this study, the iron sulfide minerals were synthesized by using a hydrothermal method. The ex-situ and in-situ X-ray diffraction (XRD) was used to examine the crystal structure and phase transformation of iron sulfide minerals. The Transmission electron microscopy (TEM) and superconducting quantum interference device (SQUID) were carried out to investigate their morphology and magnetic properties, respectively. The results suggested that the phase transformation sequence was followed the order: mackinawite → greigite → (smythite) → pyrrhotite. Two pure mineral phases of greigite and pyrrhotite were obtained under the hydrothermal conditions. The morphology of the pure greigite is granular aggregates with a particle size of approximately 30 nm and pyrrhotite presented a hexagonal sheet stacking with a particle size of thousands nanometers. The greigite had a ferri-magnetic behavior and pyrrhotite was weak ferro-magnetic. Both of them had a pseudo-single magnetic domain (PSD) based on the Day's plot from SQUID data. The complete phase-transformation pathways and high magnetization of iron sulfide minerals are observed in this study and these kind of iron sulfide minerals are worthy to further study.

Direct electrochemical stripping detection of cystic-fibrosis-related DNA linked through cadmium sulfide quantum dots

NASA Astrophysics Data System (ADS)

Marin, Sergio; Merkoçi, Arben

2009-02-01

Electrochemical detection of a cadmium sulfide quantum dots (CdS QDs)-DNA complex connected to paramagnetic microbeads (MB) was performed without the need for chemical dissolving. The method is based on dropping 20 µl of CdS QD-DNA-MB suspension on the surface of a screen-printed electrode. It is followed by magnetic collection on the surface of the working electrode and electrochemical detection using square-wave voltammetry (SWV), giving a well-shaped and sensitive analytical signal. A cystic-fibrosis-related DNA sequence was sandwiched between the two DNA probes. One DNA probe is linked via biotin-streptavidin bonding with MB and the other one via thiol groups with the CdS QD used as tags. Nonspecific signals of DNA were minimized using a blocking agent and the results obtained were successfully employed in a model DNA sensor with an interest in future applications in the clinical field. The developed nanoparticle biosensing system may offer numerous opportunities in other fields where fast, low cost and efficient detection of small volume samples is required.

Anaerobic Biostimulation for the In Situ Precipitation and Long-Term Sequestration of Metal Sulfides

DTIC Science & Technology

2009-04-01

remediation is critically needed. The five most frequently cited metals in the Williford report were arsenic, lead, cadmium, chromium and mercury . Of these...arsenic, lead, cadmium and mercury have been shown to precipitate as stable metal sulfides under highly reducing conditions. The recently...potential applications to bioprecipitation of toxic metals as sulphides . J. of Industrial Microbiology 17: 116-123. Williford, W.W., R.M. Bricka, S.L

Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot

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

Jensen, Stephen C.; Bettis Homan, Stephanie; Weiss, Emily A.

2016-01-28

This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6–4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ~5 ps to form QD•–; electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecondmore » time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Nuclear magnetic resonance analysis of the QD–molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only encourages aniline to desorb but also increases the probability of protonated intermediates; the latter effect probably ensures that recruitment of protons is not rate-limiting.« less

Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery.

PubMed

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

2007-04-01

The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.

Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 Using FeS/H2S As a Reducing Agent

NASA Technical Reports Server (NTRS)

Keefe, Anthony D.; Miller, Stanley L.; McDonald, Gene; Bada, Jeffrey

1995-01-01

An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purities, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role In the origin of metabolism or the origin of life.

Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 using FeS/H2S as a Reducing Agent

NASA Technical Reports Server (NTRS)

Keefe, Anthony D.; Miller, Stanley L.; McDonald, Gene; Bada, Jeffrey

1995-01-01

An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purines, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role in the origin of metabolism or the origin of life.

The cytochrome bd oxidase of Escherichia coli prevents respiratory inhibition by endogenous and exogenous hydrogen sulfide

PubMed Central

Korshunov, Sergey; Imlay, Karin R. C.; Imlay, James A.

2016-01-01

Summary When sulfur compounds are scarce or difficult to process, E. coli adapts by inducing the high-level expression of sulfur-compound importers. If cystine then becomes available, the cystine is rapidly overimported and reduced, leading to a burgeoning pool of intracellular cysteine. Most of the excess cysteine is exported, but some is adventitiously degraded, with the consequent release of sulfide. Sulfide is a potent ligand of copper and heme moieties, raising the prospect that it interferes with enzymes. We observed that when cystine was provided and sulfide levels rose, E. coli became strictly dependent upon cytochrome bd oxidase for continued respiration. Inspection revealed that low-micromolar levels of sulfide inhibited the proton-pumping cytochrome bo oxidase that is regarded as the primary respiratory oxidase. In the absence of the back-up cytochrome bd oxidase, growth failed. Exogenous sulfide elicited the same effect. The potency of sulfide was enhanced when oxygen concentrations were low. Natural oxic-anoxic interfaces are often sulfidic, including the intestinal environment where E. coli dwells. We propose that the sulfide resistance of the cytochrome bd oxidase is a key trait that permits respiration in such habitats. PMID:26991114

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides.

PubMed

Jood, Priyanka; Ohta, Michihiro

2015-03-16

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

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides

PubMed Central

Jood, Priyanka; Ohta, Michihiro

2015-01-01

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

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

PubMed

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

2011-05-30

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

Lead-isotopic data from sulfide minerals from the Cascade Range, Oregon and Washington

USGS Publications Warehouse

Church, S.E.; LeHuray, A.P.; Grant, A.R.; Delevaux, M.H.; Gray, J.E.

1986-01-01

Lead-isotopic studies of mineral deposits associated with Tertiary plutons found in the Cascade Range of Oregon and Washington demonstrate a rather uniform isotopic composition in various sulfide minerals ( 206Pb 204Pb = 18.84 to 19.05; 207Pb 204Pb = 15.57 to 15.62; 208Pb 204Pb = 38.49 to 38.74), show less variation than data from the volcanic rocks of the Cascade Range and fall within the mixing array defined by the MORB regression line and continental sediments. An evaluation of the role of crustal assimilation by hydrothermal convection during emplacement was made on five sulfide deposits associated with a single composite batholith, the Cloudy Pass pluton. The Pb-isotopic data and mass balance calculations suggest that only minor amounts of the lead were derived from the overlying Precambrian (?) Swakane Biotite Gneiss during emplacement. The bulk of the metal that occurs in sulfide deposits in the Cascade mineral belt appears to have been derived from subducted continental detritus. The variation of the Pb-isotopic signature of Sulfides from specific districts or deposits suggests that there is a correlation with age and structure of the crust. 206Pb 204Pb is greater than 18.92 in northern Washington and southern Oregon where deposits have intruded Mesozoic or older crust. However, the ore deposits between the northern Oregon border and central Oregon, south of Eugene, have intruded younger crust composed largely of mafic and andesitic volcanic rocks and 206Pb 204Pb lies between 18.84 and 18.92. This region, previously called the Columbia embayment, appears to be underlain by Tertiary volcanic rocks. Lead-isotopic data may be used to define the boundaries between discontinuous blocks of Mesozoic crust and Tertiary volcanic cover. ?? 1986.

Oceanic Pb-isotopic sources of proterozoic and paleozoic volcanogenic massive sulfide deposits on Prince of Wales Island and vicinity, southeastern Alaska

USGS Publications Warehouse

Ayuso, Robert A.; Karl, Susan M.; Slack, John F.; Haeussler, Peter J.; Bittenbender, Peter E.; Wandless, Gregory A.; Colvin, Anna

2005-01-01

Volcanogenic massive sulfide (VMS) deposits on Prince of Wales Island and vicinity in southeastern Alaska are associated with Late Proterozoic through Cambrian volcanosedimentary rocks of the Wales Group and with Ordovician through Early Silurian felsic volcanic rocks of the Moira Sound unit (new informal name). The massive sulfide deposits in the Wales Group include the Big Harbor, Copper City, Corbin, Keete Inlet, Khayyam, Ruby Tuesday, and Stumble-On deposits, and those in the Moira Sound unit include the Barrier Islands, Moira Copper, Niblack, and Nichols Bay deposits. Pb-isotopic signatures were determined on sulfide minerals (galena, pyrite, chalcopyrite, pyrrhotite, and sphalerite) to constrain metal sources of the massive sulfides and for comparison with data for other deposits in the region. Except for the Ruby Tuesday deposit, galena is relatively rare in most of these deposits. Pb-isotopic signatures distinguish the mainly Cu+Zn±Ag±Au massive sulfide deposits in the Wales Group from the Zn+Cu±Ag±Au massive sulfide deposits in the Moira Sound unit. Among the older group of deposits, the Khayyam deposit has the widest variation in Pb-isotopic ratios (206Pb/204Pb=17.169–18.021, 207Pb/204Pb=15.341–15.499, 208Pb/204Pb=36.546–37.817); data for the other massive sulfide deposits in the Wales Group overlap the isotopic variations in the Khayyam deposit. Pb-isotopic ratios for both groups of deposits are lower than those on the average crustal Pbevolution curve (µ=9.74), attesting to a large mantle influence in the Pb source. All the deposits show no evidence for Pb evolution primarily in the upper or lower continental crust. Samples from the younger group of deposits have scattered Pb-isotopic compositions and plot as a broad band on uranogenic and thorogenic Pb diagrams. Data for these deposits overlap the trend for massive sulfide deposits in the Wales Group but extend to significantly more radiogenic Pb-isotopic values. Pb-isotopic ratios of samples from the massive sulfide deposits in the Moira Sound unit plot on a different trend (206Pb/204Pb=17.375–19.418, 207Pb/204Pb=15.361–15.519, 208Pb/204Pb=36.856–37.241) from the steep slope defined by the massive sulfide deposits in the Wales Group. In comparison, the Pb-isotopic ratios of Devonian polymetallic (Pb-Zn-Au-Ag) quartz-sulfide veins vary widely ( 206Pb/204Pb=18.339–18.946, 207Pb/204Pb=15.447–15.561, 208Pb/204Pb=37.358–38.354), straddling the slope defined by the massive sulfide deposits in the Moira Sound unit. The general decrease in 207Pb/204Pb ratio in these deposits, relative to the average crustal Pb-evolution curve, suggests that the most likely lead sources were those associated with oceanic volcanic rocks. The massive sulfide deposits in the Wales Group may have resided within an intraoceanic tectonic setting where the mantle was the predominant contributor of metals. Some contribution from reworked arc material or recycled older, hydrothermally altered oceanic crust (including pelagic sediment) is also possible. Lead sources of the massive sulfide deposits in the Moira Sound unit also included an older source region, possibly a Late Proterozoic or Cambrian volcanosedimentary sequence and the massive sulfide deposits in the Wales Group. Preliminary regional comparison of the Pb-isotopic data indicates that the Greens Creek (Admiralty Island, Alaska) and Windy Craggy (northern British Columbia) deposits probably did not share a common lead source with the VMS deposits on Prince of Wales Island. Other sulfide occurrences on Admiralty Island are also more radiogenic than those on Prince of Wales Island. Large differences in 207Pb/204Pb ratio suggest that the lead in the VMS deposits in different parts of the Alexander terrane evolved from sources with heterogeneous U/Pb ratios, resulting from mixing of mantle and crustal components. 

GEOCHEMICAL AND BIOLOGICAL ASPECTS OF SULFIDE MINERAL DISSOLUTION: LESSONS FROM IRON MOUNTAIN, CALIFORNIA. (R826189)

EPA Science Inventory

Abstract

The oxidative dissolution of sulfide minerals leading to acid mine drainage (AMD) involves a complex interplay between microorganisms, solutions, and mineral surfaces. Consequently, models that link molecular level reactions and the microbial communities that ...

KINETICS OF ARSENATE REDUCTION BY DISSOLVED SULFIDE. (R825399)

EPA Science Inventory

Arsenic toxicity and mobility in soil and aquatic environments depends on its
speciation, with reducing environments generally leading to more hazardous
conditions with respect to this element. Aqueous sulfide (H₂S or
HS^-) is a strong reductan...

BIOLOGICAL RESPONSE TO VARIATION OF ACID-VOLATILE SULFIDES AND METALS IN FIELD-EXPOSED SPIKED SEDIMENTS

EPA Science Inventory

Vertical and temporal variations of acid-volatile sulfides (AVS) and simultaneously extracted metals (SEM) in sediment can control biological impacts of metals. To assess the significance of these variations in field sediments, sediments spiked with cadmium, copper, lead, nickel ...

PbS-PbSe IR detector arrays

NASA Technical Reports Server (NTRS)

Barrett, John R. (Inventor)

1986-01-01

A silicon wafer is provided which does not employ individually bonded leads between the IR sensitive elements and the input stages of multiplexers. The wafer is first coated with lead selenide in a first detector array area and is thereafter coated with lead sulfide within a second detector array area. The described steps result in the direct chemical deposition of lead selenide and lead sulfide upon the silicon wafer to eliminate individual wire bonding, bumping, flip chipping, planar interconnecting methods of connecting detector array elements to silicon chip circuitry, e.g., multiplexers, to enable easy fabrication of very long arrays. The electrode structure employed, produces an increase in the electrical field gradient between the electrodes for a given volume of detector material, relative to conventional electrode configurations.

Thermoelectric effects in superconductor-ferromagnet tunnel junctions on europium sulfide

NASA Astrophysics Data System (ADS)

Kolenda, S.; Sürgers, C.; Fischer, G.; Beckmann, D.

2017-06-01

We report on large thermoelectric effects in superconductor-ferromagnet tunnel junctions in proximity contact with the ferromagnetic insulator europium sulfide. The combination of a spin-splitting field and spin-polarized tunnel conductance in these systems breaks the electron-hole symmetry and leads to spin-dependent thermoelectric currents. We show that the exchange splitting induced by europium sulfide boosts the thermoelectric effect in small applied fields and can therefore eliminate the need to apply large magnetic fields, which might otherwise impede applications in thermometry or cooling.

Self-Protective Measures to Enhance Airlift Operations in Hostile Environments

DTIC Science & Technology

1989-09-01

developed theater may be so disorganized that category 2 threats may be less precisely defined and maybe found throughout the area. It is ironic that in...microns, a heat-seeker 80 TABLE 13 Infrared Sensitive Photoconductors 52 Photoconductor Wavelength Sensitivity Lead Sulfide , -60°F 1 to 3.5 microns Lead... Sulfide , Room Temperature 1 to 2.8 microns Telluride, -320°F i to 5 microns Indium Antimonide, -320°F 1 to 6 microns Germanium, Doped, Room

The low-energy, charge-transfer excited states of 4-amino-4-prime-nitrodiphenyl sulfide

NASA Technical Reports Server (NTRS)

O'Connor, Donald B.; Scott, Gary W.; Tran, Kim; Coulter, Daniel R.; Miskowski, Vincent M.; Stiegman, Albert E.; Wnek, Gary E.

1992-01-01

Absorption and emission spectra of 4-amino-4-prime-nitrodiphenyl sulfide in polar and nonpolar solvents were used to characterize and assign the low-energy excited states of the molecule. Fluorescence-excitation anisotropy spectra and fluorescence quantum yields were also used to characterize the photophysics of these states. The lowest-energy fluorescent singlet state was determined to be an intramolecular charge transfer (ICT) state involving transfer of a full electron charge from the amino to the nitro group yielding a dipole moment of about 50 D. A low-energy, intense absorption band is assigned as a transition to a different ICT state involving a partial electron charge transfer from sulfur to the nitro group.

Chemical Control of Lead Sulfide Quantum Dot Shape, Self-Assembly, and Charge Transport

NASA Astrophysics Data System (ADS)

McPhail, Martin R.

Lead(II) sulfide quantum dots (PbS QDs) are a promising excitonic material for numerous application that require that control of fluxes of charge and energy at nanoscale interfaces, such as solar energy conversion, photo- and electrocatalysis, light emitting diodes, chemical sensing, single-electron logic elements, field effect transistors, and photovoltaics. PbS QDs are particularly suitable for photonics applications because they exhibit size-tunable band-edge absorption and fluorescence across the entire near-infrared spectrum, undergo efficient multi-exciton generation, exhibit a long radiative lifetime, and possess an eight-fold degenerate ground-state. The effective integration of PbS QDs into these applications requires a thorough understanding of how to control their synthesis, self-assembly, and charge transport phenomena. In this document, I describe a series of experiments to elucidate three levels of chemical control on the emergent properties of PbS QDs: (1) the role of surface chemistry in controlling PbS QD shape during solvothermal synthesis, (2) the role of QD shape and ligand functionalization in self-assembly at a liquid-air interface, and (3) the role of QD packing structure on steady-state conductivity and transient current dynamics. At the synthetic level (1), I show that the final shape and surface chemistry of PbS QDs is highly sensitive to the formation of organosulfur byproducts by commonly used sulfur reagents. The insight into PbS QD growth gained from this work is then developed to controllably tune PbS QD shape from cubic to octahedral to hexapodal while maintaining QD size. At the following level of QD self-assembly (2), I show how QD size and shape dictate packing geometry in extended 2D arrays and how this packing can be controllably interrupted in mixed monolayers. I also study the role of ligand structure on the reorganization of QD arrays at a liquid-air interface and find that the specific packing defects in QD arrays vary depending on exchange kinetics and ligand binding geometry. At the final level of emergent macroscopic properties (3), I show that while the size-dependent conductivity of quasi-2D PbS QD arrays can be explained by a simple diffusional hopping model that only accounts for nearest-neighbor interactions, the transient photocurrent dynamics are extremely sensitive to the morphology of the entire percolation network formed by the QDs.

Transformation of Reactive Iron Minerals in a Permeable Reactive Barrier (Biowall) Used to Treat TCE in Groundwater

EPA Science Inventory

Abstract: Iron and sulfur reducing conditions are generally created in permeable reactive barrier (PRB) systems constructed for groundwater treatment, which usually leads to formation of iron sulfide phases. Iron sulfides have been shown to play an important role in degrading ch...

The speciation of antimony in sulfidic solutions: A theoretical study

NASA Astrophysics Data System (ADS)

Tossell, J. A.

1994-12-01

To assist in identifying the Sb sulfide species present in alkaline sulfide solutions, we have used ab initio quantum mechanical methods to calculate the structures, stabilities and vibrational spectra of a number of monomeric and oligomeric Sb(III) sulfides. In agreement with the interpretation of WOOD (1989), we assign a prominent feature observed at 369 cm -1 in the Raman spectrum of sulfidic Sb solutions to Sb-S stretching vibrations in a monomeric complex, although our calculations are most consistent with its assignment to the SbS 2(SH) -2 complex, rather than the fully deprotonated complex SbS 3-3. A shoulder observed at 380 cm -1 is best assigned to SbS(SH) 2-. Raman features observed at 314 and 350 cm 3-1 are assigned to Sb-S(H) symmetric stretching vibrations of the dimeric species Sb 2S 2(SH) 2, which is calculated to be thermodynamically stable, with respect to both the monomer Sb(SH) 3 and the trimer Sb 3S 3(SH) 3. The mixed-ligand complex Sb 2S 2(OH) 2 is calculated to become stable compared to Sb 2S 2(SH) 2 at high temperatures, in agreement with experimental solubility data. The Sb sulfide monomers are found to H-bond to water through their -SH or -S groups, but with only small changes in the Sb-S distances and Sb-S stretching frequencies. Accurate gas-phase proton affinities and estimated solution proton affinities are presented for the anionic species in solution and the estimated energetics are consistent with the presence of SbS 2(SH) -2, SbS(SH) 2-1 and Sb 2S 2(SH) 2 suggested by the Raman data.

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase*

PubMed Central

Mishanina, Tatiana V.; Yadav, Pramod K.; Ballou, David P.; Banerjee, Ruma

2015-01-01

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be −123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

PubMed

Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

2015-10-09

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Synthesis of Water-Soluble Antimony Sulfide Quantum Dots and Their Photoelectric Properties

NASA Astrophysics Data System (ADS)

Zhu, Jiang; Yan, Xuelian; Cheng, Jiang

2018-01-01

Antimony sulfide (Sb2S3) has been applied in photoelectric devices for a long time. However, there was lack of information about Sb2S3 quantum dots (QDs) because of the synthesis difficulties. To fill this vacancy, water-soluble Sb2S3 QDs were prepared by hot injection using hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) mixture as anionic-cationic surfactant, alkanol amide (DEA) as stabilizer, and ethylenediaminetetraacetic acid (EDTA) as dispersant. Photoelectric properties including absorbing and emission were characterized by UV-Vis-IR spectrophotometer and photoluminescence (PL) spectroscopic technique. An intensive PL emission at 880 nm was found, indicating Sb2S3 QDs have good prospects in near-infrared LED and near-infrared laser application. Sb2S3 QD thin films were prepared by self-assembly growth and then annealed in argon or selenium vapor. Their band gaps ( E g s) were calculated according to transmittance spectra. The E g of Sb2S3 QD thin film has been found to be tunable from 1.82 to 1.09 eV via annealing or selenylation, demonstrating the good prospects in photovoltaic application.

The Proteomic Response of Arabidopsis thaliana to Cadmium Sulfide Quantum Dots, and Its Correlation with the Transcriptomic Response

PubMed Central

Marmiroli, Marta; Imperiale, Davide; Pagano, Luca; Villani, Marco; Zappettini, Andrea; Marmiroli, Nelson

2015-01-01

A fuller understanding of the interaction between plants and engineered nanomaterials is of topical relevance because the latter are beginning to find applications in agriculture and the food industry. There is a growing need to establish objective safety criteria for their use. The recognition of two independent Arabidopsis thaliana mutants displaying a greater level of tolerance than the wild type plant to exposure to cadmium sulfide quantum dots (CdS QDs) has offered the opportunity to characterize the tolerance response at the physiological, transcriptomic, and proteomic levels. Here, a proteomics-based comparison confirmed the conclusions drawn from an earlier transcriptomic analysis that the two mutants responded to CdS QD exposure differently both to the wild type and to each other. Just over half of the proteomic changes mirrored documented changes at the level of gene transcription, but a substantial number of transcript/gene product pairs were altered in the opposite direction. An interpretation of the discrepancies is given, along with some considerations regarding the use and significance of -omics when monitoring the potential toxicity of ENMs for health and environment. PMID:26732871

An enhanced surface passivation effect in InGaN/GaN disk-in-nanowire light emitting diodes for mitigating Shockley-Read-Hall recombination.

PubMed

Zhao, Chao; Ng, Tien Khee; Prabaswara, Aditya; Conroy, Michele; Jahangir, Shafat; Frost, Thomas; O'Connell, John; Holmes, Justin D; Parbrook, Peter J; Bhattacharya, Pallab; Ooi, Boon S

2015-10-28

We present a detailed study of the effects of dangling bond passivation and the comparison of different sulfide passivation processes on the properties of InGaN/GaN quantum-disk (Qdisk)-in-nanowire based light emitting diodes (NW-LEDs). Our results demonstrated the first organic sulfide passivation process for nitride nanowires (NWs). The results from Raman spectroscopy, photoluminescence (PL) measurements, and X-ray photoelectron spectroscopy (XPS) showed that octadecylthiol (ODT) effectively passivated the surface states, and altered the surface dynamic charge, and thereby recovered the band-edge emission. The effectiveness of the process with passivation duration was also studied. Moreover, we also compared the electro-optical performance of NW-LEDs emitting at green wavelength before and after ODT passivation. We have shown that the Shockley-Read-Hall (SRH) non-radiative recombination of NW-LEDs can be greatly reduced after passivation by ODT, which led to a much faster increasing trend of quantum efficiency and higher peak efficiency. Our results highlighted the possibility of employing this technique to further design and produce high performance NW-LEDs and NW-lasers.

Thin-Film Quantum Dot Photodiode for Monolithic Infrared Image Sensors †

PubMed Central

Georgitzikis, Epimitheas; Vamvaka, Ioanna; Frazzica, Fortunato; Van Olmen, Jan; De Moor, Piet; Heremans, Paul; Hens, Zeger; Cheyns, David

2017-01-01

Imaging in the infrared wavelength range has been fundamental in scientific, military and surveillance applications. Currently, it is a crucial enabler of new industries such as autonomous mobility (for obstacle detection), augmented reality (for eye tracking) and biometrics. Ubiquitous deployment of infrared cameras (on a scale similar to visible cameras) is however prevented by high manufacturing cost and low resolution related to the need of using image sensors based on flip-chip hybridization. One way to enable monolithic integration is by replacing expensive, small-scale III–V-based detector chips with narrow bandgap thin-films compatible with 8- and 12-inch full-wafer processing. This work describes a CMOS-compatible pixel stack based on lead sulfide quantum dots (PbS QD) with tunable absorption peak. Photodiode with a 150-nm thick absorber in an inverted architecture shows dark current of 10−6 A/cm2 at −2 V reverse bias and EQE above 20% at 1440 nm wavelength. Optical modeling for top illumination architecture can improve the contact transparency to 70%. Additional cooling (193 K) can improve the sensitivity to 60 dB. This stack can be integrated on a CMOS ROIC, enabling order-of-magnitude cost reduction for infrared sensors. PMID:29232871

The behavior of Pt, Pd, Cu and Ni in the Se-sulfide system between 1050 and 700 °C and the role of Se in platinum-group elements fractionation in sulfide melts

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Fonseca, Raúl O. C.

2017-11-01

The behavior of Pt, Pd, Ni and Cu in Se-sulfide system and the role of Se in platinum-group elements (PGE) fractionation have been experimentally investigated at temperatures between 1050 and 700 °C in evacuated silica tubes. At 1050 °C, Se partially partitions into a vapor phase. At 980 °C, monosulfide solid solution (mss) and sulfide melt are the only stable phases. No Pt or Pd-bearing discrete selenide phases form down to 700 °C. Instead cooperite (PtS) forms at 900 °C. Both mss and sulfide melt can accommodate wt.% levels of Se over the whole temperature range covered by the experiments. The addition of Se in the sulfide system leads to an increase in the activity coefficients of Ni and Pd in sulfide melt. This is reflected by an increase in the partition coefficients of Ni and Pd between mss and sulfide melt. The Pt-Se activity coefficient in sulfide melt is lower than that of Pt-S. Owing to selenium's high solubility in sulfides, there never become oversaturated in Se to the extent that discrete selenides form. As such, base metal sulfides are expected to control the geochemical behavior of Se in natural systems. Interestingly, partition coefficients for the platinum-group elements (Os, Ir, Ru, Pt, Rh, Pd) between mss and sulfide melt are undistinguishable regardless of whether Se is present or not. These results imply that Se plays little role in the fractionation of PGE as sulfide melt cools down and crystallize. Furthermore, our experimental results provide evidence that Se is volatile at magmatic temperature and is likely to be degassed like sulfur.

Method of fabricating a PbS-PbSe IR detector array

NASA Technical Reports Server (NTRS)

Barrett, John R. (Inventor)

1987-01-01

A silicon wafer is provided which does not employ individually bonded leads between the IR sensitive elements and the input stages of multiplexers. The wafer is first coated with lead selenide in a first detector array area and is thereafter coated with lead sulfide within a second detector array area. The described steps result in the direct chemical deposition of lead selenide and lead sulfide upon the silicon wafer to eliminate individual wire bonding, bumping, flip chiping, planar interconnecting methods of connecting detector array elements to silicon chip circuitry, e.g., multiplexers, to enable easy fabrication of very long arrays. The electrode structure employed, produces an increase in the electrical field gradient between the electrodes for a given volume of detector material, relative to conventional electrode configurations.

40 CFR 98.180 - Definition of the source category.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Lead Production § 98.180 Definition of the source category. The lead production source category consists of primary lead smelters and secondary lead smelters. A primary lead smelter is a facility engaged in the production of lead metal from lead sulfide ore...

Determination of acid forming potential of massive sulfide minerals and the tailings situated in lead/zinc mining district of Balya (NW Turkey)

NASA Astrophysics Data System (ADS)

Çelebi, E. Ender; Öncel, M. Salim

2016-12-01

Weathering of sulfide minerals is a major source of acid production in nature and especially in mining territories. Pyrite is not the only principal mineral that generates acid drainage: other sulfide minerals (sphalerite, galena, chalcopyrite, etc.) may also be responsible for acid production. In addition to massive sulfide minerals, sulfide-bearing mine tailings may also produce acid drainage due to oxidation and hydrolysis reactions in waste dumps. The lead/zinc (Pb/Zn) mining region in Balya and Balıkesir, in Turkey, has operated mines intensively since the 1860s; so that characterization of the sulfide minerals and tailings situated and formed around the mining site is of great importance to secure a sustainable environment. For this purpose, acid production and neutralization potentials of massive sulfide ores of the region, and in the Pb/Zn process facility mine tailings from ten different points of tailings dam, have been determined by applied conventional Acid-Base Accounting (ABA) and Net Acid Generation (NAG) static tests after chemical and mineralogical analysis. The NAG pH and net acid production potential (NAPP) values were compared on a chart in order to classify the samples as either acid generating or non-acid generating. According to the comparisons, the sulfide minerals were classified as potentially acid forming (PAF). Massive pyrite had the highest NAPP and NAG pH value of 1966.6 kg H2SO4/ton and 1.91, respectively and the galena had the lowest NAPP value of 558.9 kg H2SO4/ton. However, the sphalerite NAG leachate pH value of 4.30 was the highest in sulfide minerals so that the sphalerite plotted near the uncertainty reference border in the PAF zone. In the mine tailings, NAPP values of 105.9 kg H2SO4/ton on average and the NAG pH values of over 7.5 were determined. In addition to these tests, water leaching (agitation test) was carried out on tailings in order to generate more information. The tailings did not generate acidic leachates as they lie on limestone bed rock which neutralized the acidity.

Atomic layer deposition of metal sulfide materials

DOE PAGES

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

2015-01-12

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

The removal of heavy metals from contaminated soil by a combination of sulfidisation and flotation.

PubMed

Vanthuyne, Mathias; Maes, André

2002-05-06

The possibility of removing cadmium, copper, lead and zinc from Belgian loamy soil by a combination of sulfidisation pre-treatment and Denver flotation was investigated. The potentially available--sulfide convertible--metal content of the metal polluted soil was estimated by EDTA (0.1 M, pH 4.65) extraction and BCR sequential extraction. EDTA extraction is better at approximating the metal percentage that is expected to be convertible into a metal sulfide phase, in contrast to the sequential extraction procedure of 'Int. J. Environ. Anal. Chem. 51 (1993) pp. 135-151' in which transition metals present as iron oxide co-precipitates are dissolved by hydroxylammoniumchloride in the second extraction step. To compare the surface characteristics of metal sulfides formed by sulfidisation with those of crystalline metal sulfides, two types of synthetic sediments were prepared and extracted with 0.1 M EDTA (pH 4.65) in anoxic conditions. Separate metal sulfides or co-precipitates with iron sulfide were formed by sulfide conditioning. The Denver flotation of both types of synthetic sediments (kerosene as collector at high background electrolyte concentrations) resulted in similar concentrating factors for freshly formed metal sulfides as for fine-grained crystalline metal sulfides. The selective flotation of metal sulfides after sulfide conditioning of a polluted soil, using kerosene or potassium ethyl xanthate as collectors and MIBC as frother, was studied at high background electrolyte concentrations. The sulfidisations were made in ambient air and inside an anoxic glove box. The concentrating factors corrected by the potentially available metal percentage, determined by 0.1 M EDTA extraction, lie between 2 and 3. The selective flotation of these finely dispersed, amorphous, metal sulfides can possibly be improved by optimising the bubble-particle interaction.

Optical sensor nanoparticles in artificial sediments--a new tool to visualize O2 dynamics around the rhizome and roots of seagrasses.

PubMed

Koren, Klaus; Brodersen, Kasper E; Jakobsen, Sofie L; Kühl, Michael

2015-02-17

Seagrass communities provide important ecosystems services in coastal environments but are threatened by anthropogenic impacts. Especially the ability of seagrasses to aerate their below-ground tissue and immediate rhizosphere to prevent sulfide intrusion from the surrounding sediment is critical for their resilience to environmental disturbance. There is a need for chemical techniques that can map the O2 distribution and dynamics in the seagrass rhizosphere upon environmental changes and thereby identify critical stress thresholds of e.g. water flow, turbidity, and O2 conditions in the water phase. In a novel experimental approach, we incorporated optical O2 sensor nanoparticles into a transparent artificial sediment matrix consisting of pH-buffered deoxygenated sulfidic agar. Seagrass growth and photosynthesis was not inhibited in the experimental setup when the below-ground biomass was immobilized in the artificial sulfidic sediment with nanoparticles and showed root growth rates (∼ 5 mm day(-1)) and photosynthetic quantum yields (∼ 0.7) comparable to healthy seagrasses in their natural habitat. We mapped the real-time below ground O2 distribution and dynamics in the whole seagrass rhizosphere during experimental manipulation of light exposure and O2 content in the overlaying water. Those manipulations showed that oxygen release from the belowground tissue is much higher in light as compared to darkness and that water column hypoxia leads to diminished oxygen levels around the rhizome/roots. Oxygen release was visualized and analyzed on a whole rhizosphere level, which is a substantial improvement to existing methods relying on point measurements with O2 microsensors or partial mapping of the rhizosphere in close contact with a planar O2 optode. The combined use of optical nanoparticle-based sensors with artificial sediments enables imaging of chemical microenvironments in the rhizosphere of aquatic plants at high spatiotemporal resolution with a relatively simple experimental setup and thus represents a significant methodological advancement for studies of environmental impacts on aquatic plant ecophysiology.

Sulfide toxicity: Mechanical ventilation and hypotension determine survival rate and brain necrosis

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

Baldelli, R.J.; Green, F.H.Y.; Auer, R.N.

1993-09-01

Occupational exposure to hydrogen sulfide is one of the leading causes of sudden death in the workplace, especially in the oil and gas industry. High-dose exposure causes immediate neurogenic apnea and death; lower doses cause [open quotes]knockdown[close quotes] (transient loss of consciousness, with apnea). Because permanent neurological sequelae have been reported, the authors sought to determine whether sulfide can directly kill central nervous system neurons. Ventilated and unventilated rats were studied to allow administration of higher doses of sulfide and to facilitate physiological monitoring. It was extremely difficult to produce cerebral necrosis with sulfide. Only one of eight surviving unventilatedmore » rats given high-dose sulfide (a dose that was lethal in [ge]50% of animals) showed cerebral necrosis. Mechanical ventilation shifted the dose that was lethal in 50% of the animals to 190 mg/kg from 94 mg/kg in the unventilated rats. Sulfide was found to potently depress blood pressure. Cerebral necrosis was absent in the ventilated rats (n = 11), except in one rat that showed profound and sustained hypotension to [le]35 Torr. Electroencephalogram activity ceased during exposure but recovered when the animals regained consciousness. The authors conclude that very-high-dose sulfide is incapable of producing cerebral necrosis by a direct histotoxic effect. 32 refs., 5 figs.« less

Highly sensitive photodetectors based on hybrid 2D-0D SnS{sub 2}-copper indium sulfide quantum dots

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

Huang, Yun; Zhan, Xueying; Xu, Kai

2016-01-04

Both high speed and efficiency of photoelectric conversion are essential for photodetectors. As an emerging layered metal dichalcogenide (LMD), tin disulfide owns intrinsic faster photodetection ability than most other LMDs but poor light absorption and low photoelectric conversion efficiency. We develop an efficient method to enhance its performance by constructing a SnS{sub 2}-copper indium sulfide hybrid structure. As a result, the responsivity reaches 630 A/W, six times stronger than pristine SnS{sub 2} and much higher than most other LMDs photodetectors. Additionally, the photocurrents are enhanced by more than 1 order of magnitude. Our work may open up a pathway to improvemore » the performance of photodetectors based on LMDs.« less

Strongly luminescent InP/ZnS core-shell nanoparticles.

PubMed

Haubold, S; Haase, M; Kornowski, A; Weller, H

2001-05-18

The wide-bandgap semiconducting material, zinc sulfide, has been coated on indium phosphide nanoclusters to a 1-2-Å thickness. The resulting InP-ZnS core-shell particle (as shown in the TEM image; scale 1 cm=5 nm) exhibits bright luminescence at room temperature with quantum efficiencies as high as 23 %. © 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors

PubMed Central

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

2016-01-01

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

Quantum-dot-tagged microbeads for multiplexed optical coding of biomolecules.

PubMed

Han, M; Gao, X; Su, J Z; Nie, S

2001-07-01

Multicolor optical coding for biological assays has been achieved by embedding different-sized quantum dots (zinc sulfide-capped cadmium selenide nanocrystals) into polymeric microbeads at precisely controlled ratios. Their novel optical properties (e.g., size-tunable emission and simultaneous excitation) render these highly luminescent quantum dots (QDs) ideal fluorophores for wavelength-and-intensity multiplexing. The use of 10 intensity levels and 6 colors could theoretically code one million nucleic acid or protein sequences. Imaging and spectroscopic measurements indicate that the QD-tagged beads are highly uniform and reproducible, yielding bead identification accuracies as high as 99.99% under favorable conditions. DNA hybridization studies demonstrate that the coding and target signals can be simultaneously read at the single-bead level. This spectral coding technology is expected to open new opportunities in gene expression studies, high-throughput screening, and medical diagnostics.

Chromatographic separation of the platinum-group elements, gold, base metals and sulfur during degassing of a compacting and solidifying igneous crystal pile

NASA Astrophysics Data System (ADS)

Boudreau, A. E.; Meurer, W. P.

The major platinum-group elements (PGE) concentrations in layered intrusions are typically associated with zones in which the sulfide abundance begins to increase. In a number of layered intrusions, there is also a distinct stratigraphic separation in the peak concentrations of the PGE from those of the base metals, gold and sulfur through these zones. These stratigraphic ``offsets'' are characterized by a lower, typically S-poor, Pt- and Pd-enriched zone overlain by a zone enriched in the base metals, S and Au. The separations amount to a few decimeters to several tens of meters. In some instances, the high Pt and Pd concentrations are associated with trivial amounts of sulfide. Theoretical considerations suggest that these offsets can be modeled as chromatographic peaks that develop during an infiltration/reaction process. Using Pd as a typical PGE and Cu as a typical base metal, a numeric model is developed that illustrates how metal separations can develop in a vapor-refining zone as fluid evolved during solidification of a cumulus pile leaches sulfide and redeposits it higher in the crystal pile. The solidification/degassing ore-element transport is coupled with a compaction model for the crystal pile. Solidification resulting from conductive cooling through the base of the compacting column leads to an increasing volatile concentration in the intercumulus liquid until it reaches fluid saturation. Separation and upward migration of this fluid lead to an upward-migrating zone of increasingly higher bulk water contents as water degassed from underlying cumulates enriches overlying, fluid-undersaturated interstitial liquids. Sulfide is resorbed from the degassing regions and is reprecipitated in these vapor-undersaturated interstitial liquids, producing a zone of relatively high modal sulfide that also migrates upward with time. Owing to its strong preference for sulfide, Pd is not significantly mobile until all sulfide is resorbed. The result is a zone of increasing PGE enrichment that follows the sulfide resorption front as solidification/degassing continues. In detail, the highest Pd concentrations occur stratigraphically below the peak in S and base metals. The high Pd/S ratio mimics values conventionally interpreted as the result of high (silicate liquid)/(sulfide liquid) mass ratios (``R'' values). However, in this case, the high Pd/S ratio is the result of a chromatographic/reaction front enrichment and not a magmatic sulfide-saturation event.

Geochemical and mineralogical characterization of the abandoned Valzinco (lead-zinc) and Mitchell (gold) mine sites prior to reclamation, Spotsylvania County, Virginia

USGS Publications Warehouse

Hammarstrom, Jane M.; Johnson, Adam N.; Seal, Robert R.; Meier, Allen L.; Briggs, Paul L.; Piatak, Nadine M.

2006-01-01

The Virginia gold-pyrite belt, part of the central Virginia volcanic-plutonic belt, hosts numerous abandoned metal mines. The belt extends from about 50 km south of Washington, D.C., for approximately 175 km to the southwest into central Virginia. The rocks that comprise the belt include metamorphosed volcanic and clastic (noncarbonate) sedimentary rocks that were originally deposited during the Ordovician). Deposits that were mined can be classified into three broad categories: 1. volcanic-associated massive sulfide deposits, 2. low-sulfide quartz-gold vein deposits, 3. gold placer deposits, which result from weathering of the vein deposits The massive sulfide deposits were historically mined for iron and pyrite (sulfur), zinc, lead, and copper but also yielded byproduct gold and silver. The most intensely mineralized and mined section of the belt is southwest of Fredericksburg, in the Mineral district of Louisa and Spotsylvania counties. The Valzinco Piatak lead-zinc mine and the Mitchell gold prospect are abandoned sites in Spotsylvania County. As a result of environmental impacts associated with historic mining, both sites were prioritized for reclamation under the Virginia Orphaned Land Program administered by the Virginia Department of Mines, Minerals, and Energy (VDMME). This report summarizes geochemical data for all solid sample media, along with mineralogical data, and results of weathering experiments on Valzinco tailings and field experiments on sediment accumulation in Knights Branch. These data provide a framework for evaluating water-rock interactionsand geoenvironmental signatures of long-abandoned mines developed in massive sulfide deposits and low-sulfide gold-quartz vein deposits in the humid temperate ecosystem domain in the eastern United States.

Acid production potentials of massive sulfide minerals and lead-zinc mine tailings: a medium-term study.

PubMed

Çelebi, Emin Ender; Öncel, Mehmet Salim; Kobya, Mehmet

2018-01-01

Weathering of sulfide minerals is a principal source of acid generation. To determine acid-forming potentials of sulfide-bearing materials, two basic approaches named static and kinetic tests are available. Static tests are short-term, and easily undertaken within a few days and in a laboratory. In contrast, kinetic tests are long-term procedures and mostly carried out on site. In this study, experiments were conducted over a medium-term period of 2 months, not as short as static tests and also not as long as kinetic tests. As a result, pH and electrical conductivity oscillations as a function of time, acid-forming potentials and elemental contents of synthetically prepared rainwater leachates of massive sulfides and sulfide-bearing lead-zinc tailings from abandoned and currently used deposition areas have been determined. Although the lowest final pH of 2.70 was obtained in massive pyrite leachate, massive chalcopyrite leachate showed the highest titrable acidity of 1.764 g H 2 SO 4 /L. On the other hand, a composite of currently deposited mine tailings showed no acidic characteristic with a final pH of 7.77. The composite abandoned mine tailing leachate had a final pH of 6.70, close to the final pH of massive galena and sphalerite leachates, and produced a slight titrable acidity of 0.130 g H 2 SO 4 /L.

The Application of Fluorescent Quantum Dots to Confocal, Multiphoton, and Electron Microscopic Imaging

PubMed Central

Deerinck, Thomas J.

2009-01-01

Fluorescent quantum dots are emerging as an important tool for imaging cells and tissues, and their unique optical and physical properties have captured the attention of the research community. The most common types of commercially available quantum dots consist of a nanocrystalline semiconductor core composed of cadmium selenide with a zinc sulfide capping layer and an outer polymer layer to facilitate conjugation to targeting biomolecules such as immunoglobulins. They exhibit high fluorescent quantum yields and have large absorption cross-sections, possess excellent photostability, and can be synthesized so that their narrow-band fluorescence emission can occur in a wide spectrum of colors. These properties make them excellent candidates for serving as multiplexing molecular beacons using a variety of imaging modalities including highly correlated microscopies. Whereas much attention has been focused on quantum-dot applications for live-cell imaging, we have sought to characterize and exploit their utility for enabling simultaneous multiprotein immunolabeling in fixed cells and tissues. Considerations for their application to immunolabeling for correlated light and electron microscopic analysis are discussed. PMID:18337229

Interparticle spacing and structural ordering in superlattice PbS nanocrystal solids undergoing ligand exchange

DOE PAGES

Weidman, Mark C.; Yager, Kevin G.; Tisdale, William A.

2014-12-12

Controlling the interparticle spacing in quantum dot (QD) thin films is the most readily accessible way to control transport rates between neighboring QDs and a critical component of device optimization. Here, we use X-ray scattering measurements to accurately measure the interparticle spacing in films of highly monodisperse lead sulfide (PbS) QDs that have undergone a variety of device-relevant ligand exchanges. We tabulate these values for use in simulations and data analysis. We find that monothiol and dithiol ligand species typically result in interparticle spacing values that are equal to the length of a single monothiol or dithiol ligand. Additionally, wemore » find that spin-coating a thick film of QDs followed by a long-duration ligand exchange results in a more complete ligand exchange than spin-coating many thin layers with short-duration ligand exchanges in between. The former method also preserves a remarkable degree of the long-range ordering that was present in the film prior to ligand exchange. These results shed light on ways to produce highly-ordered QD solids with compact and functional ligands, which could lead to enhanced interdot coupling and transport phenomena.« less

Dislocation-driven growth of two-dimensional lateral quantum-well superlattices

PubMed Central

Chen, Jianyi; Li, Dongdong

2018-01-01

The advent of two-dimensional (2D) materials has led to extensive studies of heterostructures for novel applications. 2D lateral multiheterojunctions and superlattices have been recently demonstrated, but the available growth methods can only produce features with widths in the micrometer or, at best, 100-nm scale and usually result in rough and defective interfaces with extensive chemical intermixing. Widths smaller than 5 nm, which are needed for quantum confinement effects and quantum-well applications, have not been achieved. We demonstrate the growth of sub–2-nm quantum-well arrays in semiconductor monolayers, driven by the climb of misfit dislocations in a lattice-mismatched sulfide/selenide heterointerface. Density functional theory calculations provide an atom-by-atom description of the growth mechanism. The calculated energy bands reveal type II alignment suitable for quantum wells, suggesting that the structure could, in principle, be turned into a “conduit” of conductive nanoribbons for interconnects in future 2D integrated circuits via n-type modulation doping. This misfit dislocation–driven growth can be applied to different combinations of 2D monolayers with lattice mismatch, paving the way to a wide range of 2D quantum-well superlattices with controllable band alignment and nanoscale width. PMID:29740600

40 CFR 60.181 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... lead bullion. (g) Electric smelting furnace means any furnace in which the heat necessary for smelting of the lead sulfide ore concentrate charge is generated by passing an electric current through a...

40 CFR 60.181 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... lead bullion. (g) Electric smelting furnace means any furnace in which the heat necessary for smelting of the lead sulfide ore concentrate charge is generated by passing an electric current through a...

40 CFR 60.181 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... lead bullion. (g) Electric smelting furnace means any furnace in which the heat necessary for smelting of the lead sulfide ore concentrate charge is generated by passing an electric current through a...

Sulfidation of Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts studied by Moessbauer emission spectroscopy

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

Craje, M.W.J.; Kraan, A.M. van der; Beer, V.H.J. de

1993-10-01

The structure of hydrodesulfurization catalysts is relevant to many industries. The sulfidation of uncalcined and calcined alumina-supported cobalt and cobalt-molybdenum catalysts was systematically studied by means of in situ Moessbauer emission spectroscopy (MES) at room temperature. The spectra obtained during the stepwise sulfidation of the uncalcined catalysts clearly resemble those observed for carbon-supported ones. Hence, the interpretation of the spectra of the alumina-supported catalysts is based on the conclusions drawn from the MES studies of the carbon-supported catalysts, which are less complex because Co ions do not diffuse into the support. It is demonstrated that not only in sulfided CoMo/Al[submore » 2]O[sub 3], but also in sulfided Co/Al[sub 2]O[sub 3], catalysts Co-sulfide species with a [open quotes]Co-Mo-S[close quotes]-type quadrupole splitting can be formed. It is concluded that the Co-sulfide species formed in sulfided Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts are essentially the same, only the particle size and ordering of the Co-sulfide species may differ, as in the case of Co/C and CoMo/C catalysts. The function of the Mo, which is present as MoS[sub 2], is merely to stabilize very small Co-sulfide particles, which in the limit contain only one single Co atom. Furthermore, it turns out that the value of the electric quadrupole splitting (Q.S. value) of the Co-sulfide phase in the sulfided catalysts depends on the sulfiding temperature and Co content. This observation leads to the conclusion that large Q.S. values point to the presence of very small Co-sulfide entities or particles (the lower limit being [open quotes]particles[close quotes] containing only one Co atom, such as proposed in the [open quotes]Co-Mo-S[close quotes] model), whereas small Q.S. values point to the presence of large Co-sulfide particles (the upper limit being crystalline Co[sub 9]S[sub 8]). 28 refs., 7 figs., 6 tabs.« less

Synthesis of Lead Sulfide Nanoparticles by Chemical Precipitation Method

NASA Astrophysics Data System (ADS)

Chongad, L. S.; Sharma, A.; Banerjee, M.; Jain, A.

2016-10-01

Lead sulfide (PbS) nanoparticles were prepared by chemical precipitation method (CPM) with the assistance of H2S gas. The microstructure and morphology of the synthesized nanoparticles have been investigated using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the PbS nanoparticles reveal formation of cubic phase. To investigate the quality of prepared nanoparticles, the particles size, lattice constant, strain, dislocation density etc. have been determined using XRD. TEM images reveal formation of cubic nanoparticles and the particle size determined from TEM images agree well with those from XRD.

Broadband Solar Energy Harvesting in Single Nanowire Resonators

NASA Astrophysics Data System (ADS)

Yang, Yiming; Peng, Xingyue; Hyatt, Steven; Yu, Dong

2015-03-01

Sub-wavelength semiconductor nanowires (NWs) can have optical absorption cross sections far beyond their physical sizes at resonance frequencies, offering a powerful method to simultaneously lower the material consumption and enhance photovoltaic performance. The degree of absorption enhancement is expected to substantially increase in materials with high refractive indices, but this has not yet been experimentally demonstrated. Here, we show that the absorption efficiency can be significantly improved in high-index NWs, by a direct observation of 350% external quantum efficiency (EQE) in lead sulfide (PbS) NWs. Broadband absorption enhancement is also realized in tapered NWs, where light of different wavelength is absorbed at segments with different diameters analogous to a tandem solar cell. Our results quantitatively agree with the finite-difference-time-domain (FDTD) simulations. Overall, our single PbS NW Schottky solar cells taking advantage of optical resonance, near bandgap open circuit voltage, and long minority carrier diffusion length exhibit power conversion efficiency comparable to single Si NW coaxial p-n junction cells, while the fabrication complexity is greatly reduced.

40 CFR 60.181 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... PERFORMANCE FOR NEW STATIONARY SOURCES Standards of Performance for Primary Lead Smelters § 60.181 Definitions... and in subpart A of this part. (a) Primary lead smelter means any installation or any intermediate process engaged in the production of lead from lead sulfide ore concentrates through the use of...

40 CFR 60.181 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PERFORMANCE FOR NEW STATIONARY SOURCES Standards of Performance for Primary Lead Smelters § 60.181 Definitions... and in subpart A of this part. (a) Primary lead smelter means any installation or any intermediate process engaged in the production of lead from lead sulfide ore concentrates through the use of...

Lead isotope determinations from sulfide mineral occurrences--Russian Far East

USGS Publications Warehouse

Church, Stan E.; Goryachev, Nikolai A.; Shpikerman, Vladimir I.

2013-01-01

The lead isotope database for sulfide deposits and occurrences in the Russian Far East was funded by the Mineral Resources Program, U.S. Geological Survey (USGS) in conjunction with the collaborative studies of mineral resources by the Russian Academy of Sciences and the U. S. Geological Survey (Nokleberg and others, 1996). Comparisons of these data with similar lead isotope data from Alaska published in Church, Delevaux, and others (1987) and Gaccetta and Church (1989) provide a basis for the following three-fold project objectives: 1. To utilize lead isotope signatures, in conjunction with regional mapping, to assess the relative ages and to categorize the types of mineral deposits studied, 2. To relate the lead isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and 3. To use the lead isotope data to correlate lithotectonic terranes within the northern Cordillera (Alaska, Yukon Territories and British Columbia in Canada, and the western Cordillera of the United States). The report by Church, Gray, and others (1987) shows how this fingerprinting methodology can be applied to trace the offset of lithotectonic (or lithostratigraphic as labeled by some authors) terranes.The lead isotope data presented in table 1 represent the work completed on sulfide mineral deposits located in the Russian Far East from 1993 to 1995, when this study was terminated due to lack of funding. The lead isotope data are reported here for use by investigators who may find them of value in mineral exploration. No attempt is made to summarize the voluminous literature on these mineral deposits.

Optical emission of two-dimensional arsenic sulfide prepared by plasma

NASA Astrophysics Data System (ADS)

Mochalov, Leonid; Nezhdanov, Aleksey; Logunov, Alexander; Kudryashov, Mikhail; Krivenkov, Ivan; Vorotyntsev, Andrey; Gogova, Daniela; Mashin, Aleksandr

2018-02-01

For the first time optical emission of prepared in plasma two-dimensional arsenic sulphide materials "beyond graphene" has been demonstrated. A strong structural photoluminescence exited by continuous wave operation lasers with a laser excitation wavelength of 473 nm and 632.8 nm has been observed. The influence of excitation parameters, chemical composition, structure, and annealing conditions on the intensity of photoluminescence of the chalcogenide materials has been established. Mass-spectrometry and Raman spectroscopy were coupled with quantum-chemical calculations to reveal the fragments which are the building blocks of the 2D As-S materials. A plausible mechanism of formation and modification of the arsenic sulfide luminiscenting structural units has been proposed. The properties of the 2D pole-structured and layered arsenic sulphide could be a key to advancing the 2D photosensitive devices.

Phase Stability and Electronic Structure of Prospective Sb-Based Mixed Sulfide and Iodide 3D Perovskite (CH3NH3)SbSI2.

PubMed

Li, Tianyang; Wang, Xiaoming; Yan, Yanfa; Mitzi, David B

2018-06-29

Lead-free antimony-based mixed sulfide and iodide perovskite phases have recently been reported to be synthesized experimentally and to exhibit reasonable photovoltaic performance. Through a combination of experimental validation and computational analysis, we show no evidence of the formation of the mixed sulfide and iodide perovskite phase, MASbSI 2 (MA = CH 3 NH 3 + ), and instead that the main products are a mixture of the binary and ternary compounds (Sb 2 S 3 and MA 3 Sb 2 I 9 ). Density functional theory calculations also indicate that such a mixed sulfide and iodide perovskite phase should be thermodynamically less stable compared with binary/ternary anion-segregated secondary phases and less likely to be synthesized under equilibrium conditions. Additionally, band structure calculations show that this mixed sulfide and iodide phase, if possible to synthesize (e.g., under nonequilibrium conditions), should have a suitable direct band gap for photovoltaic application.

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

USGS Publications Warehouse

Sato, M.

1992-01-01

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

Band-structure tailoring and surface passivation for highly efficient near-infrared responsive PbS quantum dot photovoltaics

NASA Astrophysics Data System (ADS)

Zhou, Ru; Niu, Haihong; Ji, Fengwei; Wan, Lei; Mao, Xiaoli; Guo, Huier; Xu, Jinzhang; Cao, Guozhong

2016-11-01

PbS is a promising light harvester for near-infrared (NIR) responsive quantum dot (QD) photovoltaics due to its narrow bulk band gap (0.41 eV) and large exciton Bohr radius (18 nm). However, the relatively low conduction band (CB) and high-density surface defects of PbS as two major drawbacks for its use in solar cells severely hamper the photovoltaic performance enhancement. In this work, a modified solution-based successive ionic layer adsorption and reaction (SILAR) utilizing mixed cationic precursors of Pb2+ and Cd2+ is explored, and such a scheme offers two benefits, band-structure tailoring and surface passivation. In-situ deposited CdS suppresses the excessive growth of PbS in the mesopores, thereby facilitating the favorable electron injection from PbS to TiO2 in view of the up-shifted CB level of QDs; the intimate interpenetration of two sulfides with each other leads to superior passivation of trap state defects on PbS, which suppresses the interfacial charge recombination. With the construction of photovoltaics based on such a hybrid (Pb,Cd)S/CdS configuration, impressive power conversion efficiency up to 4.08% has been reached, outperforming that of the conventional PbS/CdS pattern (2.95%). This work highlights the great importance of band-structure tailoring and surface passivation for constructing highly efficient PbS QD photovoltaics.

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

PubMed Central

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

2014-01-01

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

Hexagonal AlN Layers Grown on Sulfided Si(100) Substrate

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Comprehensive recovery of gold and base-metal sulfide minerals from a low-grade refractory ore

NASA Astrophysics Data System (ADS)

Li, Wen-juan; Liu, Shuang; Song, Yong-sheng; Wen, Jian-kang; Zhou, Gui-ying; Chen, Yong

2016-12-01

The comprehensive recovery of small amounts of valuable minerals such as gold and base-metal sulfide minerals from a low-grade refractory ore was investigated. The following treatment strategy was applied to a sample of this ore: gold flotation-gold concentrate leaching-lead and zinc flotation from the gold concentrate leaching residue. Closed-circuit trials of gold flotation yielded a gold concentrate that assayed at 40.23 g·t-1 Au with a recovery of 86.25%. The gold concentrate leaching rate was 98.76%. Two variants of lead-zinc flotation from the residue—preferential flotation of lead and zinc and bulk flotation of lead and zinc—were tested using the middling processing method. Foam from the reflotation was returned to the lead rougher flotation or lead-zinc bulk flotation, whereas middlings from reflotation were discarded. Sulfur concentrate was a byproduct. The combined strategy of flotation, leaching, and flotation is recommended for the treatment of this kind of ore.

Novel Photovoltaic Devices Using Ferroelectric Material and Colloidal Quantum Dots

NASA Astrophysics Data System (ADS)

Paik, Young Hun

As the global concern for the financial and environmental costs of traditional energy resources increases, research on renewable energy, most notably solar energy, has taken center stage. Many alternative photovoltaic (PV) technologies for 'the next generation solar cell' have been extensively studied to overcome the Shockley-Queisser 31% efficiency limit as well as tackle the efficiency vs. cost issues. This dissertation focuses on the novel photovoltaic mechanism for the next generation solar cells using two inorganic nanomaterials, nanocrystal quantum dots and ferroelectric nanoparticles. Lead zirconate titanate (PZT) materials are widely studied and easy to synthesize using solution based chemistry. One of the fascinating properties of the PZT material is a Bulk Photovoltaic effect (BPVE). This property has been spotlighted because it can produce very high open circuit voltage regardless of the electrical bandgap of the materials. However, the poor optical absorption of the PZT materials and the required high temperature to form the ferroelectric crystalline structure have been obstacles to fabricate efficient photovoltaic devices. Colloidal quantum dots also have fascinating optical and electrical properties such as tailored absorption spectrum, capability of the bandgap engineering due to the wide range of material selection and quantum confinement, and very efficient carrier dynamics called multiple exciton generations. In order to utilize these properties, many researchers have put numerous efforts in colloidal quantum dot photovoltaic research and there has been remarkable progress in the past decade. However, several drawbacks are still remaining to achieve highly efficient photovoltaic device. Traps created on the large surface area, low carrier mobility, and lower open circuit voltage while increasing the absorption of the solar spectrum is main issues of the nanocrystal based photovoltaic effect. To address these issues and to take the advantages of the two materials, this dissertation focused on material synthesis for low cost solution process for both materials, fabrication of various device structures and electrical/optical characterization to understand the underlying physics. We successfully demonstrated lead sulfide quantum dots (PbS QDs) and lead zirconate titanate nanoparticles (PZT NPs) in an aqueous solution and fabricated a photosensitive device. Solution based low-temperature process was used to fabricate a PbS QD and a PZT NP device. We exhibited a superior photoresponse and ferroelectric photovoltaic properties with the novel PZT NP device and studied the physics on domain wall effect and internal polarity effect. PZT NP was mainly investigated because PZT NP device is the first report as a photosensitive device with a successful property demonstration, as we know of. PZT's crystalline structure and the size of the nanocrystals were studied using X-ray diffraction and TEM (Transmission electron microscopy) respectively. We observed < 100 nm of PZT NPs and this result matched with DLS (dynamic light scattering) measurement. We fabricated ferroelectric devices using the PZT NPs for the various optical and electrical characterizations and verified ferroelectric properties including ferroelectric hysteresis loop. We also observed a typical ferroelectric photovoltaic effect from a PZT NP based device which was fabricated on an ITO substrate. We synthesized colloidal quantum dots (CQD) with the inexpensive soluble process. Fabricated PbS QD was used for the hybrid device with PZT thin films. J-V measured and the result shows superior open circuit voltage characteristics compared to conventional PbS QD PV devices, and resulting the improvement of the solar cell efficiency. This Ferroelectrics and Quantum Dots (FE-QDs) device also the first trial and the success as we know of.

Lead mobilization during tectonic reactivation of the western Baltic Shield

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

Romer, R.L.; Wright, J.E.

Lead isotope data from sulfide deposits of the western part of the Baltic Shield define mixing lines in the [sup 206]Pb/[sup 204]Pb-[sup 207]Pb/[sup 204]Pb diagram. Lead from two types of sulfide deposits have been investigated: (1) Exhalative and volcanogenic deposits that are syngenetic with their host rocks; and (2) vein deposits. The syngenetic deposits locally show a very wide range of lead isotopic compositions that reflect a variable addition of highly radiogenic lead, while the vein deposits, although they have radiogenic lead isotopic compositions, exhibit only limited isotopic variations. In different provinces of the shield, both types of deposits fallmore » on the same lead mixing array. The slope of the lead mixing lines varies as a function of the age of basement rocks and the age of the tectonic event which produced the lead mobilization and therefore relates the source rock age with the age of lead mobilization. Calculated mixing ages fall into several short time periods that correspond either to orogenic events or to major phases of continental rifting. The orogenic events are the ca 360--430 Ma Caledonian, ca 900--1100 Ma Sveconorwegian, and the ca 1800--1900 Ma Svecofennian orogenic cycles. The rifting events correspond to the formation of the ca 280 Ma Oslo rift and the Ordovician (ca 450 Ma) graben system in the area of the present Gulf of Bothnia. Each mixing age indicates that lead was mobilized, probably as a consequence of mild thermal disturbances, and that the crust was permeable to lead migration. The data show that the geographic distribution of sulfide deposits with highly radiogenic lead isotopic compositions coincides with old graben systems, orogenic belts, and orogenic forelands on the Baltic Shield. The ages of vein deposits and their geographic distribution demonstrate multiple tectonic reactivation of the interior of the Baltic Shield in response to orogenic events at its margin. 68 refs., 6 refs., 4 tabs.« less

Dislocation-driven growth of two-dimensional lateral quantum-well superlattices

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

Zhou, Wu; Zhang, Yu -Yang; Chen, Jianyi

Here, the advent of two-dimensional (2D) materials has led to extensive studies of heterostructures for novel applications. 2D lateral multiheterojunctions and superlattices have been recently demonstrated, but the available growth methods can only produce features with widths in the micrometer or, at best, 100-nm scale and usually result in rough and defective interfaces with extensive chemical intermixing. Widths smaller than 5 nm, which are needed for quantum confinement effects and quantum-well applications, have not been achieved. We demonstrate the growth of sub–2-nm quantum-well arrays in semiconductor monolayers, driven by the climb of misfit dislocations in a lattice-mismatched sulfide/selenide heterointerface. Densitymore » functional theory calculations provide an atom-by-atom description of the growth mechanism. The calculated energy bands reveal type II alignment suitable for quantum wells, suggesting that the structure could, in principle, be turned into a “conduit” of conductive nanoribbons for interconnects in future 2D integrated circuits via n-type modulation doping. This misfit dislocation–driven growth can be applied to different combinations of 2D monolayers with lattice mismatch, paving the way to a wide range of 2D quantum-well superlattices with controllable band alignment and nanoscale width.« less

Dislocation-driven growth of two-dimensional lateral quantum-well superlattices

DOE PAGES

Zhou, Wu; Zhang, Yu -Yang; Chen, Jianyi; ...

2018-03-23

Here, the advent of two-dimensional (2D) materials has led to extensive studies of heterostructures for novel applications. 2D lateral multiheterojunctions and superlattices have been recently demonstrated, but the available growth methods can only produce features with widths in the micrometer or, at best, 100-nm scale and usually result in rough and defective interfaces with extensive chemical intermixing. Widths smaller than 5 nm, which are needed for quantum confinement effects and quantum-well applications, have not been achieved. We demonstrate the growth of sub–2-nm quantum-well arrays in semiconductor monolayers, driven by the climb of misfit dislocations in a lattice-mismatched sulfide/selenide heterointerface. Densitymore » functional theory calculations provide an atom-by-atom description of the growth mechanism. The calculated energy bands reveal type II alignment suitable for quantum wells, suggesting that the structure could, in principle, be turned into a “conduit” of conductive nanoribbons for interconnects in future 2D integrated circuits via n-type modulation doping. This misfit dislocation–driven growth can be applied to different combinations of 2D monolayers with lattice mismatch, paving the way to a wide range of 2D quantum-well superlattices with controllable band alignment and nanoscale width.« less

Cadmium sulfide quantum dots supported on gallium and indium oxide for visible-light-driven hydrogen evolution from water.

PubMed

Pan, Yun-xiang; Zhuang, Huaqiang; Hong, Jindui; Fang, Zheng; Liu, Hai; Liu, Bin; Huang, Yizhong; Xu, Rong

2014-09-01

In this work, CdS quantum dots (QDs) supported on Ga2O3 and In2O3 are applied for visible-light-driven H2 evolution from aqueous solutions that contain lactic acid. With Pt as the cocatalyst, the H2 evolution rates on CdS/Pt/Ga2O3 and CdS/Pt/In2O3 are as high as 995.8 and 1032.2 μmol h(-1), respectively, under visible light (λ>420 nm) with apparent quantum efficiencies of 43.6 and 45.3% obtained at 460 nm, respectively. These are much higher than those on Pt/CdS (108.09 μmol h(-1)), Pt/Ga2O3 (0.12 μmol h(-1)), and Pt/In2O3 (0.05 μmol h(-1)). The photocatalysts have been characterized thoroughly and their band structures and photocurrent responses have been measured. The band alignment between the CdS QDs and In2O3 can lead to interfacial charge separation, which cannot occur between the CdS QDs and Ga2O3. Among the various possible factors that contribute to the high H2 evolution rates on CdS/Pt/oxide, the surface properties of the metal oxides play important roles, which include (i) the anchoring of CdS QDs and Pt nanoparticles for favorable interactions and (ii) the efficient trapping of photogenerated electrons from the CdS QDs because of surface defects (such as oxygen defects) based on photoluminescence and photocurrent studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SILAR deposition of nickel sulfide counter electrode for application in quantum dot sensitized solar cell

NASA Astrophysics Data System (ADS)

Singh, Navjot; Siwatch, Poonam; Arora, Anmol; Sharma, Jadab; Tripathi, S. K.

2018-05-01

Quantum Dot Sensitized Solar Cells are a likely replacement for Silicon-based solar cells. Counter electrodes are a fundamental aspect of QDSSC's performance. NiS being a less expensive material is a decent choice for the purpose. In this paper, we have discussed the synthesis of NiS by Successive Ionic Layer Adsorption Reaction. Optical, Crystallographic and Electrical studies have been presented. Electrical studies of the device with NiS counter electrode is compared with characteristics of the device with CNTs as the counter electrode. SILAR method is easy and less time to consume than chemical bath deposition or any other method. Results show the success of NiS synthesized by SILAR method as the counter electrode.

Selective solvent-free chromium detection using cadmium-free quantum dots

NASA Astrophysics Data System (ADS)

Meylemans, Heather A.; Baca, Alfred J.; Cambrea, Lee R.; Ostrom, Gregory S.

2017-07-01

Currently, the method of choice to test for the presence of chromium in water is to submit samples to a lab for testing. We present a simple field-ready test that is selective for the presence of chromium at concentrations of 100 ppb or greater. The Environmental Protection Agency maximum contaminant level (MCL) for total chromium is 100 ppb. This test uses a simple on/off fluorescent screening employing the use of silver indium sulfide (AgInS2) quantum dots (QDs). These QDs were impregnated into cotton pads to simplify field testing without the need for solvents or other liquid chemicals to be present. The change in fluorescence is instant and can be readily observed by eye with the use of a UV flashlight.

Functionality of bismuth sulfide quantum dots/wires-glass nanocomposite as an optical current sensor with enhanced Verdet constant

NASA Astrophysics Data System (ADS)

Panmand, Rajendra P.; Kumar, Ganapathy; Mahajan, Satish M.; Kulkarni, Milind V.; Amalnerkar, D. P.; Kale, Bharat B.; Gosavi, Suresh. W.

2011-02-01

We report optical studies with magneto-optic properties of Bi2S3 quantum dot/wires-glass nanocomposite. The size of the Q-dot was observed to be in the range 3-15 nm along with 11 nm Q-wires. Optical study clearly demonstrated the size quantization effect with drastic band gap variation with size. Faraday rotation tests on the glass nanocomposites show variation in Verdet constant with Q-dot size. Bi2S3 Q-dot/wires glass nanocomposite demonstrated 190 times enhanced Verdet constant compared to the host glass. Prima facie observations exemplify the significant enhancement in Verdet constant of Q-dot glass nanocomposites and will have potential application in magneto-optical devices.

Cadmium sulfide quantum dots/poly(acrylic acid-co-acrylic amide) composite hydrogel synthesized by gamma irradiation

NASA Astrophysics Data System (ADS)

Yang, Tao; Li, Qing; Wen, Wanxin; Hu, Liang; He, Weiwei; Liu, Hanzhou

2018-04-01

To improve the durability and stability of quantum dots (QDs) in the composite hydrogel, an irradiation induced reduction and polymerization-crosslinking method was reported herein where CdS QDs could be synthesized in situ and fastened to polymer chains due to the coordination forces between amino groups and CdS nanoparticles. The morphology and photoluminescence (PL) property of the composite hydrogel were studied. The result indicated that the CdS QDs with uniform size were dispersed evenly in the composite hydrogel, and the introduced CdS QDs had no obvious effect on the hydrogel structure. With the increases of reagent concentrations, PL intensity of the composite hydrogel was enhanced; however, the emission wavelength had no change.

Sulfidation of Nano Zerovalent Iron (nZVI) for Improved Selectivity During In-Situ Chemical Reduction (ISCR).

PubMed

Fan, Dimin; O'Brien Johnson, Graham; Tratnyek, Paul G; Johnson, Richard L

2016-09-06

The high reactivity of nano zerovalent iron (nZVI) leads to inefficient treatment due to competition with various natural reductant demand (NRD) processes, especially the reduction of water to hydrogen. Here we show that this limitation can be alleviated by sulfidation (i.e., modification by reducing sulfur compounds). nZVI synthesized on carboxylmethylcelluose (CMC-nZVI) was sulfidated with either sulfide or dithionite. The reactivity of the resulting materials was examined with three complementary assays: (i) direct measurement of hydrogen production, (ii) reduction of a colorimetric redox probe (indigo disulfonate, I2S), and (iii) dechlorination of trichloroethylene (TCE). The results indicate that sulfidation at S/Fe molar ratios of ≥0.3, effectively eliminates reaction with water, but retains significant reactivity with TCE. However, sulfidation with sulfide leaves most of the nZVI as Fe(0), whereas dithionite converts a majority of the nZVI to FeS (thus consuming much of the reducing capacity originally provided by the Fe(0)). Simplified numerical models show that the reduction kinetics of I2S and TCE are mainly dependent on the initial reducing equivalents and that the TCE reduction rate is affected by the aging of FeS. Overall, the results suggest that pretreatment of nZVI with reducing sulfur compounds could result in substantial improvement in nZVI selectivity.

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

USGS Publications Warehouse

Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.

2015-01-01

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

Heterogeneous semiconductor photocatalysts for hydrogen production from aqueous solutions of electron donors

NASA Astrophysics Data System (ADS)

Kozlova, E. A.; Parmon, V. N.

2017-09-01

Current views on heterogeneous photocatalysts for visible- and near-UV-light-driven production of molecular hydrogen from water and aqueous solutions of inorganic and organic electron donors are analyzed and summarized. Main types of such photocatalysts and methods for their preparation are considered. Particular attention is paid to semiconductor photocatalysts based on sulfides that are known to be sensitive to visible light. The known methods for increasing the quantum efficiency of the target process are discussed, including design of the structure, composition and texture of semiconductor photocatalysts and variation of the medium pH and the substrate and photocatalyst concentrations. Some important aspects of the activation and deactivation of sulfide photocatalysts and the evolution of their properties in the course of hydrogen production processes in the presence of various types of electron donors are analyzed. The bibliography includes 276 references.

OCS, stratospheric aerosols and climate

NASA Technical Reports Server (NTRS)

Turco, R. P.; Whitten, R. C.; Toon, O. B.; Pollack, J. B.; Hamill, P.

1980-01-01

The carbonyl sulfide budget in the atmosphere is examined, and the effects of stratospheric sulfate aerosol particles, formed in part from atmospheric carbonyl sulfate, on global climate are considered. From tropospheric measurements of carbon disulfide and the rate constant for the conversion of carbon disulfide to carbonyl sulfide, it is estimated that five Tg of carbonyl sulfide/year could be generated from carbon disulfide in the atmosphere. Direct sources of OCS include the refining and combustion of fossil fuels (1 Tg/year), natural and agricultural fires (0.2 to 0.3 Tg/year), and soils (0.5 Tg/year), yielding a total influx of from 1 to 10 Tg/year, up to 50% of which may be anthropogenic. Considerations of carbonyl sulfide sinks and concentrations indicate an atmospheric lifetime of one year, with OCS the major atmospheric sulfur compound. It is estimated that a ten-fold increase in atmospheric carbonyl sulfide would cause an optical depth perturbation comparable to that of a modest volcanic eruption, leading to an average global surface temperature decrease of 0.1 K, in addition to a possible greenhouse effect.

Consequences of CO2 solubility for hydrate formation from carbon dioxide containing water and other impurities.

PubMed

Kvamme, Bjørn; Kuznetsova, Tatiana; Jensen, Bjørnar; Stensholt, Sigvat; Bauman, Jordan; Sjøblom, Sara; Nes Lervik, Kim

2014-05-14

Deciding on the upper bound of water content permissible in a stream of dense carbon dioxide under pipeline transport conditions without facing the risks of hydrate formation is a complex issue. In this work, we outline and analyze ten primary routes of hydrate formation inside a rusty pipeline, with hydrogen sulfide, methane, argon, and nitrogen as additional impurities. A comprehensive treatment of equilibrium absolute thermodynamics as applied to multiple hydrate phase transitions is provided. We also discuss in detail the implications of the Gibbs phase rule that make it necessary to consider non-equilibrium thermodynamics. The analysis of hydrate formation risk has been revised for the dominant routes, including the one traditionally considered in industrial practice and hydrate calculators. The application of absolute thermodynamics with parameters derived from atomistic simulations leads to several important conclusions regarding the impact of hydrogen sulfide. When present at studied concentrations below 5 mol%, the presence of hydrogen sulfide will only support the carbon-dioxide-dominated hydrate formation on the phase interface between liquid water and hydrate formers entering from the carbon dioxide phase. This is in contrast to a homogeneous hydrate nucleation and growth inside the aqueous solution bulk. Our case studies indicate that hydrogen sulfide at higher than 0.1 mol% concentration in carbon dioxide can lead to growth of multiple hydrate phases immediately adjacent to the adsorbed water layers. We conclude that hydrate formation via water adsorption on rusty pipeline walls will be the dominant contributor to the hydrate formation risk, with initial concentration of hydrogen sulfide being the critical factor.

Hot excitons are responsible for increasing photoluminescence blinking activity in single lead sulfide/cadmium sulfide nanocrystals

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

Chen, Jia-Shiang; Zang, Huidong; Li, Mingxing

The kinetics of PL blinking for isolated PbS/CdS nanocrystals changes with the photon excitation energy, with PL blinking increasing in frequency and changing from a two-state to a multistate on/off switching when the excitation energy changes from 1S h–1S e(≈1.4 eV) to 1P h–1P e(≈2.4 eV).

Hot excitons are responsible for increasing photoluminescence blinking activity in single lead sulfide/cadmium sulfide nanocrystals

DOE PAGES

Chen, Jia-Shiang; Zang, Huidong; Li, Mingxing; ...

2017-12-08

The kinetics of PL blinking for isolated PbS/CdS nanocrystals changes with the photon excitation energy, with PL blinking increasing in frequency and changing from a two-state to a multistate on/off switching when the excitation energy changes from 1S h–1S e(≈1.4 eV) to 1P h–1P e(≈2.4 eV).

Perspective on recent developments on sulfur-containing agents and hydrogen sulfide signaling.

PubMed

Jacob, Claus; Anwar, Awais; Burkholz, Torsten

2008-10-01

The last couple of years have witnessed the coming together of several initially unconnected lines of investigation which now link natural sulfur products to hydrogen sulfide release and wide ranging cardiovascular protection. It has become apparent that sulfur compounds contained within garlic, onions, mushrooms and various edible beans and fruits may be transformed chemically or enzymatically in the human body with subsequent formation of hydrogen sulfide. The latter has emerged during the last decade from a shadowy existence as toxic gas to be recognized as the third gaseous transmitter besides nitric oxide ( (.)NO) and carbon monoxide (CO). Hydrogen sulfide is formed endogenously in the human body by enzymes such as cystathionine beta-synthase (CBS) in the brain and cystathionine gamma-lyase (CSE) in liver, vascular and non-vascular smooth muscle. Although its exact chemical and biochemical modes of action are still not fully understood, levels of hydrogen sulfide in the brain and vasculature have unambiguously been associated with human health and disease. Not surprisingly, agents releasing hydrogen sulfide, as well as inhibitors of hydrogen sulfide synthesis (CBS and CSE inhibitors) have been investigated. Apart from linking our daily diet to a healthy brain and cardiovasculature, these findings may also provide new leads for drug design. Future studies will therefore need to focus on how such compounds are formed and transformed in the relevant plants, how food processing affects their chemical constitution, and how they release hydrogen sulfide (or control its levels) in the human body. Such multidisciplinary research should ultimately answer the all-important question if a hearty diet is also good for the heart.

Ab initio calculations of supramolecular complexes of fullerene C60 with CdTe and CdS

NASA Astrophysics Data System (ADS)

Kvyatkovskii, O. E.; Zakharova, I. B.; Ziminov, V. M.

2014-06-01

This paper presents the results of ab initio quantum-chemical calculations of supramolecular complexes C60CdHal, [C60]4CdHal, and [C60]6CdHal (Hal = S, Te), which simulate the defects forming in fullerite during the absorption or adsorption of cadmium telluride (sulfide). Calculations of the electronic structure of complexes with inclusion of their relaxation to the equilibrium state have been performed in terms of the density functional theory with the B3LYP hybrid functional. The obtained enthalpies of formation of complexes show that their formation leads to the energy gain of the order of 0.5-1.5 eV depending on the complex type. It has been shown that the formation of tetrahedral complexes [C60]4CdTe with the intercalated CdTe molecule is possible only with a considerable distortion of the tetrahedral void. The energy spectrum of low-lying excited electron states for the linear and octahedral complexes has been calculated. It has been found that a decrease in symmetry with the formation of complexes leads to the appearance of excited states of allowed singlet transitions in the electron spectrum, which are forbidden in optical spectra of initial components.

Higher-order spin and charge dynamics in a quantum dot-lead hybrid system.

PubMed

Otsuka, Tomohiro; Nakajima, Takashi; Delbecq, Matthieu R; Amaha, Shinichi; Yoneda, Jun; Takeda, Kenta; Allison, Giles; Stano, Peter; Noiri, Akito; Ito, Takumi; Loss, Daniel; Ludwig, Arne; Wieck, Andreas D; Tarucha, Seigo

2017-09-22

Understanding the dynamics of open quantum systems is important and challenging in basic physics and applications for quantum devices and quantum computing. Semiconductor quantum dots offer a good platform to explore the physics of open quantum systems because we can tune parameters including the coupling to the environment or leads. Here, we apply the fast single-shot measurement techniques from spin qubit experiments to explore the spin and charge dynamics due to tunnel coupling to a lead in a quantum dot-lead hybrid system. We experimentally observe both spin and charge time evolution via first- and second-order tunneling processes, and reveal the dynamics of the spin-flip through the intermediate state. These results enable and stimulate the exploration of spin dynamics in dot-lead hybrid systems, and may offer useful resources for spin manipulation and simulation of open quantum systems.

Theoretical Studies on Heavy Metal Sulfides in Solution

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

Tossell, John A.

2007-10-31

'Calculating the stabilities, Raman and UV spectra and acidities of As sulfides in aqueous solution', J. A. Tossell, M. D. Zimmermann and G. R. Helz. Some of the Raman spectra obtained by reacting aqueous As(OH)3 with aqueous bisulfide are shown, taken from Wood, et al. (2002). To interpret these spectra we have carried out an extensive series of calculations, detailed for the case of AsS(SH){sub 2}{sup -} in Table 1 below. By employing state of the art quantum chemical techniques to determine gas-phase harmonic and anharmonic frequencies and solution phase corrections we can accurately match features in the experimental spectrummore » shown in the top figure. The AsS(SH){sub 2}{sup -}...22 H{sub 2}O nanocluster employed is shown in the lower figure. For this species we have calculated the equilibrium structure and the harmonic vibrational spectrum at the CBSB7 B3LYP level. For the free solute species AsS(SH){sub 2}{sup -} we have carried out a whole series of calculations, evaluating harmonic and anharmonic vibrational frequencies at a number of different quantum mechanical levels. In the spectra below, Fig. 3 and Fig. 5 from Wood, et al. (2002), the features around 700-800 cm{sup -1} are attributed to As-O stretches and those around 350-450 cm{sup -1} to As-S stretches. In the nanocluster an isolated vibrational feature is observed at 425 cm{sup -1}, an As=S stretch, close to the value (415 cm{sup -1}) determined by Wood, et al. (2002). Analysis of the calculated frequencies for AsS(SH){sub 2}{sup -} within a polarizable continuum model yields a similar result. Taking the highest level harmonic results, obtained from a CCSD calculation, and adding anharmonic and PCM corrections at the B3LYP level (designated (3) + (5) - (1) in Table 1) gives a frequency for the intense high frequency As=S stretch within 15 cm{sup -1} of experiment. Although there is still interesting work to be done on the stabilities and the Raman and UV spectra of As sulfides, most of the basic concepts have been worked out and we are therefore proposing to move to a new area, that of humic acids (while continuing our studies complexes formed by As oxides and sulfides, now applied to functional groups present in humic acids).« less

Kinetic studies of sulfide mineral oxidation and xanthate adsorption

NASA Astrophysics Data System (ADS)

Mendiratta, Neeraj K.

2000-10-01

Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector. Iron sulfides, such as pyrite and pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO 2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions. To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS. Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel studies have been used to elucidate the depressing action of DETA and SO2. It was observed that DETA and SO2 complement each other in maintaining lower pulp potentials and removing polysulfides. DETA also helps in deactivating pyrrhotite. Therefore, the combined use of DETA and SO2 leads to the inhibition of both the collectorless flotation and the adsorption of xanthate. The adsorption of xanthate on sulfide minerals is a mixed-potential mechanism, i.e., the anodic oxidation of xanthate requires a cathodic counterpart. Normally, the cathodic reaction is provided by the reduction of oxygen. However, oxygen can be replaced by other oxidants. Ferric ions are normally present in the flotation pulp. Their source could be either iron from the grinding circuit or the ore itself. The galvanic studies were carried out to test the possibility of using ferric ions as oxidants and positive results were obtained. Tafel studies were carried out to measure the activation energies for the adsorption of ethylxanthate on several sulfide minerals. Pyrite, pyrrhotite (pure and nickel activated), chalcocite and covellite were studied in 10 -4 M ethylxanthate solution at pH 6.8 at temperatures in the range of 22--30°C. The Tafel studies showed that xanthate adsorbs as dixanthogen (X2) on pyrite and pyrrhotite, nickel dixanthate (NiX2) on nickel-activated pyrrhotite and cuprous xanthate (CuX) on both chalcocite and covellite. However, the mechanism for xanthate adsorption on each mineral is different. The free energy of reaction estimated from the activation energies are in good agreement with thermodynamically calculated ones.

Human Cystathionine-β-Synthase Phosphorylation on Serine227 Modulates Hydrogen Sulfide Production in Human Urothelium.

PubMed

d'Emmanuele di Villa Bianca, Roberta; Mitidieri, Emma; Esposito, Davide; Donnarumma, Erminia; Donnarumm, Erminia; Russo, Annapina; Fusco, Ferdinando; Ianaro, Angela; Mirone, Vincenzo; Cirino, Giuseppe; Russo, Giulia; Sorrentino, Raffaella

2015-01-01

Urothelium, the epithelial lining the inner surface of human bladder, plays a key role in bladder physiology and pathology. It responds to chemical, mechanical and thermal stimuli by releasing several factors and mediators. Recently it has been shown that hydrogen sulfide contributes to human bladder homeostasis. Hydrogen sulfide is mainly produced in human bladder by the action of cystathionine-β-synthase. Here, we demonstrate that human cystathionine-β-synthase activity is regulated in a cGMP/PKG-dependent manner through phosphorylation at serine 227. Incubation of human urothelium or T24 cell line with 8-Bromo-cyclic-guanosine monophosphate (8-Br-cGMP) but not dibutyryl-cyclic-adenosine monophosphate (d-cAMP) causes an increase in hydrogen sulfide production. This result is congruous with the finding that PKG is robustly expressed but PKA only weakly present in human urothelium as well as in T24 cells. The cGMP/PKG-dependent phosphorylation elicited by 8-Br-cGMP is selectively reverted by KT5823, a specific PKG inhibitor. Moreover, the silencing of cystathionine-β-synthase in T24 cells leads to a marked decrease in hydrogen sulfide production either in basal condition or following 8-Br-cGMP challenge. In order to identify the phosphorylation site, recombinant mutant proteins of cystathionine-β-synthase in which Ser32, Ser227 or Ser525 was mutated in Ala were generated. The Ser227Ala mutant cystathionine-β-synthase shows a notable reduction in basal biosynthesis of hydrogen sulfide becoming unresponsive to the 8-Br-cGMP challenge. A specific antibody that recognizes the phosphorylated form of cystathionine-β-synthase has been produced and validated by using T24 cells and human urothelium. In conclusion, human cystathionine-β-synthase can be phosphorylated in a PKG-dependent manner at Ser227 leading to an increased catalytic activity.

Human Cystathionine-β-Synthase Phosphorylation on Serine227 Modulates Hydrogen Sulfide Production in Human Urothelium

PubMed Central

d’Emmanuele di Villa Bianca, Roberta; Donnarumm, Erminia; Russo, Annapina; Fusco, Ferdinando; Ianaro, Angela; Mirone, Vincenzo; Cirino, Giuseppe; Russo, Giulia; Sorrentino, Raffaella

2015-01-01

Urothelium, the epithelial lining the inner surface of human bladder, plays a key role in bladder physiology and pathology. It responds to chemical, mechanical and thermal stimuli by releasing several factors and mediators. Recently it has been shown that hydrogen sulfide contributes to human bladder homeostasis. Hydrogen sulfide is mainly produced in human bladder by the action of cystathionine-β-synthase. Here, we demonstrate that human cystathionine-β-synthase activity is regulated in a cGMP/PKG-dependent manner through phosphorylation at serine 227. Incubation of human urothelium or T24 cell line with 8-Bromo-cyclic-guanosine monophosphate (8-Br-cGMP) but not dibutyryl-cyclic-adenosine monophosphate (d-cAMP) causes an increase in hydrogen sulfide production. This result is congruous with the finding that PKG is robustly expressed but PKA only weakly present in human urothelium as well as in T24 cells. The cGMP/PKG-dependent phosphorylation elicited by 8-Br-cGMP is selectively reverted by KT5823, a specific PKG inhibitor. Moreover, the silencing of cystathionine-β-synthase in T24 cells leads to a marked decrease in hydrogen sulfide production either in basal condition or following 8-Br-cGMP challenge. In order to identify the phosphorylation site, recombinant mutant proteins of cystathionine-β-synthase in which Ser32, Ser227 or Ser525 was mutated in Ala were generated. The Ser227Ala mutant cystathionine-β-synthase shows a notable reduction in basal biosynthesis of hydrogen sulfide becoming unresponsive to the 8-Br-cGMP challenge. A specific antibody that recognizes the phosphorylated form of cystathionine-β-synthase has been produced and validated by using T24 cells and human urothelium. In conclusion, human cystathionine-β-synthase can be phosphorylated in a PKG-dependent manner at Ser227 leading to an increased catalytic activity. PMID:26368121

Performance Enhancement of 3-Mercaptopropionic Acid-Capped CdSe Quantum-Dot Sensitized Solar Cells Incorporating Single-Walled Carbon Nanotubes.

PubMed

Yang, Jonghee; Park, Taehee; Lee, Jongtaek; Lee, Junyoung; Shin, Hokyeong; Yi, Whikun

2016-03-01

We fabricated a series of linker-assisted quantum-dot-sensitized solar cells based on the ex situ self-assembly of CdSe quantum dots (QDs) onto TiO2 electrode using sulfide/polysulfide (S(2-)/Sn(2-)) as an electrolyte and Au cathode. Our cell were combined with single-walled carbon nanotubes (SWNTs) by two techniques; One was mixing SWNTs with TiO2 electrode and the other was spraying SWNTs onto Au electrode. Absorption spectra were used to confirm the adsorption of QDs onto TiO2 electrode. Cell performance was measured on samples containing and not-containing SWNTs. Samples mixing SWNTs with TiO2 showed higher cell efficiency, on the while sample spraying SWNTs onto Au electrode showed lower efficiency compared with pristine sample (not-containing SWNTs). Electrochemical impedance spectroscopy analysis suggested that SWNTs can act as either barriers or excellent carrier transfers according their position and mixing method.

Strained layer InP/InGaAs quantum well laser

NASA Technical Reports Server (NTRS)

Forouhar, Siamak (Inventor); Larsson, Anders G. (Inventor); Ksendzov, Alexander (Inventor); Lang, Robert J. (Inventor)

1993-01-01

Strained layer single or multiple quantum well lasers include an InP substrate, a pair of lattice-matched InGaAsP quarternary layers epitaxially grown on the substrate surrounding a pair of lattice matched In.sub.0.53 Ga.sub.0.47 As ternary layers surrounding one or more strained active layers of epitaxially grown, lattice-mismatched In.sub.0.75 Ga.sub.0.25 As. The level of strain is selected to control the bandgap energy to produce laser output having a wavelength in the range of 1.6 to 2.5 .mu.m. The multiple quantum well structure uses between each active layer. Diethyl zinc is used for p-type dopant in an InP cladding layer at a concentration level in the range of about 5.times.10.sup.17 /cm.sup.3 to about 2.times.10.sup.18 /cm.sup.3. Hydrogen sulfide is used for n-type dopant in the substrate.

Intracellular bimodal nanoparticles based on quantum dots for high-field MRI at 21.1 T.

PubMed

Rosenberg, Jens T; Kogot, Joshua M; Lovingood, Derek D; Strouse, Geoffrey F; Grant, Samuel C

2010-09-01

Multimodal, biocompatible contrast agents for high magnetic field applications represent a new class of nanomaterials with significant potential for tracking of fluorescence and MR in vitro and vivo. Optimized for high-field MR applications-including biomedical imaging at 21.1 T, the highest magnetic field available for MRI-these nanoparticles capitalize on the improved performance of chelated Dy(3+) with increasing magnetic field coupled to a noncytotoxic Indium Phosphide/Zinc Sulfide (InP/ZnS) quantum dot that provides fluorescence detection, MR responsiveness, and payload delivery. By surface modifying the quantum dot with a cell-penetrating peptide sequence coupled to an MR contrast agent, the bimodal nanomaterial functions as a self-transfecting high-field MR/optical contrast agent for nonspecific intracellular labeling. Fluorescent images confirm sequestration in perinuclear vesicles of labeled cells, with no apparent cytotoxicity. These techniques can be extended to impart cell selectivity or act as a delivery vehicle for genetic or pharmaceutical interventions. 2010 Wiley-Liss, Inc.

A Study of Knowledge-Based Systems for Photo Interpretation.

DTIC Science & Technology

1980-06-01

special models have been developed by V. F. Hollister and A. N. Campbell to aid in the selection of drilling targets for porphyry copper and...type lead/zinc N. Campbell 20 Kuroko-type massive sulfide C. F. Park, Jr. 34 Komatiitic-type nickel sulfide A. J. Naldrett 72 Butte-type porphyry copper ...M. T. Einaudi 104 Yerington-type porphyry copper M. T. Einaudi 143 Island-arc-type porphyry copper D. Cox 116 Roll-front sandstone uranium R. I

Anglesite and silver recovery from jarosite residues through roasting and sulfidization-flotation in zinc hydrometallurgy.

PubMed

Han, Haisheng; Sun, Wei; Hu, Yuehua; Jia, Baoliang; Tang, Honghu

2014-08-15

Hazardous jarosite residues contain abundant valuable minerals that are difficult to be recovered by traditional flotation process. This study presents a new route, roasting combined with sulfidization-flotation, for the recovery of anglesite and silver from jarosite residues of zinc hydrometallurgy. Surface appearance and elemental distribution of jarosite residues was examined by scanning electron microscopy and energy dispersive X-ray spectrometry analysis, respectively. Decomposition and transformation mechanisms of jarosite residues were illustrated by differential thermal analysis. Results showed that after roasting combined with flotation, the grade and recovery of lead were 43.89% and 66.86%, respectively, and those of silver were 1.3 kg/t and 81.60%, respectively. At 600-700 °C, jarosite was decomposed to release encapsulated valuable minerals such as anglesite (PbSO4) and silver mineral; silver jarosite decomposed into silver sulfate (Ag2SO4); and zinc ferrite (ZnO · Fe2O3) decomposed into zinc sulfate (ZnSO4) and hematite (Fe2O3). Bared anglesite and silver minerals were modified by sodium sulfide and easily collected by flotation collectors. This study demonstrates that the combination of roasting and sulfidization-flotation provides a promising process for the recovery of zinc, lead, and silver from jarosite residues of zinc hydrometallurgy. Copyright © 2014 Elsevier B.V. All rights reserved.

Optical, Structural and Paramagnetic Properties of Eu-Doped Ternary Sulfides ALnS2 (A = Na, K, Rb; Ln = La, Gd, Lu, Y)

PubMed Central

Jarý, Vítězslav; Havlák, Lubomír; Bárta, Jan; Buryi, Maksym; Mihóková, Eva; Rejman, Martin; Laguta, Valentin; Nikl, Martin

2015-01-01

Eu-doped ternary sulfides of general formula ALnS2 (A = Na, K, Rb; Ln = La, Gd, Lu, Y) are presented as a novel interesting material family which may find usage as X-ray phosphors or solid state white light emitting diode (LED) lighting. Samples were synthesized in the form of transparent crystalline hexagonal platelets by chemical reaction under the flow of hydrogen sulfide. Their physical properties were investigated by means of X-ray diffraction, time-resolved photoluminescence spectroscopy, electron paramagnetic resonance, and X-ray excited fluorescence. Corresponding characteristics, including absorption, radioluminescence, photoluminescence excitation and emission spectra, and decay kinetics curves, were measured and evaluated in a broad temperature range (8–800 K). Calculations including quantum local crystal field potential and spin-Hamiltonian for a paramagnetic particle in D3d local symmetry and phenomenological model dealing with excited state dynamics were performed to explain the experimentally observed features. Based on the results, an energy diagram of lanthanide energy levels in KLuS2 is proposed. Color model xy-coordinates are used to compare effects of dopants on the resulting spectrum. The application potential of the mentioned compounds in the field of white LED solid state lighting or X-ray phosphors is thoroughly discussed. PMID:28793612

Electrochemical immunoassay for the detection of IgM antibodies using polydopamine particles loaded with PbS quantum dots as labels.

PubMed

Ortega, Greter A; Zuaznabar-Gardona, Julio C; Reguera, Edilso

2018-09-30

Here, we report for the first time, an electrochemical immunoassay to detect IgM antibodies using lead sulfide quantum dots (PbS QDs) as electrochemical labels. In this sense, dendritic-like polydopamine particles loaded with PbS QDs were synthesized by the self-polymerization of dopamine in basic media in the presence of QDs (PbS@PDA) and further tagged with anti-IgM antibodies, dengue specific antigens, and streptavidin moieties. The analytical features of the sandwich immunoassay on ELISA microplate were carried out with the PbS@PDA-labeled anti-IgM as secondary antibody. The system was interrogated by acid dissolution of PbS@PDA, followed by differential pulse anodic stripping voltammetry in the presence of Bi(III) ions using carbon screen-printed electrodes. The results indicate that the voltammetric current increased with the increasing of the concentration of target IgM within a range of 0-0.5 mg mL -1 . The limit of detection of this electrochemical immunoassay was evaluated to 130 ng. The measures of satisfactory recoveries from 88.5% to 114% of spiked samples indicate that such a method has good specificity and is applicable to the quantification of IgM antibodies in complex biological samples. No significant differences at the 0.05 significance level were encountered in the analysis of IgM samples between the electrochemical immunoassay and a Bradford assay. Copyright © 2018 Elsevier B.V. All rights reserved.

Ultrafine particles derived from mineral processing: A case study of the Pb-Zn sulfide ore with emphasis on lead-bearing colloids.

PubMed

Mikhlin, Yuri; Vorobyev, Sergey; Romanchenko, Alexander; Karasev, Sergey; Karacharov, Anton; Zharkov, Sergey

2016-03-01

Although mining and mineral processing industry is a vast source of heavy metal pollutants, the formation and behavior of micrometer- and nanometer-sized particles and their aqueous colloids entered the environment from the technological media has received insufficient attention to date. Here, the yield and characteristics of ultrafine mineral entities produced by routine grinding of the Pb-Zn sulfide ore (Gorevskoe ore deposit, Russia) were studied using laser diffraction analysis (LDA), dynamic light scattering (DLS) and zeta potential measurement, microscopy, X-ray photoelectron spectroscopy, with most attention given to toxic lead species. It was revealed, in particular, that the fraction of particles less that 1 μm in the ground ore typical reaches 0.4 vol. %. The aquatic particles in supernatants were micrometer size aggregates with increased content of zinc, sulfur, calcium as compared with the bulk ore concentrations. The hydrodynamic diameter of the colloidal species decreased with time, with their zeta potentials remaining about -12 mV. The colloids produced from galena were composed of 20-50 nm PbS nanoparticles associated with lead sulfate and thiosulfate, while the surface oxidation products at precipitated galena were largely lead oxyhydroxides. The size and zeta potential of the lead-bearing colloids decreased with time down to about 100 nm and from -15 mV to -30 mV, respectively. And, conversely, lead sulfide nanoparticles were mobilized before the aggregates during redispersion of the precipitates in fresh portions of water. The potential environmental impact of the metal-bearing colloids, which is due to the large-scale production and relative stability, is discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed Central

Li, Shiue-Lin; Nealson, Kenneth H.

2015-01-01

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

Biological synthesis of nanosized sulfide semiconductors: current status and future prospects.

PubMed

da Costa, João Pinto; Girão, Ana Violeta; Trindade, Tito; Costa, Maria Clara; Duarte, Armando; Rocha-Santos, Teresa

2016-10-01

There have been extensive and comprehensive reviews in the field of metal sulfide precipitation in the context of environmental remediation. However, these works have focused mainly on the removal of metals from aqueous solutions-usually, metal-contaminated effluents-with less emphasis on the precipitation process and on the end-products, frequently centering on metal removal efficiencies. Recently, there has been an increasing interest not only in the possible beneficial effects of these bioremediation strategies for metal-rich effluents but also on the formed precipitates. These metal sulfide materials are of special relevance in industry, due to their optical, electronic, and mechanical properties. Hence, identifying new routes for synthesizing these materials, as well as developing methodologies allowing for the control of the shape and size of particulates, is of environmental, economic, and practical importance. Multiple studies have shown proof-of-concept for the biological synthesis of inorganic metallic sulfide nanoparticles (NPs), resorting to varied organisms or cell components, though this information has scarcely been structured and compiled in a systematic manner. In this review, we overview the biological synthesis methodologies of nanosized metal sulfides and the advantages of these strategies when compared to more conventional chemical routes. Furthermore, we highlight the possibility of the use of numerous organisms for the synthesis of different metal sulfide NPs, with emphasis on sulfate-reducing bacteria (SRB). Finally, we put in perspective the potential of these methodologies in the emerging research areas of biohydrometallurgy and nanobiotechnology for the uptake of metals in the form of metal sulfide nanoparticles. A more complete understanding of the principles underlying the (bio)chemistry of formation of solids in these conditions may lead to the large-scale production of such metal sulfides, while simultaneously allowing an enhanced control over the size and shape of these biogenic nanomaterials.

Particle Size/ Grain Size Correlation and Mechanical Properties of Spark Plasma Sintered 8Y-ZrO2, MgAl2O4, and Al2O3 Based Composites

NASA Astrophysics Data System (ADS)

Karandikar, Keyur Kashinath

Solution-processed nanomaterials such as lead sulfide (PbS) colloidal quantum dots (CQDs) combine various manufacturing benefits and facile spectral tunability. However, the low mobility of CQD films limits its power conversion efficiency in photovoltaic cells. Here, I employ a novel femtosecond transient absorption (fs-TA) technique to determine the mobility of PbS CQD films that have undergone state of the art surface treatments. A significant mobility increase from 3 x 10-2 to 5 x 10 -1 cm2 V-1 s-1 was determined for iodide passivated and novel perovskite-shelled PbS CQDs, respectively. I performed, for the first time, temperature-dependent ultrafast carrier dynamics in perovskite-shelled CQDs using fs-TA, and determined an activation energy of 14 meV required for carrier hopping. Complementary studies that used time-of-flight measurements to determine the mobility in solar cell configuration corroborated the fs-TA method. Taken together, these results indicate a promising avenue toward improved CQD solar cells.

Eco-friendly intracellular biosynthesis of CdS quantum dots without changing Escherichia coli's antibiotic resistance.

PubMed

Yan, Zheng-Yu; Du, Qing-Qing; Qian, Jing; Wan, Dong-Yu; Wu, Sheng-Mei

2017-01-01

In the paper, a green and efficient biosynthetical technique was reported for preparing cadmium sulfide (CdS) quantum dots, in which Escherichia coli (E. coli) was chosen as a biomatrix. Fluorescence emission spectra and fluorescent microscopic photographs revealed that as-produced CdS quantum dots had an optimum fluorescence emission peak located at 470nm and emitted a blue-green fluorescence under ultraviolet excitation. After extracted from bacterial cells and located the nanocrystals' foci in vivo, the CdS quantum dots showed a uniform size distribution by transmission electron microscope. Through the systematical investigation of the biosynthetic conditions, including culture medium replacement, input time point of cadmium source, working concentrations of raw inorganic ions, and co-cultured time spans of bacteria and metal ions in the bio-manufacture, the results revealed that CdS quantum dots with the strongest fluorescence emission were successfully prepared when E. coli cells were in stationary phase, with the replacement of culture medium and following the incubation with 1.0×10 -3 mol/L cadmium source for 2 days. Results of antimicrobial susceptibility testing indicated that the sensitivities to eight types of antibiotics of E. coli were barely changed before and after CdS quantum dots were prepared in the mild temperature environment, though a slight fall of antibiotic resistance could be observed, suggesting hinted the proposed technique of producing quantum dots is a promising environmentally low-risk protocol. Copyright © 2016 Elsevier Inc. All rights reserved.

Reactivation of dead sulfide species in lithium polysulfide flow battery for grid scale energy storage.

PubMed

Jin, Yang; Zhou, Guangmin; Shi, Feifei; Zhuo, Denys; Zhao, Jie; Liu, Kai; Liu, Yayuan; Zu, Chenxi; Chen, Wei; Zhang, Rufan; Huang, Xuanyi; Cui, Yi

2017-09-06

Lithium polysulfide batteries possess several favorable attributes including low cost and high energy density for grid energy storage. However, the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium (called "dead" sulfide species) leads to continuous capacity degradation in high mass loading cells, which represents a great challenge. To address this problem, herein we propose a strategy to reactivate dead sulfide species by reacting them with sulfur powder with stirring and heating (70 °C) to recover the cell capacity, and further demonstrate a flow battery system based on the reactivation approach. As a result, ultrahigh mass loading (0.125 g cm -3 , 2 g sulfur in a single cell), high volumetric energy density (135 Wh L -1 ), good cycle life, and high single-cell capacity are achieved. The high volumetric energy density indicates its promising application for future grid energy storage.Lithium polysulfide batteries suffer from the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium. Here the authors show a reactivation strategy by a reaction with cheap sulfur powder under stirring and heating to recover the cell capacity.

Platinum-group elements fractionation by selective complexing, the Os, Ir, Ru, Rh-arsenide-sulfide systems above 1020 °C

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Bragagni, Alessandro

2017-11-01

The platinum-group element (PGE) contents in magmatic ores and rocks are normally in the low μg/g (even in the ng/g) level, yet they form discrete platinum-group mineral (PGM) phases. IPGE (Os, Ir, Ru) + Rh form alloys, sulfides, and sulfarsenides while Pt and Pd form arsenides, tellurides, bismuthoids and antimonides. We experimentally investigate the behavior of Os, Ru, Ir and Rh in As-bearing sulfide system between 1300 and 1020 °C and show that the prominent mineralogical difference between IPGE (+Rh) and Pt and Pd reflects different chemical preference in the sulfide melt. At temperatures above 1200 °C, Os shows a tendency to form alloys. Ruthenium forms a sulfide (laurite RuS2) while Ir and Rh form sulfarsenides (irarsite IrAsS and hollingworthite RhAsS, respectively). The chemical preference of PGE is selective: IPGE + Rh form metal-metal, metal-S and metal-AsS complexes while Pt and Pd form semimetal complexes. Selective complexing followed by mechanical separation of IPGE (and Rh)-ligand from Pt- and Pd-ligand associations lead to PGE fractionation.

Development of highly sensitive electrochemical genosensor based on multiwalled carbon nanotubes-chitosan-bismuth and lead sulfide nanoparticles for the detection of pathogenic Aeromonas.

PubMed

Fernandes, António Maximiano; Abdalhai, Mandour H; Ji, Jian; Xi, Bing-Wen; Xie, Jun; Sun, Jiadi; Noeline, Rasoamandrary; Lee, Byong H; Sun, Xiulan

2015-01-15

In this paper, we reported the construction of new high sensitive electrochemical genosensor based on multiwalled carbon nanotubes-chitosan-bismuth complex (MWCNT-Chi-Bi) and lead sulfide nanoparticles for the detection of pathogenic Aeromonas. Lead sulfide nanoparticles capped with 5'-(NH2) oligonucleotides thought amide bond was used as signalizing probe DNA (sz-DNA) and thiol-modified oligonucleotides sequence was used as fixing probe DNA (fDNA). The two probes hybridize with target Aeromonas DNA (tDNA) sequence (fDNA-tDNA-szDNA). The signal of hybridization is detected by differential pulse voltammetry (DPV) after electrodeposition of released lead nanoparticles (PbS) from sz-DNA on the surface of glass carbon electrode decorated with MWCNT-Chi-Bi, which improves the deposition and traducing electrical signal. The optimization of incubation time, hybridization temperature, deposition potential, deposition time and the specificity of the probes were investigated. Our results showed the highest sensibility to detect the target gene when compared with related biosensors and polymerase chain reaction (PCR). The detection limit for this biosensor was 1.0×10(-14) M. We could detect lower than 10(2) CFU mL(-1) of Aeromonas in spiked tap water. This method is rapid and sensitive for the detection of pathogenic bacteria and would become a potential application in biomedical diagnosis, food safety and environmental monitoring. Copyright © 2014 Elsevier B.V. All rights reserved.

Reactivation of dead sulfide species in lithium polysulfide flow battery for grid scale energy storage

DOE PAGES

Jin, Yang; Zhou, Guangmin; Shi, Feifei; ...

2017-09-06

Lithium polysulfide batteries possess several favorable attributes including low cost and high energy density for grid energy storage. However, the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium (called “dead” sulfide species) leads to continuous capacity degradation in high mass loading cells, which represents a great challenge. To address this problem, herein we propose a strategy to reactivate dead sulfide species by reacting them with sulfur powder with stirring and heating (70 °C) to recover the cell capacity, and further demonstrate a flow battery system based on the reactivation approach. As a result, ultrahighmore » mass loading (0.125 g cm –3, 2g sulfur in a single cell), high volumetric energy density (135 Wh L –1), good cycle life, and high single-cell capacity are achieved. The high volumetric energy density indicates its promising application for future grid energy storage.« less

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

DOE PAGES

Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

2016-04-05

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

Reactivation of dead sulfide species in lithium polysulfide flow battery for grid scale energy storage

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

Jin, Yang; Zhou, Guangmin; Shi, Feifei

Lithium polysulfide batteries possess several favorable attributes including low cost and high energy density for grid energy storage. However, the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium (called “dead” sulfide species) leads to continuous capacity degradation in high mass loading cells, which represents a great challenge. To address this problem, herein we propose a strategy to reactivate dead sulfide species by reacting them with sulfur powder with stirring and heating (70 °C) to recover the cell capacity, and further demonstrate a flow battery system based on the reactivation approach. As a result, ultrahighmore » mass loading (0.125 g cm –3, 2g sulfur in a single cell), high volumetric energy density (135 Wh L –1), good cycle life, and high single-cell capacity are achieved. The high volumetric energy density indicates its promising application for future grid energy storage.« less

Thermal Constraints from Siderophile Trace Elements in Acapulcoite-Lodranite Metals

NASA Technical Reports Server (NTRS)

Herrin, Jason S.; Mittlefehldt, D. W.; Humayun, M.

2006-01-01

A fundamental process in the formation of differentiated bodies is the segregation of metal-sulfide and silicate phases, leading to the formation of a metallic core. The only known direct record of this process is preserved in some primitive achondrites, such as the acapulcoite-lodranites. Meteorites of this clan are the products of thermal metamorphism of a chondritic parent. Most acapulcoites have experienced significant partial melting of the metal-sulfide system but not of silicates, while lodranites have experienced partial melting and melt extraction of both. The clan has experienced a continuum of temperatures relevant to the onset of metal mobility in asteroidal bodies and thus could yield insight into the earliest stages of core formation. Acapulcoite GRA 98028 contains relict chondrules, high modal sulfide/metal, has the lowest 2-pyroxene closure temperature, and represents the least metamorphosed state of the parent body among the samples examined. Comparison of the metal-sulfide component of other clan members to GRA 98028 can give an idea of the effects of metamorphism.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

NASA Astrophysics Data System (ADS)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-01

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

PubMed

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

PubMed Central

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Base and precious metal occurrences along the San Andreas Fault, Point Delgada, California

USGS Publications Warehouse

McLaughlin, Robert J.; Sorg, D.H.; Ohlin, H.N.; Heropoulos, Chris

1979-01-01

Previously unrecognized veins containing lead, zinc, and copper sulfide minerals at Point Delgada, Calif., are associated with late Mesozoic(?) and Tertiary volcanic and sedimentary rocks of the Franciscan assemblage. Sulfide minerals include pyrite, sphalerite, galena, and minor chalcopyrite, and galena-rich samples contain substantial amounts of silver. These minerals occur in a quartz-carbonate gangue along northeast-trending faults and fractures that exhibit (left?) lateral and vertical slip. The sense of fault movement and the northeasterly strike are consistent with predicted conjugate fault sets of the present San Andreas fault system. The sulfide mineralization is younger than the Franciscan rocks of Point Delgada and King Range, and it may have accompanied or postdated the inception of San Andreas faulting. Mineralization largely preceded uplift, the formation of a marine terrace, and the emplacement of landslide-related debris-flow breccias that overlie the mineralized rocks and truncate the sulfide veins. These field relations indicate that the sulfide mineralization and inception of San Andreas faulting were clearly more recent than the early Miocene and that the mineralization could be younger than about 1.2 m.y. The sulfide veins at Point Delgada may be of economic significance. However, prior to any exploitation of the occurrence, economic and environmental conflicts of interest involving private land ownership, the Shelter Cove home development, and proximity of the coast must be resolved.

Removal of EDB and 1,2-DCA by Abiotic Reaction with Iron(II) Sulfide

EPA Science Inventory

Ethylene Dibromide (EDB) and 1,2-Dichloroethane (1,2-DCA) were used as lead scavengers in leaded motor gasoline in the USA until the late 1980s. Leaded gasoline in contact with ground water should produce concentrations of EDB near 1900 µg/L, and concentrations of 1,2-DCA near 3...

Infrared photoconductivity and photovoltaic response from nanoscale domains of PbS alloyed with thorium and oxygen

NASA Astrophysics Data System (ADS)

Arad-Vosk, N.; Beach, R.; Ron, A.; Templeman, T.; Golan, Y.; Sarusi, G.; Sa'ar, A.

2018-03-01

Thin films of lead sulfide alloyed with thorium and oxygen were deposited on GaAs substrates and processed to produce a photo-diode structure. Structural, optical and electrical characterizations indicate the presence of small nanoscale domains (NDs) that are characterized by dense packaging, high quality interfaces and a blue-shift of the energy bandgap toward the short wavelength infrared range of the spectrum. Photocurrent spectroscopy revealed a considerable photoconductivity that is correlated with excitation of carriers in the NDs of lead sulfide alloyed with thorium and oxygen. Furthermore, the appearance of a photovoltaic effect under near infrared illumination indicates a quasi-type II band alignment at the interface of the GaAs and the film of NDs.

Infrared photoconductivity and photovoltaic response from nanoscale domains of PbS alloyed with thorium and oxygen.

PubMed

Arad-Vosk, N; Beach, R; Ron, A; Templeman, T; Golan, Y; Sarusi, G; Sa'ar, A

2018-03-16

Thin films of lead sulfide alloyed with thorium and oxygen were deposited on GaAs substrates and processed to produce a photo-diode structure. Structural, optical and electrical characterizations indicate the presence of small nanoscale domains (NDs) that are characterized by dense packaging, high quality interfaces and a blue-shift of the energy bandgap toward the short wavelength infrared range of the spectrum. Photocurrent spectroscopy revealed a considerable photoconductivity that is correlated with excitation of carriers in the NDs of lead sulfide alloyed with thorium and oxygen. Furthermore, the appearance of a photovoltaic effect under near infrared illumination indicates a quasi-type II band alignment at the interface of the GaAs and the film of NDs.

Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

USGS Publications Warehouse

Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

1999-01-01

Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and lower model Th/U. These Pb isotope differences are inferred to result from differences in their respective post-1.7 Ga magmatic histories. Throughout Arizona, Pb isotope compositions of Late Cretaceous and early Tertiary plutons and associated sulfide minerals are distinct from those of Jurassic plutons and also middle Tertiary igneous rocks and sulfide minerals. These differences most likely reflect changes in tectonic setting and magmatic sources. Within Late Cretaceous and early Tertiary igneous complexes that host economic porphyry copper deposits, there is commonly a decrease in Pb isotope composition from older to younger plutons. This decrease in Pb isotope values with time suggests an increasing involvement of crust with lower U/Pb than average crust in the source(s) of Late Cretaceous and early Tertiary magmas. Lead isotope compositions of the youngest porphyries in the igneous complexes are similar to those in most sulfide minerals within the associated porphyry copper deposit. This Pb isotope similarity argues for a genetic link between them. However, not all Pb in the sulfide minerals in porphyry copper deposits is magmatically derived. Some sulfide minerals, particularly those that are late stage, or distal to the main orebody, or in Proterozoic or Paleozoic rocks, have elevated Pb isotope compositions displaced toward the gross average Pb isotope composition of the local country rocks. The more radiogenic isotopic compositions argue for a contribution of Pb from those rocks at the site of ore deposition. Combining the Pb isotope data with available geochemical, isotopic, and petrologic data suggests derivation of the young porphyry copper-related plutons, most of their Pb, and other metals from a hybridized lower continental crustal source. Because of the likely involvement of subduction-related mantle-derived basaltic magma in the hybridized lower crustal source, an indiscernible mantle contribution is probable in the porphyry magmas. Clearly, in addition

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

PubMed

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

2003-01-01

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

Natural Pyrrhotite as a Catalyst in Prebiotic Chemical Evolution

PubMed Central

López Ibáñez de Aldecoa, Alejandra; Velasco Roldán, Francisco; Menor-Salván, César

2013-01-01

The idea of an autotrophic organism as the first living being on Earth leads to the hypothesis of a protometabolic, complex chemical system. In one of the main hypotheses, the first metabolic systems emerged from the interaction between sulfide minerals and/or soluble iron-sulfide complexes and fluids rich in inorganic precursors, which are reduced and derived from crustal or mantle activity. Within this context, the possible catalytic role of pyrrhotite, one of the most abundant sulfide minerals, in biomimetic redox and carbon fixation reactions was studied. Our results showed that pyrrhotite, under simulated hydrothermal conditions, could catalyze the pyruvate synthesis from lactate and that a dynamic system formed by coupling iron metal and iron-sulfur species in an electrochemical cell could promote carbon fixation from thioacetate esters. PMID:25369819

Theoretical studies of the low-lying states of ScO, ScS, VO, and VS

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

1986-01-01

Bonding in the low-lying states of ScO, ScS, VO, and VS is theoretically studied. Excellent agreement is obtained with experimental spectroscopic constants for the low-lying states of ScO and VO. The results for VS and ScS show that the bonding in the oxides and sulfides is similar, but that the smaller electronegativity in S leads to a smaller ionic component in the bonding. The computed D0 of the sulfides are about 86 percent of the corresponding oxides, and the low-lying excited states are lower in the sulfides than in the corresponding oxides. The CPF method is shown to be an accurate and cost-effective method for obtaining reliable spectroscopic constants for these systems.

Flow-injection chemiluminescence analysis for sensitive determination of atenolol using cadmium sulfide quantum dots.

PubMed

Khataee, Alireza; Lotfi, Roya; Hasanzadeh, Aliyeh; Iranifam, Mortaza; Joo, Sang Woo

2016-03-15

A sensitive, rapid and simple flow-injection chemiluminescence (CL) system based on the light emitted from KMnO4-cadmium sulfide quantum dots (CdS QDs) reaction in the presence of cetyltrimethylammonium bromide (CTAB) in acidic medium was developed as a CL probe for the sensitive determination of atenolol. Optical and structural features of CdS QDs capped with l-cysteine, which synthesized via hydrothermal approach, were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), and UV-Vis spectroscopy. The CL intensity of KMnO4-CdS QDs-CTAB was remarkably enhanced in the presence of trace level of atenolol. Under optimum experimental conditions, there is a linear relationship between the increase in CL intensity of KMnO4-CdS QDs-CTAB system and atenolol concentration in a range of 0.001 to 4.0 mg L(-1) and 4.0 to 18.0 mg L(-1), with a detection limit (3σ) of 0.0010 mg L(-1). A possible mechanism for KMnO4-CdS QDs-CTAB-atenolol CL reaction is proposed. To prove the practical application of the KMnO4-CdS QDs-CTAB CL method, the method was applied for the determination of atenolol in spiked environmental water samples and commercial pharmaceutical formulation. Furthermore, corona discharge ionization ion mobility spectrometry (CD-IMS) technique was utilized for determination of atenolol. Copyright © 2015 Elsevier B.V. All rights reserved.

High Electrocatalytic Activity of Vertically Aligned Single-Walled Carbon Nanotubes towards Sulfide Redox Shuttles.

PubMed

Hao, Feng; Dong, Pei; Zhang, Jing; Zhang, Yongchang; Loya, Phillip E; Hauge, Robert H; Li, Jianbao; Lou, Jun; Lin, Hong

2012-01-01

Vertically aligned single-walled carbon nanotubes (VASWCNTs) have been successfully transferred onto transparent conducting oxide glass and implemented as efficient low-cost, platinum-free counter electrode in sulfide -mediated dye-sensitized solar cells (DSCs), featuring notably improved electrocatalytic activity toward thiolate/disulfide redox shuttle over conventional Pt counter electrodes. Impressively, device with VASWCNTs counter electrode demonstrates a high fill factor of 0.68 and power conversion efficiency up to 5.25%, which is significantly higher than 0.56 and 3.49% for that with a conventional Pt electrode. Moreover, VASWCNTs counter electrode produces a charge transfer resistance of only 21.22 Ω towards aqueous polysulfide electrolyte commonly applied in quantum dots-sensitized solar cells (QDSCs), which is several orders of magnitude lower than that of a typical Pt electrode. Therefore, VASWCNTs counter electrodes are believed to be a versatile candidate for further improvement of the power conversion efficiency of other iodine-free redox couple based DSCs and polysulfide electrolyte based QDSCs.

Cu(In,Ga)Se2 solar cells with In2S3 buffer layer deposited by thermal evaporation

NASA Astrophysics Data System (ADS)

Kim, SeongYeon; Rana, Tanka R.; Kim, JunHo; Yun, JaeHo

2017-12-01

We report on physical vapor deposition of indium sulfide (In2S3) buffer layers and its application to Cu(In,Ga)Se2 (CIGSe) thin film solar cell. The Indium sulfide buffer layers were evaporated onto CIGSe at various substrate temperatures from room temperature (RT) to 350 °C. The effect of deposition temperature of buffer layers on the solar cell device performance were investigated by analyzing temperature dependent current-voltage ( J- V- T), external quantum efficiency (EQE) and Raman spectroscopy. The fabricated device showed the highest power conversion efficiency of 6.56% at substrate temperature of 250 °C, which is due to the decreased interface recombination. However, the roll-over in J- V curves was observed for solar cell device having buffer deposited at substrate temperature larger than 250 °C. From the measurement results, the interface defect and roll-over related degradation were found to have limitation on the performance of solar cell device.

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

NASA Astrophysics Data System (ADS)

Nambissan, P. M. G.

2013-06-01

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

Synthesis of finely divided molybdenum sulfide nanoparticles in propylene carbonate solution

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

Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon1.fr

2014-05-01

Molybdenum sulfide nanoparticles have been prepared from the reflux solution reaction involving ammonium heptamolybdate and elemental sulfur in propylene carbonate. Addition to the reaction mixture of starch as a natural capping agent leads to lesser agglomeration and smaller size of the particles. Nanoparticles of MoS{sub x} (x≈4) of 10–30 nm size are highly divided and form stable colloidal suspensions in organic solvents. Mo K edge EXAFS of the amorphous materials shows rapid exchange of oxygen to sulfur in the molybdenum coordination sphere during the solution reaction. Thermal treatment of the amorphous sulfides MoS{sub x} under nitrogen or hydrogen flow atmore » 400 °C allows obtaining mesoporous MoS{sub 2} materials with very high pore volume and specific surface area, up to 0.45 cm{sup 3}/g and 190 m{sup 2}/g, respectively. The new materials show good potential for the application as unsupported hydrotreating catalysts. - Graphical abstract: Solution reaction in propylene carbonate allows preparing weakly agglomerated molybdenum sulfide with particle size 20 nm and advantageous catalytic properties. - Highlights: • Solution reaction in propylene carbonate yields MoS{sub x} particles near 20 nm size. • Addition of starch as capping agent reduces particles size and hinder agglomeration. • EXAFS at Mo K edge shows rapid oxygen to sulfur exchange in the solution. • Thermal treatment leads to MoS{sub 2} with very high porosity and surface area.« less

Reduction of acid rock drainage using steel slag in cover systems over sulfide rock waste piles.

PubMed

de Almeida, Rodrigo Pereira; Leite, Adilson do Lago; Borghetti Soares, Anderson

2015-04-01

The extraction of gold, coal, nickel, uranium, copper and other earth-moving activities almost always leads to environmental damage. In metal and coal extraction, exposure of sulfide minerals to the atmosphere leads to generation of acid rock drainage (ARD) and in underground mining to acid mine drainage (AMD) due to contamination of infiltrating groundwater. This study proposes to develop a reactive cover system that inhibits infiltration of oxygen and also releases alkalinity to increase the pH of generated ARD and attenuate metal contaminants at the same time. The reactive cover system is constructed using steel slag, a waste product generated from steel industries. This study shows that this type of cover system has the potential to reduce some of the adverse effects of sulfide mine waste disposal on land. Geochemical and geotechnical characterization tests were carried out. Different proportions of sulfide mine waste and steel slag were studied in leachate extraction tests. The best proportion was 33% of steel slag in dry weight. Other tests were conducted as follows: soil consolidation, saturated permeability and soil water characteristic curve. The cover system was numerically modeled through unsaturated flux analysis using Vadose/w. The solution proposed is an oxygen transport barrier that allows rain water percolation to treat the ARD in the waste rock pile. The results showed that the waste pile slope is an important factor and the cover system must have 5 m thickness to achieve an acceptable effectiveness. © The Author(s) 2015.

Morphology controllable time-dependent CoS nanoparticle thin films as efficient counter electrode for quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Reddy, Araveeti Eswar; Rao, S. Srinivasa; Gopi, Chandu V. V. M.; Anitha, Tarugu; Thulasi-Varma, Chebrolu Venkata; Punnoose, Dinah; Kim, Hee-Je

2017-11-01

Cobalt sulfide (CoS) agglomerated nanoparticle thin films obtained by a facile chemical bath method at different deposition times. The CoS counter electrode (CE) deposited at 3 h deposition time (CC-3h) based quantum dot sensitized solar cells (QDSSCs) achieves higher power conversion efficiency (η) of 3.67% than those of CC-2h (1.83%), CC-4h (2.52%), and Pt (1.48%) CEs, under one sun illumination (100 mW cm-2, AM 1.5 G). The electrochemical analysis revealed that CC-3h CE shows a smaller charge transfer resistance (9.22 Ω) at the CE/electrolyte interface than the CC-2h (23.34 Ω), CC-4h (19.73 Ω) and Pt (139.92 Ω) CEs, respectively.

Selective detection of dopamine in the presence of ascorbic acid via fluorescence quenching of InP/ZnS quantum dots.

PubMed

Ankireddy, Seshadri Reddy; Kim, Jongsung

2015-01-01

Dopamine is a neurotransmitter of the catecholamine family and has many important roles, especially in human brain. Several diseases of the nervous system, such as Parkinson's disease, attention deficit hyperactivity disorder, restless legs syndrome, are believed to be related to deficiency of dopamine. Several studies have been performed to detect dopamine by using electrochemical analysis. In this study, quantum dots (QDs) were used as sensing media for the detection of dopamine. The surface of the QDs was modified with l-cysteine by coupling reaction to increase the selectivity of dopamine. The fluorescence of cysteine-capped indium phosphide/zinc sulfide QDs was quenched by dopamine with various concentrations in the presence of ascorbic acid. This method shows good selectivity for dopamine detection, and the detection limit was 5 nM.

Response of gut health and microbiota to sulfide exposure in Pacific white shrimp Litopenaeus vannamei.

PubMed

Suo, Yantong; Li, Erchao; Li, Tongyu; Jia, Yongyi; Qin, Jian G; Gu, Zhimin; Chen, Liqiao

2017-04-01

Sulfide is a natural and widely distributed toxicant. It can be commonly found on the interface between water and sediment in the aquatic environment. The Pacific white shrimp Litopenaeus vannamei starts life in the benthic zone soon after the mysis stage, an early stage of post larvae. Therefore, L. vannamei is inevitably affected by exposure to sulfide released from pond sediment. This study explored the toxicant effect of different concentrations of sulfide on the intestinal health and microbiota of Pacific white shrimp by monitoring the change of expression of inflammatory, immune related cytokines, and the structure of the intestinal microbiota. The gut histology, expressions of inflammatory and immune related cytokines (tumor necrosis factor-alpha, C-type lectin 3, myostatin and heat shock transcription factor 1), and the microbiota were determined in L. vannamei after exposure to 0 (control), 425.5 (1/10 LC 50-96 h), and 851 μg/L (1/5 LC 50-96 h) of sulfide for 21 days. With the increase of sulfide concentration, intestinal injury was aggravated and the inflammatory and immune related cytokines generated a range of reactions. The expression of myostatin (MSTN) was significantly down-regulated by the concentration of sulfide exposure. No difference in the expression of heat shock transcription factor 1 (HSF1) was found between the control and shrimp exposed to 425.5 μg/L, but significantly higher HSF1 expression was found in shrimp exposed to 851 μg/L of sulfide. Significantly higher values of tumor necrosis factor-alpha (TNF-α) and C-type lectin 3 (CTL3) were found in the shrimp exposed to 425.5 μg/L of sulfide compared to the control, but a lower value was found in the shrimp exposed to 851 μg/L (P < 0.05). Sulfide also changed the intestinal microbial communities. The abundance of pathogenic bacteria, such as Cyanobacteria, Vibrio and Photobacterium, increased significantly with exposure to the increasing concentration of sulfide. The abundance of some anti-stress bacteria, such as Chlorobi and Fusobacterium, increased. Nitrospirae which can alleviate nitrite toxicity decreased. Microbacterium, Parachlamydia, and Shewanella were all commonly found and down-regulated in both sulfide groups, which is associated with an adaptation to sulfide stimulation. This study indicates that chronic exposure to sub-lethal levels of sulfide could lead to damage of the gut structure, stimulate the response of the inflammatory and immune systems, and shape the structure of the gut microbiota in L. vannamei. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Homolytic cleavage of both heme-bound hydrogen peroxide and hydrogen sulfide leads to the formation of sulfheme

DOE PAGES

Arbelo-Lopez, Hector D.; Simakov, Nikolay A.; Smith, Jeremy C.; ...

2016-06-29

Many heme-containing proteins with a histidine in the distal E7 (HisE7) position can form sulfheme in the presence of hydrogen sulfide (H 2S) and a reactive oxygen species such as hydrogen peroxide. For reasons unknown, sulfheme derivatives are formed specifically on solvent-excluded heme pyrrole B. Sulfhemes severely decrease the oxygen-binding affinity in hemoglobin (Hb) and myoglobin (Mb). Here, use of hybrid quantum mechanical/molecular mechanical methods has permitted characterization of the entire process of sulfheme formation in the HisE7 mutant of hemoglobin I (HbI) from Lucina pectinata. This process includes a mechanism for H 2S to enter the solvent-excluded active sitemore » through a hydrophobic channel to ultimately form a hydrogen bond with H 2O 2 bound to Fe(III). Proton transfer from H 2O 2 to His64 to form compound (Cpd) 0, followed by hydrogen transfer from H 2S to the Fe(III) H 2O 2 complex, results in homolytic cleavage of the O–O and S–H bonds to form a reactive thiyl radical (HS*), ferryl heme Cpd II, and a water molecule. Subsequently, the addition of HS to Cpd II, followed by three proton transfer reactions, results in the formation of a three-membered ring ferric sulfheme that avoids migration of the radical to the protein matrix, in contrast to that in other peroxidative reactions. The transformation of this three-membered episulfide ring structure to the five-membered thiochlorin ring structure occurs through a significant potential energy barrier, although both structures are nearly isoenergetic. Both three- and five-membered ring structures reveal longer N B–Fe(III) bonds compared with other pyrrole nitrogen–Fe(III) bonds, which would lead to decreased oxygen binding. Altogether, these results are in agreement with a wide range of experimental data and provide fertile ground for further investigations of sulfheme formation in other heme proteins and additional effects of H 2S on cell signaling and reactivity.« less

Homolytic cleavage of both heme-bound hydrogen peroxide and hydrogen sulfide leads to the formation of sulfheme

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

Arbelo-Lopez, Hector D.; Simakov, Nikolay A.; Smith, Jeremy C.

Many heme-containing proteins with a histidine in the distal E7 (HisE7) position can form sulfheme in the presence of hydrogen sulfide (H 2S) and a reactive oxygen species such as hydrogen peroxide. For reasons unknown, sulfheme derivatives are formed specifically on solvent-excluded heme pyrrole B. Sulfhemes severely decrease the oxygen-binding affinity in hemoglobin (Hb) and myoglobin (Mb). Here, use of hybrid quantum mechanical/molecular mechanical methods has permitted characterization of the entire process of sulfheme formation in the HisE7 mutant of hemoglobin I (HbI) from Lucina pectinata. This process includes a mechanism for H 2S to enter the solvent-excluded active sitemore » through a hydrophobic channel to ultimately form a hydrogen bond with H 2O 2 bound to Fe(III). Proton transfer from H 2O 2 to His64 to form compound (Cpd) 0, followed by hydrogen transfer from H 2S to the Fe(III) H 2O 2 complex, results in homolytic cleavage of the O–O and S–H bonds to form a reactive thiyl radical (HS*), ferryl heme Cpd II, and a water molecule. Subsequently, the addition of HS to Cpd II, followed by three proton transfer reactions, results in the formation of a three-membered ring ferric sulfheme that avoids migration of the radical to the protein matrix, in contrast to that in other peroxidative reactions. The transformation of this three-membered episulfide ring structure to the five-membered thiochlorin ring structure occurs through a significant potential energy barrier, although both structures are nearly isoenergetic. Both three- and five-membered ring structures reveal longer N B–Fe(III) bonds compared with other pyrrole nitrogen–Fe(III) bonds, which would lead to decreased oxygen binding. Altogether, these results are in agreement with a wide range of experimental data and provide fertile ground for further investigations of sulfheme formation in other heme proteins and additional effects of H 2S on cell signaling and reactivity.« less

Arsenic in New England: Mineralogical and geochemical studies of sources and enrichment pathways

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.

2003-01-01

Detailed mineralogical, geochemical and radiogenic isotopic studies of iron-sulfide and secondary iron oxy-hydroxide minerals in natural bedrock in coastal Maine and New Hampshire test the link between arsenic-rich sulfide minerals in bedrock and secondary oxy-hydroxide minerals. Samples were selected from over 70 bedrock localities, including 22 within the regionally extensive and sulfide-mineral-rich Penobscot Formation and 10 associated with mineral deposits from coastal New Hampshire and Maine, and coupled with data from drill core collected at several sites including areas where well waters contain anomalous As abundances (e.g., Northport, ME). The data were used to establish a diversity of primary and secondary mineralogical hosts for arsenic in bedrock of this part of New England. The studies show that bedrock mineralogy is critical to contributing arsenic to groundwater and suggest a number of mineralogical pathways for arsenic that define weathering processes. The studies show that lead isotopic compositions of the sulfides and iron oxy-hydroxides overlap and establish a genetic link between the sulfides and secondary minerals. The data and interpretive results were presented at Arsenic in New England -- A multidisciplinary Scientific Conference, Manchester, New Hampshire, May 29-31, 2002, sponsored by the New Hampshire Consortium on Arsenic, are available in abstract and poster (full size = 84 by 36 inch sheet) formats.

In Situ Transformation of MOFs into Layered Double Hydroxide Embedded Metal Sulfides for Improved Electrocatalytic and Supercapacitive Performance.

PubMed

Yilmaz, Gamze; Yam, Kah Meng; Zhang, Chun; Fan, Hong Jin; Ho, Ghim Wei

2017-07-01

Direct adoption of metal-organic frameworks (MOFs) as electrode materials shows impoverished electrochemical performance owing to low electrical conductivity and poor chemical stability. In this study, we demonstrate self-templated pseudomorphic transformation of MOF into surface chemistry rich hollow framework that delivers highly reactive, durable, and universal electrochemically active energy conversion and storage functionalities. In situ pseudomorphic transformation of MOF-derived hollow rhombic dodecahedron template and sulfurization of nickel cobalt layered double hydroxides (NiCo-LDHs) lead to the construction of interlayered metal sulfides (NiCo-LDH/Co 9 S 8 ) system. The embedment of metal sulfide species (Co 9 S 8 ) at the LDH intergalleries offers optimal interfacing of the hybrid constituent elements and materials stability. The hybrid NiCo-LDH/Co 9 S 8 system collectively presents an ideal porous structure, rich redox chemistry, and high electrical conductivity matrix. This leads to a significant enhancement in its complementary electrocatalytic hydrogen evolution and supercapacitive energy storage properties. This work establishes the potential of MOF derived scaffold for designing of novel class hybrid inorganic-organic functional materials for electrochemical applications and beyond. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition Metal Nanomaterials by Bacterial Precipitation: Synthesis and Characterization of Cadmium Sulfide Quantum Dots

NASA Astrophysics Data System (ADS)

Marusak, Katherine Elizabeth

We present a new method to fabricate semiconducting, transition metal nanoparticles (NPs) with tunable bandgap energies using engineered Escherichia coli. These bacteria overexpress the Treponema denticola cysteine desulfhydrase gene to facilitate precipitation of cadmium sulfide (CdS) NPs. Multiple characterization techniques reveal that the bacterially precipitated NPs are agglomerates of mostly quantum dots, with diameters that can range from 3 to 15 nm, embedded in a carbon-rich matrix. Notably, the measured photoelectrochemical current generated by these NPs is comparable to values reported in the literature and higher than that of synthesized chemical bath deposited CdS NPs. We showed that we can manipulate the bandgap energy of the NPs by controlling their size through varying the precursor concentrations. Our calculated bandgap energies ranged between 2.67 eV (i.e., quantum confined CdS) to 2.36 eV ( i.e., bulk CdS). By adding the CdCl2 precursor at a specific stage of the bacterial growth cycle, we were able to induce extracellular CdS NP precipitation. Additionally, we adapted extracellular precipitation strategies to form CdS NPs on surfaces as bacterial/PC membrane composites and characterized them by spectroscopic and imaging methods, including energy dispersive spectroscopy, and scanning and transmission electron microscopy. This method allowed us to control the localization of NP precipitation throughout the layered bacterial/membrane composite, by varying the timing of the cadmium precursor addition. Additionally, we demonstrated the photodegradation of methyl orange using the CdS functionalized porous membranes, thus confirming the photocatalytic properties of our composites for eventual translation to device development. We finally also explored the precipitation of other metallic NPs using our bacterial system, using enzyme extracted from our bacterial system, and using commercially available, his-tagged enzyme. We hope to extend this research to tethering enzymes on surfaces to direct NP precipitation. Taken all together, our results show the great promise bacteria have for the fabrication of tunable, transition metal NPs with useful electronic properties.

The Evolution of Sulfide in Shallow Aquatic Ecosystem Sediments: An Analysis of the Roles of Sulfate, Organic Carbon, and Iron and Feedback Constraints Using Structural Equation Modeling

NASA Astrophysics Data System (ADS)

Pollman, C. D.; Swain, E. B.; Bael, D.; Myrbo, A.; Monson, P.; Shore, M. D.

2017-11-01

The generation of elevated concentrations of sulfide in sediment pore waters that are toxic to rooted macrophytes is problematic in both marine and freshwaters. In marine waters, biogeochemical conditions that lead to toxic levels of sulfide generally relate to factors that affect oxygen dynamics or the sediment iron concentration. In freshwaters, increases in surface water sulfate have been implicated in decline of Zizania palustris (wild rice), which is important in wetlands across the Great Lakes region of North America. We developed a structural equation (SE) model to elucidate key variables that govern the evolution of sulfide in pore waters in shallow aquatic habitats that are potentially capable of supporting wild rice. The conceptual basis for the model is the hypothesis that dissimilatory sulfate reduction is limited by the availability of both sulfate and total organic carbon (TOC) in the sediment. The conceptual model also assumes that pore water sulfide concentrations are constrained by the availability of pore water iron and that sediment iron supports the supply of dissolved iron to the pore water. A key result from the SE model is that variations in three external variables (sulfate, sediment TOC, and sediment iron) contribute nearly equally to the observed variations in pore water sulfide. As a result, management efforts to mitigate against the toxic effects of pore water sulfide on macrophytes such as wild rice should approach defining a protective sulfate threshold as an exercise tailored to the geochemistry of each site that quantitatively considers the effects of ambient concentrations of sediment Fe and TOC.

Influence of porewater sulfide on methylmercury production and partitioning in sulfate-impacted lake sediments.

PubMed

Bailey, Logan T; Mitchell, Carl P J; Engstrom, Daniel R; Berndt, Michael E; Coleman Wasik, Jill K; Johnson, Nathan W

2017-02-15

In low-sulfate and sulfate-limited freshwater sediments, sulfate loading increases the production of methylmercury (MeHg), a potent and bioaccumulative neurotoxin. Sulfate loading to anoxic sediments leads to sulfide production that can inhibit mercury methylation, but this has not been commonly observed in freshwater lakes and wetlands. In this study, sediments were collected from sulfate-impacted, neutral pH, surface water bodies located downstream from ongoing and historic mining activities to examine how chronic sulfate loading produces porewater sulfide, and influences MeHg production and transport. Sediments were collected over two years, during several seasons from lakes with a wide range of overlying water sulfate concentration. Samples were characterized for in-situ solid phase and porewater MeHg, Hg methylation potentials via incubations with enriched stable Hg isotopes, and sulfur, carbon, and iron content and speciation. Porewater sulfide reflected historic sulfur loading and was strongly related to the extractable iron content of sediment. Overall, methylation potentials were consistent with the accumulation of MeHg on the solid phase, but both methylation potentials and MeHg were significantly lower at chronically sulfate-impacted sites with a low solid-phase Fe:S ratio. At these heavily sulfate-impacted sites that also contained elevated porewater sulfide, both MeHg production and partitioning are influenced: Hg methylation potentials and sediment MeHg concentrations are lower, but occasionally porewater MeHg concentrations in sediment are elevated, particularly in the spring. The dual role of sulfide as a ligand for inorganic mercury (decreasing bioavailability) and methylmercury (increasing partitioning into porewater) means that elucidating the role of iron and sulfur loads as they define porewater sulfide is key to understanding sulfate's influence on MeHg production and partitioning in sulfate-impacted freshwater sediment. Copyright © 2016 Elsevier B.V. All rights reserved.

CdSe/AsS core-shell quantum dots: preparation and two-photon fluorescence.

PubMed

Wang, Junzhong; Lin, Ming; Yan, Yongli; Wang, Zhe; Ho, Paul C; Loh, Kian Ping

2009-08-19

Arsenic(II) sulfide (AsS)-coated CdSe core-shell nanocrystals can be prepared by a cluster-complex deposition approach under mild conditions. At 60 degrees C, growth of an AsS shell onto a CdSe nanocrystal can be realized through the crystallization of a cluster complex of AsS/butylamine in a mixed solvent of isopropanol/chloroform. The new, type I core-shell nanocrystal exhibits markedly enhanced one-photon fluorescence as well two-photon upconversion fluorescence. The nanocrystals can be used for infrared-excited upconversion cellular labeling.

Enhanced elementary sulfur recovery in integrated sulfate-reducing, sulfur-producing rector under micro-aerobic condition.

PubMed

Xu, Xi-jun; Chen, Chuan; Wang, Ai-jie; Fang, Ning; Yuan, Ye; Ren, Nan-qi; Lee, Duu-jong

2012-07-01

Biological treatment of sulfate-laden wastewater consists of two separate reactors to reduce sulfate to sulfide by sulfate-reducing bacteria (SRB) and to oxidize sulfide to sulfur (S(0)) by sulfide oxidation bacteria (SOB). To have SRB+SOB in a single reactor faced difficulty of low S(0) conversion. This study for the first time revealed that dissolved oxygen (DO) level can be used to manipulate SRB+SOB reactions in a single reactor. This work demonstrated successful operation of an integrated SRB+SOB reactor under micro-aerobic condition. At DO = 0.10-0.12 mg l(-1), since the activities of SOB were enhanced by limited oxygen, the removal efficiency for sulfate reached 81.5% and the recovery of S(0) peaked at 71.8%, higher than those reported in literature. At increased DO, chemical oxidation of sulfide with molecular oxygen competed with SOB so conversion of S(0) started to decline. At DO>0.30 mg l(-1) activities of SRB were inhibited, leading to failure of the SRB+SOB reactor. Copyright © 2012 Elsevier Ltd. All rights reserved.

The role of hydrogen sulfide in aging and age-related pathologies.

PubMed

Perridon, Bernard W; Leuvenink, Henri G D; Hillebrands, Jan-Luuk; van Goor, Harry; Bos, Eelke M

2016-09-27

When humans grow older, they experience inevitable and progressive loss of physiological function, ultimately leading to death. Research on aging largely focuses on the identification of mechanisms involved in the aging process. Several proposed aging theories were recently combined as the 'hallmarks of aging'. These hallmarks describe (patho-)physiological processes that together, when disrupted, determine the aging phenotype. Sustaining evidence shows a potential role for hydrogen sulfide (H 2 S) in the regulation of aging. Nowadays, H 2 S is acknowledged as an endogenously produced signaling molecule with various (patho-) physiological effects. H 2 S is involved in several diseases including pathologies related to aging. In this review, the known, assumed and hypothetical effects of hydrogen sulfide on the aging process will be discussed by reviewing its actions on the hallmarks of aging and on several age-related pathologies.

40Ar/39Ar Dating of Zn-Pb-Ag Mineralization in the Northern Brooks Range, Alaska

USGS Publications Warehouse

Werdon, Melanie B.; Layer, Paul W.; Newberry, Rainer J.

2004-01-01

The 40Ar/39Ar laser step-heating method potentially can be used to provide absolute ages for a number of formerly undatable, low-temperature ore deposits. This study demonstrates the use of this method by determining absolute ages for Zn-Pb-Ag sediment-hosted massive sulfide deposits and vein-breccia occurrences found throughout a 300-km-long, east-west-trending belt in the northern Brooks Range, Alaska. Massive sulfide deposits are hosted by Mississippian to Pennsylvanian(?) black carbonaceous shale, siliceous mudstone, and lesser chert and carbonate turbidites of the Kuna Formation (e.g., Red Dog, Anarraaq, Lik (Su), and Drenchwater). The vein-breccia occurrences (e.g., Husky, Story Creek, West Kivliktort Mountain, Vidlee, and Kady) are hosted by a deformed but only weakly metamorphosed package of Upper Devonian to Lower Mississippian mixed continental and marine clastic rocks (the Endicott Group) that stratigraphically underlie the Kuna Formation. The vein-breccias are mineralogically similar to, but not spatially associated with, known massive sulfide deposits. The region's largest shale-hosted massive sulfide deposit is Red Dog; it has reserves of 148 Mt grading 16.6 percent zinc, 4.5 percent lead, and 77 g of silver per tonne. Hydrothermally produced white mica in a whole-rock sample from a sulfide-bearing igneous sill within the Red Dog deposit yielded a plateau age of 314.5 Ma. The plateau age of this whole-rock sample records the time at which temperatures cooled below the argon closure temperature of the white mica and is interpreted to represent the minimum age limit for massive sulfide-related hydrothermal activity in the Red Dog deposit. Sulfide-bearing quartz veins at Drenchwater crosscut a hypabyssal intrusion with a maximum biotite age of 337.0 Ma. Despite relatively low sulfide deposition temperatures in the vein-breccia occurrences (162°-251°C), detrital white mica in sandstone immediately adjacent to large vein-breccia zones was partially to completely recrystallized. The 40Ar/39Ar age spectra and inverse isochron plots of the multicomponent whole-rock sandstone samples are more complex than those of single minerals. However, different minerals have different Ca/K and Cl/K ratios and closure temperatures, and these properties were used to identify portions of spectra dominated by argon release from specific minerals. 40Ar/39Ar laser step-heating analyses of Late Devonian sandstone whole rocks produced spectra that record a two-stage resetting history: a Carboniferous hydrothermal event first and later Mesozoic to Tertiary events, which are in agreement with geologic constraints. The 40Ar/39Ar ages and the similar mineralogy, lead isotope composition, and relative stratigraphic positions support the interpretation that the shale-hosted massive sulfide deposits and most vein-breccia occurrences are temporally and genetically related, and that they are different expressions of Carboniferous basinal dewatering.

Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations.

PubMed

Liu, Jing-yong; Huang, Shu-jie; Sun, Shui-yu; Ning, Xun-an; He, Rui-zhe; Li, Xiao-ming; Chen, Tao; Luo, Guang-qian; Xie, Wu-ming; Wang, Yu-Jie; Zhuo, Zhong-xu; Fu, Jie-wen

2015-04-01

Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning of Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na2S and Na2SO4) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na2SO4 and Na2S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO4(s) at low temperatures (<1000 K). The equilibrium calculation prediction also suggested that SiO2, CaO, TiO2, and Al2O3 containing materials function as condensed phase solids in the temperature range of 800-1100 K as sorbents to stabilize Pb. However, in the presence of sulfur or chlorine or the co-existence of sulfur and chlorine, these sorbents were inactive. The effect of sulfur on Pb partitioning in the sludge incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the concentration of Si, Ca and Al-containing compounds in the sludge. These findings provide useful information for understanding the partitioning behavior of Pb, facilitating the development of strategies to control the volatilization of Pb during sludge incineration. Copyright © 2014 Elsevier Ltd. All rights reserved.

Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).

NASA Astrophysics Data System (ADS)

Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente

2015-04-01

The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.

Sulfur and sulfides in chondrules

NASA Astrophysics Data System (ADS)

Marrocchi, Yves; Libourel, Guy

2013-10-01

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

Effects of the capping ligands, linkers and oxide surface on the electron injection mechanism of copper sulfide quantum dot-sensitized solar cells.

PubMed

Suárez, Javier Amaya; Plata, Jose J; Márquez, Antonio M; Sanz, Javier Fdez

2017-06-07

Quantum dot-sensitized solar cells, QDSCs, are a clean and effective alternative to fossil fuels to reduce CO 2 emissions. However, the different components that constitute the QDSCs and the difficulty of isolating experimentally their effects on the performance of the whole system slow down the development of more efficient devices. In this work, DFT calculations are combined with a bottom-up approach to differentiate the effect of each component on the electronic structure and absorption spectra. First, Cu 2 S QDs were built including a U parameter to effectively describe the localization of electrons. The effect of capping agents is addressed using ligands with different electron-donating/withdrawing groups. The role of linkers and their adsorption on the oxide surface are also examined. Finally, we propose a main indirect electron injection mechanism based on the position of the peaks of the spectra.

In vivo biodistribution and behavior of CdTe/ZnS quantum dots.

PubMed

Zhao, Yan; Zhang, Yue; Qin, Gaofeng; Cheng, Jinjun; Zeng, Wenhao; Liu, Shuchen; Kong, Hui; Wang, Xueqian; Wang, Qingguo; Qu, Huihua

2017-01-01

The unique features of quantum dots (QDs) make them desirable fluorescent tags for cell and developmental biology applications that require long-term, multitarget, and highly sensitive imaging. In this work, we imaged fluorescent cadmium telluride/zinc sulfide (CdTe/ZnS) QDs in organs, tissues, and cells, and analyzed the mechanism of their lymphatic uptake and cellular distribution. We observed that the fluorescent CdTe/ZnS QDs were internalized by lymph nodes in four cell lines from different tissue sources. We obtained the fluorescence intensity-QD concentrations curve by quantitative analysis. Our results demonstrate that cells containing QDs can complete mitosis normally and that distribution of QDs was uniform across cell types and involved the vesicular transport system, including the endoplasmic reticulum. This capacity for CdTe/ZnS QD targeting provides insights into the applicability and limitations of fluorescent QDs for imaging biological specimens.

Selective detection of dopamine in the presence of ascorbic acid via fluorescence quenching of InP/ZnS quantum dots

PubMed Central

Ankireddy, Seshadri Reddy; Kim, Jongsung

2015-01-01

Dopamine is a neurotransmitter of the catecholamine family and has many important roles, especially in human brain. Several diseases of the nervous system, such as Parkinson’s disease, attention deficit hyperactivity disorder, restless legs syndrome, are believed to be related to deficiency of dopamine. Several studies have been performed to detect dopamine by using electrochemical analysis. In this study, quantum dots (QDs) were used as sensing media for the detection of dopamine. The surface of the QDs was modified with l-cysteine by coupling reaction to increase the selectivity of dopamine. The fluorescence of cysteine-capped indium phosphide/zinc sulfide QDs was quenched by dopamine with various concentrations in the presence of ascorbic acid. This method shows good selectivity for dopamine detection, and the detection limit was 5 nM. PMID:26347250

One-pot hydrothermal synthesis of ZnS quantum dots/graphene hybrids as a dual anode for sodium ion and lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Rupeng; Wang, Yu; Jia, Mengqiu; Xu, Junjie; Pan, Erzhuang

2018-04-01

Committed to research high-performance sodium-ion batteries(SIBs) and lithium-ion batteries(LIBs) anode materials is attractive but challenging. Among the many promising anode materials, sulfides are considered as promising available anode material. In this paper, we successfully synthesized uniformly dispersed ZnS quantum dots (QDs) with sub-10-nm-scale on graphene nanosheets via a facile hydrothermal method. The prepared ZnS/graphene composites was studied as a dual anode for sodium-ion and lithium-ion batteries. Tested against SIBs, the nanocomposites exhibits an impressive specific capacity of 491 mAh/g at 100 mA/g after 100 cycles. Tested against LIBs, the nanocomposites delivers a superior specific capacity of 759 mAh/g at 100 mA/g after 100 cycles. This excellent performance is mainly due to the fact that graphene can improve the conductivity of the composites and effectively prevent the agglomeration and pulverization of ZnS quantum dots during cycling. Meanwhile, ZnS quantum dots with sub-10-nm-scale may also shorten diffuse path and reduce migration barrier, which is in favor of the full utilization of the active material and the improvement of the stability of the structure

Quantum transport in coupled resonators enclosed synthetic magnetic flux

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

Jin, L., E-mail: jinliang@nankai.edu.cn

Quantum transport properties are instrumental to understanding quantum coherent transport processes. Potential applications of quantum transport are widespread, in areas ranging from quantum information science to quantum engineering, and not restricted to quantum state transfer, control and manipulation. Here, we study light transport in a ring array of coupled resonators enclosed synthetic magnetic flux. The ring configuration, with an arbitrary number of resonators embedded, forms a two-arm Aharonov–Bohm interferometer. The influence of magnetic flux on light transport is investigated. Tuning the magnetic flux can lead to resonant transmission, while half-integer magnetic flux quantum leads to completely destructive interference and transmissionmore » zeros in an interferometer with two equal arms. -- Highlights: •The light transport is investigated through ring array of coupled resonators enclosed synthetic magnetic field. •Aharonov–Bohm ring interferometer of arbitrary configuration is investigated. •The half-integer magnetic flux quantum leads to destructive interference and transmission zeros for two-arm at equal length. •Complete transmission is available via tuning synthetic magnetic flux.« less

Long-term effects of sulfidized silver nanoparticles in sewage sludge on soil microflora.

PubMed

Kraas, Marco; Schlich, Karsten; Knopf, Burkhard; Wege, Franziska; Kägi, Ralf; Terytze, Konstantin; Hund-Rinke, Kerstin

2017-12-01

The use of silver nanoparticles (AgNPs) in consumer products such as textiles leads to their discharge into wastewater and consequently to a transfer of the AgNPs to soil ecosystems via biosolids used as fertilizer. In urban wastewater systems (e.g., sewer, wastewater treatment plant [WWTP], anaerobic digesters) AgNPs are efficiently converted into sparingly soluble silver sulfides (Ag 2 S), mitigating the toxicity of the AgNPs. However, long-term studies on the bioavailability and effects of sulfidized AgNPs on soil microorganisms are lacking. Thus we investigated the bioavailability and long-term effects of AgNPs (spiked in a laboratory WWTP) on soil microorganisms. Before mixing the biosolids into soil, the sludges were either anaerobically digested or directly dewatered. The effects on the ammonium oxidation process were investigated over 140 d. Transmission electron microscopy (TEM) suggested an almost complete sulfidation of the AgNPs analyzed in all biosolid samples and in soil, with Ag 2 S predominantly detected in long-term incubation experiments. However, despite the sulfidation of the AgNPs, soil ammonium oxidation was significantly inhibited, and the degree of inhibition was independent of the sludge treatment. The results revealed that AgNPs sulfidized under environmentally relevant conditions were still bioavailable to soil microorganisms. Consequently, Ag 2 S may exhibit toxic effects over the long term rather than the short term. Environ Toxicol Chem 2017;36:3305-3313. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC. © 2017 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

Disentanglement versus decoherence of two qubits in thermal noise.

PubMed

Zampetaki, A V; Diakonos, F K

2012-08-31

We show that the influence of thermal noise, simulated by a 2D ferromagnetic Ising spin lattice on a pair of noninteracting, initially entangled qubits, represented by quantum spins, leads to unexpected evolution of quantum correlations. The high temperature noise leads to ultraslow decay of the quantum correlations. Decreasing the noise temperature we observe a decrease of the characteristic decay time scale. When the noise originates from a critical state, a revival of the quantum correlations is observed. This revival becomes oscillatory with a slowly decaying amplitude when the temperature is decreased below the critical region, leading to persistence of the quantum correlations.

Tunable ultrasmall visible-to-extended near-infrared emitting silver sulfide quantum dots for integrin-targeted cancer imaging.

PubMed

Tang, Rui; Xue, Jianpeng; Xu, Baogang; Shen, Duanwen; Sudlow, Gail P; Achilefu, Samuel

2015-01-27

The large size of many near-infrared (NIR) fluorescent nanoparticles prevents rapid extravasation from blood vessels and subsequent diffusion to tumors. This confines in vivo uptake to the peritumoral space and results in high liver retention. In this study, we developed a viscosity modulated approach to synthesize ultrasmall silver sulfide quantum dots (QDs) with distinct tunable light emission from 500 to 1200 nm and a QD core diameter between 1.5 and 9 nm. Conjugation of a tumor-avid cyclic pentapeptide (Arg-Gly-Asp-DPhe-Lys) resulted in monodisperse, water-soluble QDs (hydrodynamic diameter < 10 nm) without loss of the peptide's high binding affinity to tumor-associated integrins (KI = 1.8 nM/peptide). Fluorescence and electron microscopy showed that selective integrin-mediated internalization was observed only in cancer cells treated with the peptide-labeled QDs, demonstrating that the unlabeled hydrophilic nanoparticles exhibit characteristics of negatively charged fluorescent dye molecules, which typically do not internalize in cells. The biodistribution profiles of intravenously administered QDs in different mouse models of cancer reveal an exceptionally high tumor-to-liver uptake ratio, suggesting that the small sized QDs evaded conventional opsonization and subsequent high uptake in the liver and spleen. The seamless tunability of the QDs over a wide spectral range with only a small increase in size, as well as the ease of labeling the bright and noncytotoxic QDs with biomolecules, provides a platform for multiplexing information, tracking the trafficking of single molecules in cells, and selectively targeting disease biomarkers in living organisms without premature QD opsonization in circulating blood.

Ultrasmall visible-to-near-infrared emitting silver-sulfide quantum dots for cancer detection and imaging

NASA Astrophysics Data System (ADS)

Tang, Rui; Xu, Baogang; Shen, Duanwen; Sudlow, Gail; Achilefu, Samuel

2018-02-01

The large size of many near infrared (NIR) fluorescent nanoparticles prevents rapid extravasation from blood vessels and subsequent diffusion to tumors. This confines in vivo uptake to the peritumoral space and results in high liver retention. We developed a viscosity modulated approach to synthesize ultrasmall silver sulfide quantum dots (QDs) with distinct tunable light emission from visible to near-infrared in spectrum and a QD core diameter between less than 5 nm. Further functionalization of these Ag2S QDs with different type of molecules such as targeting peptides, retains monodisperse, relatively small water soluble QDs without loss of the functionality of the peptide's high binding affinity to cancerous tumor. Fluorescence and electron microscopy showed that selective integrin-mediated internalization was observed only in cancer cells treated with the peptide-labeled QDs, demonstrating that the unlabeled hydrophilic nanoparticles exhibit characteristics of negatively charged fluorescent dye molecules, which typically do not internalize in cells. The biodistribution profiles of intravenously administered QDs in different mouse models of cancer reveal an exceptionally high tumor-to-liver uptake ratio, suggesting that the small sized QDs evaded conventional opsonization and subsequent high uptake in the liver and spleen. The seamless tunability of the QDs over a wide spectral range with only a small increase in size, as well as the ease of labeling the bright and non-cytotoxic QDs with biomolecules, provides a platform for multiplexing information, tracking the trafficking of single molecules in cells, and selectively targeting disease biomarkers in living organisms without premature QD opsonization in circulating blood.

Atacamite and paratacamite from the ultramafic-hosted Logatchev seafloor vent field (14°45′N, Mid-Atlantic Ridge)

USGS Publications Warehouse

Dekov, Vesselin; Boycheva, Tanya; Halenius, Ulf; Petersen, Sven; Billstrom, Kjell; Stummeyer, Jens; Kamenov, G.; Shanks, W.

2011-01-01

Atacamite and paratacamite are ubiquitous minerals associated with Cu-rich massive sulfides at the Logatchev hydrothermal field (Mid-Atlantic Ridge). In this work we provide new details on the mineralogy and geochemistry of these basic cupric chlorides. Our data support the notion that atacamite and paratacamite formation at submarine vent fields is an alteration process of hydrothermal Cu-sulfides. Secondary Cu-sulfides (bornite, covellite) are unstable at ambient seawater conditions and will dissolve. Dissolution is focused at the sulfide–seawater contact, leading to release of Fe2+ and Cu+ and formation of residual chalcocite through an intermediate Cu5S4 phase. Most of the released Fe2+ oxidizes immediately and precipitates as FeOOH directly on the chalcocite rims whereas Cu as chloride complexes (CuCl2−, CuCl32-) remains in solution at the same Eh. Cuprous–chloride complexes migrate from the reaction zone and upon increasing Eh precipitate as Cu2Cl(OH)3. As a consequence of this, the sulfide–seawater reaction interface is clearly marked by thin chalcocite–FeOOH bands and the entire assemblage is mantled by atacamite (or paratacamite). Our mineralogical, petrographic, geochemical and isotopic studies suggest that there are two types of atacamite (and/or paratacamite) depending on their mode of precipitation. Type 1 atacamite precipitated directly on the parent sulfides as evidenced by mantling of the sulfides, absence of detrital mineral grains, a preserved conspicuous positive Eu anomaly and a negligible negative Ce anomaly similar to those of the parent sulfide. In addition, Au concentrations are slightly lower than those of the parent sulfides, which suggest minimal transport of Au-ions after their release from the sulfides. Furthermore, the low content of the rare earth elements implies short contact time with the ambient seawater. The Sr–Nd–Pb-isotopic signatures of type 1 atacamite confirm the genetic association with the parent sulfides and indicate formation spatially very close to the latter. Type 2 atacamite precipitated at some distance from the parent sulfides, which means that the cuprous–chloride complexes have moved away from the sulfide alteration zone before precipitation. The evidence for this is absence of direct association of atacamite with sulfides. In addition, this atacamite contains a substantial proportion of detrital minerals, which implies precipitation in the sediments, distal to the parent sulfides. As a consequence of the detrital impurities the contents of elements like Cr, Cs, Hf, Nb, Rb, Th and Zr are higher than in type 1 atacamite (and/or paratacamite). Au contents are lower than those of type 1 atacamite (and/or paratacamite) which implies prolonged Au transport in solution before precipitation. Furthermore, the rare earth element distribution patterns have no positive Eu anomaly suggesting that the positive Eu anomaly of the parent sulfide has been erased after dissolution and prolonged contact of the fluid with ambient seawater (with negative Eu anomaly). Finally, the Sr–Nd-isotope signature differs from that of the parent sulfide and indicates a considerable terrigenous input.

Covellite CuS as a matrix for "invisible" gold: X-ray spectroscopic study of the chemical state of Cu and Au in synthetic minerals

NASA Astrophysics Data System (ADS)

Tagirov, Boris R.; Trigub, Alexander L.; Kvashnina, Kristina O.; Shiryaev, Andrey A.; Chareev, Dmitriy A.; Nickolsky, Maximilian S.; Abramova, Vera D.; Kovalchuk, Elena V.

2016-10-01

Geological processes leading to formation of sulfide ores often result in precipitation of gold-bearing sulfides which can contain high concentrations of this metal in ;invisible; (or ;refractory;) state. Covellite (CuS) is ubiquitous mineral in many types of the ore deposits, and numerous studies of the natural ores show that covellite can contain high concentrations of Au. At the same time, Au-bearing covellite withstands cooling in contrast to other minerals of the Cu-Fe-S system (chalcocite, bornite, chalcopyrite), where Au exsolves at low temperatures. This makes covellite a convenient model system for investigation of the chemical state (local environment and valence) of the ;invisible; Au in copper-sulfide ores (copper-porphyry, epithermal, volcanogenic massive sulfide, SEDEX deposits). Therefore, it is necessary to determine the location of Au in the covellite matrix as it will have important implications for the methods employed by mineral processing industry to extract Au from sulfide ores. Here we investigate the chemical state of Cu and Au in synthetic covellite containing up to 0.3 wt.% of Au in the ;invisible; state. The covellite crystals were synthesized by hydrothermal and salt flux methods. Formation of the chemically bound Au is indicated by strong dependence of the concentration of Au in covellite on the sulfur fugacity in the experimental system (d(log C(Au))/d(log f(S2)) ∼ 0.65). The Au concentration of covellite grows with increasing temperature from 400 to 450 °C, whereas further temperature increase to 500 °C has only minor effect. The synthesized minerals were studied using X-ray absorption fine structure spectroscopy (XAFS) in high energy resolution fluorescence detection (HERFD) mode. Ab initio simulations of Cu K edge XANES spectra show that the Cu oxidation state in two structural positions in covellite (tetrahedral and triangular coordination with S atoms) is identical: the total loss of electronic charge for the 3d shell is ∼0.3 for both positions of Cu. This result is confirmed by theoretical analysis of electron density performed using quantum theory of atoms in molecules (QTAIM). Modeling of the Au L3 edge EXAFS/XANES spectra showed that Au in covellite exists in the form of the isomorphous solid solution formed by substitution for Cu atoms in triangular coordination with the Me-S distance in the first coordination shell increased by 0.18 Å relative to the pure CuS structure. The ;formal; oxidation state of Au in covellite is +1. The Bader partial atomic charge for Au in covellite is lower than the charge of Cu (+0.2 e vs. +0.5 e) indicating that the degree of covalency for the Au-bearing covellite is higher than that of pure CuS. The analysis of electronic density of states shows that this structural position of Au results in strong interactions between hybridized Au s,p,d, S p, and Cu p,d orbitals. Such chemical bonding of Au to S and Cu can result in the formation of Au-bearing solid solution with other minerals in the Cu-Fe-S system.

Hydrothermal ore-forming processes in the light of studies in rock- buffered systems: I. Iron-copper-zinc-lead sulfide solubility relations

USGS Publications Warehouse

Hemley, J.J.; Cygan, G.L.; Fein, J.B.; Robinson, G.R.; d'Angelo, W. M.

1992-01-01

Experimental studies, using cold-seal and extraction vessel techniques, were conducted on Fe, Pb, Zn, and Cu sulfide solubilities in chloride soultions at temperatures from 300?? to 700??C and pressures from 0.5 to 2 kbars. The solutions were buffered in pH by quartz monzonite and the pure potassium feldspar-muscovite-quartz assemblage and in fS2-fO2 largely by the assemblage pyrite-pyrrhotite-magnetite. Solubilities increase with increasing temperature and total chloride, and decrease with increasing pressure. The effect of increasing chloride concentration on solubility reflects primarily a shift to lower pH via the silicate buffer reactions. Similarity in behaviour with respect to the temperature and pressure of Fe, Zn, and Pb sulfide solubilities points to similarity in chloride speciation, and the neutral species appear to be dominant in the high-temperature region. -from Authors

Integration of Semiconducting Sulfides for Full-Spectrum Solar Energy Absorption and Efficient Charge Separation.

PubMed

Zhuang, Tao-Tao; Liu, Yan; Li, Yi; Zhao, Yuan; Wu, Liang; Jiang, Jun; Yu, Shu-Hong

2016-05-23

The full harvest of solar energy by semiconductors requires a material that simultaneously absorbs across the whole solar spectrum and collects photogenerated electrons and holes separately. The stepwise integration of three semiconducting sulfides, namely ZnS, CdS, and Cu2-x S, into a single nanocrystal, led to a unique ternary multi-node sheath ZnS-CdS-Cu2-x S heteronanorod for full-spectrum solar energy absorption. Localized surface plasmon resonance (LSPR) in the nonstoichiometric copper sulfide nanostructures enables effective NIR absorption. More significantly, the construction of pn heterojunctions between Cu2-x S and CdS leads to staggered gaps, as confirmed by first-principles simulations. This band alignment causes effective electron-hole separation in the ternary system and hence enables efficient solar energy conversion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of hydrogen sulfide in aging and age-related pathologies

PubMed Central

Perridon, Bernard W.; Leuvenink, Henri G.D.; Hillebrands, Jan-Luuk; van Goor, Harry; Bos, Eelke M.

2016-01-01

When humans grow older, they experience inevitable and progressive loss of physiological function, ultimately leading to death. Research on aging largely focuses on the identification of mechanisms involved in the aging process. Several proposed aging theories were recently combined as the ‘hallmarks of aging’. These hallmarks describe (patho-)physiological processes that together, when disrupted, determine the aging phenotype. Sustaining evidence shows a potential role for hydrogen sulfide (H2S) in the regulation of aging. Nowadays, H2S is acknowledged as an endogenously produced signaling molecule with various (patho-) physiological effects. H2S is involved in several diseases including pathologies related to aging. In this review, the known, assumed and hypothetical effects of hydrogen sulfide on the aging process will be discussed by reviewing its actions on the hallmarks of aging and on several age-related pathologies. PMID:27683311

Exponential energy growth due to slow parameter oscillations in quantum mechanical systems.

PubMed

Turaev, Dmitry

2016-05-01

It is shown that a periodic emergence and destruction of an additional quantum number leads to an exponential growth of energy of a quantum mechanical system subjected to a slow periodic variation of parameters. The main example is given by systems (e.g., quantum billiards and quantum graphs) with periodically divided configuration space. In special cases, the process can also lead to a long period of cooling that precedes the acceleration, and to the desertion of the states with a particular value of the quantum number.

Preliminary Study of ZnS:Mn2+ Quantum Dots Response Under UV and X-Ray Irradiation

NASA Astrophysics Data System (ADS)

Saatsakis, G.; Valais, I.; Michail, C.; Fountzoula, C.; Fountos, G.; Koukou, V.; Martini, N.; Kalyvas, N.; Bakas, A.; Sianoudis, I.; Kandarakis, I.; Panayiotakis, G. S.

2017-11-01

Quantum Dots are semiconductor nanocrystals, with their optical properties controlled by their size, shape and material composition. The aim of the present study is to examine the scintillation properties of Manganese Doped Zinc Sulfide (ZnS:Mn 2+) Quantum Dot (QDs) nanocrystals under UV and X-ray irradiation. ZnS:Mn 2+ Quantum Dots, with typical diameter of ZnS dots of 13-20nm (also called scintillation QDs, stQDs), were developed and acquired by Mesolight Inc. The initial stQD sample was a solution of 75mg of ZnS:Mn 2+ dissolved in 100μL of Toluene, having a concentration of 75% w/v. Emission characteristics under UV and X-Ray excitation were examined. Two ultraviolet sources were incorporated (315 nm and 365 nm) as well as a medical X-ray tube with tube voltage from 50 to 130 kVp. Parameters such as Energy Quantum Efficiency under UV excitation and Luminescence Efficiency-LE (light energy flux over exposure rate) under X-ray excitation were examined. Luminescence Efficiency (LE) of ZnS:Mn 2+ was higher than that exhibited by previously examined QDs, (ZnCdSeS:ZnS and ZnCuInS:ZnS). The ability of ZnS:Mn 2+ to transform UV photons energy into optical photons energy, tends to increase while the incident UV wavelength decreases. Energy Quantum Efficiency of the sample exhibited a 6% increase when exposed to 315nm UV light compared to 365 nm. The emission spectrum of the stQDs, exhibited a narrow peak (~585nm) in the yellow range.

Ti3C2 MXene co-catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production

PubMed Central

Ran, Jingrun; Gao, Guoping; Li, Fa-Tang; Ma, Tian-Yi; Du, Aijun; Qiao, Shi-Zhang

2017-01-01

Scalable and sustainable solar hydrogen production through photocatalytic water splitting requires highly active and stable earth-abundant co-catalysts to replace expensive and rare platinum. Here we employ density functional theory calculations to direct atomic-level exploration, design and fabrication of a MXene material, Ti3C2 nanoparticles, as a highly efficient co-catalyst. Ti3C2 nanoparticles are rationally integrated with cadmium sulfide via a hydrothermal strategy to induce a super high visible-light photocatalytic hydrogen production activity of 14,342 μmol h−1 g−1 and an apparent quantum efficiency of 40.1% at 420 nm. This high performance arises from the favourable Fermi level position, electrical conductivity and hydrogen evolution capacity of Ti3C2 nanoparticles. Furthermore, Ti3C2 nanoparticles also serve as an efficient co-catalyst on ZnS or ZnxCd1−xS. This work demonstrates the potential of earth-abundant MXene family materials to construct numerous high performance and low-cost photocatalysts/photoelectrodes. PMID:28045015

Ti3C2 MXene co-catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production

NASA Astrophysics Data System (ADS)

Ran, Jingrun; Gao, Guoping; Li, Fa-Tang; Ma, Tian-Yi; Du, Aijun; Qiao, Shi-Zhang

2017-01-01

Scalable and sustainable solar hydrogen production through photocatalytic water splitting requires highly active and stable earth-abundant co-catalysts to replace expensive and rare platinum. Here we employ density functional theory calculations to direct atomic-level exploration, design and fabrication of a MXene material, Ti3C2 nanoparticles, as a highly efficient co-catalyst. Ti3C2 nanoparticles are rationally integrated with cadmium sulfide via a hydrothermal strategy to induce a super high visible-light photocatalytic hydrogen production activity of 14,342 μmol h-1 g-1 and an apparent quantum efficiency of 40.1% at 420 nm. This high performance arises from the favourable Fermi level position, electrical conductivity and hydrogen evolution capacity of Ti3C2 nanoparticles. Furthermore, Ti3C2 nanoparticles also serve as an efficient co-catalyst on ZnS or ZnxCd1-xS. This work demonstrates the potential of earth-abundant MXene family materials to construct numerous high performance and low-cost photocatalysts/photoelectrodes.

Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

NASA Astrophysics Data System (ADS)

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

2012-04-01

Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to 13 mg L-1 and reduced Cu and Mn from 8 and 3 mg L-1 to below the detection limits, respectively. The experimental results suggested that the amendment of surface coating agents can be a promising alternative for inhibition of sulfide oxidation at AMD sites.

Sulfur and lead isotope geochemistry of hypogene mineralization at the Barite Hill Gold Deposit, Carolina Slate Belt, southeastern United States: A window into and through regional metamorphism

USGS Publications Warehouse

Seal, Robert R.; Ayuso, Robert A.; Foley, Nora K.; Clark, Sandra H.B.

2001-01-01

The Barite Hill gold deposit, at the southwestern end of the Carolina slate belt in the southeastern United States, is one of four gold deposits in the region that have a combined yield of 110 metric tons of gold over the past 10 years. At Barite Hill, production has dominantly come from oxidized ores. Sulfur isotope data from hypogene portions of the Barite Hill gold deposit vary systematically with pyrite–barite associations and provide insights into both the pre-metamorphic Late Proterozoic hydrothermal and the Paleozoic regional metamorphic histories of the deposit. The δ34S values of massive barite cluster tightly between 25.0 and 28.0‰, which closely match the published values for Late Proterozoic seawater and thus support a seafloor hydrothermal origin. The δ34S values of massive sulfide range from 1.0 to 5.3‰ and fall within the range of values observed for modern and ancient seafloor hydrothermal sulfide deposits. In contrast, δ34S values for finer-grained, intergrown pyrite (5.1–6.8‰) and barite (21.0–23.9‰) are higher and lower than their massive counterparts, respectively. Calculated sulfur isotope temperatures for the latter barite–pyrite pairs (Δ=15.9–17.1‰) range from 332–355 °C and probably reflect post-depositional equilibration at greenschist-facies regional metamorphic conditions. Thus, pyrite and barite occurring separately from one another provide pre-metamorphic information about the hydrothermal origin of the deposit, whereas pyrite and barite occurring together equilibrated to record the metamorphic conditions. Preliminary fluid inclusion data from sphalerite are consistent with a modified seawater source for the mineralizing fluids, but data from quartz and barite may reflect later metamorphic and (or) more recent meteoric water input. Lead isotope values from pyrites range for 206Pb/204Pb from 18.005–18.294, for 207Pb/204Pb from 15.567–15.645, and for 208Pb/204Pb from 37.555–38.015. The data indicate derivation of the ore leads from the country rocks, which themselves show evidence for contributions from relatively unradiogenic, mantle-like lead, and more evolved or crustal lead. Geological relationships, and stable and radiogenic isotopic data, suggest that the Barite Hill gold deposit formed on the Late Proterozoic seafloor through exhalative hydrothermal processes similar to those that were responsible for the massive sulfide deposits of the Kuroko district, Japan. On the basis of similarities with other gold-rich massive sulfide deposits and modern seafloor hydrothermal systems, the gold at Barite Hill was probably introduced as an integral part of the formation of the massive sulfide deposit.

Analysis on the Oversize Blast Furnace Desulfurization and a Sulfide Capacity Prediction Model Based on Congregated Electron Phase

NASA Astrophysics Data System (ADS)

Zhenyang, Wang; Jianliang, Zhang; Gang, An; Zhengjian, Liu; Zhengming, Cheng; Junjie, Huang; Jingwei, Zhang

2016-02-01

Through analyzed and regressed the actual productive desulfurization data from the oversize blast furnace (5500 m3) in north China, the relationship between the sulfur distribution parameters and the slag composition in actual production situation was investigated. As the slag and hot metal phases have their own balance sulfur content or sulfur partial pressure in gas phase, respectively, the non-equilibrium of sulfur among gas, slag, and metal phases leads to the transmission and distribution of sulfur. Combined with sulfur transmission reactions between gas, slag and metal phases, C/CO pairs equilibrium, and Wagner model, the measured sulfide capacity can be acquired using sulfur distribution ratio, sulfur activity coefficient, and oxygen activity in hot metal. Based on the theory of congregated electron phase, a new sulfide capacity prediction model (CEPM) has been developed, which has a good liner relationship with the measured sulfide capacity. Thus, using the burden structure for BF, the ironmaking slag composition can be obtained simply and can be used to reliably predict the ironmaking slag desulfurization ability a few hours later after charging under a certain temperature by CEPM.

Strategies to diagnose and control microbial souring in natural gas storage reservoirs and produced water systems

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

Morris, E.A.; Derr, R.M.; Pope, D.H.

1995-12-31

Hydrogen sulfide production (souring) in natural gas storage reservoirs and produced water systems is a safety and environmental problem that can lead to operational shutdown when local hydrogen sulfide standards are exceeded. Systems affected by microbial souring have historically been treated using biocides that target the general microbial community. However, requirements for more environmentally friendly solutions have led to treatment strategies in which sulfide production can be controlled with minimal impact to the system and environment. Some of these strategies are based on microbial and/or nutritional augmentation of the sour environment. Through research sponsored by the Gas Research Institute (GRI)more » in Chicago, Illinois, methods have been developed for early detection of microbial souring in natural gas storage reservoirs, and a variety of mitigation strategies have been evaluated. The effectiveness of traditional biocide treatment in gas storage reservoirs was shown to depend heavily on the methods by which the chemical is applied. An innovative strategy using nitrate was tested and proved ideal for produced water and wastewater systems. Another strategy using elemental iodine was effective for sulfide control in evaporation ponds and is currently being tested in microbially sour natural gas storage wells.« less

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

PubMed

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

2017-01-01

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

Mercury isotope constraints on the source for sediment-hosted lead-zinc deposits in the Changdu area, southwestern China

NASA Astrophysics Data System (ADS)

Xu, Chunxia; Yin, Runsheng; Peng, Jiantang; Hurley, James P.; Lepak, Ryan F.; Gao, Jianfeng; Feng, Xinbin; Hu, Ruizhong; Bi, Xianwu

2018-03-01

The Lanuoma and Cuona sediment-hosted Pb-Zn deposits hosted by Upper Triassic limestone and sandstone, respectively, are located in the Changdu area, SW China. Mercury concentrations and Hg isotopic compositions from sulfide minerals and potential source rocks (e.g., the host sedimentary rocks and the metamorphic basement) were investigated to constrain metal sources and mineralization processes. In both deposits, sulfide minerals have higher mercury (Hg) concentrations (0.35 to 1185 ppm) than the metamorphic basement rocks (0.05 to 0.15 ppm) and sedimentary rocks (0.02 to 0.08 ppm). Large variations of mass-dependent fractionation (3.3‰ in δ202Hg) and mass-independent fractionation (0.3‰ in Δ199Hg) of Hg isotopes were observed. Sulfide minerals have Hg isotope signatures that are similar to the hydrothermal altered rocks around the deposit, and similar to the metamorphic basement, but different from barren sedimentary rocks. The variation of Δ199Hg suggests that Hg in sulfides was mainly derived from the underlying metamorphic basement. Mercury isotopes could be a geochemical tracer in understanding metal sources in hydrothermal ore deposits.

Toxicity and Bioavailability of Metals in the Missouri River Adjacent to a Lead Refinery

DTIC Science & Technology

2001-12-01

Missouri River adjacent to the facility. Groundwater was also collected from the facility. Waters and sediments were analyzed for inorganic...highly elevated in the groundwater , but not in river sediment pore waters . Lead concentrations were moderately elevated in whole sediment at one site...but lead concentrations in pore waters were low due to apparent sequestration by acid-volatile sulfides. The groundwater sample was highly toxic to

Quantum dynamics of the intramolecular vibrational energy redistribution in OCS: From localization to quasi-thermalization

NASA Astrophysics Data System (ADS)

Pérez, J. B.; Arce, J. C.

2018-06-01

We report a fully quantum-dynamical study of the intramolecular vibrational energy redistribution (IVR) in the electronic ground state of carbonyl sulfide, which is a prototype of an isolated many-body quantum system with strong internal couplings and non-Rice-Ramsperger-Kassel-Marcus (RRKM) behavior. We pay particular attention to the role of many-body localization and the approach to thermalization, which currently are topics of considerable interest, as they pertain to the very foundations of statistical mechanics and thermodynamics. We employ local-mode (valence) coordinates and consider initial excitations localized in one local mode, with energies ranging from low to near the dissociation threshold, where the classical dynamics have been shown to be chaotic. We propagate the nuclear wavepacket on the potential energy surface by means of the numerically exact multiconfiguration time-dependent Hartree method and employ mean local energies, time-dependent and time-averaged populations in quantum number space, energy distributions, entanglement entropies, local population distributions, microcanonical averages, and dissociation probabilities, as diagnostic tools. This allows us to identify a continuous localization → delocalization transition in the energy flow, associated with the onset of quantum chaos, as the excitation energy increases up to near the dissociation threshold. Moreover, we find that at this energy and ˜1 ps the molecule nearly thermalizes. Furthermore, we observe that IVR is so slow that the molecule begins to dissociate well before such quasi-thermalization is complete, in accordance with earlier classical-mechanical predictions of non-RRKM behavior.

Quantum dynamics of the intramolecular vibrational energy redistribution in OCS: From localization to quasi-thermalization.

PubMed

Pérez, J B; Arce, J C

2018-06-07

We report a fully quantum-dynamical study of the intramolecular vibrational energy redistribution (IVR) in the electronic ground state of carbonyl sulfide, which is a prototype of an isolated many-body quantum system with strong internal couplings and non-Rice-Ramsperger-Kassel-Marcus (RRKM) behavior. We pay particular attention to the role of many-body localization and the approach to thermalization, which currently are topics of considerable interest, as they pertain to the very foundations of statistical mechanics and thermodynamics. We employ local-mode (valence) coordinates and consider initial excitations localized in one local mode, with energies ranging from low to near the dissociation threshold, where the classical dynamics have been shown to be chaotic. We propagate the nuclear wavepacket on the potential energy surface by means of the numerically exact multiconfiguration time-dependent Hartree method and employ mean local energies, time-dependent and time-averaged populations in quantum number space, energy distributions, entanglement entropies, local population distributions, microcanonical averages, and dissociation probabilities, as diagnostic tools. This allows us to identify a continuous localization → delocalization transition in the energy flow, associated with the onset of quantum chaos, as the excitation energy increases up to near the dissociation threshold. Moreover, we find that at this energy and ∼1 ps the molecule nearly thermalizes. Furthermore, we observe that IVR is so slow that the molecule begins to dissociate well before such quasi-thermalization is complete, in accordance with earlier classical-mechanical predictions of non-RRKM behavior.

Interpretation of Quantum Nonlocality by Conformal Quantum Geometrodynamics

NASA Astrophysics Data System (ADS)

De Martini, Francesco; Santamato, Enrico

2014-10-01

The principles and methods of the Conformal Quantum Geometrodynamics (CQG) based on the Weyl's differential geometry are presented. The theory applied to the case of the relativistic single quantum spin leads a novel and unconventional derivation of Dirac's equation. The further extension of the theory to the case of two spins in EPR entangled state and to the related violation of Bell's inequalities leads, by a non relativistic analysis, to an insightful resolution of the enigma implied by quantum nonlocality.

Fluorescent and cathodoluminescent phophors structurally related to sodalite

DOEpatents

Phillips, Mark L. F.; Shea, Lauren E.

1998-01-01

Blue, quantum-confined phosphors for field-emission displays made by reducing metal (M) sulfoaluminates at high temperature. This yields phases of the type M.sub.4 (AlO.sub.2).sub.6 S. Bulk sulfide contaminant mixed with the reduced sulfoaluminate phase is removed by treating it with a chelating agent in nonaqueous solution. A photometric cathodoluminescence efficiency of 9 lumen/watt at 1000 V for Sr.sub.3 PbS(AlO.sub.2).sub.6 is observed. Undoped Sr.sub.4 S(AlO).sub.6 displays 5 lumen/watt at 1000 V, with excellent blue chromatic saturation.

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

USGS Publications Warehouse

Garnit, Hechmi; Bouhel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker

2012-01-01

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

NASA Astrophysics Data System (ADS)

Garnit, Hechmi; Bouhlel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker

2012-06-01

The Sekarna Zn-Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn-Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation-inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000-20,000 ppm) and galena (12-189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80-130°C. The final ice melting temperatures range from -22°C to -11°C, which correspond to salinities of 15-24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (-11.2‰ to -9.3‰) and galena (-16‰ to -12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.

Sedimentary sulfides in dune sands of Spiekeroog Island, southern North Sea: A biogeochemical study of sulfur isotope partitioning

NASA Astrophysics Data System (ADS)

Seibert, Stephan; Schubert, Florian; Schmiedinger, Iris; Böttcher, Michael E.; Massmann, Gudrun

2017-04-01

The formation of iron sulfides in sandy sediments and the associated development of stable isotope signatures is still mechanistically not understood. In dune sands under impact of both fresh and saline water several physico-chemical gradients may develop leading to distinctly different biogeochemical zones. In the present study, a 10 m long core from a dune base at the North Eastern part of Spiekeroog Island, southern North Sea, was investigated for the elemental and stable isotope composition. The pyrite (TRIS) content was quantitatively extracted via an acidic Cr(II) distillation procedure and the stable sulfur isotope composition was determined by means of C-irmMS. The pore waters display a downcore increase in salt contents and a mixing between fresh and salt water. The accumulation of metabolites at depth indicate an increasing superimposition of mixing by microbial decomposition of dissolved organic matter with only limited net sulfate reduction. This indicates an essential open system with respect to dissolved sulfate. The sands were found to be very low in TOC, TIC, and TRIS and dominated by quartz minerals. Under the assumption that North Sea water sulfate was the only substantial sulfate source (d34S = + 21per mil), the sedimentary sulfides indicate an overall sulfur isotope discrimination upon microbial sulfate reduction between 39 and 52 per mil, which is within the range of results from other fully marine sands from the Spiekeroog area and laboratory studies with pure cultures of sulfate-reducing bacteria under low cellular sulfate reduction rates. Further investigations are on the way to understand the processes leading to the iron sulfide formation in these organic-poor substrates.

A field investigation of the relationship between zinc and acid volatile sulfide concentrations in freshwater sediments

USGS Publications Warehouse

Ankley, Gerald T.; Liber, Karsten; Call, Daniel J.; Markee, Thomas P.; Canfield, Timothy J.; Ingersoll, Christopher G.

1996-01-01

Understanding relationships between cationic metals such as cadmium, copper, nickel, lead and zinc, and amorphous iron sulfides, measured as acid volatile sulfide (AVS), is key to predicting metal bioavailability and toxicity insediments. The objective of the present study was to assess seasonal and spatial variations of AVS in freshwater sediments contaminated with zinc. Sediments were sampled from three streams with varying levels of zinc contamination at two different times, March and June of 1995, representing cold- and warm-weather situations. Interstitial (pore) water concentrations of zinc, and solid phase concentrations of AVS and zinc were measured in surficial and deep sediment horizons. Toxicity tests (10-d) with the amphipodHyalella azteca were conducted using intact cores. Sediment zinc concentrations from six sites within the primary test stream differed by about five-fold, and also varied seasonally. Acid volatile sulfide concentrations were generally lower than those of zinc, and pore water zinc concentrations typically were elevated. There was a positive correlation between solid-phase AVS and zinc concentrations, suggesting that the system was dominated by zinc, as opposed to iron sulfides. In contrast to expectations arising from some studies of seasonal variations of AVS in iron-dominated systems, AVS concentrations were smaller in June than in March. However, this was likely due to a major storm event and associated sediment scouring before the June sampling, rather than to seasonal processes related to variations in temperature and dissolved oxygen. Based upon an indirect analysis of depth variations in AVS, there was some indication that zinc sulfide might be less prone to oxidation than iron sulfide. There was a strong correlation between toxicity of the sediment samples toH. azteca and interstitial water concentrations of zinc; however, the possible contribution of other contaminants to sediment toxicity cannot be dismissed.

Original behavior of pore water radiolysis in cement-based materials containing sulfide: Coupling between experiments and simulations

NASA Astrophysics Data System (ADS)

Bouniol, P.; Guillot, W.; Dauvois, V.; Dridi, W.; Le Caër, S.

2018-09-01

Blended cements with high content of blast furnace slag (CEM III/C) can be used for nuclear waste conditioning because of their low hydration heat as compared to ordinary Portland cements (CEM I). They however contain some sulfide, an impurity whose role needs to be investigated. Indeed, they can have an effect on the radiolytic H2 production under irradiation. To study the impact of sulfide species on H2 production, gamma irradiation, at a dose rate of 356 Gy h-1, was performed during 6 months in a closed system without O2 on a cement paste made with CEM III/C. At short time, the radiolytic H2 production rate is higher than that measured using CEM I. On the basis of reaction data collected in the literature on sulfur species, radiolysis simulations performed for both systems confirm this behavior. Moreover, they suggest that the sulfide concentration, initially imposed in pore solution by the slag is of the order of 180 mM, and is responsible for this H2 production. For the first two irradiation months, the following phenomena are then evidenced in CEM III/C: 1) conversion of sulfide into polysulfide anions; 2) pH increase; 3) production of H2 due to the H•+ H2S reaction having a very high rate constant. Nevertheless, in the medium term, the residual sulfide concentration is not sufficient any more for this mechanism to occur. It imposes a reducing environment, leading to a very efficient recombination of H2 in pore solution. The resulting equilibrium state is reinforced by the high liquid saturation level in the cement paste porosity. Therefore, even if the presence of sulfide species in blended cements momentarily increases the H2 production rate, it strongly reduces it at long times.

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

PubMed Central

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

2013-01-01

In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ). OMZs can sporadically accumulate hydrogen sulfide (H2S), which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km2, which contained ∼2.2×104 tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km3 the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide) to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that could fuel further sulfate reduction and potentially stabilize the sulfidic OMZ waters. PMID:23990875

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

PubMed

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

2013-01-01

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

A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re-Os isotope systematics

NASA Astrophysics Data System (ADS)

Westerlund, K. J.; Shirey, S. B.; Richardson, S. H.; Carlson, R. W.; Gurney, J. J.; Harris, J. W.

2006-09-01

An extensive study of peridotitic sulfide inclusion bearing diamonds and their prospective harzburgitic host rocks from the 53 Ma Panda kimberlite pipe, Ekati Mine, NWT Canada, has been undertaken with the Re-Os system to establish their age and petrogenesis. Diamonds with peridotitic sulfide inclusions have poorly aggregated nitrogen (<30% N as B centers) at N contents of 200-800 ppm which differs from that of chromite and silicate bearing diamonds and indicates residence in the cooler portion of the Slave craton lithospheric mantle. For most of the sulfide inclusions, relatively low Re contents (average 0.457 ppm) and high Os contents (average 339 ppm) lead to extremely low 187Re/188Os, typically << 0.05. An age of 3.52 ± 0.17 Ga (MSWD = 0.46) and a precise initial 187Os/188Os of 0.1093 ± 0.0001 are given by a single regression of 11 inclusions from five diamonds that individually provide coincident internal isochrons. This initial Os isotopic composition is 6% enriched in 187Os over 3.5 Ga chondritic or primitive mantle. Sulfide inclusions with less radiogenic initial Os isotopic compositions reflect isotopic heterogeneity in diamond forming fluids. The harzburgites have even lower initial 187Os/188Os than the sulfide inclusions, some approaching the isotopic composition of 3.5 Ga chondritic mantle. In several cases isotopically distinct sulfides occur in different growth zones of the same diamond. This supports a model where C-O-H-S fluids carrying a radiogenic Os signature were introduced into depleted harzburgite and produced diamonds containing sulfides conforming to the 3.5 Ga isochron. Reaction of this fluid with harzburgite led to diamonds with less radiogenic inclusions while elevating the Os isotope ratios of some harzburgites. Subduction is a viable way of introducing such fluids. This implies a role for subduction in creating early continental nuclei at 3.5 Ga and generating peridotitic diamonds.

New constraints on the origin of the Skaergaard intrusion Cu-Pd-Au mineralization: Insights from high-resolution X-ray computed tomography

NASA Astrophysics Data System (ADS)

Godel, Bélinda; Rudashevsky, Nikolay S.; Nielsen, Troels F. D.; Barnes, Stephen J.; Rudashevsky, Vladimir N.

2014-03-01

This contribution presents the first detailed three-dimensional (3D) in situ analysis of samples from the Platinova Reef using high-resolution X-ray computed tomography (HRXCT) and 3D image processing and quantification coupled with microscopic and mineralogical investigations. Our HRXCT analyses reveal the complex textural relationships between Cu-rich sulfides (bulk composition close to bornite), skaergaardite (PdCu), Au-rich phases, silicates and Fe-Ti oxides and provide unequivocal textural evidences, not observed previously. The association in 3D between Cu-rich sulfide globules, PdCu alloy and ilmenite is inconsistent with a hydrothermal origin of the Cu-Pd mineralization. In contrast, our results combined with phase diagrams strongly support a primary magmatic origin for the Cu-Pd mineralization where Cu and Pd-rich, Fe-poor sulfide liquid represents a cumulus phase that forms by in-situ nucleation. These sulfide droplets and attached skaergaardite grains were trapped during the formation and crystallization of the Fe-Ti oxides. Subsequent, post-cumulus processes led to the partial to total dissolution of the sulfide not entirely enclosed by the Fe-Ti oxides (i.e., not protected from reaction) leading to the observed variability in Cu and Pd composition at the aggregate (sulfide + PdCu) scale and to the occurrence of free PdCu alloys. In contrast to the PdCu alloy, gold-bearing minerals are never observed entirely enclosed within the Fe-Ti oxide. Two hypotheses can be envisaged for the formation of the gold enriched layer in the upper part of the section. Gold may have either precipitated from high-temperature late magmatic Cl-rich fluids. Alternatively, gold may have been enriched during fractional crystallization after sulfide had been suppressed from the liquidus after the Pd layer crystallized and then deposited along redox barriers.

Quantum interference effect in electron tunneling through a quantum-dot-ring spin valve

PubMed Central

2011-01-01

Spin-dependent transport through a quantum-dot (QD) ring coupled to ferromagnetic leads with noncollinear magnetizations is studied theoretically. Tunneling current, current spin polarization and tunnel magnetoresistance (TMR) as functions of the bias voltage and the direct coupling strength between the two leads are analyzed by the nonequilibrium Green's function technique. It is shown that the magnitudes of these quantities are sensitive to the relative angle between the leads' magnetic moments and the quantum interference effect originated from the inter-lead coupling. We pay particular attention on the Coulomb blockade regime and find the relative current magnitudes of different magnetization angles can be reversed by tuning the inter-lead coupling strength, resulting in sign change of the TMR. For large enough inter-lead coupling strength, the current spin polarizations for parallel and antiparallel magnetic configurations will approach to unit and zero, respectively. PACS numbers: PMID:21711779

Physics of frequency-modulated comb generation in quantum-well diode lasers

NASA Astrophysics Data System (ADS)

Dong, Mark; Cundiff, Steven T.; Winful, Herbert G.

2018-05-01

We investigate the physical origin of frequency-modulated combs generated from single-section semiconductor diode lasers based on quantum wells, isolating the essential physics necessary for comb generation. We find that the two effects necessary for comb generation—spatial hole burning (leading to multimode operation) and four-wave mixing (leading to phase locking)—are indeed present in some quantum-well systems. The physics of comb generation in quantum wells is similar to that in quantum dot and quantum cascade lasers. We discuss the nature of the spectral phase and some important material parameters of these diode lasers.

Direct lead isotope analysis in Hg-rich sulfides by LA-MC-ICP-MS with a gas exchange device and matrix-matched calibration.

PubMed

Zhang, Wen; Hu, Zhaochu; Günther, Detlef; Liu, Yongsheng; Ling, Wenli; Zong, Keqing; Chen, Haihong; Gao, Shan

2016-12-15

In situ Pb isotope data of sulfide samples measured by LA-MC-ICP-MS provide valuable geochemical information for studies of the origin and evolution of ore deposits. However, the severe isobaric interference of 204 Hg on 204 Pb and the lack of matrix-matched sulfide reference materials limit the precision of Pb isotopic analyses for Hg-rich sulfides. In this study, we observe that Hg forms vapor and can be completely removed from sample aerosol particles produced by laser ablation using a gas exchange device. Additionally, this device does not influence the signal intensities of Pb isotopes. The within-run precision, the external reproducibility and the analytical accuracy are significantly improved for the Hg-rich sulfide samples using this mercury-vapor-removing device. Matrix effects are observed when using silicate glass reference materials as the external standards to assess the relationship of mass fractionation factors between Tl and Pb in sulfide samples, resulting in a maximum deviation of ∼0.20% for 20x Pb/ 204 Pb. Matrix-matched reference materials are therefore required for the highly precise and accurate Pb isotope analyses of sulfide samples. We investigated two sulfide samples, MASS-1 (the Unites States Geological Survey reference materials) and Sph-HYLM (a natural sphalerite), as potential candidates. Repeated analyses of the two proposed sulfide reference materials by LA-MC-ICP-MS yield good external reproducibility of <0.04% (RSD, k = 2) for 20x Pb/ 206 Pb and <0.06% (RSD, k = 2) for 20x Pb/ 204 Pb with the exception of 20x Pb/ 204 Pb in MASS-1, which provided an external reproducibility of 0.24% (RSD, k = 2). Because the concentration of Pb in MASS-1 (76 μg g -1 ) is ∼5.2 times lower than that in Sph-HYLM (394 ± 264 μg g -1 ). The in situ analytical results of MASS-1 and Sph-HYLM are consistent with the values obtained by solution MC-ICP-MS, demonstrating the reliability and robustness of our analytical protocol. Copyright © 2016 Elsevier B.V. All rights reserved.

XAS Study at Mo and Co K-Edges of the Sulfidation of a CoMo / Al2O3 Hydrotreating Catalyst

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

Pichon, C.; Gandubert, A. D.; Legens, C.

2007-02-02

Because of its impact on environment, the removal of sulfur is an indispensable step, called hydrotreatment, in the refining of petroleum. One of the most commonly used hydrotreating catalysts is CoMo-type catalyst which is composed of molybdenum disulfide slabs promoted by cobalt atoms (CoMoS phase) and well dispersed on a high specific area alumina. As far as the highest sulfur content allowed in gasoline and diesel is continually decreasing, more and more efficient and active hydrotreating catalysts are required. In order to optimize the reactivity of the CoMo-type catalyst in hydrotreatment, a better understanding of the processes used to producemore » the active phase (CoMoS slabs) of the catalyst is necessary. The study reported here deals with the sulfiding mechanism of the slabs and the influence of temperature on the phenomenon. Ex situ X-ray absorption spectroscopy (XANES and EXAFS) was used to study the evolution of the structure of CoMo-type catalyst sulfided at various temperatures (from 293 to 873 K). XAS analysis was performed at both molybdenum and cobalt K-edges to obtain a cross-characterization of the sulfidation of the slabs. It evidenced the formation of various compounds, including two molybdenum oxides, MoS3 (or MoS3-like compound) and Co9S8, at specific steps of the sulfiding process. It showed the role of intermediate played by MoS3 (or MoS3-like compound) during the formation of the slabs and the competition between the appearance of promoted slabs (CoMoS phase) and Co9S8. At last, it leaded to the proposal of a mechanism for the sulfidation of the catalyst.« less

Sulfides from Martian and Lunar Basalts: Comparative Chemistry for Ni Co Cu and Se

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

J Papike; P Burger; C Shearer

2011-12-31

Here Mars and Moon are used as 'natural laboratories' with Moon displaying lower oxygen fugacities ({approx}IW-1) than Mars ({approx}IW to FMQ). Moon has lower concentrations of Ni and Co in basaltic melts than does Mars. The major sulfides are troilite (FeS) in lunar basalts and pyrrhotite (Fe{sub 1-x}S) in martian basalts. This study focuses on the concentrations of Ni, Co, Cu, and Se. We chose these elements because of their geochemical importance and the feasibility of analyzing them with a combination of synchrotron X-ray fluorescence (SXRF) and electron microprobe (EPMA) techniques. The selenium concentrations could only be analyzed, at highmore » precision, with SXRF techniques as they are <150 ppm, similar to concentrations seen in carbonaceous chondrites and interplanetary dust particles (IDPs). Nickel and Co are in higher concentrations in martian sulfides than lunar and are higher in martian olivine-bearing lithologies than olivine-free varieties. The sulfides in individual samples show very large ranges in concentration (e.g., Ni ranges from 50 000 ppm to <5 ppm). These large ranges are mainly due to compositional heterogeneities within individual grains due to diffusion and phase separation. Electron microprobe wavelength-dispersive (WDS) mapping of Ni, Co, and Cu show the diffusion trajectories. Nickel and Co have almost identical diffusion trajectories leading to the likely nucleation of pentlandite (Ni,Co,Fe){sub 9}S{sub 8}, and copper diffuses along separate pathways likely toward chalcopyrite nucleation sites (CuFeS{sub 2}). The systematics of Ni and Co in lunar and martian sulfides clearly distinguish the two parent bodies, with martian sulfides displaced to higher Ni and Co values.« less

Treatment of high-strength sulfate wastewater using an autotrophic biocathode in view of elemental sulfur recovery.

PubMed

Blázquez, Enric; Gabriel, David; Baeza, Juan Antonio; Guisasola, Albert

2016-11-15

Treatment of high-strength sulfate wastewaters is becoming a research issue not only for its optimal management but also for the possibility of recovering elemental sulfur. Moreover, sulfate-rich wastewater production is expected to grow due to the increased SO 2 emission contained in flue gases which are treated by chemical absorption in water. Bioelectrochemical systems (BESs) are a promising alternative for sulfate reduction with a lack of electron donor, since hydrogen can be generated in situ from electricity. However, complete sulfate reduction leads to hydrogen sulfide as final sulfur compound. This work is the first to demonstrate that, in addition to an efficient sulfate-rich wastewater treatment, elemental sulfur could be recovered in a biocathode of a BES under oxygen limiting conditions. The key of the process is the biological oxidation of sulfide to elemental sulfur simultaneously to the sulfate reduction in the cathode using the oxygen produced in the anode that diffuses through the membrane. High sulfate reduction rates (up to 388 mg S-SO 4 2-  L -1  d -1 ) were observed linked to a low production of sulfide. Accumulation of elemental sulfur over graphite fibers of the biocathode was demonstrated by energy dispersive spectrometry, discarding the presence of metal sulfides. Microbial community analysis of the cathode biofilm demonstrated the presence of sulfate-reducing bacteria (mainly Desulfovibrio sp.) and sulfide-oxidizing bacteria (mainly Sulfuricurvum sp.). Hence, this biocathode allows simultaneous biological sulfate reduction and biological sulfide oxidation to elemental sulfur, opening up a novel process for recovering sulfur from sulfate-rich wastewaters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of Structural Defects on Biomineralized ZnS Nanoparticle Dissolution: An in-Situ Electron Microscopy Study.

PubMed

Eskelsen, Jeremy R; Xu, Jie; Chiu, Michelle; Moon, Ji-Won; Wilkins, Branford; Graham, David E; Gu, Baohua; Pierce, Eric M

2018-02-06

The dissolution of metal sulfides, such as ZnS, is an important biogeochemical process affecting fate and transport of trace metals in the environment. However, current studies of in situ dissolution of metal sulfides and the effects of structural defects on dissolution are lacking. Here we have examined the dissolution behavior of ZnS nanoparticles synthesized via several abiotic and biological pathways. Specifically, we have examined biogenic ZnS nanoparticles produced by an anaerobic, metal-reducing bacterium Thermoanaerobacter sp. X513 in a Zn-amended, thiosulfate-containing growth medium in the presence or absence of silver (Ag), and abiogenic ZnS nanoparticles were produced by mixing an aqueous Zn solution with either H 2 S-rich gas or Na 2 S solution. The size distribution, crystal structure, aggregation behavior, and internal defects of the synthesized ZnS nanoparticles were examined using high-resolution transmission electron microscopy (TEM) coupled with X-ray energy dispersive spectroscopy. The characterization results show that both the biogenic and abiogenic samples were dominantly composed of sphalerite. In the absence of Ag, the biogenic ZnS nanoparticles were significantly larger (i.e., ∼10 nm) than the abiogenic ones (i.e., ∼3-5 nm) and contained structural defects (e.g., twins and stacking faults). The presence of trace Ag showed a restraining effect on the particle size of the biogenic ZnS, resulting in quantum-dot-sized nanoparticles (i.e., ∼3 nm). In situ dissolution experiments for the synthesized ZnS were conducted with a liquid-cell TEM (LCTEM), and the primary factors (i.e., the presence or absence structural defects) were evaluated for their effects on the dissolution behavior using the biogenic and abiogenic ZnS nanoparticle samples with the largest average particle size. Analysis of the dissolution results (i.e., change in particle radius with time) using the Kelvin equation shows that the defect-bearing biogenic ZnS nanoparticles (γ = 0.799 J/m 2 ) have a significantly higher surface energy than the abiogenic ZnS nanoparticles (γ = 0.277 J/m 2 ). Larger defect-bearing biogenic ZnS nanoparticles were thus more reactive than the smaller quantum-dot-sized ZnS nanoparticles. These findings provide new insight into the factors that affect the dissolution of metal sulfide nanoparticles in relevant natural and engineered scenarios, and have important implications for tracking the fate and transport of sulfide nanoparticles and associated metal ions in the environment. Moreover, our study exemplified the use of an in situ method (i.e., LCTEM) to investigate nanoparticle behavior (e.g., dissolution) in aqueous solutions.

An ultrasensitive and selective method for the determination of Ceftriaxone using cysteine capped cadmium sulfide fluorescence quenched quantum dots as fluorescence probes

NASA Astrophysics Data System (ADS)

Samadi, Naser; Narimani, Saeedeh

2016-06-01

In this paper, L-cysteine (Cys) coated CdS quantum dots (QDs) have been prepared, which have excellent water-solubility and are highly stable in aqueous solution. These QDs is proposed as sensitizers for the determination of Ceftriaxone. The quantum dot nanoparticles were structurally and optically characterized by Ultra Violet-Visible absorption Spectroscopy (UV-vis absorption spectroscopy), Fourier transform infrared spectroscopy (FT-IR spectra) and photoluminescence (PL) emission spectroscopy. High resolution transmission electron microscopy (HRTEM) confirms that the Cys-CdS QDs have a spherical structure with good crystallinity. Therefore, a new simple and selective PL analysis system was developed for the determination of Ceftriaxone (CFX). Under the optimum conditions, The response of L-Cys capped CdS QDs as the probe was linearly proportional to the concentration of Ceftriaxone ions in the range of 1.6 × 10- 9-1.1 × 10- 3 M with a correlation coefficient (R2) of 0.9902. The limit of detection of this system was found to be 1.3 nM. This method is simple, sensitive and low cost.

Investigation of thioglycerol stabilized ZnS quantum dots in electroluminescent device performance

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

Ethiraj, Anita Sagadevan, E-mail: anita.ethiraj@vit.ac.in; Center for Nanotechnology Research, VIT University, Vellore, TamilNadu-632014; Rhen, Dani

2016-05-06

The present work is focused on the investigation of thioglycerol (TG) stabilized Zinc Sulfide Quantum dots (ZnS QDs) in the hybrid electroluminescence (EL) device. Optical absorption spectroscopy clearly indicates the formation of narrow size distributed ZnS in the quantum confinement regime. X-ray Diffraction (XRD), Photoluminescence (PL), Energy Dispersive X-ray Spectroscopy (EDS) data supports the same. The hybrid EL device with structure of ITO (indium tin oxide)//PEDOT:PSS ((poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)//HTL (α NPD- N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-phenyl)-4,4′-diamine// PVK:ZnS QDs//ETL(PBD- 2-tert-butylphenyl- 5-biphenyl-1,3,4-oxadiazole)//LiF:Al (Device 1) was fabricated. Reference device without the ZnS QDs were also prepared (Device 2). The results show that the ZnS QDs based device exhibitedmore » bright electroluminescence emission of 24 cd/m{sup 2} at a driving voltage of 16 Volts under the forward bias conditions as compared to the reference device without the ZnS QDs, which showed 6 cd/m{sup 2} at ∼22 Volts.« less

The role of ophiolite in metallogeny of the Sikhote-Alin region

NASA Astrophysics Data System (ADS)

Kazachenko, V. T.; Perevoznikova, E. V.; Lavrik, S. N.; Skosareva, N. V.

2012-06-01

Metalliferous sediments of the Triassic siliceous formation of the Sikhote-Alin (manganese-silicate rocks and cherts with dispersed rhodochrosite, silicate-magnetite ores, and jasper) and skarns of the Dalnegorsk and Olginsk ore districts were initially the wash away products (Late Anisian-end of the Triassic) of the lateritic weathering crust on ophiolite in the islands. Manganese, iron, and other metals were deposited in the sediments of both lagoons (present-day, skarns) and island water areas (manganese-silicate and siliceousrhodochrosite rocks, silicate-magnetite ores, and jasper). Skarns contain boric and polymetallic ores thus indicating the occurrence of both shallow (periodically drying up) and quite deep (with hydrogen sulfide contamination zones) lagoons. Lead was deposited in protoliths of the skarn deposits in lagoons from the beginning of the Carboniferous to the beginning of the Late Anisian (initial island submergence). Tin, tin-leadzinc (with Ag), and silver-lead-zinc (with Sn and Au) vein deposits (Late Cretaceous-Paleogene) of the Taukha and Zhuravlevka Terrains contain lead deposited in the sediments flanking the islands of water areas with the hydrogen sulfide contamination zones, in the Carboniferous-Permian and Triassic metalliferous sediments.

Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations

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

Liu, Jing-yong, E-mail: www053991@126.com; Huang, Shu-jie; Sun, Shui-yu

2015-04-15

Highlights: • A thermodynamic equilibrium calculation was carried out. • Effects of three types of sulfurs on Pb distribution were investigated. • The mechanism for three types of sulfurs acting on Pb partitioning were proposed. • Lead partitioning and species in bottom ash and fly ash were identified. - Abstract: Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning ofmore » Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na{sub 2}S and Na{sub 2}SO{sub 4}) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na{sub 2}SO{sub 4} and Na{sub 2}S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO{sub 4}(s) at low temperatures (<1000 K). The equilibrium calculation prediction also suggested that SiO{sub 2}, CaO, TiO{sub 2}, and Al{sub 2}O{sub 3} containing materials function as condensed phase solids in the temperature range of 800–1100 K as sorbents to stabilize Pb. However, in the presence of sulfur or chlorine or the co-existence of sulfur and chlorine, these sorbents were inactive. The effect of sulfur on Pb partitioning in the sludge incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the concentration of Si, Ca and Al-containing compounds in the sludge. These findings provide useful information for understanding the partitioning behavior of Pb, facilitating the development of strategies to control the volatilization of Pb during sludge incineration.« less

Electron Microscopy Characterizations and Atom Probe Tomography of Intergranular Attack in Alloy 600 Exposed to PWR Primary Water

NASA Astrophysics Data System (ADS)

Olszta, Matthew J.; Schreiber, Daniel K.; Thomas, Larry E.; Bruemmer, Stephen M.

Detailed examinations of intergranular attack (IGA) in alloy 600 were performed after exposure to simulated PWR primary water at 325°C for 500 h. High-resolution analyses of IGA characteristics were conducted on specimens with either a 1 µm diamond or 1200-grit SiC surface finish using scanning electron microscopy, transmission electron microscopy and atom probe tomography techniques. The diamond-polish finish with very little preexisting subsurface damage revealed attack of high-energy grain boundaries that intersected the exposed surface to depths approaching 2 µm. In all cases, IGA from the surface is localized oxidation consisting of porous, nanocrystalline MO-structure and spinel particles along with regions of faceted wall oxidation. Surprisingly, this continuous IG oxidation transitions to discontinuous, discrete Cr-rich sulfide particles up to 50 nm in diameter. In the vicinity of the sulfides, the grain boundaries were severely Cr depleted (to <1 at%) and enriched in S. The 1200 grit SiC finish surface exhibited a preexisting highly strained recrystallized layer of elongated nanocrystalline matrix grains. Similar IG oxidation and leading sulfide particles were found, but the IGA depth was typically confined to the near-surface ( 400 nm) recrystallized region. Difference in IGA for the two surface finishes indicates that the formation of grain boundary sulfides occurs during the exposure to PWR primary water. The source of S remains unclear, however it is not present as sulfides in the bulk alloy nor is it segregated to bulk grain boundaries.

Double channel emission from a redox active single component quantum dot complex.

PubMed

Bhandari, Satyapriya; Roy, Shilaj; Pramanik, Sabyasachi; Chattopadhyay, Arun

2015-01-13

Herein we report the generation and control of double channel emission from a single component system following a facile complexation reaction between a Mn(2+) doped ZnS colloidal quantum dot (Qdot) and an organic ligand (8-hydroxy quinoline; HQ). The double channel emission of the complexed quantum dot-called the quantum dot complex (QDC)-originates from two independent pathways: one from the complex (ZnQ2) formed on the surface of the Qdot and the other from the dopant Mn(2+) ions of the Qdot. Importantly, reaction of ZnQ2·2H2O with the Qdot resulted in the same QDC formation. The emission at 500 nm with an excitation maximum at 364 nm is assigned to the surface complex involving ZnQ2 and a dangling sulfide bond. On the other hand, the emission at 588 nm-with an excitation maximum at 330 nm-which is redox tunable, is ascribed to Mn(2+) dopant. The ZnQ2 complex while present in QDC has superior thermal stability in comparison to the bare complex. Interestingly, while the emission of Mn(2+) was quenched by an electron quencher (benzoquinone), that due to the surface complex remained unaffected. Further, excitation wavelength dependent tunability in chromaticity color coordinates makes the QDC a potential candidate for fabricating a light emitting device of desired color output.

Enhancement of the photovoltaic performance in P3HT: PbS hybrid solar cells using small size PbS quantum dots

NASA Astrophysics Data System (ADS)

Firdaus, Yuliar; Vandenplas, Erwin; Justo, Yolanda; Gehlhaar, Robert; Cheyns, David; Hens, Zeger; Van der Auweraer, Mark

2014-09-01

Different approaches of surface modification of the quantum dots (QDs), namely, solution-phase (octylamine, octanethiol) and post-deposition (acetic acid, 1,4-benzenedithiol) ligand exchange were used in the fabrication of hybrid bulk heterojunction solar cell containing poly (3-hexylthiophene) (P3HT) and small (2.4 nm) PbS QDs. We show that replacing oleic acid by shorter chain ligands improves the figures of merit of the solar cells. This can possibly be attributed to a combination of a reduced thickness of the barrier for electron transfer and an optimized phase separation. The best results were obtained for post-deposition ligand exchange by 1,4-benzenedithiol, which improves the power conversion efficiency of solar cells based on a bulk heterojunction of lead sulfide (PbS) QDs and P3HT up to two orders of magnitude over previously reported hybrid cells based on a bulk heterojunction of P3HT:PbS QDs, where the QDs are capped by acetic acid ligands. The optimal performance was obtained for solar cells with 69 wt. % PbS QDs. Besides the ligand effects, the improvement was attributed to the formation of an energetically favorable bulk heterojunction with P3HT, when small size (2.4 nm) PbS QDs were used. Dark current density-voltage (J-V) measurements carried out on the device provided insight into the working mechanism: the comparison between the dark J-V characteristics of the bench mark system P3HT:PCBM and the P3HT:PbS blends allows us to conclude that a larger leakage current and a more efficient recombination are the major factors responsible for the larger losses in the hybrid system.

Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence

PubMed Central

Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K. L.; Sum, Tze Chien; Huang, Wei

2017-01-01

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 1015 cm−3, defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence. PMID:28239146

Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence.

PubMed

Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K L; Sum, Tze Chien; Huang, Wei

2017-02-27

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 10 15  cm -3 , defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence.

Simultaneous measurement of sulfur and lead isotopes in sulfides using nanosecond laser ablation coupled with two multi-collector inductively coupled plasma mass spectrometers

NASA Astrophysics Data System (ADS)

Yuan, Honglin; Liu, Xu; Chen, Lu; Bao, Zhian; Chen, Kaiyun; Zong, Chunlei; Li, Xiao-Chun; Qiu, Johnson Wenhong

2018-04-01

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100-3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides an effective tool to determine S and Pb isotope compositions of sulfides formed through multi-stage deposition routes.

Magneto-controlled aptasensor for simultaneous electrochemical detection of dual mycotoxins in maize using metal sulfide quantum dots coated silica as labels.

PubMed

Wang, Chengquan; Qian, Jing; An, Keqi; Huang, Xingyi; Zhao, Lufang; Liu, Qian; Hao, Nan; Wang, Kun

2017-03-15

Currently there is an urgent need for multi-mycotoxin detection methods due to the co-occurrence of multiple mycotoxins in food raw materials and their augmented toxicity. Herein, a magneto-controlled aptasensor has been developed for simultaneous electrochemical detection of ochratoxin A (OTA) and fumonisin B1 (FB1), two typical mycotoxins found in food crops world-wide. This aptasensor was designed using the high specificity between the target and aptamer with heavy CdTe or PbS quantum dots (QDs) coated silica as labels and the complementary DNA functionalized magnetic beads as capture probes. In presence of targets, the aptamer preferred to form the target-aptamer binding which forced the partial release of the preloaded labels from the magnetic beads. After a one-step incubation and a simple magnetic separation, the electrochemical signals of Cd 2+ and Pb 2+ dissolved from the reserved labels which had negative correlation with targets contents, was measured based on the difference of peak potentials. This aptasensor provided a wide detection range of 10pgmL -1 to 10ngmL -1 for OTA and 50pgmL -1 to 50ngmL -1 for FB1, and succeeded in real maize samples. This method provides a new avenue for high throughput screen of mycotoxins due to the advantages of simple instrument, low sample consumption, short assay times, and lower detection costs per assay. Moreover, it could be readily expanded for the simultaneous detection of a large panel of mycotoxins by using different metal sulfide QDs when their specific aptamers are available. Copyright © 2016 Elsevier B.V. All rights reserved.

Environmentally Benign Stab Detonators

DTIC Science & Technology

2006-07-11

composition. In addition we will work with our DoD partner TACOM-ARDEC in identifying and testing more environmentally suitable replacement transfer...components identified is shown in Figure 1 below. Figure 1. Photo of M55 stab detonator Al cup with initiation train and components. Common...primer mixes, such as NOL-130, are made up of lead styphnate (basic) 40%, lead azide ( dextrinated ) 20%, barium nitrate 20%, antimony sulfide 15%, and

High Quantum Yield Blue Emission from Lead-Free Inorganic Antimony Halide Perovskite Colloidal Quantum Dots.

PubMed

Zhang, Jian; Yang, Ying; Deng, Hui; Farooq, Umar; Yang, Xiaokun; Khan, Jahangeer; Tang, Jiang; Song, Haisheng

2017-09-26

Colloidal quantum dots (QDs) of lead halide perovskite have recently received great attention owing to their remarkable performances in optoelectronic applications. However, their wide applications are hindered from toxic lead element, which is not environment- and consumer-friendly. Herein, we utilized heterovalent substitution of divalent lead (Pb 2+ ) with trivalent antimony (Sb 3+ ) to synthesize stable and brightly luminescent Cs 3 Sb 2 Br 9 QDs. The lead-free, full-inorganic QDs were fabricated by a modified ligand-assisted reprecipitation strategy. A photoluminescence quantum yield (PLQY) was determined to be 46% at 410 nm, which was superior to that of other reported halide perovskite QDs. The PL enhancement mechanism was unraveled by surface composition derived quantum-well band structure and their large exciton binding energy. The Br-rich surface and the observed 530 meV exciton binding energy were proposed to guarantee the efficient radiative recombination. In addition, we can also tune the inorganic perovskite QD (Cs 3 Sb 2 X 9 ) emission wavelength from 370 to 560 nm via anion exchange reactions. The developed full-inorganic lead-free Sb-perovskite QDs with high PLQY and stable emission promise great potential for efficient emission candidates.

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

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

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

DOE PAGES

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui; ...

2018-03-09

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

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

PubMed

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

2012-01-17

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

Detachment of particulate iron sulfide during shale-water interaction

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Kreisserman, Y.

2017-12-01

Hydraulic fracturing, a commonly used technique to extract oil and gas from shales, is controversial in part because of the threat it poses to water resources. The technique involves the injection into the subsurface of large amounts of fluid, which can become contaminated by fluid-rock interaction. The dissolution of pyrite is thought to be a primary pathway for the contamination of fracturing fluids with toxic elements, such as arsenic and lead. In this study, we use direct observations with atomic force microscopy to show that the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment of embedded pyrite grains. To simulate the way fluid interacts with a fractured shale surface, we also reacted rock samples in a flow-through cell, and used environmental scanning electron microscopy to compare the surfaces before and after interaction with water. Crucially, our results show that the flux of particulate iron sulfide into the fluid may be orders of magnitude higher than the flux of pyrite from chemical dissolution. This result suggests that mechanical detachment of pyrite grains could be the dominant mode by which arsenic and other inorganic elements are mobilized in the subsurface. Thus, during hydraulic fracturing operations and in groundwater systems containing pyrite, the transport of many toxic species may be controlled by the transport of colloidal iron sulfide particles.

Tungsten speciation in sulfidic waters: Stability and lability of thiotungstates

NASA Astrophysics Data System (ADS)

Cui, M.; Johannesson, K. H.

2017-12-01

Tungsten (W) is an important metal that has been widely used in industries. It normally occurs as the monomeric tungstate oxyanion in circumneutral to alkaline pH natural waters but tends to form polytungstates species at low pH and high W concentrations. A number of studies show that W is strongly correlated with dissolved sulfide in natural waters. Laboratory investigations have presented evidence that, like Mo, W undergoes sulfidation in four steps that conserve tungstate and lead to the formation of tetrathiotungstate. In addition, natural waters may be seasonally anoxic, thus W speciation is likely to be kinetically controlled. Our previous studies showed that the speciation of tungsten is important in controlling its fate and transport in natural waters. Thiotungstate and tungstate are adsorbed differently to the mineral surfaces such as goethite and pyrite. In our present study, we have observed that the sulfidation reactions of W are acid catalyzed. We suggest that in environments such as sediment porewaters, the presence of Brønsted acids, will promote conversion of tungstate to thiotungstates. However, the conversion of the predominant anion from a hard to a soft base alters W's geochemical behavior, increasing its susceptibility to scavenging. Thus, an important product of this research will be an improved understanding of the scavenging pathways of W in euxinic environments.

Polymersomes containing iron sulfide (FeS) as primordial cell model : for the investigation of energy providing redox reactions.

PubMed

Alpermann, Theodor; Rüdel, Kristin; Rüger, Ronny; Steiniger, Frank; Nietzsche, Sandor; Filiz, Volkan; Förster, Stephan; Fahr, Alfred; Weigand, Wolfgang

2011-04-01

According to Wächtershäuser's "Iron-Sulfur-World" one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wächtershäuser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the "Iron-Sulfur-World" is based on the catalytic and energy reproducing redox system FeS+H2S-->FeS2+H2. The energy release out of this redox reaction (∆RG°=-38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life.

Fluorescence and Cytotoxicity of Cadmium Sulfide Quantum Dots Stabilized on Clay Nanotubes.

PubMed

Stavitskaya, Anna V; Novikov, Andrei A; Kotelev, Mikhail S; Kopitsyn, Dmitry S; Rozhina, Elvira V; Ishmukhametov, Ilnur R; Fakhrullin, Rawil F; Ivanov, Evgenii V; Lvov, Yuri M; Vinokurov, Vladimir A

2018-05-31

Quantum dots (QD) are widely used for cellular labeling due to enhanced brightness, resistance to photobleaching, and multicolor light emissions. CdS and Cd x Zn₁ - x S nanoparticles with sizes of 6⁻8 nm were synthesized via a ligand assisted technique inside and outside of 50 nm diameter halloysite clay nanotubes (QD were immobilized on the tube's surface). The halloysite⁻QD composites were tested by labeling human skin fibroblasts and prostate cancer cells. In human cell cultures, halloysite⁻QD systems were internalized by living cells, and demonstrated intense and stable fluorescence combined with pronounced nanotube light scattering. The best signal stability was observed for QD that were synthesized externally on the amino-grafted halloysite. The best cell viability was observed for Cd x Zn₁ - x S QD immobilized onto the azine-grafted halloysite. The possibility to use QD clay nanotube core-shell nanoarchitectures for the intracellular labeling was demonstrated. A pronounced scattering and fluorescence by halloysite⁻QD systems allows for their promising usage as markers for biomedical applications.

A bifacial quantum dot-sensitized solar cell with all-cadmium sulfide photoanode

NASA Astrophysics Data System (ADS)

Ma, Chunqing; Tang, Qunwei; Liu, Danyang; Zhao, Zhiyuan; He, Benlin; Chen, Haiyan; Yu, Liangmin

2015-02-01

Pursuit of a high power conversion efficiency and reduction of electricity-generation cost has been a persistent objective for quantum dot-sensitized solar cells (QDSSCs). We present here the fabrication of a QDSSC comprising a nanoflower-structured CdS anode, a liquid electrolyte having S2-/Sn2- redox couples, and a transparent CoSe counter electrode. Nanoflower-structured CdS anodes are prepared by a successive ionic layer adsorption and reaction (SILAR) method and subsequently hydrothermal strategy free of any surfactant or template. The CdS nanoparticles synthesized by a SILAR method act as "seed crystal" for growth of CdS nanoflowers. The average electron lifetime is markedly elevated in nanoflower-structured CdS anode in comparison with CdS nanoparticle or nanoporous CdS microsphere anode. Herein, we study the effect of synthesis method on CdS morphology and solar cell's photovoltaic performance, showing a power conversion efficiency of 1.67% and 1.17% for nanoflower-structured CdS QDSSC under front and rear irradiations, respectively.

Studies on the interaction between 7-(dimethyl amino)-4-(trifluoromethyl)-2H-1-benzopyran-2-one and cadmium sulfide quantum dots

NASA Astrophysics Data System (ADS)

Kuriakose, Alina C.; Pradeep, C.; Nampoori, V. P. N.; Thomas, Sheenu

2018-04-01

Quantum dots (QDs) are well known for their optical properties which differ from those of bulk semiconductors. Herein, we have created an energy transfer platform that combines CdS QDs with a coumarin based dye C485 [7-(dimethyl amino)-4-(trifluoromethyl)-2H-1-benzopyran-2-one]. Spectroscopic studies of energy transfer between the dye donor and CdS QDs as acceptors reveal the occurrence of dynamic quenching. Analysis of the steady-state and time resolved fluorescence measurements of C485 in the presence of CdS QDs infers fluorescence resonance (Förster type) energy transfer (FRET) as responsible for the quenching phenomena. The energy transfer efficiency as well as energy transfer distance for the donor-acceptor pair is calculated using steady-state fluorescence method. Luminescence enhancement of CdS QDs play a critical role in device performance for solar applications and also in the field of biological applications.

Nano-scale engineering using lead chalcogenide nanocrystals for opto-electronic applications

NASA Astrophysics Data System (ADS)

Xu, Fan

Colloidal quantum dots (QDs) or nanocrystals of inorganic semiconductors exhibit exceptional optoelectronic properties such as tunable band-gap, high absorption cross-section and narrow emission spectra. This thesis discusses the characterizations and physical properties of lead-chalcogenide nanocrystals, their assembly into more complex nanostructures and applications in solar cells and near-infrared light-emitting devices. In the first part of this work, we demonstrate that the band edge emission of PbS quantum dots can be tuned from the visible to the mid-infrared region through size control, while the self-attachment of PbS nanocrystals can lead to the formation of 1-D nanowires, 2-D quantum dot monolayers and 3-D quantum dot solids. In particular, the assembly of closely-packed quantum dot solids has attracted enormous attention. A series of distinctive optoelectronic properties has been observed, such as superb multiple exciton generation efficiencies, efficient hot-electron transfer and cold-exciton recycling. Since the surfactant determines the quantum dot surface passivation and inter dot electronic coupling, we examine the influence of different cross-linking surfactants on the optoelectronic properties of the quantum dot solids. Then, we discuss the ability to tune the quantum dot band-gap combined with the controllable assembly of lead-chalcogenide quantum dots, which opens new possibilities to engineer the properties of quantum dot solids. The PbS and PbSe quantum dot cascade structures and PbS/PbSe quantum dot heterojunctions are assembled using the layer-by-layer deposition method. We show that exciton funnelling and trap state-bound exciton recycling in the quantum dot cascade structure dramatically enhances the quantum dots photoluminescence. Moreover, we show that both type-I and type-II PbS/PbSe quantum dot heterojunctions can be assembled by carefully choosing the quantum dot sizes. In type-I heterojunctions, the excited electron-hole pairs tend to localize in narrower band-gap quantum dots, leading to significant photoluminescence enhancement. In contrast, the staggered energy bands in type-II heterojunctions lead to rapid exciton separation at the junctions that considerably quenches the photoluminescence. As such, this strategy can be fruitfully employed to enhance performances in nanocrystal-based photovoltaic devices. Using this approach, we achieve efficient PbS nanocrystal-based solar cells using an ITO/ TiO2/ PbS QDs/Au architecture, where a porous TiO2 nanowire network is employed as electron transporting layer. Our best heterojunction solar cells exhibit a decent short circuit current of 2.5 mA/cm2, a large open circuit voltage of 0.6 V and a power converting efficiency of 5.4 % under 8.5 mW/cm2 low-light illumination. On the other hand, nanocrystal-based near infrared LED devices are fabricated using a simple ITO-PbS QDs-Al device structure. There, the active quantum dot layer serves as both the electron- and hole-transporting layer. With appropriate surface chemistry treatment on quantum dots, a high-brightness near-infrared LED device is achieved.

Exotic quantum order in low-dimensional systems

NASA Astrophysics Data System (ADS)

Girvin, S. M.

1998-08-01

Strongly correlated quantum systems in low dimensions often exhibit novel quantum ordering. This ordering is sometimes hidden and can be revealed only by examining new "dual" types of correlations. Such ordering leads to novel collection modes and fractional quantum numbers. Examples will be presented from quantum spin chains and the quantum Hall effect.

Fluorescent and cathodoluminescent phosphors structurally related to sodalite

DOEpatents

Phillips, M.L.F.; Shea, L.E.

1998-09-29

Blue, quantum-confined phosphors are disclosed for field-emission displays made by reducing metal (M) sulfoaluminates at high temperature. This yields phases of the type M{sub 4}(AlO{sub 2}){sub 6}S. Bulk sulfide contaminant mixed with the reduced sulfoaluminate phase is removed by treating it with a chelating agent in nonaqueous solution. A photometric cathodoluminescence efficiency of 9 lumen/watt at 1,000 V for Sr{sub 3}PbS(AlO{sub 2}){sub 6} is observed. Undoped Sr{sub 4}S(AlO){sub 6} displays 5 lumen/watt at 1,000 V, with excellent blue chromatic saturation. 2 figs.

Toxicological evaluation of Cd-based fluorescent nanoprobes by means of in vivo studies

NASA Astrophysics Data System (ADS)

Farias, Patricia M. A.; Ma-Hock, Lan; Landsiedel, Robert; van Ravenzwaay, Bennard

2018-02-01

Cadmium still represents a stigma for many research- and/or industrial applications. Some deleterious effects are attributed to Cadmium. In the present work, highly fluorescent Cadmium sulfide quantum dots are investigated by e.g. physical-chemical characterization. Most important however is their application as fluorescent probes for bio-imaging in living cells and tissues. This work presents their toxicological evaluation by means of in vivo studies. Bio-imaging experiments are performed without any pre-treatment. The toxicological studies performed, strongly indicate that the use of Cadmium based nanoparticles as fluorescent probes may be nonhazardous and not induce side effects for cells/tissues.

Sulfur-, oxygen-, and carbon-isotope studies of Ag-Pb-Zn vein-breccia occurrences, sulfide-bearing concretions, and barite deposits in the north-central Brooks Range, with comparisons to shale-hosted stratiform massive sulfide deposits: A section in Geologic studies in Alaska by the U.S. Geological Survey, 1998

USGS Publications Warehouse

Kelley, Karen D.; Leach, David L.; Johnson, Craig A.

2000-01-01

Stratiform shale-hosted massive sulfide deposits, sulfidebearing concretions and vein breccias, and barite deposits are widespread in sedimentary rocks of Late Devonian to Permian age in the northern Brooks Range. All of the sulfide-bearing concretions and vein breccias are hosted in mixed continental-marine clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. The clastic rocks and associated sulfide occurrences underlie chert and shale of Mississippian-Pennsylvanian(?) age that contain large stratiform massive sulfide deposits like that at Red Dog. The relative stratigraphic position of the vein breccias, as well as previously published mineralogical, geochemical, and lead-isotope data, suggest that the vein breccias formed coevally with overlying shale-hosted massive sulfide deposits and that they may represent pathways of oreforming hydrothermal fluids. Barite deposits are hosted either in Mississippian chert and limestone (at essentially the same stratigraphic position as the shale-hosted massive sulfide deposits) or Permian chert and shale. Although most barite deposits have no associated base-metal mineralization, barite occurs with massive sulfide deposits at the Red Dog deposit.Galena and sphalerite from most vein breccias have δ34S values from –7.3 to –0.7‰ (per mil) and –5.1 to 3.6‰, respectively; sphalerite from sulfide-bearing concretions have δ34S values of 0.7 and 4.7‰. This overall range in δ34S values largely overlaps with the range previously determined for galena and sphalerite from shale-hosted massive sulfide deposits at Red Dog and Drenchwater. The Kady vein-breccia occurrence is unusual in having higher δ34S values for sphalerite (12.1 to 12.9‰) and pyrite (11.3‰), consistent with previously published values for the shale-hosted Lik deposit. The correspondence in sulfur isotopic compositions between the stratiform and vein-breccia deposits suggests that they share a common source of reduced sulfur, or derived reduced sulfur by similar geochemical processes. Most likely, the reduced sulfur was derived by biogenic sulfate reduction (BSR) or thermochemical sulfate reduction (TSR) of seawater sulfate during Devonian-Mississippian time.The δ18O values of quartz from the vein breccias are between 16.6 and 19.9‰. Using the sphalerite-galena sulfur isotopic temperature of 188°±25°C, the calulated hydrothermal fluids had δ18O values of 4.2 to 7.5‰. The calculated range of δ18O values of the fluids is similar to that of pore fluids in equilibrium with sedimentary rocks during diagenesis at 100°– 190°C.

Germanium and indium

USGS Publications Warehouse

Shanks, W.C. Pat; Kimball, Bryn E.; Tolcin, Amy C.; Guberman, David E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Germanium and indium are two important elements used in electronics devices, flat-panel display screens, light-emitting diodes, night vision devices, optical fiber, optical lens systems, and solar power arrays. Germanium and indium are treated together in this chapter because they have similar technological uses and because both are recovered as byproducts, mainly from copper and zinc sulfides.The world’s total production of germanium in 2011 was estimated to be 118 metric tons. This total comprised germanium recovered from zinc concentrates, from fly ash residues from coal burning, and from recycled material. Worldwide, primary germanium was recovered in Canada from zinc concentrates shipped from the United States; in China from zinc residues and coal from multiple sources in China and elsewhere; in Finland from zinc concentrates from the Democratic Republic of the Congo; and in Russia from coal.World production of indium metal was estimated to be about 723 metric tons in 2011; more than one-half of the total was produced in China. Other leading producers included Belgium, Canada, Japan, and the Republic of Korea. These five countries accounted for nearly 95 percent of primary indium production.Deposit types that contain significant amounts of germanium include volcanogenic massive sulfide (VMS) deposits, sedimentary exhalative (SEDEX) deposits, Mississippi Valley-type (MVT) lead-zinc deposits (including Irish-type zinc-lead deposits), Kipushi-type zinc-lead-copper replacement bodies in carbonate rocks, and coal deposits.More than one-half of the byproduct indium in the world is produced in southern China from VMS and SEDEX deposits, and much of the remainder is produced from zinc concentrates from MVT deposits. The Laochang deposit in Yunnan Province, China, and the VMS deposits of the Murchison greenstone belt in Limpopo Province, South Africa, provide excellent examples of indium-enriched deposits. The SEDEX deposits at Bainiuchang, China (located in southeastern Yunnan Province), and the Dabaoshan SEDEX deposit (located in the Nanling region of China) contain indium-enriched sphalerite. Another major potential source of indium occurs in the polymetallic tin-tungsten belt in the Eastern Cordillera of the Andes Mountains of Bolivia. Deposits there occur as dense arrays of narrow, elongate, indium-enriched tin oxide-polymetallic sulfide veins in volcanic rocks and porphyry stocks.Information about the behavior of germanium and indium in the environment is limited. In surface weathering environments, germanium and indium may dissolve from host minerals and form complexes with chloride, fluoride, hydroxide, organic matter, phosphate, or sulfate compounds. The tendency for germanium and indium to be dissolved and transported largely depends upon the pH and temperature of the weathering solutions. Because both elements are commonly concentrated in sulfide minerals, they can be expected to be relatively mobile in acid mine drainage where oxidative dissolution of sulfide minerals releases metals and sulfuric acid, resulting in acidic pH values that allow higher concentrations of metals to be dissolved into solution.

A ground electromagnetic survey used to map sulfides and acid sulfate ground waters at the abandoned Cabin Branch Mine, Prince William Forest Park, northern Virginia gold-pyrite belt

USGS Publications Warehouse

Wynn, Jeffrey C.

2000-01-01

INTRODUCTION AND BACKGROUND: Prince William Forest Park is situated at the northeastern end of the Virginia Gold-Pyrite belt northwest of the town of Dumfries, VA. The U. S. Marine Corps Reservation at Quantico borders the park on the west and south, and occupies part of the same watershed. Two abandoned mines are found within the park: the Cabin Branch pyrite mine, a historic source of acid mine drainage, and the Greenwood gold mine, a source of mercury contamination. Both are within the watershed of Quantico Creek (Fig.1). The Cabin Branch mine (also known as the Dumfries mine) lies about 2.4 km northwest of the town of Dumfries. It exploited a 300 meter-long, lens-shaped body of massive sulfide ore hosted by metamorphosed volcanic rocks; during its history over 200,000 tons of ore were extracted and processed locally. The site became part of the National Capitol Region of the National Park Service in 1940 and is currently managed by the National Park Service. In 1995 the National Park Service, in cooperation with the Virginia Department of Mines, Minerals, and Energy reclaimed the Cabin Branch site. The Virginia Gold-Pyrite belt, also known as the central Virginia volcanic-plutonic belt, is host to numerous abandoned metal mines (Pavlides and others, 1982), including the Cabin Branch deposit. The belt itself extends from its northern terminus near Cabin Branch, about 50 km south of Washington, D.C., approximately 175 km to the southwest into central Virginia. It is underlain by metamorphosed volcanic and clastic (non-carbonate) sedimentary rocks, originally deposited approximately 460 million years ago during the Ordovician Period (Horton and others, 1998). Three kinds of deposits are found in the belt: volcanic-associated massive sulfide deposits, low-sulfide quartz-gold vein deposits, and gold placer deposits. The massive sulfide deposits such as Cabin Branch were historically mined for their sulfur, copper, zinc, and lead contents, but also yielded byproduct gold and silver. The environmental impact of massive sulfide deposits can be substantial. These deposits are characterized by high concentrations of heavy-metal sulfide minerals, hosted by silicate rocks. Thus, weathering of these deposits and their mine wastes has the potential to generate heavy-metal laden sulfuric acid that can have negative impacts on aquatic ecosystems. In addition, lead associated with solid mine wastes has the potential for human health impacts through ingestion. The heavy metals that are encountered in these deposits and are most likely to cause environmental impacts include copper, zinc, lead, cadmium, and arsenic. In addition, the weathering of pyrite releases large amounts of iron, and the acid generated attacks the country rocks and causes the release of large amounts of aluminum, which also can severely impact aquatic ecosystems. A reclamation attempt was made at the site in 1995, including construction of storm-water diversion trenches around the abandoned mine area, grading tailings away from the stream bank, addition of pulverized limestone and topsoil, and revegetation. The post-reclamation chemistry of shallow groundwaters (<3 meters deep) shows a neutral pH on the southwestern bank of the stream but pH of 4.1 to 4.5 on the northeastern bank. The dominant ions are Fe2+ and SO42- (Seal, Haffner, Meier, and Pollio, 1999) A ground electromagnetic survey was conducted over the site in 1999 as part of a wider study ( Seal, Haffner, and Meier, 1998a,b, 1999). It was hoped that a 3-D map of the soil conductivity derived from the survey could provide insight into the distribution of the mobilized sulfides present under the ground. This study was conducted in cooperation with the National Park Service

The mineralogical transformation of a polymetallic sulfide ore during partial roasting

NASA Astrophysics Data System (ADS)

Evrard, Louis

2001-12-01

A partial desulfurization roasting process has been tested on a typical copper-zinc sulfide concentrate in a Nichols Herreshoff monohearth pilot furnace. In this process, the sulfur is partially removed and iron, to a certain degree, is preferentially oxidized. The mineralogical characterizations of the reaction products at different residence times enable the recognition of a sequence of reactions and various textural relationships during the roasting. The testing showed that a controlled desulfurization at a temperature as low as 650°C can lead to the decomposition of chalcopyrite, resulting in the formation of discrete particles of Cu2S having a size ranging from five to 20 micrometers or more.

Chiral quantum optics.

PubMed

Lodahl, Peter; Mahmoodian, Sahand; Stobbe, Søren; Rauschenbeutel, Arno; Schneeweiss, Philipp; Volz, Jürgen; Pichler, Hannes; Zoller, Peter

2017-01-25

Advanced photonic nanostructures are currently revolutionizing the optics and photonics that underpin applications ranging from light technology to quantum-information processing. The strong light confinement in these structures can lock the local polarization of the light to its propagation direction, leading to propagation-direction-dependent emission, scattering and absorption of photons by quantum emitters. The possibility of such a propagation-direction-dependent, or chiral, light-matter interaction is not accounted for in standard quantum optics and its recent discovery brought about the research field of chiral quantum optics. The latter offers fundamentally new functionalities and applications: it enables the assembly of non-reciprocal single-photon devices that can be operated in a quantum superposition of two or more of their operational states and the realization of deterministic spin-photon interfaces. Moreover, engineered directional photonic reservoirs could lead to the development of complex quantum networks that, for example, could simulate novel classes of quantum many-body systems.

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

PubMed

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

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Macroalgae, pore water sulfides and eelgrass in Yaquina estuary, Oregon

EPA Science Inventory

The hypothesis that relatively high nutrients in estuaries of the Pacific Northwest (PNW) can lead to eutrophication and degradation of critical eelgrass habitat was examined. Yaquina estuary was surveyed for cover and above-ground biomass of benthic macroalgae (Ulva spp.) and n...

Super-hydrophilic copper sulfide films as light absorbers for efficient solar steam generation under one sun illumination

NASA Astrophysics Data System (ADS)

Guo, Zhenzhen; Ming, Xin; Wang, Gang; Hou, Baofei; Liu, Xinghang; Mei, Tao; Li, Jinhua; Wang, Jianying; Wang, Xianbao

2018-02-01

Solar steam technology is one of the simplest, most direct and effective ways to harness solar energy through water evaporation. Here, we report the development using super-hydrophilic copper sulfide (CuS) films with double-layer structures as light absorbers for solar steam generation. In the double-layer structure system, a porous mixed cellulose ester (MCE) membrane is used as a supporting layer, which enables water to get into the CuS light absorbers through a capillary action to provide continuous water during solar steam generation. The super-hydrophilic property of the double-layer system (CuS/MCE) leads to a thinner water film close to the air-water interface where the surface temperature is sufficiently high, leading to more efficient evaporation (˜80 ± 2.5%) under one sun illumination. Furthermore, the evaporation efficiencies still keep a steady value after 15 cycles of testing. The super-hydrophilic CuS film is promising for practical application in water purification and evaporation as a light absorption material.

A Novel Optical Diagnostic for In Situ Measurements of Lithium Polysulfides in Battery Electrolytes.

PubMed

Saqib, Najmus; Silva, Cody J; Maupin, C Mark; Porter, Jason M

2017-07-01

An optical diagnostic technique to determine the order and concentration of lithium polysulfides in lithium-sulfur (Li-S) battery electrolytes has been developed. One of the major challenges of lithium-sulfur batteries is the problem of polysulfide shuttling between the electrodes, which leads to self-discharge and loss of active material. Here we present an optical diagnostic for quantitative in situ measurements of lithium polysulfides using attenuated total reflection Fourier transform infrared (FT-IR) spectroscopy. Simulated infrared spectra of lithium polysulfide molecules were generated using computational quantum chemistry routines implemented in Gaussian 09. The theoretical spectra served as a starting point for experimental characterization of lithium polysulfide solutions synthesized by the direct reaction of lithium sulfide and sulfur. Attenuated total reflection FT-IR spectroscopy was used to measure absorption spectra. The lower limit of detection with this technique is 0.05 M. Measured spectra revealed trends with respect to polysulfide order and concentration, consistent with theoretical predictions, which were used to develop a set of equations relating the order and concentration of lithium polysulfides in a sample to the position and area of a characteristic infrared absorption band. The diagnostic routine can measure the order and concentration to within 5% and 0.1 M, respectively.

ZnS, CdS and HgS nanoparticles via alkyl-phenyl dithiocarbamate complexes as single source precursors.

PubMed

Onwudiwe, Damian C; Ajibade, Peter A

2011-01-01

The synthesis of II-VI semiconductor nanoparticles obtained by the thermolysis of certain group 12 metal complexes as precursors is reported. Thermogravimetric analysis of the single source precursors showed sharp decomposition leading to their respective metal sulfides. The structural and optical properties of the prepared nanoparticles were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) UV-Vis and photoluminescence spectroscopy. The X-ray diffraction pattern showed that the prepared ZnS nanoparticles have a cubic sphalerite structure; the CdS indicates a hexagonal phase and the HgS show the presence of metacinnabar phase. The TEM image demonstrates that the ZnS nanoparticles are dot-shaped, the CdS and the HgS clearly showed a rice and spherical morphology respectively. The UV-Vis spectra exhibited a blue-shift with respect to that of the bulk samples which is attributed to the quantum size effect. The band gap of the samples have been calculated from absorption spectra and werefound to be about 4.33 eV (286 nm), 2.91 eV (426 nm) and 4.27 eV (290 nm) for the ZnS, CdS and HgS samples respectively.

ZnS, CdS and HgS Nanoparticles via Alkyl-Phenyl Dithiocarbamate Complexes as Single Source Precursors

PubMed Central

Onwudiwe, Damian C.; Ajibade, Peter A.

2011-01-01

The synthesis of II-VI semiconductor nanoparticles obtained by the thermolysis of certain group 12 metal complexes as precursors is reported. Thermogravimetric analysis of the single source precursors showed sharp decomposition leading to their respective metal sulfides. The structural and optical properties of the prepared nanoparticles were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) UV-Vis and photoluminescence spectroscopy. The X-ray diffraction pattern showed that the prepared ZnS nanoparticles have a cubic sphalerite structure; the CdS indicates a hexagonal phase and the HgS show the presence of metacinnabar phase. The TEM image demonstrates that the ZnS nanoparticles are dot-shaped, the CdS and the HgS clearly showed a rice and spherical morphology respectively. The UV-Vis spectra exhibited a blue-shift with respect to that of the bulk samples which is attributed to the quantum size effect. The band gap of the samples have been calculated from absorption spectra and werefound to be about 4.33 eV (286 nm), 2.91 eV (426 nm) and 4.27 eV (290 nm) for the ZnS, CdS and HgS samples respectively. PMID:22016607

Guar Gum Stimulates Biogenic Sulfide Production at Elevated Pressures: Implications for Shale Gas Extraction

PubMed Central

Nixon, Sophie L.; Walker, Leanne; Streets, Matthew D. T.; Eden, Bob; Boothman, Christopher; Taylor, Kevin G.; Lloyd, Jonathan R.

2017-01-01

Biogenic sulfide production is a common problem in the oil industry, and can lead to costly hydrocarbon processing and corrosion of extraction infrastructure. The same phenomenon has recently been identified in shale gas extraction by hydraulic fracturing, and organic additives in fracturing fluid have been hypothesized to stimulate this process. Constraining the relative effects of the numerous organic additives on microbial metabolism in situ is, however, extremely challenging. Using a bespoke bioreactor system we sought to assess the potential for guar gum, the most commonly used gelling agent in fracturing fluids, to stimulate biogenic sulfide production by sulfate-reducing microorganisms at elevated pressure. Two pressurized bioreactors were fed with either sulfate-amended freshwater medium, or low-sulfate natural surface water, in addition to guar gum (0.05 w/v%) and an inoculum of sulfate-reducing bacteria for a period of 77 days. Sulfide production was observed in both bioreactors, even when the sulfate concentration was low. Analysis of 16S rRNA gene sequences indicate that heterotrophic bacteria closely associated with the genera Brevundimonas and Acinetobacter became enriched early in the bioreactor experiments, followed by an increase in relative abundance of 16S rRNA genes associated with sulfate-reducing bacteria (Desulfosporosinus and Desulfobacteraceae) at later time points. Results demonstrate that guar gum can stimulate acid- and sulfide-producing microorganisms at elevated pressure, and may have implications for the potential role in microbially induced corrosion during hydraulic fracturing operations. Key differences between experimental and in situ conditions are discussed, as well as additional sources of carbon and energy for biogenic sulfide production during shale gas extraction. Our laboratory approach can be tailored to better simulate deep subsurface conditions in order to probe the role of other fracturing fluid additives and downhole parameters on microbial metabolisms observed in these systems. Such baseline studies will prove essential for effective future development of shale gas worldwide. PMID:28469616

Realizing high-rate sulfur reduction under sulfate-rich conditions in a biological sulfide production system to treat metal-laden wastewater deficient in organic matter.

PubMed

Sun, Rongrong; Zhang, Liang; Zhang, Zefeng; Chen, Guang-Hao; Jiang, Feng

2017-12-22

Biological sulfur reduction can theoretically produce sufficient sulfide to effectively remove and recover heavy metals in the treatment of organics-deficient sulfate-rich metal-laden wastewater such as acid mine drainage and metallurgic wastewater, using 75% less organics than biological sulfate reduction. However, it is still unknown whether sulfur reduction can indeed compete with sulfate reduction, particularly under high-strength sulfate conditions. The aim of this study was to investigate the long-term feasibility of biological sulfur reduction under high sulfate conditions in a lab-scale sulfur-reducing biological sulfide production (BSP) system with sublimed sulfur added. In the 169-day trial, an average sulfide production rate (SPR) as high as 47 ± 9 mg S/L-h was achieved in the absence of sulfate, and the average SPR under sulfate-rich conditions was similar (53 ± 10 mg S/L-h) when 1300 mg S/L sulfate were fed with the influent. Interestingly, sulfate was barely reduced even at such a high strength and contributed to only 1.5% of total sulfide production. Desulfomicrobium was identified as the predominant sulfidogenic bacterium in the bioreactor. Batch tests further revealed that this sulfidogenic bacteria used elemental sulfur as the electron acceptor instead of the highly bioavailable sulfate, during which polysulfide acted as an intermediate, leading to an even higher bioavailability of sulfur than sulfate. The pathway of sulfur to sulfide conversion via polysulfide in the presence of both sulfur and sulfate was discussed. Collectively, when conditions favor polysulfide formation, sulfur reduction can be a promising and attractive technology to realize a high-rate and low-cost BSP process for treating sulfate-rich metal-laden wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Guar Gum Stimulates Biogenic Sulfide Production at Elevated Pressures: Implications for Shale Gas Extraction.

PubMed

Nixon, Sophie L; Walker, Leanne; Streets, Matthew D T; Eden, Bob; Boothman, Christopher; Taylor, Kevin G; Lloyd, Jonathan R

2017-01-01

Biogenic sulfide production is a common problem in the oil industry, and can lead to costly hydrocarbon processing and corrosion of extraction infrastructure. The same phenomenon has recently been identified in shale gas extraction by hydraulic fracturing, and organic additives in fracturing fluid have been hypothesized to stimulate this process. Constraining the relative effects of the numerous organic additives on microbial metabolism in situ is, however, extremely challenging. Using a bespoke bioreactor system we sought to assess the potential for guar gum, the most commonly used gelling agent in fracturing fluids, to stimulate biogenic sulfide production by sulfate-reducing microorganisms at elevated pressure. Two pressurized bioreactors were fed with either sulfate-amended freshwater medium, or low-sulfate natural surface water, in addition to guar gum (0.05 w/v%) and an inoculum of sulfate-reducing bacteria for a period of 77 days. Sulfide production was observed in both bioreactors, even when the sulfate concentration was low. Analysis of 16S rRNA gene sequences indicate that heterotrophic bacteria closely associated with the genera Brevundimonas and Acinetobacter became enriched early in the bioreactor experiments, followed by an increase in relative abundance of 16S rRNA genes associated with sulfate-reducing bacteria ( Desulfosporosinus and Desulfobacteraceae) at later time points. Results demonstrate that guar gum can stimulate acid- and sulfide-producing microorganisms at elevated pressure, and may have implications for the potential role in microbially induced corrosion during hydraulic fracturing operations. Key differences between experimental and in situ conditions are discussed, as well as additional sources of carbon and energy for biogenic sulfide production during shale gas extraction. Our laboratory approach can be tailored to better simulate deep subsurface conditions in order to probe the role of other fracturing fluid additives and downhole parameters on microbial metabolisms observed in these systems. Such baseline studies will prove essential for effective future development of shale gas worldwide.

Characterizing the Uptake, Accumulation and Toxicity of Silver Sulfide Nanoparticles in Plants

EPA Science Inventory

Silver nanoparticles (Ag-NPs) are used in a wide range of everyday products, leading to increasing concerns regarding their accumulation in soils and subsequent impact on plants. Using single particle inductively coupled plasma mass spectrometry (spICP-MS) and synchrotron-based t...

Demonstration and Validation of a Regenerated Cellulose Dialysis Membrane Diffusion Sampler for Monitoring Groundwater Quality and Remediation Progress at DoD Sites

DTIC Science & Technology

2007-02-01

years if kept refrigerated in its preservative solution of ethanol, sodium benzoate , and ethylene diamine tetra-acetic acid (EDTA). Alternatively... sodium bicarbonate solution, EDTA, and sodium azide solution to remove residual gylcerol, sulfide, cadmium, chromium, copper, iron, nickel, zinc, and lead...Magnesium Cadmium Nickel Potassium Chromium Selenium Sodium Copper Vanadium Aluminum Iron Zinc Arsenic Lead Antimony Manganese Anions (1-3 days

Entanglement and Coherence in Quantum State Merging.

PubMed

Streltsov, A; Chitambar, E; Rana, S; Bera, M N; Winter, A; Lewenstein, M

2016-06-17

Understanding the resource consumption in distributed scenarios is one of the main goals of quantum information theory. A prominent example for such a scenario is the task of quantum state merging, where two parties aim to merge their tripartite quantum state parts. In standard quantum state merging, entanglement is considered to be an expensive resource, while local quantum operations can be performed at no additional cost. However, recent developments show that some local operations could be more expensive than others: it is reasonable to distinguish between local incoherent operations and local operations which can create coherence. This idea leads us to the task of incoherent quantum state merging, where one of the parties has free access to local incoherent operations only. In this case the resources of the process are quantified by pairs of entanglement and coherence. Here, we develop tools for studying this process and apply them to several relevant scenarios. While quantum state merging can lead to a gain of entanglement, our results imply that no merging procedure can gain entanglement and coherence at the same time. We also provide a general lower bound on the entanglement-coherence sum and show that the bound is tight for all pure states. Our results also lead to an incoherent version of Schumacher compression: in this case the compression rate is equal to the von Neumann entropy of the diagonal elements of the corresponding quantum state.

Growth of lead tin telluride crystals in gels

NASA Technical Reports Server (NTRS)

Barber, Patrick G.

1986-01-01

Improved gels and several geometries were investigated for use in growing crystals. The use of lead sulfide test crystals proved workable, but it was impossible to obtain and maintain a sufficiently concentrated telluride ion solution to successfully grow lead telluride crystals. It appears that oxygen in the solution is capable of oxidizing the telluride ion up to tellurium metal. The method may still be successful, but only if precautions are taken to eliminate dissolved oxygen from the gels and aqueous solutions and to maintain a suitable concentration of telluride, Te(2)-(aq.).

Testing Quantum Gravity Induced Nonlocality via Optomechanical Quantum Oscillators.

PubMed

Belenchia, Alessio; Benincasa, Dionigi M T; Liberati, Stefano; Marin, Francesco; Marino, Francesco; Ortolan, Antonello

2016-04-22

Several quantum gravity scenarios lead to physics below the Planck scale characterized by nonlocal, Lorentz invariant equations of motion. We show that such nonlocal effective field theories lead to a modified Schrödinger evolution in the nonrelativistic limit. In particular, the nonlocal evolution of optomechanical quantum oscillators is characterized by a spontaneous periodic squeezing that cannot be generated by environmental effects. We discuss constraints on the nonlocality obtained by past experiments, and show how future experiments (already under construction) will either see such effects or otherwise cast severe bounds on the nonlocality scale (well beyond the current limits set by the Large Hadron Collider). This paves the way for table top, high precision experiments on massive quantum objects as a promising new avenue for testing some quantum gravity phenomenology.

Antineoplastic Activity Comparison of Bovine Serum Albumin--Conjugated Sulfides Semiconductor Nanomaterials.

PubMed

Wang, Hua-Jie; Huang, Jing-Chun; Wu, Sha-Sha; Wang, Cai-Feng; Yu, Xue-Hong; Cao, Ying

2015-04-01

Although tumor is one of the most frequently occurring diseases and a leading cause of death, nanotechnology, one of the frontier sciences, is exhibiting its great potential to tumor treatments. The aim of this study was to design a facile and environmentally-friendly method to prepare bovine serum albumin-conjugated heavy metal sulfides nano-materials, including Ag2S, PbS and CdS. Here, bovine serum albumin was introduced in order to direct the synthesis of nano-materials by using its template effect and supply more sites for further modification in future. The crystal structure and morphology were analyzed by XRD and TEM, respectively. Additionally, the antineoplastic activity of nano-materials was compared by cell viability analysis, optical and electron microscopy observation after exposure of the human hepatoma cell line. The results showed that the inhibition effect of heavy metal sulfides on tumor cells was in the order of nano-PbS > bulk CdS > nano-Ag2S > nano-CdS > bulk PbS > bulk Ag2S. It could be concluded that heavy metal sulfides had significantly negative impact on human hepatoma cells growth but it could not be obviously generalized that nano-particles were always more effective to kill tumor cells than bulk materials. The size and surface reactivity might be the important factors causing the difference.

Involvement of ERK in NMDA receptor-independent cortical neurotoxicity of hydrogen sulfide

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

Kurokawa, Yuko; Sekiguchi, Fumiko; Kubo, Satoko

2011-11-04

Highlights: Black-Right-Pointing-Pointer Hydrogen sulfide causes NMDA receptor-independent neurotoxicity in mouse fetal cortical neurons. Black-Right-Pointing-Pointer Activation of ERK mediates the toxicity of hydrogen sulfide. Black-Right-Pointing-Pointer Apoptotic mechanisms are involved in the hydrogen-induced cell death. -- Abstract: Hydrogen sulfide (H{sub 2}S), a gasotransmitter, exerts both neurotoxicity and neuroprotection, and targets multiple molecules including NMDA receptors, T-type calcium channels and NO synthase (NOS) that might affect neuronal viability. Here, we determined and characterized effects of NaHS, an H{sub 2}S donor, on cell viability in the primary cultures of mouse fetal cortical neurons. NaHS caused neuronal death, as assessed by LDH release and trypanmore » blue staining, but did not significantly reduce the glutamate toxicity. The neurotoxicity of NaHS was resistant to inhibitors of NMDA receptors, T-type calcium channels and NOS, and was blocked by inhibitors of MEK, but not JNK, p38 MAP kinase, PKC and Src. NaHS caused prompt phosphorylation of ERK and upregulation of Bad, followed by translocation of Bax to mitochondria and release of mitochondrial cytochrome c, leading to the nuclear condensation/fragmentation. These effects of NaHS were suppressed by the MEK inhibitor. Our data suggest that the NMDA receptor-independent neurotoxicity of H{sub 2}S involves activation of the MEK/ERK pathway and some apoptotic mechanisms.« less

Structural Mechanism of the Interaction of Alzheimer Disease Aβ Fibrils with the Non-steroidal Anti-inflammatory Drug (NSAID) Sulindac Sulfide.

PubMed

Prade, Elke; Bittner, Heiko J; Sarkar, Riddhiman; Lopez Del Amo, Juan Miguel; Althoff-Ospelt, Gerhard; Multhaup, Gerd; Hildebrand, Peter W; Reif, Bernd

2015-11-27

Alzheimer disease is the most severe neurodegenerative disease worldwide. In the past years, a plethora of small molecules interfering with amyloid-β (Aβ) aggregation has been reported. However, their mode of interaction with amyloid fibers is not understood. Non-steroidal anti-inflammatory drugs (NSAIDs) are known γ-secretase modulators; they influence Aβ populations. It has been suggested that NSAIDs are pleiotrophic and can interact with more than one pathomechanism. Here we present a magic angle spinning solid-state NMR study demonstrating that the NSAID sulindac sulfide interacts specifically with Alzheimer disease Aβ fibrils. We find that sulindac sulfide does not induce drastic architectural changes in the fibrillar structure but intercalates between the two β-strands of the amyloid fibril and binds to hydrophobic cavities, which are found consistently in all analyzed structures. The characteristic Asp(23)-Lys(28) salt bridge is not affected upon interacting with sulindac sulfide. The primary binding site is located in the vicinity of residue Gly(33), a residue involved in Met(35) oxidation. The results presented here will assist the search for pharmacologically active molecules that can potentially be employed as lead structures to guide the design of small molecules for the treatment of Alzheimer disease. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Hydrogeochemistry and microbiology of mine drainage: An update

USGS Publications Warehouse

Nordstrom, D. Kirk; Blowes, D.W; Ptacek, C.J.

2015-01-01

The extraction of mineral resources requires access through underground workings, or open pit operations, or through drillholes for solution mining. Additionally, mineral processing can generate large quantities of waste, including mill tailings, waste rock and refinery wastes, heap leach pads, and slag. Thus, through mining and mineral processing activities, large surface areas of sulfide minerals can be exposed to oxygen, water, and microbes, resulting in accelerated oxidation of sulfide and other minerals and the potential for the generation of low-quality drainage. The oxidation of sulfide minerals in mine wastes is accelerated by microbial catalysis of the oxidation of aqueous ferrous iron and sulfide. These reactions, particularly when combined with evaporation, can lead to extremely acidic drainage and very high concentrations of dissolved constituents. Although acid mine drainage is the most prevalent and damaging environmental concern associated with mining activities, generation of saline, basic and neutral drainage containing elevated concentrations of dissolved metals, non-metals, and metalloids has recently been recognized as a potential environmental concern. Acid neutralization reactions through the dissolution of carbonate, hydroxide, and silicate minerals and formation of secondary aluminum and ferric hydroxide phases can moderate the effects of acid generation and enhance the formation of secondary hydrated iron and aluminum minerals which may lessen the concentration of dissolved metals. Numerical models provide powerful tools for assessing impacts of these reactions on water quality.

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

NASA Astrophysics Data System (ADS)

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

2017-06-01

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth's history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES) spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes-many containing organic ligands-we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H2S(aq)] < 11 μM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO3, MoOxS4-x2- (intermediate thiomolybdates), and [MoOx(cat)4-x]2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS42- (tetrathiomolybdate).

Physiological and Genetic Analyses Leading to Identification of a Biochemical Role for the moeA (Molybdate Metabolism) Gene Product in Escherichia coli†

PubMed Central

Hasona, Adnan; Ray, Ramesh M.; Shanmugam, K. T.

1998-01-01

A unique class of chlorate-resistant mutants of Escherichia coli which produced formate hydrogenlyase and nitrate reductase activities only when grown in medium with limiting amounts of sulfur compounds was isolated. These mutants failed to produce the two molybdoenzyme activities when cultured in rich medium or glucose-minimal medium. The mutations in these mutants were localized in the moeA gene. Mutant strains with polar mutations in moeA which are also moeB did not produce active molybdoenzymes in any of the media tested. moeA mutants with a second mutation in either cysDNCJI or cysH gene lost the ability to produce active molybdoenzyme even when grown in medium limiting in sulfur compounds. The CysDNCJIH proteins along with CysG catalyze the conversion of sulfate to sulfide. Addition of sulfide to the growth medium of moeA cys double mutants suppressed the MoeA− phenotype. These results suggest that in the absence of MoeA protein, the sulfide produced by the sulfate activation/reduction pathway combines with molybdate in the production of activated molybdenum. Since hydrogen sulfide is known to interact with molybdate in the production of thiomolybdate, it is possible that the MoeA-catalyzed activated molybdenum is a form of thiomolybdenum species which is used in the synthesis of molybdenum cofactor from Mo-free molybdopterin. PMID:9515915

Experimental formation of Pb, Sn, Ge and Sb sulfides, selenides and chlorides in the presence of sal ammoniac: A contribution to the understanding of the mineral formation processes in coal wastes self-burning

NASA Astrophysics Data System (ADS)

Laufek, František; Veselovsky, František; Drábek, Milan; Kříbek, Bohdan; Klementová, Mariana

2017-04-01

The formation of sulfides, selenides and chlorides was experimentally studied at 800 or 900°C in the presence of sal ammoniac in a sealed silica glass tube. Synthetic PbS, PbSe, SnS, GeS, SnGeS2, PbSnS3, SnS and Sb2S3 or natural uraninite were used as a starting charge. Depending on the chemical composition of the sulfide/selenide charge, galena, unnamed SnGeS3 phase, herzenbergite, berndite, ottenmannite, stibnite and unnamed SnSb2S4 and Sn2Sb3S6 phases were identified in sublimates, together with cotunnite and an unnamed (NH4)2SnCl6 phase. When natural uraninite in a mixture with sal ammoniac was used as a charge, the reaction product comprised abundant cotunnite and minor challacolloite due to volatilization of radiogenic lead. When sulfur was introduced to the charge with uraninite and sal ammoniac, galena was found in reaction products. The results of our experiments revealed that if sulfide or selenide phases and NH4Cl are placed in a thermal gradient, it is possible to accelerate their mobility through a process of hydrogen chloride vapor transport. Within the transport process, new solid products are either isochemical or non-isochemical. The isochemical composition of resulting phases with charge probably represents simple sublimation of the original solid phase in form of self-vapor. The non-isochemical phases are probably formed due to combination of sublimation and condensation of various gas components including gaseous HCl. The valency change of metals (e.g. Sn2+ to Sn3+) in several reaction products indicates redox reactions in the gas mixture or during the solidification of resulting products. The role of ammoniac is not clear; however, formation of unnamed (NH4)2SnCl6 compound identified in one of our experiment, indicate possible formation of ammonium complexes. In contrast to experiments where sulfides or selenides were used as a part of charge, mobility of uraninite was not proved under experimental conditions employed. It is consistent with an absence of uranium minerals in products of self-burning. The product of uraninite thermal decomposition was predominantly lead chloride (cotunnite) resulting from the release of radiogenic lead from uraninite structure. However, when sulfur was added to the charge, skeletal crystals of galena were found in the reaction products. Acknowledgments: This study was carried out within the Czech Science Foundation grant project "A model of mobilization and geochemical cycles of potentially hazardous elements and organic compounds in burnt coal heaps" (GACR 15-11674S panel P210).

Quantum and Private Capacities of Low-Noise Channels

NASA Astrophysics Data System (ADS)

Leditzky, Felix; Leung, Debbie; Smith, Graeme

2018-04-01

We determine both the quantum and the private capacities of low-noise quantum channels to leading orders in the channel's distance to the perfect channel. It has been an open problem for more than 20 yr to determine the capacities of some of these low-noise channels such as the depolarizing channel. We also show that both capacities are equal to the single-letter coherent information of the channel, again to leading orders. We thus find that, in the low-noise regime, superadditivity and degenerate codes have a negligible benefit for the quantum capacity, and shielding does not improve the private capacity beyond the quantum capacity, in stark contrast to the situation when noisier channels are considered.

Generic emergence of classical features in quantum Darwinism.

PubMed

Brandão, Fernando G S L; Piani, Marco; Horodecki, Paweł

2015-08-12

Quantum Darwinism posits that only specific information about a quantum system that is redundantly proliferated to many parts of its environment becomes accessible and objective, leading to the emergence of classical reality. However, it is not clear under what conditions this mechanism holds true. Here we prove that the emergence of classical features along the lines of quantum Darwinism is a general feature of any quantum dynamics: observers who acquire information indirectly through the environment have effective access at most to classical information about one and the same measurement of the quantum system. Our analysis does not rely on a strict conceptual splitting between a system-of-interest and its environment, and allows one to interpret any system as part of the environment of any other system. Finally, our approach leads to a full operational characterization of quantum discord in terms of local redistribution of correlations.

Generic emergence of classical features in quantum Darwinism

NASA Astrophysics Data System (ADS)

Brandão, Fernando G. S. L.; Piani, Marco; Horodecki, Paweł

2015-08-01

Quantum Darwinism posits that only specific information about a quantum system that is redundantly proliferated to many parts of its environment becomes accessible and objective, leading to the emergence of classical reality. However, it is not clear under what conditions this mechanism holds true. Here we prove that the emergence of classical features along the lines of quantum Darwinism is a general feature of any quantum dynamics: observers who acquire information indirectly through the environment have effective access at most to classical information about one and the same measurement of the quantum system. Our analysis does not rely on a strict conceptual splitting between a system-of-interest and its environment, and allows one to interpret any system as part of the environment of any other system. Finally, our approach leads to a full operational characterization of quantum discord in terms of local redistribution of correlations.

Photonic Programmable Tele-Cloning Network.

PubMed

Li, Wei; Chen, Ming-Cheng

2016-06-29

The concept of quantum teleportation allows an unknown quantum states to be broadcasted and processed in a distributed quantum network. The quantum information injected into the network can be diluted to distant multi-copies by quantum cloning and processed by arbitrary quantum logic gates which were programed in advance in the network quantum state. A quantum network combines simultaneously these fundamental quantum functions could lead to new intriguing applications. Here we propose a photonic programmable telecloning network based on a four-photon interferometer. The photonic network serves as quantum gate, quantum cloning and quantum teleportation and features experimental advantage of high brightness by photon recycling.

Electrochemical properties of monolithic nickel sulfide electrodes for use in sodium batteries

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

Go, Dae-Yeon; Park, Jinsoo, E-mail: jsp@ikw.ac.kr; Noh, Pan-Jin

2014-10-15

Highlights: • We succeeded in preparing monolithic Ni{sub 3}S{sub 2} integrated electrode through the sulfuration. • The sulfuration is a facile and useful method to synthesize metal sulfides with nanostructure. • As-prepared monolithic Ni{sub 3}S{sub 2} electrodes showed very stable and cycle performance over charge/discharge cycling. - Abstract: Monolithic nickel sulfide electrodes were prepared using a facile synthesis method, sulfuration and annealing. As-prepared Ni{sub 3}S{sub 2} electrodes were characterized by X-ray diffractometry and field emission scanning electron microscopy. Thermal stability was determined by thermal gravimetric analysis and differential scanning calorimetry. Electrochemical properties were measured by galvanostatic charge and discharge cyclingmore » for Na-ion batteries. Three kinds of Ni{sub 3}S{sub 2} electrodes were prepared by varying the sulfuration time (5, 15 and 25 min). The electrochemical results indicated that the capacities increased with an increase in sulfuration time and the cycle performance was stable as a result of monolithic integration of nanostructured Ni{sub 3}S{sub 2} on Ni plates, leading to low interfacial resistance.« less

Aqueous Phase Synthesis and Enhanced Field Emission Properties of ZnO-Sulfide Heterojunction Nanowires

PubMed Central

Wang, Guojing; Li, Zhengcao; Li, Mingyang; Chen, Chienhua; Lv, Shasha; Liao, Jiecui

2016-01-01

ZnO-CdS, ZnO-ZnS, and ZnO-Ag2S core-shell heterojunction structures were fabricated using low-temperature, facile and simple aqueous solution approaches. The polycrystalline sulfide shells effectively enhance the field emission (FE) properties of ZnO nanowires arrays (NWAs). This results from the formation of the staggered gap heterointerface (ZnO-sulfide) which could lead to an energy well at the interfaces. Hence, electrons can be collected when an electric field is applied. It is observed that ZnO-ZnS NWAs have the lowest turn-on field (3.0 Vμm−1), compared with ZnO-CdS NWAs (6.3 Vμm−1) and ZnO-Ag2S NWAs (5.0 Vμm−1). This may be associated with the pyramid-like ZnS shell which increases the number of emission nanotips. Moreover, the Fowler-Nordheim (F-N) plot displays a nonlinear relationship in the low and high electric field regions caused by the double well potential effect of the heterojunction structures. PMID:27387653

An Improved Process for Precipitating Cyanide Ions from the Barren Solution at Different pHs

NASA Astrophysics Data System (ADS)

Figueroa, Gabriela V.; Parga, José R.; Valenzuela, Jesus L.; Vázquez, Victor; Valenzuela, Alejandro; Rodriguez, Mario

2016-02-01

In recent decades, the use of metal sulfides instead of hydroxide precipitation in hydrometallurgical processes has gained prominence. Some arguments for its preferential use are as follows: a high degree of metal removal at relatively low pH values, the sparingly soluble nature of sulfide precipitates, favorable dewatering characteristics, and the stability of the formed metal sulfides. The Merrill-Crowe zinc-precipitation process has been applied worldwide in a large number of operations for the recovery of gold and silver from cyanide solutions. However, in some larger plants, the quality of this precious precipitate is low because copper, zinc and especially lead are precipitated along with gold and silver. This results in higher consumption of zinc dust and flux during the smelting of the precipitate, the formation of the matte, and a shorter crucible life. The results show that pH has a significant effect on the removal efficiency of zinc and copper cyanide ions. The optimal pH range was determined to be 3-4, and the removal efficiency of zinc and copper cyanide ions was up to 99%.

Carbon Isotope Fractionation in Reactions of 1,2-Dibromoethane with FeS and Hydrogen Sulfide

EPA Science Inventory

EDB (1,2-dibromoethane) is frequently detected at sites impacted by leaded gasoline. In reducing environments, EDB is highly susceptible to abiotic degradation. A study was conducted to evaluate the potential of compound-specific isotope analysis (CSIA) in assessing abiotic degr...

A cryptic sulfur cycle driven by iron in the methane zone of marine sediment (Aarhus Bay, Denmark)

NASA Astrophysics Data System (ADS)

Holmkvist, Lars; Ferdelman, Timothy G.; Jørgensen, Bo Barker

2011-06-01

Sulfate reduction and sulfur-iron geochemistry were studied in 5-6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate-methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe 2+, accumulated in the pore water. Sulfate reduction rates measured by 35S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate-methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive "background" concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300-500 cm depth were 0.2-1 pmol SO 42- cm -3 d -1, i.e., 4-5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100-1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, "potential sulfate reduction" which showed that a physiologically intact community of sulfate reducing bacteria was present. The "background" sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO 2 which is reduced with H 2 to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate-methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur-iron-carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.

InAs Colloidal Quantum Dots Synthesis via Aminopnictogen Precursor Chemistry.

PubMed

Grigel, Valeriia; Dupont, Dorian; De Nolf, Kim; Hens, Zeger; Tessier, Mickael D

2016-10-05

Despite their various potential applications, InAs colloidal quantum dots have attracted considerably less attention than more classical II-VI materials because of their complex syntheses that require hazardous precursors. Recently, amino-phosphine has been introduced as a cheap, easy-to-use and efficient phosphorus precursor to synthesize InP quantum dots. Here, we use aminopnictogen precursors to implement a similar approach for synthesizing InAs quantum dots. We develop a two-step method based on the combination of aminoarsine as the arsenic precursor and aminophosphine as the reducing agent. This results in state-of-the-art InAs quantum dots with respect to the size dispersion and band-gap range. Moreover, we present shell coating procedures that lead to the formation of InAs/ZnS(e) core/shell quantum dots that emit in the infrared region. This innovative synthesis approach can greatly facilitate the research on InAs quantum dots and may lead to synthesis protocols for a wide range of III-V quantum dots.

Quantum Biometrics with Retinal Photon Counting

NASA Astrophysics Data System (ADS)

Loulakis, M.; Blatsios, G.; Vrettou, C. S.; Kominis, I. K.

2017-10-01

It is known that the eye's scotopic photodetectors, rhodopsin molecules, and their associated phototransduction mechanism leading to light perception, are efficient single-photon counters. We here use the photon-counting principles of human rod vision to propose a secure quantum biometric identification based on the quantum-statistical properties of retinal photon detection. The photon path along the human eye until its detection by rod cells is modeled as a filter having a specific transmission coefficient. Precisely determining its value from the photodetection statistics registered by the conscious observer is a quantum parameter estimation problem that leads to a quantum secure identification method. The probabilities for false-positive and false-negative identification of this biometric technique can readily approach 10-10 and 10-4, respectively. The security of the biometric method can be further quantified by the physics of quantum measurements. An impostor must be able to perform quantum thermometry and quantum magnetometry with energy resolution better than 10-9ℏ , in order to foil the device by noninvasively monitoring the biometric activity of a user.

Metal Transport, Heavy Metal Speciation and Microbial Fixation Through Fluvial Subenvironments, Lower Coeur D'Alene River Valley, Idaho

NASA Astrophysics Data System (ADS)

Hooper, R. L.; Mahoney, J. B.

2001-12-01

The lower Coeur d'Alene River Valley of northern Idaho is the site of extensive lead and zinc contamination resulting from both direct riverine tailings disposal and flood remobilization of contaminated sediments derived from the Coeur d'Alene mining district upstream. Variations in the hydrologic regime, redox conditions, porosity/permeability, organic content and microbial activity results in complicated metal transport pathways. Documentation of these pathways is a prerequisite to effective remediation, and requires accurate analysis of lateral and vertical variations. An analytical approach combining sequential extraction, electron microscopy, and microanalysis provides a comprehensive assessment of particulate speciation in this complex hydrologic system. Rigorously controlled sample preparation and a new sequential extraction protocol provide unprecedented insight into the role of metal sequestration in fluvial subenvironments. Four subenvironments were investigated: bedload, overbank (levee), marsh, and lacustrine. Periodic floods remobilize primary ore minerals and secondary minerals from upstream tailings (primarily oxyhydroxides, sulfides and carbonates). The bedload in the lower valley is a reducing environment and acts as a sink for detrital carbonates and sulfides moving downstream. In addition, authigenic/biogenic Fe, Pb and Zn sulfides and phosphates are common in bedload sediments near the sediment/water interface. Flood redistribution of oxide, sulfide and carbonate phases results in periodic contaminant recharge generating a complex system of metal dissolution, mobilization, migration and precipitation. In levee environments, authigenic sulfides from flood scouring are quickly oxidized resulting in development of oxide coated grain surfaces. Stability of detrital minerals on the levee is variable depending on sediment permeability, grain size and mineralogy resulting in a complex stratigraphy of oxide zones mottled with zones dominated by detrital and authigenic carbonate and sulfide phases. Marshes subjected to periodic subaerial exposure/flooding are even more complex and dominated by authigenic and biogenic mineralization. Lacustrine environments are dominated by nanocrystalline inorganic and biogenic sulfide minerals in the upper third of the contaminated sediment column with increasing amounts of silt sized detrital sulfides (especially sphalerite) closer to the premining surface. In pH-neutral subenvironments within the wetlands and lateral lakes of the lower Coeur d'Alene River Valley, microbial fixation plays a critical role in sequestering metals. Complex metal oxyhydroxide phases provided via flood recharge to river edge, marsh and lacustrine environments rapidly dissolve upon encountering anoxic conditions. Microbial activity is extremely effective in removing heavy metals from the water column, producing a nanocrystalline biofilm substrate characterized by ZnS (sphalerite) and non-stoichiometric PbS, FeS, and mixed metal sulfides. These solid phases are inherently unstable, and the sequestered metals become readily available through changes in redox or pH conditions, particularly dam-controlled annual fluctuations in base level, or during removal by bottom-feeding aquatic water fowl. The recognition of the inherent complexity and instability of microbially produced sulfidic material in a pH-neutral environment has important implications for remediation efforts utilizing wetland filtration methods.

Causes of High-temperature Superconductivity in the Hydrogen Sulfide Electron-phonon System

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Mazur, E. A.

The electron and phonon spectra, as well as the density of electron and phonon states of the stable orthorhombic structure of hydrogen sulfide (SH2) at pressures 100-180 GPa have been calculated. It is found that the set of parallel planes of hydrogen atoms is formed at pressure ∼175 GPa as a result of structural changes in the unit cell of the crystal under pressure. There should be complete concentration of hydrogen atoms in these planes. As a result the electron properties of the system acquire a quasi-two-dimensional character. The features of in phase and antiphase oscillations of hydrogen atoms in these planes leading to two narrow high-energy peaks in the phonon density of states are investigated.

Reasons for high-temperature superconductivity in the electron-phonon system of hydrogen sulfide

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Mazur, E. A.

2015-08-01

We have calculated the electron and phonon spectra, as well as the densities of the electron and phonon states, of the stable orthorhombic structure of hydrogen sulfide SH2 in the pressure interval 100-180 GPa. It is found that at a pressure of 175 GPa, a set of parallel planes of hydrogen atoms is formed due to a structural modification of the unit cell under pressure with complete accumulation of all hydrogen atoms in these planes. As a result, the electronic properties of the system become quasi-two-dimensional. We have also analyzed the collective synphase and antiphase vibrations of hydrogen atoms in these planes, leading to the occurrence of two high-energy peaks in the phonon density of states.

Microbial communities, processes and functions in acid mine drainage ecosystems.

PubMed

Chen, Lin-xing; Huang, Li-nan; Méndez-García, Celia; Kuang, Jia-liang; Hua, Zheng-shuang; Liu, Jun; Shu, Wen-sheng

2016-04-01

Acid mine drainage (AMD) is generated from the oxidative dissolution of metal sulfides when water and oxygen are available largely due to human mining activities. This process can be accelerated by indigenous microorganisms. In the last several decades, culture-dependent researches have uncovered and validated the roles of AMD microorganisms in metal sulfides oxidation and acid generation processes, and culture-independent studies have largely revealed the diversity and metabolic potentials and activities of AMD communities, leading towards a full understanding of the microbial diversity, functions and interactions in AMD ecosystems. This review describes the diversity of microorganisms and their functions in AMD ecosystems, and discusses their biotechnological applications in biomining and AMD bioremediation according to their capabilities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Exogenous sodium sulfide improves morphological and physiological responses of a hybrid Populus species to nitrogen dioxide.

PubMed

Hu, Yanbo; Bellaloui, Nacer; Sun, Guangyu; Tigabu, Mulualem; Wang, Jinghong

2014-06-15

Gaseous nitrogen dioxide (NO2) can disturb normal plant growth and trigger complex physiological responses. NO2-induced responses are influenced by biotic or abiotic factors. In this study, we investigated the effects of exogenous sodium sulfide (Na2S, 5mmolL(-1)) on epidermis and stomata related physico-chemical responses of hybrid poplar cuttings (Pouplus alba×P. berolinensis) to gaseous NO2 (4μl1(-1)) for three time periods (0, 14 and 48h). We also investigated hydrogen sulfide (H2S), nitrate-nitrogen and nitrate reductase activity (NR) in control and Na2S treated plants. Our results showed that NO2 exposure for 48h led to the decline of NR, maximal PSII quantum yield (Fv/Fm), net photosynthetic rate (Pn), and dark respiration rate (Rd). The maximum rate for the post-illumination carbon dioxide burst (PIB) occurred in 48-h exposed leaves 13-15s after darkening. Moreover, NO2 exposure resulted in a significant increase in nitrogen percentage (from 0 to 33%) and a decrease in the macro and micro-elements of leaf surface. Spraying Na2S aqueous solution on the leaf surfaces significantly increased the thicknesses of palisade/spongy tissue and H2S content. Na2S pretreatment alleviated NO2-caused toxic effects as indicated by increased NR and higher values of Pn, Fv/Fm, and actual photochemical efficiency in light (ФPSII) compared with the control. Na2S pretreatment had no significant impacts on PIB-based photorespiration or elements composition of a leaf surface. Copyright © 2013 Elsevier GmbH. All rights reserved.

Genuine Quantum Signatures in Synchronization of Anharmonic Self-Oscillators.

PubMed

Lörch, Niels; Amitai, Ehud; Nunnenkamp, Andreas; Bruder, Christoph

2016-08-12

We study the synchronization of a Van der Pol self-oscillator with Kerr anharmonicity to an external drive. We demonstrate that the anharmonic, discrete energy spectrum of the quantum oscillator leads to multiple resonances in both phase locking and frequency entrainment not present in the corresponding classical system. Strong driving close to these resonances leads to nonclassical steady-state Wigner distributions. Experimental realizations of these genuine quantum signatures can be implemented with current technology.

Non-hydrolytic Sol-gel Synthesis of Tin Sulfides

NASA Astrophysics Data System (ADS)

Kaur, Rajvinder

The non-hydrolytic sol-gel (NHSG) process is an effective low temperature route well known for preparing homogeneous metal oxides. Thermodynamically as well as kinetically favored products, which cannot be prepared with the traditional solid-state routes, can be produced using NHSG. This project is focused on the exploration of NHSG synthesis of binary tin sulfides. In the past few years, metal sulfides have been the subject of significant interest. Much effort has been devoted to understand these materials because of their potential applications in electronic, optical, and superconductor devices.4 Among these materials, tin sulfides are materials of technological importance, which are being explored as semiconductors, anode materials for Li ion batteries, photoconductors, photocatalysts and absorber layer materials in photovoltaic solar cell devices. All of these applications depend upon features like homogeneity, oxidation state, high surface area and purity of the materials. These properties can be difficult to achieve by employing traditional synthetic routes, which require high temperatures due to slow diffusion, limiting the products to thermodynamically stable phases and prohibiting control over properties like particle size and surface area. A variety of low temperature methods are being explored due to the increased demand for such advanced materials. This project is focused on exploring the NHSG approach to synthesize binary tin sulfides, with the main goal of establishing conditions for the targeted synthesis of different tin sulfide polymorphs with controlled particle size. Being non-oxide materials, tin sulfides can be air sensitive, which requires special attention in handling. All reactions were carried out in absence of oxygen. This project explores the reaction of tin halides with thioethers in a dry solvent medium, leading to the formation of tin sulfides. There are a number of synthetic parameters that can be varied for the NHSG approach. A systematic study was carried out to understand the influence of all reaction variables, which include tin halides, thioethers, solvents, time, temperature, stoichiometry and concentration. Fine tuning of all reaction variables was carried out. The crystallization and phase stability of the as-recovered products was further studied by heat treatments of the samples. A detailed investigation of synthetic variables during NHSG reactions resulted in controlled synthesis of two crystalline tin sulfide polymorphs, SnS and SnS2. A third polymorph, Sn2S3, could be obtained after heat treatments in the temperature range of 400 to 500 °C. Conditions for the targeted synthesis of particles with various sizes and morphologies were established. Samples were characterized by powder X-ray diffraction, electron microscopy in combination with EDS, CHNS analysis and thermo gravimetric/differential thermal analysis.

Origin of the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Evidence from regional Pb and Sr isotope sources

USGS Publications Warehouse

Ayuso, R.A.; Kelley, K.D.; Leach, D.L.; Young, L.E.; Slack, J.F.; Wandless, G.; Lyon, A.M.; Dillingham, J.L.

2004-01-01

Pb and Sr isotope data were obtained on the shale-hosted Zn-Pb-Ag Red Dog deposits (Qanaiyaq, Main, Aqqaluk, and Paalaaq), other shale-hosted deposits near Red Dog, and Zn-Pb-Ag sulfide and barite deposits in the western and central Brooks Range. The Red Dog deposits and other shale-hosted Zn-Pb-Ag deposits near Red Dog are hosted in the Mississippian Kuna Formation, which is underlain by a sequence of marine-deltaic clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. Ag-Pb-Zn vein-breccias are found in the Endicott Group. Galena formed during the main mineralization stages in the Red Dog deposits and from the Anarraaq and Wulik deposits have overlapping Pb isotope compositions in the range 206Pb/204Pb = 18.364 to 18.428, 207Pb/204Pb = 15.553 to 15.621, and 208Pb/204Pb = 38.083 to 38.323. Galena and sphalerite formed during the main ore-forming stages in the Red Dog deposits define a narrow field on standard uranogenic and thorogenic Pb isotope diagrams. Lead in sulfides of the Red Dog district is less radiogenic (238U/204Pb: ?? = 9.51-9.77) than is indicated by the average crustal lead evolution model (?? = 9.74), a difference consistent with a long history of evolution at low ratios of ?? before the Carboniferous. The homogeneous regional isotopic reservoir of Pb may indicate large-scale transport and leaching of minerals with various ?? ratios and Th/Pb ratios. Younger and genetically unrelated fluids did not significantly disturb the isotopic compositions of galena and sphalerite after the main mineralization event in the Red Dog district. Some pyrite shows evidence of minor Pb remobilization. The overall lead isotope homogeneity in the shale-hosted massive sulfide deposits is consistent with three types of control: a homogeneous regional source, mixing of lead during leaching of a thick sedimentary section and fluid transport, or mixing at the site of deposition. Isotopic variability of the hydrothermal fluids, as represented by galena in the Red Dog district, appears to be consistent with a simple mixing system. Evidence indicates that galena was deposited from largely similar hydrothermal solutions throughout the Red Dog district. A shared regional isotopic reservoir is also supported by the correspondence of Pb isotope compositions of galena in deposits of the Red Dog district and galena in clastic rocks (vein-breccias). Leaching of metals and progressive extraction of radiogenic lead from the clastic rocks in the Endicott Group may account for the trend of increasing 206Pb/204Pb in galena of the Red Dog district. Galena in the Red Dog deposits is unlikely to have been derived entirely from the same isotopic reservoir as that represented by the lead in the Kuna Formation or from the igneous rocks in the Red Dog district. Sr isotope data for barite, calcite, and witherite from the Red Dog deposits are compared with data from regional barite that is associated with sulfides and from barite in sulfide-poor occurrences. Fluids with heterogeneous Sr isotope signatures are indicated. Barite in the Main deposit extends to higher ratios of 87Sr/86Sr (0.709034-0.709899) than barite in the Anarraaq deposit (0.708615-0.709256). All barite is more radiogenic than Carboniferous seawater. Other Mississippian(?) shale-hosted deposits and mineral occurrences containing barite in the Red Dog district and barite in regional occurrences east of Red Dog in the western and central Brooks Range also have heterogeneous 87Sr/86Sr ratios. Carbonate (87Sr/86Sr = 0.710319-0.713637) and witherite (87 Sr/86 Sr = 0.710513) in the Main deposit are more radiogenic than barite. In contrast, carbonate (87Sr/86Sr = 0.708196-0.709740) intergrown with massive sulfides at Anarraaq has isotopic compositions similar to that of barite. Paragenetic and isotop ic studies suggest that early barite is similar to barite typically formed in cold seeps along continental margins. This early fine-grained barite formed before the main mineralizat

RAPID COMMUNICATIONS: Long-distance quantum teleportation assisted with free-space entanglement distribution

NASA Astrophysics Data System (ADS)

Ren, Ji-Gang; Yang, Bin; Yi, Zhen-Huan; Zhou, Fei; Chen, Kai; Peng, Cheng-Zhi; Pan, Jian-Wei

2009-08-01

Faithful long-distance quantum teleportation necessitates prior entanglement distribution between two communicated locations. The particle carrying on the unknown quantum information is then combined with one particle of the entangled states for Bell-state measurements, which leads to a transfer of the original quantum information onto the other particle of the entangled states. However in most of the implemented teleportation experiments nowadays, the Bell-state measurements are performed even before successful distribution of entanglement. This leads to an instant collapse of the quantum state for the transmitted particle, which is actually a single-particle transmission thereafter. Thus the true distance for quantum teleportation is, in fact, only in a level of meters. In the present experiment we design a novel scheme which has overcome this limit by utilizing fiber as quantum memory. A complete quantum teleportation is achieved upon successful entanglement distribution over 967 meters in public free space. Active feed-forward control techniques are developed for real-time transfer of quantum information. The overall experimental fidelities for teleported states are better than 89.6%, which signify high-quality teleportation.

Investigations on structural and optical properties of starch capped ZnS nanoparticles synthesized by microwave irradiation method

NASA Astrophysics Data System (ADS)

Lalithadevi, B.; Mohan Rao, K.; Ramananda, D.

2018-05-01

Following a green synthesis method, zinc sulfide (ZnS) nanoparticles were prepared by chemical co-precipitation technique using starch as capping agent. Microwave irradiation was used as heating source. X-ray diffraction studies indicated that nanopowders obtained were polycrystalline possessing ZnS simple cubic structure. Transmission electron microscopic studies indicated that starch limits the agglomeration by steric stabilization. Interaction between ZnS and starch was confirmed by Fourier transform infrared spectroscopy as well as Raman scattering studies. Quantum size effects were observed in optical absorption studies while quenching of defect states on nanoparticles was improved with increase in starch addition as indicated by photoluminescence spectra.

Photon-induced formation of CdS nanocrystals in selected areas of polymer matrices

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

Athanassiou, Athanassia; Cingolani, Roberto; Tsiranidou, Elsa

2007-10-08

We demonstrate light-induced formation of semiconductor quantum dots in TOPAS registered polymer matrix with very high control of their size and their spatial localization. Irradiation with UV laser pulses of polymer films embedding Cd thiolate precursors results in the formation of cadmium sulfide nanocrystals well confined in the irradiation area, through a macroscopically nondestructive procedure for the host matrix. With increasing number of laser pulses, we accomplish the formation of nanoparticles with gradually increasing dimensions, resulting in the dynamic change of the spectra emitted by the formed nanocomposite areas. The findings are supported by x-ray diffraction and transmission electron microscopymore » measurements.« less

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

Kanzler, Charlotte R.; Lian, Peng; Trainer, Emma Leverich

Alkylated mercury species (monomethylmercury, MeHg, and dimethylmercury, DMeHg) exhibit significant bioaccumulation, and pose significant risks to ecosystems and human health. Although decades of research have been devoted to understanding MeHg formation and degradation, little is known about the DMeHg formation in aquatic systems. Here, we combine complementary experimental and computational approaches to examine MeHg speciation and DMeHg formation in sulfidic aqueous solutions, with an emphasis on the formation and decomposition of the binuclear bis(methylmercuric(II)) sulfide complex (CH3Hg)2S. Experimental data indicate that the reaction 2CH3Hg+ + HS- = (CH3Hg)2S has a log K = 26.0. Thus, the binuclear (CH3Hg)2S complex ismore » likely to be the dominant MeHg species under high MeHg concentrations typically used in experimental investigations of MeHg degradation by sulfate-reducing bacteria (SRB). Our finding of a significant abiotic removal mechanism for MeHg in sulfidic solutions through the formation of relatively insoluble (CH3Hg)2S suggests careful reexamination of reported “oxidative demethylation” of MeHg by SRB and perhaps other obligate anaerobes. We provide evidence for slow decomposition of (CH3Hg)2S to DMeHg and HgS, with a first-order rate constant k = 1.5 0.4 x 10-6 h-1. Quantum chemical calculations suggest that the reaction proceeds by a novel mechanism involving rearrangement of the (CH3Hg)2S complex facilitated by strong Hg-Hg interactions that activate a methyl group for intramolecular transfer. Predictions of DMeHg formation rates under a variety of field and laboratory conditions indicate that this pathway for DMeHg formation will be significant in laboratory experiments utilizing high MeHg concentrations, favoring (CH3Hg)2S formation. In natural systems with relatively high MeHg/[H2S]T ratios (the oxic/anoxic interface, for example), DMeHg production may be observed, and warrants further investigation.Experimental and computational evidence show that dimethylmercury is produced from decomposition of bis(methylmercury(ii)) sulfide.« less

Quantum origins of objectivity

NASA Astrophysics Data System (ADS)

Horodecki, R.; Korbicz, J. K.; Horodecki, P.

2015-03-01

In spite of all of its successes, quantum mechanics leaves us with a central problem: How does nature create a bridge from fragile quanta to the objective world of everyday experience? Here we find that a basic structure within quantum mechanics that leads to the perceived objectivity is a so-called spectrum broadcast structure. We uncover this based on minimal assumptions, without referring to any dynamical details or a concrete model. More specifically, working formally within the decoherence theory setting with multiple environments (called quantum Darwinism), we show how a crucial for quantum mechanics notion of nondisturbance due to Bohr [N. Bohr, Phys. Rev. 48, 696 (1935), 10.1103/PhysRev.48.696] and a natural definition of objectivity lead to a canonical structure of a quantum system-environment state, reflecting objective information records about the system stored in the environment.

Fermion-to-qubit mappings with varying resource requirements for quantum simulation

NASA Astrophysics Data System (ADS)

Steudtner, Mark; Wehner, Stephanie

2018-06-01

The mapping of fermionic states onto qubit states, as well as the mapping of fermionic Hamiltonian into quantum gates enables us to simulate electronic systems with a quantum computer. Benefiting the understanding of many-body systems in chemistry and physics, quantum simulation is one of the great promises of the coming age of quantum computers. Interestingly, the minimal requirement of qubits for simulating Fermions seems to be agnostic of the actual number of particles as well as other symmetries. This leads to qubit requirements that are well above the minimal requirements as suggested by combinatorial considerations. In this work, we develop methods that allow us to trade-off qubit requirements against the complexity of the resulting quantum circuit. We first show that any classical code used to map the state of a fermionic Fock space to qubits gives rise to a mapping of fermionic models to quantum gates. As an illustrative example, we present a mapping based on a nonlinear classical error correcting code, which leads to significant qubit savings albeit at the expense of additional quantum gates. We proceed to use this framework to present a number of simpler mappings that lead to qubit savings with a more modest increase in gate difficulty. We discuss the role of symmetries such as particle conservation, and savings that could be obtained if an experimental platform could easily realize multi-controlled gates.

Photonic Programmable Tele-Cloning Network

PubMed Central

Li, Wei; Chen, Ming-Cheng

2016-01-01

The concept of quantum teleportation allows an unknown quantum states to be broadcasted and processed in a distributed quantum network. The quantum information injected into the network can be diluted to distant multi-copies by quantum cloning and processed by arbitrary quantum logic gates which were programed in advance in the network quantum state. A quantum network combines simultaneously these fundamental quantum functions could lead to new intriguing applications. Here we propose a photonic programmable telecloning network based on a four-photon interferometer. The photonic network serves as quantum gate, quantum cloning and quantum teleportation and features experimental advantage of high brightness by photon recycling. PMID:27353838

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

NASA Astrophysics Data System (ADS)

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

2003-02-01

Long term environmentally sound disposal of the millions of tons of mining residue is a serious challenge to the international mining industry. This paper evaluates, through a numerical investigation, the potential performance of desulfurized tailings as a cover material for the reduction of acidic drainage from sulfidic tailings. This evaluation is facilitated through a comparison of various cover types as decommissioning options. The cover types considered consist of a desulfurized tailings material cover exposed to ambient climate conditions, a water cover (flooded tailings), and a combination cover type. As part of the evaluation of cover performances, the effect of climatic variability on the potential rate of sulfide oxidation in tailings with an open ground surface, was also assessed. The numerical analysis was conducted using the model PYROX, which was modified to allow for variably-saturated conditions, time varying moisture contents, and to account for the temperature dependence of Henry's law and gas diffusion. In the case study presented here, the benign cover material consists of a low sulfide waste stream (cassiterite float tails, CFT), a by-product of the production of tin concentrate (cassiterite, SnO 2). Modelling results after a simulation period of 100 years indicate that a water cover alone or an exposed CFT cover alone are both less effective options than the combined cover type. A water cover alone leads to a reduction of approximately 99.1%, in the oxidation rate relative to uncovered tailings while the combined cover type results in the lowest potential extent of sulfide oxidation after mine closure-an approximately 99.8% reduction. Importantly, a CFT cover exposed to ambient environmental conditions can still substantially reduce the sulfide oxidation rate, by approximately 75-82% over a 100-year time period, relative to uncovered tailings. Variability in precipitation (and hence percent saturation of the surface layer) had less of an effect on the potential sulfide oxidation rate than did the cover type. The performance of the exposed CFT cover varied by less than 10%, within the range of climatic conditions expected at the Renison Bell mine site in southwest Tasmania, Australia. Although the modelling results indicate that the combined water and CFT cover is the best option, this approach achieves only a minor improvement over the water cover alone.

Phosphorescence detection of manganese(VII) based on Mn-doped ZnS quantum dots

NASA Astrophysics Data System (ADS)

Deng, Pan; Lu, Li-Qiang; Cao, Wei-Cheng; Tian, Xi-Ke

2017-02-01

The phosphorescent L-cysteine modified manganese-doped zinc sulfide quantum dots (L-cys-MnZnS QDs) was developed for a highly sensitive detection of permanganate anions (MnO4-). L-cys-MnZnS QDs, which were easily synthesized in aqueous media using safe and low-cost materials, can emit intense phosphorescence even though the solution was not deoxygenated. However, the phosphorescence of L-cys-Mn-ZnS QDs was strongly quenched by MnO4- ascribed to the oxidation of L-cys and the increase of surface defects on L-cys-MnZnS QDs. Under the optimal conditions, L-cys-MnZnS QDs offer high selectivity over other anions for MnO4- determination, and good linear Stern-Volmer equation was obtained for MnO4- in the range of 0.5-100 μM with a detection limit down to 0.24 μM. The developed method was finally applied to the detection of MnO4- in water samples, and the spike-recoveries fell in the range of 95-106%.

Imaging pancreatic cancer using bioconjugated InP quantum dots.

PubMed

Yong, Ken-Tye; Ding, Hong; Roy, Indrajit; Law, Wing-Cheung; Bergey, Earl J; Maitra, Anirban; Prasad, Paras N

2009-03-24

In this paper, we report the successful use of non-cadmium-based quantum dots (QDs) as highly efficient and nontoxic optical probes for imaging live pancreatic cancer cells. Indium phosphide (core)-zinc sulfide (shell), or InP/ZnS, QDs with high quality and bright luminescence were prepared by a hot colloidal synthesis method in nonaqueous media. The surfaces of these QDs were then functionalized with mercaptosuccinic acid to make them highly dispersible in aqueous media. Further bioconjugation with pancreatic cancer specific monoclonal antibodies, such as anticlaudin 4 and antiprostate stem cell antigen (anti-PSCA), to the functionalized InP/ZnS QDs, allowed specific in vitro targeting of pancreatic cancer cell lines (both immortalized and low passage ones). The receptor-mediated delivery of the bioconjugates was further confirmed by the observation of poor in vitro targeting in nonpancreatic cancer based cell lines which are negative for the claudin-4-receptor. These observations suggest the immense potential of InP/ZnS QDs as non-cadmium-based safe and efficient optical imaging nanoprobes in diagnostic imaging, particularly for early detection of cancer.

Quantum walks of interacting fermions on a cycle graph

PubMed Central

Melnikov, Alexey A.; Fedichkin, Leonid E.

2016-01-01

Quantum walks have been employed widely to develop new tools for quantum information processing recently. A natural quantum walk dynamics of interacting particles can be used to implement efficiently the universal quantum computation. In this work quantum walks of electrons on a graph are studied. The graph is composed of semiconductor quantum dots arranged in a circle. Electrons can tunnel between adjacent dots and interact via Coulomb repulsion, which leads to entanglement. Fermionic entanglement dynamics is obtained and evaluated. PMID:27681057

Population Switching and Charge Sensing in Quantum Dots: A Case for a Quantum Phase Transition

NASA Astrophysics Data System (ADS)

Goldstein, Moshe; Berkovits, Richard; Gefen, Yuval

2010-06-01

A broad and a narrow level of a quantum dot connected to two external leads may swap their respective occupancies as a function of an external gate voltage. By mapping this problem onto a multiflavored Coulomb gas we show that such population switching is not abrupt. However, trying to measure it by adding a third electrostatically coupled lead may render this switching an abrupt first order quantum phase transition. This is related to the interplay of the Mahan mechanism versus the Anderson orthogonality catastrophe, in similitude to the Fermi edge singularity. A concrete setup for experimental observation of this effect is also suggested.

Removal of EDB and 1,2-DCA by Abiotic Reaction with Iron (II) Sulfide

EPA Science Inventory

To properly evaluate the risk associated with exposure to EDB and 1,2-DCA in ground water from old spills of leaded gasoline, it is necessary to understand the mechanisms that may attenuate concentrations of these compounds in ground water. TCE reacts rapidly with iron (II) sulf...

Redox reactions and weak buffering capacity lead to acidification in the Chesapeake Bay.

PubMed

Cai, Wei-Jun; Huang, Wei-Jen; Luther, George W; Pierrot, Denis; Li, Ming; Testa, Jeremy; Xue, Ming; Joesoef, Andrew; Mann, Roger; Brodeur, Jean; Xu, Yuan-Yuan; Chen, Baoshan; Hussain, Najid; Waldbusser, George G; Cornwell, Jeffrey; Kemp, W Michael

2017-08-28

The combined effects of anthropogenic and biological CO 2 inputs may lead to more rapid acidification in coastal waters compared to the open ocean. It is less clear, however, how redox reactions would contribute to acidification. Here we report estuarine acidification dynamics based on oxygen, hydrogen sulfide (H 2 S), pH, dissolved inorganic carbon and total alkalinity data from the Chesapeake Bay, where anthropogenic nutrient inputs have led to eutrophication, hypoxia and anoxia, and low pH. We show that a pH minimum occurs in mid-depths where acids are generated as a result of H 2 S oxidation in waters mixed upward from the anoxic depths. Our analyses also suggest a large synergistic effect from river-ocean mixing, global and local atmospheric CO 2 uptake, and CO 2 and acid production from respiration and other redox reactions. Together they lead to a poor acid buffering capacity, severe acidification and increased carbonate mineral dissolution in the USA's largest estuary.The potential contribution of redox reactions to acidification in coastal waters is unclear. Here, using measurements from the Chesapeake Bay, the authors show that pH minimum occurs at mid-depths where acids are produced via hydrogen sulfide oxidation in waters mixed upward from anoxic depths.

Quantum Backreaction on Three-Dimensional Black Holes and Naked Singularities.

PubMed

Casals, Marc; Fabbri, Alessandro; Martínez, Cristián; Zanelli, Jorge

2017-03-31

We analytically investigate backreaction by a quantum scalar field on two rotating Bañados-Teitelboim-Zanelli (BTZ) geometries: that of a black hole and that of a naked singularity. In the former case, we explore the quantum effects on various regions of relevance for a rotating black hole space-time. We find that the quantum effects lead to a growth of both the event horizon and the radius of the ergosphere, and to a reduction of the angular velocity, compared to the unperturbed values. Furthermore, they give rise to the formation of a curvature singularity at the Cauchy horizon and show no evidence of the appearance of a superradiant instability. In the case of a naked singularity, we find that quantum effects lead to the formation of a horizon that shields it, thus supporting evidence for the rôle of quantum mechanics as a cosmic censor in nature.

Uncertainty in quantum mechanics: faith or fantasy?

PubMed

Penrose, Roger

2011-12-13

The word 'uncertainty', in the context of quantum mechanics, usually evokes an impression of an essential unknowability of what might actually be going on at the quantum level of activity, as is made explicit in Heisenberg's uncertainty principle, and in the fact that the theory normally provides only probabilities for the results of quantum measurement. These issues limit our ultimate understanding of the behaviour of things, if we take quantum mechanics to represent an absolute truth. But they do not cause us to put that very 'truth' into question. This article addresses the issue of quantum 'uncertainty' from a different perspective, raising the question of whether this term might be applied to the theory itself, despite its unrefuted huge success over an enormously diverse range of observed phenomena. There are, indeed, seeming internal contradictions in the theory that lead us to infer that a total faith in it at all levels of scale leads us to almost fantastical implications.

High-pressure phase diagram of hydrogen and deuterium sulfides from first principles: Structural and vibrational properties including quantum and anharmonic effects

NASA Astrophysics Data System (ADS)

Bianco, Raffaello; Errea, Ion; Calandra, Matteo; Mauri, Francesco

2018-06-01

We study the structural and vibrational properties of the high-temperature superconducting sulfur trihydride and trideuteride in the high-pressure I m 3 ¯m and R 3 m phases by first-principles density-functional-theory calculations. On lowering pressure, the rhombohedral transition I m 3 ¯m →R 3 m is expected, with hydrogen-bond desymmetrization and occurrence of trigonal lattice distortion. With both Perdew-Burke-Ernzerhof (PBE) and Becke-Lee-Yang-Parr (BLYP) exchange-correlation functional, in hydrostatic conditions we find that, contrary to what is suggested in some recent experiments, if the rhombohedral distortion exists it affects mainly the hydrogen bonds, whereas the resulting cell distortion is minimal. We estimate that the occurrence of a stress anisotropy of approximately 10 % could explain this discrepancy. Assuming hydrostatic conditions, we calculate the critical pressure at which the rhombohedral transition occurs. Quantum and anharmonic effects, which are relevant in this system, are included at nonperturbative level with the stochastic self-consistent harmonic approximation. Within this approach, we determine the transition pressure by calculating the free-energy Hessian, a method that allows to estimate the critical pressure with much higher precision (and much lower computational cost) compared with the free-energy "finite-difference" approach previously used. Using PBE and BLYP, we find that quantum anharmonic effects are responsible for a strong reduction of the critical pressure with respect to the one obtained with the classical harmonic approach. Interestingly, for the two functionals, even if the transition pressures at classical harmonic level differ by 83 GPa, the transition pressures including quantum anharmonic effects differ only by 23 GPa. Moreover, we observe a prominent isotope effect, as we estimate higher transition pressure for D3S than for H3S . Finally, within the stochastic self-consistent harmonic approximation, with PBE we calculate the anharmonic phonon spectral functions in the I m 3 ¯m phase. The strong anharmonicity of the system is confirmed by the occurrence of very large anharmonic broadenings leading to complex non-Lorentzian line shapes. Generally, for the high-energy hydrogen bond-stretching modes, the anharmonic phonon broadening is of the same magnitude of the electron-phonon one. However, for the vibrational spectra at zone center, accessible, e.g., by infrared spectroscopy, the broadenings are very small (linewidth at most around 2 meV) and anharmonic phonon quasiparticles are well defined.

Frustration and quantum criticality

NASA Astrophysics Data System (ADS)

Vojta, Matthias

2018-06-01

This review article is devoted to the interplay between frustrated magnetism and quantum critical phenomena, covering both theoretical concepts and ideas as well as recent experimental developments in correlated-electron materials. The first part deals with local-moment magnetism in Mott insulators and the second part with frustration in metallic systems. In both cases, frustration can either induce exotic phases accompanied by exotic quantum critical points or lead to conventional ordering with unconventional crossover phenomena. In addition, the competition of multiple phases inherent to frustrated systems can lead to multi-criticality.

Application of bacteriophages specific to hydrogen sulfide-producing bacteria in raw poultry by-products.

PubMed

Gong, Chao; Liu, Xiaohua; Jiang, Xiuping

2014-03-01

Hydrogen sulfide-producing bacteria (SPB) can spoil raw animal materials and release harmful hydrogen sulfide (H2S) gas. The objective of this study was to apply a SPB-specific bacteriophage cocktail to control H2S production by SPB in different raw poultry by-products in the laboratory (20, 30, and 37°C) and greenhouse (average temperature 29 to 31°C, humidity 34.8 to 59.8%, and light intensity 604.8 Wm(2)) by simulating transportation and a rendering facility. The amount of H2S production was determined using either test strips impregnated with lead acetate or a H2S monitor. In the laboratory, phage treatment applied to fresh chicken meat inoculated with SPB, spoiled chicken meat, chicken guts, and chicken feathers reduced H2S production by approximately 25 to 69% at temperatures from 20 to 37°C. In the greenhouse, phage treatment achieved approximately a 30 to 85% reduction of H2S yield in chicken offal and feathers. Among all phage treatments, multiplicity of infection (MOI) of 100 exhibited the highest inhibitory activities against SPB on H2S production. Several factors such as initial SPB level, temperature, and MOI affect lytic activities of bacteriophages. Our study demonstrated that the phage cocktail is effective to reduce the production of H2S by SPB significantly in raw animal materials. This biological control method can control SPB in raw poultry by-products at ambient temperatures, leading to a safer working environment and high quality product with less nutrient degradation for the rendering industry.

The Pendulum as a Vehicle for Transitioning from Classical to Quantum Physics: History, Quantum Concepts, and Educational Challenges

ERIC Educational Resources Information Center

Barnes, Marianne B.; Garner, James; Reid, David

2004-01-01

In this article we use the pendulum as the vehicle for discussing the transition from classical to quantum physics. Since student knowledge of the classical pendulum can be generalized to all harmonic oscillators, we propose that a quantum analysis of the pendulum can lead students into the unanticipated consequences of quantum phenomena at the…

First-principles study of low Miller index Ni3S2 surfaces in hydrotreating conditions.

PubMed

Aray, Yosslen; Vega, David; Rodriguez, Jesus; Vidal, Alba B; Grillo, Maria Elena; Coll, Santiago

2009-03-12

Density functional theory (DFT) calculations combined with surface thermodynamic arguments and the Gibbs-Curie-Wulff equilibrium morphology formalism have been employed to explore the effect of the reaction conditions, temperature (T), and gas-phase partial pressures (PH2 and PH2S) on the stability of nickel sulfide (Ni3S2) surfaces. Furthermore, the strength and nature of chemical bonds for selected Ni3S2 surface cuts were investigated with the quantum theory of atoms in molecules methodology. A particular analysis of the electrostatic potential within this theoretical framework is performed to study the potential activity of nickel sulfide nanoparticles as hydrodesulfurization (HDS) catalysts. The calculated thermodynamic surface stabilities and the resulting equilibrium morphology model suggest that unsupported Ni3S2 nanoparticles mainly expose (111) and (111) type surface faces in HDS conditions. Analysis of the electrostatic potential mapped onto a selected electron density isocontour (0.001 au) on those expose surface reveals a poor potential reactivity toward electron-donating reagents (i.e., low Lewis acidity). Consequently, a very low attraction between coordinatively unsaturated active sites (Lewis sites) exposed at the catalytic particles and the S atoms coming from reagent polluting molecules does inactive these kinds of particles for HDS.

Synthesis of Cesium Lead Halide Perovskite Quantum Dots

ERIC Educational Resources Information Center

Shekhirev, Mikhail; Goza, John; Teeter, Jacob D.; Lipatov, Alexey; Sinitskii, Alexander

2017-01-01

Synthesis of quantum dots is a valuable experiment for demonstration and discussion of quantum phenomena in undergraduate chemistry curricula. Recently, a new class of all-inorganic perovskite quantum dots (QDs) with a formula of CsPbX[subscript 3] (X = Cl, Br, I) was presented and attracted tremendous attention. Here we adapt the synthesis of…

Enhancing non-local correlations in the bipartite partitions of two qubit-system with non-mutual interaction

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

Mohamed, A.-B.A., E-mail: abdelbastm@yahoo.com; Faculty of Science, Assiut University, Assiut; Joshi, A., E-mail: mcbamji@gmail.com

2016-03-15

Several quantum-mechanical correlations, notably, quantum entanglement, measurement-induced nonlocality and Bell nonlocality are studied for a two qubit-system having no mutual interaction. Analytical expressions for the measures of these quantum-mechanical correlations of different bipartite partitions of the system are obtained, for initially two entangled qubits and the two photons are in their vacuum states. It is found that the qubits-fields interaction leads to the loss and gain of the initial quantum correlations. The lost initial quantum correlations transfer from the qubits to the cavity fields. It is found that the maximal violation of Bell’s inequality is occurring when the quantum correlationsmore » of both the logarithmic negativity and measurement-induced nonlocality reach particular values. The maximal violation of Bell’s inequality occurs only for certain bipartite partitions of the system. The frequency detuning leads to quick oscillations of the quantum correlations and inhibits their transfer from the qubits to the cavity modes. It is also found that the dynamical behavior of the quantum correlation clearly depends on the qubit distribution angle.« less

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

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

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth’s history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES)more » spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes—many containing organic ligands—we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H 2S (aq)] < 11 µM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO 3, MoO xS 4-x 2- (intermediate thiomolybdates), and [MoO x(cat) 4-x] 2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS 4 2- (tetrathiomolybdate).« less

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

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

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth’s history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES)more » spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes—many containing organic ligands—we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H2S(aq)] < 11 µM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO3, MoOxS4-x2- (intermediate thiomolybdates), and [MoOx(cat)4-x]2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS42- (tetrathiomolybdate).« less

Evidence of Sulfate-Dependent Anaerobic Methane Oxidation within an Area Impacted by Coalbed Methane-Related Gas Migration

NASA Astrophysics Data System (ADS)

Wolfe, A. L.; Wikin, R. T.

2017-12-01

We evaluated water quality characteristics in the northern Raton Basin of Colorado and documented the response of the Poison Canyon aquifer system several years after upward migration of methane gas occurred from the deeper Vermejo Formation coalbed production zone. Over a 17-month study period, water samples were obtained from domestic water wells and monitoring wells located within the impacted area, and analyzed for 245 constituents, including organic compounds, nutrients, major and trace elements, dissolved gases, and isotopic tracers for carbon, sulfur, oxygen, and hydrogen. Multiple lines of evidence suggest that sulfate-dependent methane biodegradation, which involves the oxidation of methane (CH4) to carbon dioxide (CO2) using sulfate (SO42-) as the terminal electron acceptor, is occurring: (i) consumption of methane and sulfate and production of sulfide and bicarbonate, (ii) methane loss coupled to production of higher molecular weight (C2+) gaseous hydrocarbons, (iii) patterns of 13C enrichment and depletion in methane and dissolved inorganic carbon, and (iv) a systematic shift in sulfur and oxygen isotope ratios of sulfate, indicative of microbial sulfate reduction. Groundwater-methane attenuation is linked to the production of dissolved sulfide, and elevated dissolved sulfide concentrations represent an undesirable secondary water quality impact. The biogeochemical response of the aquifer system has not mobilized naturally occurring trace metals, including arsenic, chromium, cobalt, nickel, and lead, likely due to the microbial production of hydrogen sulfide, which favors stabilization of metals in aquifer solids.

Potential for drug interactions mediated by polymorphic flavin-containing monooxygenase 3 in human livers.

PubMed

Shimizu, Makiko; Shiraishi, Arisa; Sato, Ayumi; Nagashima, Satomi; Yamazaki, Hiroshi

2015-02-01

Human flavin-containing monooxygenase 3 (FMO3) in the liver catalyzes a variety of oxygenations of nitrogen- and sulfur-containing medicines and xenobiotic substances. Because of growing interest in drug interactions mediated by polymorphic FMO3, benzydamine N-oxygenation by human FMO3 was investigated as a model reaction. Among the 41 compounds tested, trimethylamine, methimazole, itopride, and tozasertib (50 μM) suppressed benzydamine N-oxygenation at a substrate concentration of 50 μM by approximately 50% after co-incubation. Suppression of N-oxygenation of benzydamine, trimethylamine, itopride, and tozasertib and S-oxygenation of methimazole and sulindac sulfide after co-incubation with the other five of these six substrates was compared using FMO3 proteins recombinantly expressed in bacterial membranes. Apparent competitive inhibition by methimazole (0-50 μM) of sulindac sulfide S-oxygenation was observed with FMO3 proteins. Sulindac sulfide S-oxygenation activity of Arg205Cys variant FMO3 protein was likely to be suppressed more by methimazole than wild-type or Val257Met variant FMO3 protein was. These results suggest that genetic polymorphism in the human FMO3 gene may lead to changes of drug interactions for N- or S-oxygenations of xenobiotics and endogenous substances and that a probe battery system of benzydamine N-oxygenation and sulindac sulfide S-oxygenation activities is recommended to clarify the drug interactions mediated by FMO3. Copyright © 2014 The Japanese Society for the Study of Xenobiotics. Published by Elsevier Ltd. All rights reserved.

Eddy covariance carbonyl sulfide flux measurements with a quantum cascade laser absorption spectrometer

NASA Astrophysics Data System (ADS)

Gerdel, Katharina; Spielmann, Felix Maximilian; Hammerle, Albin; Wohlfahrt, Georg

2017-09-01

The trace gas carbonyl sulfide (COS) has lately received growing interest from the eddy covariance (EC) community due to its potential to serve as an independent approach for constraining gross primary production and canopy stomatal conductance. Thanks to recent developments of fast-response high-precision trace gas analysers (e.g. quantum cascade laser absorption spectrometers, QCLAS), a handful of EC COS flux measurements have been published since 2013. To date, however, a thorough methodological characterisation of QCLAS with regard to the requirements of the EC technique and the necessary processing steps has not been conducted. The objective of this study is to present a detailed characterisation of the COS measurement with the Aerodyne QCLAS in the context of the EC technique and to recommend best EC processing practices for those measurements. Data were collected from May to October 2015 at a temperate mountain grassland in Tyrol, Austria. Analysis of the Allan variance of high-frequency concentration measurements revealed the occurrence of sensor drift under field conditions after an averaging time of around 50 s. We thus explored the use of two high-pass filtering approaches (linear detrending and recursive filtering) as opposed to block averaging and linear interpolation of regular background measurements for covariance computation. Experimental low-pass filtering correction factors were derived from a detailed cospectral analysis. The CO2 and H2O flux measurements obtained with the QCLAS were compared with those obtained with a closed-path infrared gas analyser. Overall, our results suggest small, but systematic differences between the various high-pass filtering scenarios with regard to the fraction of data retained in the quality control and flux magnitudes. When COS and CO2 fluxes are combined in the ecosystem relative uptake rate, systematic differences between the high-pass filtering scenarios largely cancel out, suggesting that this relative metric represents a robust key parameter comparable between studies relying on different post-processing schemes.

Eddy covariance carbonyl sulfide flux measurements with a quantum cascade laser absorption spectrometer

NASA Astrophysics Data System (ADS)

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

2016-04-01

Carbonyl sulfide (COS) is the most abundant sulfur containing trace gas present in the troposphere at concentrations of around 500 ppt. Recent interest in COS by the ecosystem-physiological community has been sparked by the fact that COS co-diffuses into plant leaves pretty much the same way as carbon dioxide (CO2) does, but in contrast to CO2, COS is not known to be emitted by plants. Thus uptake of COS by vegetation has the potential to be used as a tracer for canopy gross photosynthesis, which cannot be measured directly, however represents a key term in the global carbon cycle. Since a few years, quantum cascade laser absorption spectrometers (QCLAS) are commercially available with the precision, sensitivity and time response suitable for eddy covariance (EC) flux measurements. While there exist a handful of published reports on EC flux measurements in the recent literature, no rigorous investigation of the applicability of QCLAS for EC COS flux measurements has been carried out so far, nor have been EC processing and QA/QC steps developed for carbon dioxide and water vapor flux measurements within FLUXNET been assessed for COS. The aim of this study is to close this knowledge gap, to discuss critical steps in the post-processing chain of COS EC flux measurements and to devise best-practice guidelines for COS EC flux data processing. To this end we collected EC COS (and CO2, H2O and CO) flux measurements above a temperate mountain grassland in Austria over the vegetation period 2015 with a commercially available QCLAS. We discuss various aspects of EC data post-processing, in particular issues with the time-lag estimation between sonic anemometer and QCLAS signals and QCLAS time series detrending, as well as QA/QC, in particular flux detection limits, random flux uncertainty, the interaction of various processing steps with common EC QA/QC filters (e.g. detrending and stationarity tests), u*-filtering, etc.

[XANES study of lead speciation in duckweed].

PubMed

Chu, Bin-Bin; Luo, Li-Qiang; Xu, Tao; Yuan, Jing; Sun, Jian-Ling; Zeng, Yuan; Ma, Yan-Hong; Yi, Shan

2012-07-01

Qixiashan lead-zinc mine of Nanjing was one of the largest lead zinc deposits in East China Its exploitation has been over 50 years, and the environmental pollution has also been increasing. The lead concentration in the local environment was high, but lead migration and toxic mechanism has not been clear. Therefore, biogeochemistry research of the lead zinc mine was carried out. Using ICP-MS and Pb-L III edge XANES, lead concentration and speciation were analyzed respectively, and duckweed which can tolerate and enriched heavy metals was found in the pollution area. The results showed that the lead concentration of duckweed was 39.4 mg x kg(-1). XANES analysis and linear combination fit indicated that lead stearate and lead sulfide accounted for 65% and 36.9% respectively in the lead speciation of duckweed, suggesting that the main lead speciation of duckweed was sulfur-containing lead-organic acid.

Reasons for high-temperature superconductivity in the electron–phonon system of hydrogen sulfide

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

Degtyarenko, N. N.; Mazur, E. A., E-mail: eugen-masur@mail.ru

We have calculated the electron and phonon spectra, as well as the densities of the electron and phonon states, of the stable orthorhombic structure of hydrogen sulfide SH{sub 2} in the pressure interval 100–180 GPa. It is found that at a pressure of 175 GPa, a set of parallel planes of hydrogen atoms is formed due to a structural modification of the unit cell under pressure with complete accumulation of all hydrogen atoms in these planes. As a result, the electronic properties of the system become quasi-two-dimensional. We have also analyzed the collective synphase and antiphase vibrations of hydrogen atomsmore » in these planes, leading to the occurrence of two high-energy peaks in the phonon density of states.« less

The behavior of sulfur in industrial pyrometallurgical slags

NASA Astrophysics Data System (ADS)

Nagamori, Meguru

1994-08-01

Dissolution of sulfur in industrial slags, even at such a low level as 1 mass% S or so, increases the solubility of certain valuable metals by an order of magnitude. The phenomenon is accounted for in terms of Flood-Førland-Grjotheim's model for dianionic salt solutions, whereas its rigorous analysis requires the digaseous Gibbs-Duhem integration. In the research described here, the distribution of sulfur among gas, slag, and metallic iron phases in the bath smelting of iron ore was computer-simulated based on a two-sites model coupled with sulfide capacity data. The solubilities of Ag, Cu, Co, and Ni in industrial slags are reviewed by applying the sulfidic-oxidic dissolution model to copper-matte smelting, nickel-slag cleaning (Falconbridge, Canada), and the imperial smelting process for zinc and lead (Hachinohe, Japan).

Room temperature synthesis of ReS2 through aqueous perrhenate sulfidation

NASA Astrophysics Data System (ADS)

Borowiec, Joanna; Gillin, William P.; Willis, Maureen A. C.; Boi, Filippo S.; He, Y.; Wen, J. Q.; Wang, S. L.; Schulz, Leander

2018-02-01

In this study, a direct sulfidation reaction of ammonium perrhenate (NH4ReO4) leading to a synthesis of rhenium disulfide (ReS2) is demonstrated. These findings reveal the first example of a simplistic bottom-up approach to the chemical synthesis of crystalline ReS2. The reaction presented here takes place at room temperature, in an ambient and solvent-free environment and without the necessity of a catalyst. The atomic composition and structure of the as-synthesized product were characterized using several analysis techniques including energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and differential scanning calorimetry. The results indicated the formation of a lower symmetry (1Tʹ) ReS2 with a low degree of layer stacking.

Room temperature synthesis of ReS2 through aqueous perrhenate sulfidation.

PubMed

Borowiec, Joanna; Gillin, William P; Willis, Maureen A C; Boi, Filippo S; He, Y; Wen, J Q; Wang, S L; Schulz, Leander

2018-01-11

In this study, a direct sulfidation reaction of ammonium perrhenate (NH 4 ReO 4 ) leading to a synthesis of rhenium disulfide (ReS 2 ) is demonstrated. These findings reveal the first example of a simplistic bottom-up approach to the chemical synthesis of crystalline ReS 2 . The reaction presented here takes place at room temperature, in an ambient and solvent-free environment and without the necessity of a catalyst. The atomic composition and structure of the as-synthesized product were characterized using several analysis techniques including energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and differential scanning calorimetry. The results indicated the formation of a lower symmetry (1T') ReS 2 with a low degree of layer stacking.

Determining the exact number of dye molecules attached to colloidal CdSe/ZnS quantum dots in Förster resonant energy transfer assemblies

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

Kaiser, Uwe; Jimenez de Aberasturi, Dorleta; Vázquez-González, Margarita

2015-01-14

Semiconductor quantum dots functionalized with organic dye molecules are important tools for biological sensor applications. Energy transfer between the quantum dot and the attached dyes can be utilized for sensing. Though important, the determination of the real number of dye molecules attached per quantum dot is rather difficult. In this work, a method will be presented to determine the number of ATTO-590 dye molecules attached to CdSe/ZnS quantum dots based on time resolved spectral analysis. The energy transfer from the excited quantum dot to the attached ATTO-590 dye leads to a reduced lifetime of the quantum dot's excitons. The highermore » the concentration of dye molecules, the shorter the excitonic lifetime becomes. However, the number of dye molecules attached per quantum dot will vary. Therefore, for correctly explaining the decay of the luminescence upon photoexcitation of the quantum dot, it is necessary to take into account the distribution of the number of dyes attached per quantum dot. A Poisson distribution of the ATTO-590 dye molecules not only leads to excellent agreement between experimental and theoretical decay curves but also additionally yields the average number of dye molecules attached per quantum dot. In this way, the number of dyes per quantum dot can be conveniently determined.« less

``New'' energy states lead to phonon-less optoelectronic properties in nanostructured silicon

NASA Astrophysics Data System (ADS)

Singh, Vivek; Yu, Yixuan; Korgel, Brian; Nagpal, Prashant

2014-03-01

Silicon is arguably one of the most important technological material for electronic applications. However, indirect bandgap of silicon semiconductor has prevented optoelectronic applications due to phonon assistance required for photon light absorption/emission. Here we show, that previously unexplored surface states in nanostructured silicon can couple with quantum-confined energy levels, leading to phonon-less exciton-recombination and photoluminescence. We demonstrate size dependence (2.4 - 8.3 nm) of this coupling observed in small uniform silicon nanocrystallites, or quantum-dots, by direct measurements of their electronic density of states and low temperature measurements. To enhance the optical absorption of the these silicon quantum-dots, we utilize generation of resonant surface plasmon polariton waves, which leads to several fold increase in observed spectrally-resolved photocurrent near the quantum-confined bandedge states. Therefore, these enhanced light emission and absorption enhancement can have important implications for applications of nanostructured silicon for optoelectronic applications in photovoltaics and LEDs.

GEOLOGY, SULFUR ISOTOPES AND THE ORIGIN OF THE HEATH STEELE ORE DEPOSITS, NEWCASTLE, N.B., CANADA

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

Dechow, E.

The Heath Steele mine is located 35 miles northwest of Newcastle, New Brunswick, Canada. Middle Ordovician Tetagouche Group rocks, consisting of siliceous and basic volcanic rocks, and fine-grained quartz sericite schists and porphyry, have been folded into a steeply plunging recumbent anticline. The ore deposits of zinc, lead, and copper are associated with minor folding and/or sheared dilatent zones at or near the contact between porphyry and fine-grained senicitic schist. Mineralogically the sulfide bodies consist of early, euhedral arsenopyrite, magnetite, and pyrite, followed by interstitial pyrrhotite, sphalerite, chalcopyrite and galena. Minor minerals are ternantite-tetrahedrite, bismuthinite, marcasite, hematite, and some graphite.more » Supergene minerals consist of chalcocite, covellite, and marcasite with a little native silver. Little hypogene replacement has taken place between the minerals, which show a "porphyritic" texture. Sulfur isotope ratios were determined for over 150 sulfide and sulfate specimens from five of the seven ore bodies, and from granite, acid and basic volcanics, porphyry, and sediments. The results indicate that there is no detectable fractionation either during hypogene mineralization or supergene enrichment. The spread (21.82 to 22.02) covered by the ratios is narrow, and suggestive of a well homogenized source of mineral solutions. The enrichment of S/sup 34/ in the ore sulfides and the presence of graphite, evident from mineralographic studies and mass spectrometric analysis, suggests reduction of original sulfates (known to be enriched in S/sup 34/) by organic carbon at temperatures in excess of 500 deg C. A calculation based on the isotopic exchange reaction between sulfide and sulfate under equilibrium conditions and the spread of the ratios indicates a temperature of 700 to 800 deg C for the source. Finally the ratios determined for sulfides in a gneissic granite close to Heath Steele have the same ratio as the ore. These factors are considered to be diagnostic of a magmatic hydrothermal origin for the orp deposits. It is believed that an original source bed has been buried until suitable temperatures were reached to cause granitization, reduction of sulfates, and mobilization of the resulting sulfides to form ore deposits at favorable loci. (auth)« less

Unradiogenic Pb Anomalies in Historical Lavas of Piton de la Fournaise (Reunion Island)

NASA Astrophysics Data System (ADS)

Vlastelic, I.

2008-12-01

A detailed investigation (218 samples) of Pb isotope variations in the most recent (1975-2007), well- documented and densely sampled eruptions of Piton de la Fournaise has been undertaken (Vlastelic et al, in press). Lead isotopes exhibit smooth temporal fluctuations (18.87<206Pb/204Pb<18.94) on which superimpose rare (5), but pronounced unradiogenic spikes (206Pb/204Pb down to 17.63). In 208Pb/204Pb vs. 206Pb/204Pb space, normal and anomalous samples plot along a single linear array. In 207Pb/204Pb vs. 206Pb/204Pb space, normal samples define an array whose slope (0.16) is commonly observed in ocean island basalts, whereas anomalous samples define less steep arrays (slopes down to 0.04). It follows that some of the anomalous samples have unusually high 207Pb/204Pb for their 206Pb/204Pb. These latter are enriched in Pb by a factor three. The lack of reproducibility of isotopic analyses suggests that samples are heterogeneous at a sub-millimeter scale. The origin of the unradiogenic anomalies is enigmatic. Leaching experiments rule out anthropogenic contamination. Interaction of plume melts with a contaminant genetically unrelated to the Reunion plume is possible although not supported by trace-element and Sr-Nd isotope signatures indistinguishable from normal lavas. On the other hand, interaction with or entrainment of Pb-rich, most likely unradiogenic sulfides could affect specifically Pb isotope compositions. Inspection of the well-know eruptions history reveals that the isotopic anomalies coincide with transitions from basalts to oceanites (lavas rich in cumulative olivine). Olivine and sulfides, which are both denser than silicate melts, could be entrained with magma pulses, which give rise to high-flux oceanite eruptions. Some sulfides may originate from the oceanic crust. Others may originate from sulfide solidus depth (c.a. 160 km) where sulfides melts are expected to pond (Hart and Gaetani, 2006). These deep sulfides melts could be remnants of past melting events of the Reunion plume. References Hart, S.R., Gaetani, G.A., 2006. Contrib. Mineral. Petrol. 152, 295-308. Vlastelic, I., et al., 2008. J. Volcanol. Geotherm. Res., in press.

The geology of the Morro Velho gold deposit in the Archean Rio das Velhas greenstone belt, Quadrilátero Ferrífero, Brazil

USGS Publications Warehouse

Vial, Diogenes Scipioni; DeWitt, Ed; Lobato, Lydia Maria; Thorman, Charles H.

2007-01-01

The Morro Velho gold deposit, Quadrilátero Ferrífero region, Minas Gerais, Brazil, is hosted by rocks at the base of the Archean Rio das Velhas greenstone belt. The deposit occurs within a thick carbonaceous phyllite package, containing intercalations of felsic and intermediate volcaniclastic rocks and dolomites. Considering the temporal and spatial association of the deposit with the Rio das Velhas orogeny, and location in close proximity to a major NNW-trending fault zone, it can be classified as an orogenic gold deposit. Hydrothermal activity was characterized by intense enrichment in alteration zones of carbonates, sulfides, chlorite, white mica±biotite, albite and quartz, as described in other Archean lode-type gold ores. Two types of ore occur in the deposit: dark gray quartz veins and sulfide-rich gold orebodies. The sulfide-rich orebodies range from disseminated concentrations of sulfide minerals to massive sulfide bodies. The sulfide assemblage comprises (by volume), on average, 74% pyrrhotite, 17% arsenopyrite, 8% pyrite and 1% chalcopyrite. The orebodies have a long axis parallel to the local stretching lineation, with continuity down the plunge of fold axis for at least 4.8 km. The group of rocks hosting the Morro Velho gold mineralization is locally referred to as lapa seca. These were isoclinally folded and metamorphosed prior to gold mineralization. The lapa seca and the orebodies it hosts are distributed in five main tight folds related to F1 (the best examples are the X, Main and South orebodies, in level 25), which are disrupted by NE- to E-striking shear zones. Textural features indicate that the sulfide mineralization postdated regional peak metamorphism, and that the massive sulfide ore has subsequently been neither metamorphosed nor deformed. Lead isotope ratios indicate a model age of 2.82 ± 0.05 Ga for both sulfide and gold mineralization. The lapa seca are interpreted as the results of a pre-gold alteration process and may be divided into carbonatic, micaceous and quartzose types. The carbonatic lapa seca is subdivided into gray and brown subtypes. Non-mineralized, gray carbonatic lapa seca forms the hanging wall to the orebodies, and is interpreted as the product of extreme CO2 metasomatism during hydrothermal alteration. This dolomitic lapa seca ranges in composition from relatively pure limestone and dolomite to silty limestone and dolomite. The brown carbonatic and micaceous lapa secas are the host rocks to gold. These units are interpreted to correspond to the sheared and hydrothermal products of metamorphosed volcaniclastic and/or volcanic rocks of varying composition from dacitic to andesitic, forming various types of schists and phyllites. The high-grade, massive sulfide orebodies occur at the base of the gray carbonatic lapa seca. Both disseminated mineralization and quartz veins are hosted by micaceous lapa seca. The data are consistent with a model of epigenetic mineralization for the lapa seca, from a hydrothermal fluid derived in part from the Archean basement or older crust material.

V-doped SnS2: a new intermediate band material for a better use of the solar spectrum.

PubMed

Wahnón, Perla; Conesa, José C; Palacios, Pablo; Lucena, Raquel; Aguilera, Irene; Seminovski, Yohanna; Fresno, Fernando

2011-12-07

Intermediate band materials can boost photovoltaic efficiency through an increase in photocurrent without photovoltage degradation thanks to the use of two sub-bandgap photons to achieve a full electronic transition from the valence band to the conduction band of a semiconductor structure. After having reported in previous works several transition metal-substituted semiconductors as able to achieve the electronic structure needed for this scheme, we propose at present carrying out this substitution in sulfides that have bandgaps of around 2.0 eV and containing octahedrally coordinated cations such as In or Sn. Specifically, the electronic structure of layered SnS(2) with Sn partially substituted by vanadium is examined here with first principles quantum methods and seen to give favourable characteristics in this respect. The synthesis of this material in nanocrystalline powder form is then undertaken and achieved using solvothermal chemical methods. The insertion of vanadium in SnS(2) is found to produce an absorption spectrum in the UV-Vis-NIR range that displays a new sub-bandgap feature in agreement with the quantum calculations. A photocatalytic reaction-based test verifies that this sub-bandgap absorption produces highly mobile electrons and holes in the material that may be used for the solar energy conversion, giving experimental support to the quantum calculations predictions.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

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

2006-05-02

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

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

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

2003-01-01

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

Numerical characteristics of quantum computer simulation

NASA Astrophysics Data System (ADS)

Chernyavskiy, A.; Khamitov, K.; Teplov, A.; Voevodin, V.; Voevodin, Vl.

2016-12-01

The simulation of quantum circuits is significantly important for the implementation of quantum information technologies. The main difficulty of such modeling is the exponential growth of dimensionality, thus the usage of modern high-performance parallel computations is relevant. As it is well known, arbitrary quantum computation in circuit model can be done by only single- and two-qubit gates, and we analyze the computational structure and properties of the simulation of such gates. We investigate the fact that the unique properties of quantum nature lead to the computational properties of the considered algorithms: the quantum parallelism make the simulation of quantum gates highly parallel, and on the other hand, quantum entanglement leads to the problem of computational locality during simulation. We use the methodology of the AlgoWiki project (algowiki-project.org) to analyze the algorithm. This methodology consists of theoretical (sequential and parallel complexity, macro structure, and visual informational graph) and experimental (locality and memory access, scalability and more specific dynamic characteristics) parts. Experimental part was made by using the petascale Lomonosov supercomputer (Moscow State University, Russia). We show that the simulation of quantum gates is a good base for the research and testing of the development methods for data intense parallel software, and considered methodology of the analysis can be successfully used for the improvement of the algorithms in quantum information science.

Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

PubMed

Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

2007-04-01

The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

Synthesis and characterization of ZnO/ZnSe NWs/PbS QDs solar cell

NASA Astrophysics Data System (ADS)

Kamruzzaman, M.; Zapien, J. A.

2017-04-01

The capture of solar energy has gained the attention for the next generation solar cell. ZnO/ZnSe NW arrays were synthesized on an FTO glass substrate using a simple and facile hydrothermal and ion-exchange approaches. The lead sulfide (PbS) QDs was infiltrated into ZnO/ZnSe NWs via SILAR method for making inorganic quantum dot sensitized ZnO/ZnSe/PbS QDs solar cell. The surface morphology, structural, optical, and J-V characteristics have been investigated. The ZnO/ZnSe NW is a core-shell like structure, and the absorption edge shifted from the UV region (ZnO NWs) to the near infrared region for ZnO/ZnSe NWs/PbS QDs. For PbS QDs-sensitized solar cell, the obtained value of η = 1.1%, J sc = 20.60 mA/cm2, V oc = 155 mV, and FF = 34.7%, respectively. The photovoltaic performance of the device in this study is still inferior. However, it is the first report regarding to ZnO/ZnZe NWs/PbS QDs solar cell. The achieving high absorption and large short circuit current density may interest in further improvement of the device performance by suppressing surface defects, optimizing the quality of ZnO/ZnSe NWs and PbS QDs.

A programmable quantum current standard from the Josephson and the quantum Hall effects

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

Poirier, W., E-mail: wilfrid.poirier@lne.fr; Lafont, F.; Djordjevic, S.

We propose a way to realize a programmable quantum current standard (PQCS) from the Josephson voltage standard and the quantum Hall resistance standard (QHR) exploiting the multiple connection technique provided by the quantum Hall effect (QHE) and the exactness of the cryogenic current comparator. The PQCS could lead to breakthroughs in electrical metrology like the realization of a programmable quantum current source, a quantum ampere-meter, and a simplified closure of the quantum metrological triangle. Moreover, very accurate universality tests of the QHE could be performed by comparing PQCS based on different QHRs.

Ecological succession leads to chemosynthesis in mats colonizing wood in sea water.

PubMed

Kalenitchenko, Dimitri; Dupraz, Marlène; Le Bris, Nadine; Petetin, Carole; Rose, Christophe; West, Nyree J; Galand, Pierre E

2016-09-01

Chemosynthetic mats involved in cycling sulfur compounds are often found in hydrothermal vents, cold seeps and whale falls. However, there are only few records of wood fall mats, even though the presence of hydrogen sulfide at the wood surface should create a perfect niche for sulfide-oxidizing bacteria. Here we report the growth of microbial mats on wood incubated under conditions that simulate the Mediterranean deep-sea temperature and darkness. We used amplicon and metagenomic sequencing combined with fluorescence in situ hybridization to test whether a microbial succession occurs during mat formation and whether the wood fall mats present chemosynthetic features. We show that the wood surface was first colonized by sulfide-oxidizing bacteria belonging to the Arcobacter genus after only 30 days of immersion. Subsequently, the number of sulfate reducers increased and the dominant Arcobacter phylotype changed. The ecological succession was reflected by a change in the metabolic potential of the community from chemolithoheterotrophs to potential chemolithoautotrophs. Our work provides clear evidence for the chemosynthetic nature of wood fall ecosystems and demonstrates the utility to develop experimental incubation in the laboratory to study deep-sea chemosynthetic mats.

Microbial community analysis in the autotrophic denitrification process using spent sulfidic caustic by denaturing gradient gel electrophoresis of PCR-amplified genes.

PubMed

Lee, J-H; Lee, S-M; Choi, G-C; Park, H-S; Kang, D-H; Park, J-J

2011-01-01

Spent sulfidic caustic (SSC) produced from petrochemical plants contains a high concentration of hydrogen sulfide and alkalinity, and some almost non-biodegradable organic compounds such as benzene, toluene, ethylbenzene and xylenes (BTEX). SSC is mainly incinerated with auxiliary fuel, leading to secondary pollution problems. The reuse of this waste is becoming increasingly important from economic and environmental viewpoints. To denitrify wastewater with low COD/N ratio, additional carbon sources are required. Thus, autotrophic denitrification has attracted increasing attention. In this study, SSC was injected as an electron donor for sulfur-based autotrophic denitrification in the modified Ludzack-Ettinger (MLE) process. The efficiencies of nitrification, COD, and total nitrogen (TN) removal were evaluated with varying SSC dosage. Adequate SSC injection exhibited stable autotrophic denitrification. No BTEX were detected in the monitored BTEX concentrations of the effluent. To analyse the microbial community of the MLE process, PCR-DGGE based on 16 S rDNA with EUB primers, TD primers and nirK gene with nirK primers was performed in order to elucidate the application of the MLE process to SSC.

Tailored Organic Electrode Material Compatible with Sulfide Electrolyte for Stable All-Solid-State Sodium Batteries.

PubMed

Chi, Xiaowei; Liang, Yanliang; Hao, Fang; Zhang, Ye; Whiteley, Justin; Dong, Hui; Hu, Pu; Lee, Sehee; Yao, Yan

2018-03-01

All-solid-state sodium batteries (ASSSBs) with nonflammable electrolytes and ubiquitous sodium resource are a promising solution to the safety and cost concerns for lithium-ion batteries. However, the intrinsic mismatch between low anodic decomposition potential of superionic sulfide electrolytes and high operating potentials of sodium-ion cathodes leads to a volatile cathode-electrolyte interface and undesirable cell performance. Here we report a high-capacity organic cathode, Na 4 C 6 O 6 , that is chemically and electrochemically compatible with sulfide electrolytes. A bulk-type ASSSB shows high specific capacity (184 mAh g -1 ) and one of the highest specific energies (395 Wh kg -1 ) among intercalation compound-based ASSSBs. The capacity retentions of 76 % after 100 cycles at 0.1 C and 70 % after 400 cycles at 0.2 C represent the record stability for ASSSBs. Additionally, Na 4 C 6 O 6 functions as a capable anode material, enabling a symmetric all-organic ASSSB with Na 4 C 6 O 6 as both cathode and anode materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of Aeolian Dry Deposition of Reactive Iron Minerals on Sulfur Cycling in Sediments of the Gulf of Aqaba

PubMed Central

Blonder, Barak; Boyko, Valeria; Turchyn, Alexandra V.; Antler, Gilad; Sinichkin, Uriel; Knossow, Nadav; Klein, Rotem; Kamyshny, Alexey

2017-01-01

The Gulf of Aqaba is an oligotrophic marine system with oxygen-rich water column and organic carbon-poor sediments (≤0.6% at sites that are not influenced by anthropogenic impact). Aeolian dust deposition from the Arabian, Sinai, and Sahara Deserts is an important source of sediment, especially at the deep-water sites of the Gulf, which are less affected by sediment transport from the Arava Desert during seasonal flash floods. Microbial sulfate reduction in sediments is inferred from the presence of pyrite (although at relatively low concentrations), the presence of sulfide oxidation intermediates, and by the sulfur isotopic composition of sulfate and solid-phase sulfides. Saharan dust is characterized by high amounts of iron minerals such as hematite and goethite. We demonstrated, that the resulting high sedimentary content of reactive iron(III) (hydr)oxides, originating from this aeolian dry deposition of desert dust, leads to fast re-oxidation of hydrogen sulfide produced during microbial sulfate reduction and limits preservation of reduced sulfur in the form of pyrite. We conclude that at these sites the sedimentary sulfur cycle may be defined as cryptic. PMID:28676799

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

PubMed Central

Lüthy, Lucas; Fritz, Markus; Bachofen, Reinhard

2000-01-01

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

Combined plasma gas-phase synthesis and colloidal processing of InP/ZnS core/shell nanocrystals.

PubMed

Gresback, Ryan; Hue, Ryan; Gladfelter, Wayne L; Kortshagen, Uwe R

2011-01-12

Indium phosphide nanocrystals (InP NCs) with diameters ranging from 2 to 5 nm were synthesized with a scalable, flow-through, nonthermal plasma process at a rate ranging from 10 to 40 mg/h. The NC size is controlled through the plasma operating parameters, with the residence time of the gas in the plasma region strongly influencing the NC size. The NC size distribution is narrow with the standard deviation being less than 20% of the mean NC size. Zinc sulfide (ZnS) shells were grown around the plasma-synthesized InP NCs in a liquid phase reaction. Photoluminescence with quantum yields as high as 15% were observed for the InP/ZnS core-shell NCs.

Combined plasma gas-phase synthesis and colloidal processing of InP/ZnS core/shell nanocrystals

PubMed Central

2011-01-01

Indium phosphide nanocrystals (InP NCs) with diameters ranging from 2 to 5 nm were synthesized with a scalable, flow-through, nonthermal plasma process at a rate ranging from 10 to 40 mg/h. The NC size is controlled through the plasma operating parameters, with the residence time of the gas in the plasma region strongly influencing the NC size. The NC size distribution is narrow with the standard deviation being less than 20% of the mean NC size. Zinc sulfide (ZnS) shells were grown around the plasma-synthesized InP NCs in a liquid phase reaction. Photoluminescence with quantum yields as high as 15% were observed for the InP/ZnS core-shell NCs. PMID:21711589

Combined plasma gas-phase synthesis and colloidal processing of InP/ZnS core/shell nanocrystals

NASA Astrophysics Data System (ADS)

Gresback, Ryan; Hue, Ryan; Gladfelter, Wayne L.; Kortshagen, Uwe R.

2011-12-01

Indium phosphide nanocrystals (InP NCs) with diameters ranging from 2 to 5 nm were synthesized with a scalable, flow-through, nonthermal plasma process at a rate ranging from 10 to 40 mg/h. The NC size is controlled through the plasma operating parameters, with the residence time of the gas in the plasma region strongly influencing the NC size. The NC size distribution is narrow with the standard deviation being less than 20% of the mean NC size. Zinc sulfide (ZnS) shells were grown around the plasma-synthesized InP NCs in a liquid phase reaction. Photoluminescence with quantum yields as high as 15% were observed for the InP/ZnS core-shell NCs.

KINETICS OF Mn-BASED SORBENTS FOR HOT COAL GAS DESULFURIZATION

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

J.J. BERNS; K.A. SADECKI; M.T. HEPWORTH

1997-09-15

Mixed manganese oxide sorbents have been investigated for high-temperature removal of hydrogen sulfide (the primary sulfur bearing compound) from hot coal gases. The sorbents were screened by thermodynamic equilibrium considerations for sulfidation. Preliminary experimental work using thermogravimetric analysis (TGA) indicated titania to be a superior substrate than alumina. Four formulations showing superior reactivity in a TGA were then tested in an ambient pressure fixed-bed reactor to determine steady state H 2 S concentrations, breakthrough times and effectiveness of the sorbent when subjected to cyclic sulfidation and regeneration testing. Eight tests were conducted with each test consisting of five cycles ofmore » sulfidation and regeneration. Sulfidation occurred at 600 o C using a simulated coal gas at an empty-bed space velocity of approximately 12,000 per hour. Manganese-based sorbents with molar ratios > 1:1 Mn:Substrate were effective in reducing the H 2 S concentration in simulated coal gases to less than 100 ppmv over five cycles. Actual breakthrough time for formulation C6-2-1100 was as high as 73% of breakthrough time based on wt% Mn in sorbent at 600 o C. Regeneration tests determined that loaded pellets can be essentially completely regenerated in an air/steam mixture at 750 o C with minimal sulfate formation. The leading formulation (designated C6-2) from the fixed-bed tests was then further tested under varying sorbent induration temperature, sulfidation temperature and superficial gas velocity. Four tests were conducted with each test consisting of four cycles of sulfidation and regeneration. Results showed that the induration temperature of the sorbent and the reaction temperature greatly affected the H 2 S removal capacity of the sorbent while the superficial gas velocity between 1090 and 1635 cm/min had minimal affect on the sorbent's breakthrough capacity. Testing showed that the sorbent's strength was a strong function of the sorbent induration temperature. Sorbent also showed 30 to 53% loss of its strength over four cycles of sulfidation and regeneration. The former being sorbent indurated at 1115 o C and the prior being sorbent indurated at 1100 o C. A mathematical model was developed to describe the reaction of H 2 S with the mixed metal oxide in a fixed-bed reactor, where the individual pellets react according to the shrinking core model. The effective diffusivity within a single pellet was estimated by adjusting its value until a good match between the experimental and model H 2 S breakthrough curves was obtained. Predicted sorbent conversion at the conclusion of test FB3A compared well with experimental sulfur analysis.« less

Dehydrogenase activity and quality of leachates in Technosols with gossan and sulfide materials from the São Domingos mine

NASA Astrophysics Data System (ADS)

Santos, Erika; Abreu, Manuela; Macías, Felipe; de Varennes, Amarílis

2014-05-01

Wastes produced by mining activity in São Domingos (Portuguese Iberian Pyrite Belt) were disposed over a large area. To speed up the ecological rehabilitation in this mine, an integrative strategy using different amendments+mine wastes was used to produce Technosols with enhanced soil functions. To evaluate the efficiency of these Technosols the dehydrogenase activity and chemical quality of leachates were monitored. Technosols were composed of different mine wastes (gossan and sulfide materials), collected at the São Domingos mine, and mixtures of amendments applied at 30 and 75 Mg/ha (rockwool+agriculture wastes+wastes from liquors distillation of strawberry tree fruits (Arbutus unedo L.) and/or carobs (Ceratonia siliqua L. fruits)). Three assays, under controlled conditions, were carried out: (1 and 2) Sulfide or gossan materials with/without amendments; (3) Sulfide wastes, with/without amendments, incubated during four months and then with application of an overlayer of gossan (~3 cm thick) with/without the same amendments. Dehydrogenase activity (DHA) and chemical characteristics of leachates (multielemental concentration, pH, and electric conductivity) were determined after four/seven/thirteen months of incubation. Sulfide wastes had more hazardous characteristics (pH~2 and total concentrations (g/kg) of Al (58.1), As (1.1), Cu (2.1), Fe (107.3), Pb (11.7), S (65.3) and Zn (1.1) than the gossan materials (pH=4.3; g/kg, Al: 24.8, As: 3.0, Cu: 0.2, Fe: 129, Pb: 9.2, S: 13.7, Zn: 0.04). Amendments application to gossan (assay 2) enhanced DHA in both sampling periods (µg TPF g dry weight 16 h-1, Control: 0,72-1,78; Amended treatments: 2.49-16.36 depending on mixture/application rate/sampling period). Greater application rates stimulated DHA (more than 1.5-fold with 75 Mg/ha). No differences were observed in DHA in the gossan layer with/without amendments (assay 3) suggesting a negative impact on gossan microrganisms from sulfide materials located below. In fact, for sulfide materials (assays 1 and 3), the amendments did not lead to increases in DHA (µg TPF g dry weight 16 h-1, Control: 0.87-2.72; Amended treatments: 0.23-2.11, depending on assay/sampling period/treatment). In assay 3, the DHA of each mine waste presented, in general, smaller enzymatic activity compared to the same treatments from the other assays. The amendments reduced the electrical condutivity (35-60 %) in the leachates from Technosols with sulfide materials but the pH of leachates increased in all cases between 0.5 and 1.5 units, depending on assay/treatment/sampling period.

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

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

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

Nonlocality, no-signalling, and Bellʼs theorem investigated by Weyl conformal differential geometry

NASA Astrophysics Data System (ADS)

De Martini, Francesco; Santamato, Enrico

2014-12-01

The principles and methods of conformal quantum geometrodynamics based on Weyl differential geometry are presented. The theory applied to the case of the relativistic single quantum spin-\\frac{1}{2} leads to a novel and unconventional derivation of the Dirac equation. The further extension of the theory to the case of two-spins-\\frac{1}{2} in the EPR entangled state and to the related violation of Bell inequalities leads, by an exact non-relativistic analysis, to an insightful resolution of all paradoxes implied by quantum nonlocality.

A path model for Whittaker vectors

NASA Astrophysics Data System (ADS)

Di Francesco, Philippe; Kedem, Rinat; Turmunkh, Bolor

2017-06-01

In this paper we construct weighted path models to compute Whittaker vectors in the completion of Verma modules, as well as Whittaker functions of fundamental type, for all finite-dimensional simple Lie algebras, affine Lie algebras, and the quantum algebra U_q(slr+1) . This leads to series expressions for the Whittaker functions. We show how this construction leads directly to the quantum Toda equations satisfied by these functions, and to the q-difference equations in the quantum case. We investigate the critical limit of affine Whittaker functions computed in this way.

Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

PubMed Central

Hasler-Sheetal, Harald; Holmer, Marianne

2015-01-01

Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments. PMID:26030258

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

PubMed

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-10-23

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Exciton shelves for charge and energy transport in third-generation quantum-dot devices

NASA Astrophysics Data System (ADS)

Goodman, Samuel; Singh, Vivek; Noh, Hyunwoo; Casamada, Josep; Chatterjee, Anushree; Cha, Jennifer; Nagpal, Prashant

2014-03-01

Quantum dots are semiconductor nanocrystallites with size-dependent quantum-confined energy levels. While they have been intensively investigated to utilize hot-carriers for photovoltaic applications, to bridge the mismatch between incident solar photons and finite bandgap of semiconductor photocells, efficient charge or exciton transport in quantum-dot films has proven challenging. Here we show development of new coupled conjugated molecular wires with ``exciton shelves'', or different energy levels, matched with the multiple energy levels of quantum dots. Using single nanoparticle and ensemble device measurements we show successful extraction and transport of both bandedge and high-energy charge carriers, and energy transport of excitons. We demonstrate using measurements of electronic density of states, that careful matching of energy states of quantum-dot with molecular wires is important, and any mismatch can generate midgap states leading to charge recombination and reduced efficiency. Therefore, these exciton-shelves and quantum dots can lead to development of next-generation photovoltaic and photodetection devices using simultaneous transport of bandedge and hot-carriers or energy transport of excitons in these nanostructured solution-processed films.

Catalyzed Preparation of Amorphous Chalcogenides

DTIC Science & Technology

1998-01-30

hydrogen sulfide through lanthanum isopropoxide in dry benzene, as the solvent. The powder obtained was heat-treated in hydrogen sulfide finally 15...producing single-phase crystalline lanthanum sulfide (La2S3) . Amorphous particles were also prepared by reacting titanium tetrapropoxide [Ti...OC3H7)4] and hydrogen sulfide. Resulting powder was heat-treated in flowing hydrogen sulfide to produce crystalline titanium sulfide (TiS2) . 20

As, Bi, Hg, S, Sb, Sn and Te geochemistry of the J-M Reef, Stillwater Complex, Montana: constraints on the origin of PGE-enriched sulfides in layered intrusions

USGS Publications Warehouse

Zientek, M.L.; Fries, T.L.; Vian, R.W.

1990-01-01

The J-M Reef is an interval of disseminated sulfides in the Lower Banded series of the Stillwater Complex that is enriched in the platinum group elements (PGE). Palladium and Pt occur in solid solution in base-metal sulfides and as discrete PGE minerals. PGE minerals include sulfides, tellurides, arsenides, antimonides, bismuthides, and alloys with Fe, Sn, Hg, and Au. Several subpopulations can be delineated based on whole-rock chemical analyses for As, Bi, Cu, Hg, Pd, Pt, S, Sb and Te for samples collected from and adjacent to the J-M Reef. In general, samples from within the reef have higher Pt/Cu, Pd/Cu, Pd/Pt, Te/Bi and S/(Te+Bi) than those collected adjacent to the reef. Vertical compositional profiles through the reef suggest that Pd/Cu and Pt/Cu decrease systematically upsection from mineralized to barren rock. The majority of samples with elevated As, Sb and Hg occur adjacent to the reef, not within it, or in sulfide-poor rocks. Neither magma mixing nor fluid migration models readily explain why the minor quantities of sulfide minerals immediately adjacent to the sulfide-enriched layers that form the J-M Reef have different element ratios than the sulfide minerals that form the reef. If all the sulfides formed by exsolution during a magma mixing event and the modal proportion of sulfide now in the rocks are simply the result of mechanical processes that concentrated the sulfides into some layers and not others, then the composition of the sulfide would not be expected to be different. Models that rely upon ascending liquids or fluids are incompatible with the presence of sulfides that are not enriched in PGE immediately below or interlayered with the PGE-enriched sulfides layers. PGE-enriched postcumulus fluids should have reacted to the same extent with sulfides immediately outside the reef as within the reef. One explanation is that some of the sulfide minerals in the rocks outside the reef have a different origin than those that make up the reef. The sulfide minerals that form the reef may represent a cumulus sulfide phase that formed as the result of a magma-mixing event, achieved its high PGE contents at that time, and accumulated to form a layer. The rocks outside the reef may contain a large proportion of postcumulus sulfide minerals that formed as the last dregs of intercumulus liquids trapped in the interstitial spaces between the cumulus grains reached sulfur saturation and exsolved a sulfide liquid or precipitated a sulfide mineral. The PGE contents of these sulfides would be expected to be less than the cumulus sulfides that form the reef since they would have equilibrated with a much smaller volume of silicate liquid. Another explanation is that some of the sulfide droplets that formed as a result of the mixing event were trapped as inclusions in silicate minerals soon after they formed. This would reduce the amount of magma these sulfide droplets could equilibrate with and effectively reduce their PGE tenor. ?? 1990.

In search of superluminal quantum communications: recent experiments and possible improvements

NASA Astrophysics Data System (ADS)

Cocciaro, B.; Faetti, S.; Fronzoni, L.

2013-06-01

As shown in the famous EPR paper (Einstein, Podolsky e Rosen, 1935), Quantum Mechanics is non-local. The Bell theorem and the experiments by Aspect and many others, ruled out the possibility of explaining quantum correlations between entangled particles using local hidden variables models (except for implausible combinations of loopholes). Some authors (Bell, Eberhard, Bohm and Hiley) suggested that quantum correlations could be due to superluminal communications (tachyons) that propagate isotropically with velocity vt > c in a preferred reference frame. For finite values of vt, Quantum Mechanics and superluminal models lead to different predictions. Some years ago a Geneva group and our group did experiments on entangled photons to evidence possible discrepancies between experimental results and quantum predictions. Since no discrepancy was found, these experiments established only lower bounds for the possible tachyon velocities vt. Here we propose an improved experiment that should lead us to explore a much larger range of possible tachyon velocities Vt for any possible direction of velocity vec V of the tachyons preferred frame.

Quantum localization for a kicked rotor with accelerator mode islands.

PubMed

Iomin, A; Fishman, S; Zaslavsky, G M

2002-03-01

Dynamical localization of classical superdiffusion for the quantum kicked rotor is studied in the semiclassical limit. Both classical and quantum dynamics of the system become more complicated under the conditions of mixed phase space with accelerator mode islands. Recently, long time quantum flights due to the accelerator mode islands have been found. By exploration of their dynamics, it is shown here that the classical-quantum duality of the flights leads to their localization. The classical mechanism of superdiffusion is due to accelerator mode dynamics, while quantum tunneling suppresses the superdiffusion and leads to localization of the wave function. Coupling of the regular type dynamics inside the accelerator mode island structures to dynamics in the chaotic sea proves increasing the localization length. A numerical procedure and an analytical method are developed to obtain an estimate of the localization length which, as it is shown, has exponentially large scaling with the dimensionless Planck's constant (tilde)h<1 in the semiclassical limit. Conditions for the validity of the developed method are specified.

Effect of a low-temperature-grown GaAs layer on InAs quantum-dot photoluminescence

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

Kosarev, A. N.; Chaldyshev, V. V., E-mail: chald.gvg@mail.ioffe.ru; Preobrazhenskii, V. V.

2016-11-15

The photoluminescence of InAs semiconductor quantum dots overgrown by GaAs in the low-temperature mode (LT-GaAs) using various spacer layers or without them is studied. Spacer layers are thin GaAs or AlAs layers grown at temperatures normal for molecular-beam epitaxy (MBE). Direct overgrowth leads to photoluminescence disappearance. When using a thin GaAs spacer layer, the photoluminescence from InAs quantum dots is partially recovered; however, its intensity appears lower by two orders of magnitude than in the reference sample in which the quantum-dot array is overgrown at normal temperature. The use of wider-gap AlAs as a spacer-layer material leads to the enhancementmore » of photoluminescence from InAs quantum dots, but it is still more than ten times lower than that of reference-sample emission. A model taking into account carrier generation by light, diffusion and tunneling from quantum dots to the LT-GaAs layer is constructed.« less

Quantum corrections to Bekenstein-Hawking black hole entropy and gravity partition functions

NASA Astrophysics Data System (ADS)

Bytsenko, A. A.; Tureanu, A.

2013-08-01

Algebraic aspects of the computation of partition functions for quantum gravity and black holes in AdS3 are discussed. We compute the sub-leading quantum corrections to the Bekenstein-Hawking entropy. It is shown that the quantum corrections to the classical result can be included systematically by making use of the comparison with conformal field theory partition functions, via the AdS3/CFT2 correspondence. This leads to a better understanding of the role of modular and spectral functions, from the point of view of the representation theory of infinite-dimensional Lie algebras. Besides, the sum of known quantum contributions to the partition function can be presented in a closed form, involving the Patterson-Selberg spectral function. These contributions can be reproduced in a holomorphically factorized theory whose partition functions are associated with the formal characters of the Virasoro modules. We propose a spectral function formulation for quantum corrections to the elliptic genus from supergravity states.

Locally adapted fish populations maintain small-scale genetic differentiation despite perturbation by a catastrophic flood event

PubMed Central

2010-01-01

Background Local adaptation to divergent environmental conditions can promote population genetic differentiation even in the absence of geographic barriers and hence, lead to speciation. Perturbations by catastrophic events, however, can distort such parapatric ecological speciation processes. Here, we asked whether an exceptionally strong flood led to homogenization of gene pools among locally adapted populations of the Atlantic molly (Poecilia mexicana, Poeciliidae) in the Cueva del Azufre system in southern Mexico, where two strong environmental selection factors (darkness within caves and/or presence of toxic H2S in sulfidic springs) drive the diversification of P. mexicana. Nine nuclear microsatellites as well as heritable female life history traits (both as a proxy for quantitative genetics and for trait divergence) were used as markers to compare genetic differentiation, genetic diversity, and especially population mixing (immigration and emigration) before and after the flood. Results Habitat type (i.e., non-sulfidic surface, sulfidic surface, or sulfidic cave), but not geographic distance was the major predictor of genetic differentiation. Before and after the flood, each habitat type harbored a genetically distinct population. Only a weak signal of individual dislocation among ecologically divergent habitat types was uncovered (with the exception of slightly increased dislocation from the Cueva del Azufre into the sulfidic creek, El Azufre). By contrast, several lines of evidence are indicative of increased flood-induced dislocation within the same habitat type, e.g., between different cave chambers of the Cueva del Azufre. Conclusions The virtual absence of individual dislocation among ecologically different habitat types indicates strong natural selection against migrants. Thus, our current study exemplifies that ecological speciation in this and other systems, in which extreme environmental factors drive speciation, may be little affected by temporary perturbations, as adaptations to physico-chemical stressors may directly affect the survival probability in divergent habitat types. PMID:20731863

Locally adapted fish populations maintain small-scale genetic differentiation despite perturbation by a catastrophic flood event.

PubMed

Plath, Martin; Hermann, Bernd; Schröder, Christiane; Riesch, Rüdiger; Tobler, Michael; García de León, Francisco J; Schlupp, Ingo; Tiedemann, Ralph

2010-08-23

Local adaptation to divergent environmental conditions can promote population genetic differentiation even in the absence of geographic barriers and hence, lead to speciation. Perturbations by catastrophic events, however, can distort such parapatric ecological speciation processes. Here, we asked whether an exceptionally strong flood led to homogenization of gene pools among locally adapted populations of the Atlantic molly (Poecilia mexicana, Poeciliidae) in the Cueva del Azufre system in southern Mexico, where two strong environmental selection factors (darkness within caves and/or presence of toxic H2S in sulfidic springs) drive the diversification of P. mexicana. Nine nuclear microsatellites as well as heritable female life history traits (both as a proxy for quantitative genetics and for trait divergence) were used as markers to compare genetic differentiation, genetic diversity, and especially population mixing (immigration and emigration) before and after the flood. Habitat type (i.e., non-sulfidic surface, sulfidic surface, or sulfidic cave), but not geographic distance was the major predictor of genetic differentiation. Before and after the flood, each habitat type harbored a genetically distinct population. Only a weak signal of individual dislocation among ecologically divergent habitat types was uncovered (with the exception of slightly increased dislocation from the Cueva del Azufre into the sulfidic creek, El Azufre). By contrast, several lines of evidence are indicative of increased flood-induced dislocation within the same habitat type, e.g., between different cave chambers of the Cueva del Azufre. The virtual absence of individual dislocation among ecologically different habitat types indicates strong natural selection against migrants. Thus, our current study exemplifies that ecological speciation in this and other systems, in which extreme environmental factors drive speciation, may be little affected by temporary perturbations, as adaptations to physico-chemical stressors may directly affect the survival probability in divergent habitat types.

The polar sulfur cycle in the Werenskioldbreen, Spitsbergen: Possible implications for understanding the deposition of sulfate minerals in the North Polar Region of Mars

NASA Astrophysics Data System (ADS)

Szynkiewicz, Anna; Modelska, Magdalena; Buczyński, Sebastian; Borrok, David M.; Merrison, Jonathan P.

2013-04-01

In this study we investigated the polar cycling of sulfur (S) associated with the Werenskioldbreen glacier in Spitsbergen (Svalbard). Sulfide-derived S comprised 0.02-0.42 wt% of the fine-grained fraction of proglacial sediments. These sediments originated from glacial erosion of Precambrian sulfide-rich quartz and carbonate veins. In summer 2008, the δ34S of dissolved SO4 in glacier melt waters (+9‰ to +17‰) was consistent with SO4 generation from oxidation of primary sulfide minerals in the bedrock (+9‰ to +16‰). The calculated monthly SO4 load was ˜6881 kg/month/km2 in the main glacier stream. Subsequent evaporation and freezing of glacial waters lead to precipitation, accumulation, and temporary storage of sulfate salt efflorescences in the proglacial zone. These salts are presumably ephemeral, as they dissolve during annual snow/glacial melt events. Hydrated sulfates such as gypsum are also important constituents of the low-elevation areas around the polar ice cap of Planum Boreum on Mars. The origin of this gypsum on Mars might be better understood by using the investigated polar S cycle in Spitsbergen as a foundation. Assuming a trace sulfide content in the basaltic bedrock on Mars, the weathering of sulfides within the fine, porous texture of the ancient aeolian strata (basal unit) underlying Planum Boreum could have created elevated SO4 fluxes (and gypsum precipitation) during episodic thawing/melting events in the past. Limited water activity and prevailing dry conditions on the surface of Mars are the likely factors that accounted for the larger accumulation and preservation of polar gypsum on the surface and its broad aeolian distribution around Planum Boreum. This suggestion is also supported by an experiment showing that gypsum sand can be transported, under dry conditions, over great distances (˜2000 km) without a significant loss of mass.

Volcanic sulfur degassing and the role of sulfides in controlling volcanic metal emissions

NASA Astrophysics Data System (ADS)

Edmonds, M.; Liu, E.

2017-12-01

Volcanoes emit prodigious quantities of sulfur and metals, their behaviour inextricably linked through pre-eruptive sulfide systematics and through degassing and speciation in the volcanic plume. Fundamental differences exist in the metal output of ocean island versus arc volcanoes, with volcanoes in Hawaii and Iceland outgassing large fluxes of gaseous and particulate chalcophiles; and arc volcanoes' plumes, in contrast, enriched in Zn, Cu, Tl and Pb. Metals and metalloids partition into a magmatic vapor phase from silicate melt at crustal pressures. Their abundance in magmatic vapor is influenced strongly by sulfide saturation and by the composition of the magmatic vapor phase, particularly with respect to chloride. These factors are highly dependent on tectonic setting. Metal outgassing is controlled by magma water content and redox: deep saturation in vapor and minimal sulfide in arc basalts yields metal-rich vapor; shallow degassing and resorption of sulfides feeds the metal content of volcanic gas in ocean islands. We present a detailed study of the sulfide systematics of the products of the 2014-2015 Holuhraun basaltic fissure eruption (Bárðarbunga volcanic system, Iceland) to illustrate the interplay between late water and sulfur outgassing; sulfide saturation and breakdown; and metal partitioning into a vapor phase. Sulfide globules, representing quenched droplets of an immiscible sulfide liquid, are preserved within erupted tephra. Sulfide globules in rapidly quenched tephra are preserved within both matrix glass and as inclusions in crystals. The stereologically-corrected 3D size distribution of sulfide globules ranges from <1 µm to 43 µm, with a modal diameter of 14-17 µm (by number). Sulfides are not uniformly distributed, and are commonly observed in association with either sub-millimetre-scale plagioclase-clinopyroxene-olivine glomerocrysts or with bubbles. Maximum dissolved sulfur concentrations of 1750 ppm in melt inclusions and matrix glass next to sulfides are consistent with empirical determinations of the sulfur content at sulfide saturation for MORB. The Holuhraun magma was sulfide-saturated on eruption and co-existed with an immiscible sulfide liquid throughout much of ol-cpx-plag crystallisation. Individual globules are associated with locally elevated dissolved sulfur concentrations, with concentration gradients away from sulfides preserved over distances of 10-40 µm from the melt-sulfide interfaces. We discuss the mechanisms of sulfide breakdown and its importance in supplying sulfur and metals to the atmosphere during eruption.

Enhanced sulfidation xanthate flotation of malachite using ammonium ions as activator.

PubMed

Wu, Dandan; Ma, Wenhui; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

2017-05-18

In this study, ammonium ion was used to enhance the sulfidation flotation of malachite. The effect of ammonium ion on the sulfidation flotation of malachite was investigated using microflotation test, inductively coupled plasma (ICP) analysis, zeta potential measurements, and scanning electron microscope analysis (SEM). The results of microflotation test show that the addition of sodium sulfide and ammonium sulfate resulted in better sulfidation than the addition of sodium sulfide alone. The results of ICP analysis indicate that the dissolution of enhanced sulfurized malachite surface is significantly decreased. Zeta potential measurements indicate that a smaller isoelectric point value and a large number of copper-sulfide films formed on the malachite surface by enhancing sulfidation resulted in a large amount of sodium butyl xanthate absorbed onto the enhanced sulfurized malachite surface. EDS semi-quantitative analysis and XPS analysis show that malachite was easily sulfurized by sodium sulfide with ammonium ion. These results show that the addition of ammonium ion plays a significant role in the sulfidation of malachite and results in improved flotation performance.

Hydrogen sulfide production from cysteine and homocysteine by periodontal and oral bacteria.

PubMed

Yoshida, Akihiro; Yoshimura, Mamiko; Ohara, Naoya; Yoshimura, Shigeru; Nagashima, Shiori; Takehara, Tadamichi; Nakayama, Koji

2009-11-01

Hydrogen sulfide is one of the predominant volatile sulfur compounds (VSCs) produced by oral bacteria. This study developed and evaluated a system for detecting hydrogen sulfide production by oral bacteria. L-methionine-alpha-deamino-gamma-mercaptomethane-lyase (METase) and beta carbon-sulfur (beta C-S) lyase were used to degrade homocysteine and cysteine, respectively, to produce hydrogen sulfide. Enzymatic reactions resulting in hydrogen sulfide production were assayed by reaction with bismuth trichloride, which forms a black precipitate when mixed with hydrogen sulfide. The enzymatic activities of various oral bacteria that result in hydrogen sulfide production and the capacity of bacteria from periodontal sites to form hydrogen sulfide in reaction mixtures containing L-cysteine or DL-homocysteine were assayed. With L-cysteine as the substrate, Streptococcus anginosus FW73 produced the most hydrogen sulfide, whereas Porphyromonas gingivalis American Type Culture Collection (ATCC) 33277 and W83 and Fusobacterium nucleatum ATCC 10953 produced approximately 35% of the amount produced by the P. gingivalis strains. Finally, the hydrogen sulfide found in subgingival plaque was analyzed. Using bismuth trichloride, the hydrogen sulfide produced by oral bacteria was visually detectable as a black precipitate. Hydrogen sulfide production by oral bacteria was easily analyzed using bismuth trichloride. However, further innovation is required for practical use.

From quantum foundations to applications and back.

PubMed

Gisin, Nicolas; Fröwis, Florian

2018-07-13

Quantum non-locality has been an extremely fruitful subject of research, leading the scientific revolution towards quantum information science, in particular, to device-independent quantum information processing. We argue that the time is ripe to work on another basic problem in the foundations of quantum physics, the quantum measurement problem, which should produce good physics in theoretical, mathematical, experimental and applied physics. We briefly review how quantum non-locality contributed to physics (including some outstanding open problems) and suggest ways in which questions around macroscopic quantumness could equally contribute to all aspects of physics.This article is part of a discussion meeting issue 'Foundations of quantum mechanics and their impact on contemporary society'. © 2018 The Author(s).

Enhanced conductive loss in nickel–cobalt sulfide nanostructures for highly efficient microwave absorption and shielding

NASA Astrophysics Data System (ADS)

Li, Wanrong; Zhou, Min; Lu, Fei; Liu, Hongfei; Zhou, Yuxue; Zhu, Jun; Zeng, Xianghua

2018-06-01

Microwave-absorbing materials with light weight and high efficiency are desirable in addressing electromagnetic interference (EMI) problems. Herein, a nickel–cobalt sulfide (NCS) nanostructure was employed as a robust microwave absorber, which displayed an optimized reflection loss of  ‑49.1 dB in the gigahertz range with a loading of only 20 wt% in an NCS/paraffin wax composite. High electrical conductivity was found to contribute prominent conductive loss in NCS, leading to intense dielectric loss within a relatively low mass loading. Furthermore, owing to its high electrical conductivity and remarkable dielectric loss to microwaves, the prepared NCS exhibited excellent performance in EMI shielding. The EMI shielding efficiency of the 50 wt% NCS/paraffin composite exceeded 55 dB at the X-band, demonstrating NCS is a versatile candidate for solving EMI problems.

Lead isotope database of unpublished results from sulfide mineral occurrences-California, Idaho, Oregon, and Washington

USGS Publications Warehouse

Church, S.E.

2010-01-01

The Pb isotope database for sulfide deposits and occurrences in the Western United States was funded by the Mineral Resources Program, U.S. Geological Survey (USGS). Reports on Pb isotope data from Alaska were published in Church and others (1987a) and Gaccetta and Church (1989). The primary objectives of the project were three-fold: * To utilize Pb isotope signatures, in conjunction with the regional mapping, to assess the relative ages and to categorize the types of deposits studied, * To relate the Pb isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and * To use the Pb isotope data to correlate lithotectonic terranes within the northern Cordillera. The report by Church and others (1987b) shows how this fingerprinting methodology can be applied to trace the offset of lithostratigraphic terranes

Photoluminescence spectral study of single cadmium selenide/zinc sulfide colloidal nanocrystals in poly(methyl methacrylate) and quantum dots molecules

NASA Astrophysics Data System (ADS)

Shen, Yaoming

Quantum dots (QDs)and Nano-crystals (NCs) have been studies for decades. Because of the nanoscale quantum confinement, delta shape like energy density states and narrowband emitters properties, they hold great promise for numerous optoelectronics and photonics applications. They could be used for tunable lasers, white LED, Nano-OLED, non-volatile memory and solar cells. They are also the most promising candidates for the quantum computing. The benefits for NCs over QDs is that NCs can be incorporated into a variety of polymers as well as thin films of bulk semiconductors. These exceptional flexibility and structural control distinguish NCs from the more traditional QD structures fabricated using epitaxial growth techniques. In my research of work, I studied the photoluminescence (PL) and absorption character of ensemble NCs incorporated in Polymethyl methacrylate (PMMA). To understand the behavior of the NCs in PMMA, it is important to measure a singe NC to avoid the inhomogenous broading of many NCs. So I particularly studied the behavior of a single NC in PMMA matrix. A microphotoluminescence setup to optically isolate a single nanocrystal is used. Random spectral shift and blinking behavior (on and off) are found. Addition to that, two color spectral shifting, is a major phenomena found in the system. Other interesting results such as PL intensity changes (decreasing or increasing with time) and quenching effect are observed and explained too. From the correlation function, we can distinguish the phonon replicas. The energy of these phonons can be calculated very accurately from the experiment result. The Huang-Rhys factors can be estimated too. Self-assembled semiconductor quantum dots (QDs), from highly strained-layer heteroepitaxy in the Stranski-Krastanow (S-K) growth mode, have been intensively studied because of the delta-function-like density of states, which is significant for optoelectronic applications. Spontaneous formation of semiconductor quantum-dot molecules (QDMs), which are clusters of a few QDs, has attracted attention as a possible implementation of future quantum devices such as quantum cellular antomata. With the advances in crystal growth techniques, the fabrication methods for nanostructures have been improved continuously. Lateral QDMs have been achieved. As a side topic, lateral QDMs have been studied and the result is presented in the last chapter.

BFV approach to geometric quantization

NASA Astrophysics Data System (ADS)

Fradkin, E. S.; Linetsky, V. Ya.

1994-12-01

A gauge-invariant approach to geometric quantization is developed. It yields a complete quantum description for dynamical systems with non-trivial geometry and topology of the phase space. The method is a global version of the gauge-invariant approach to quantization of second-class constraints developed by Batalin, Fradkin and Fradkina (BFF). Physical quantum states and quantum observables are respectively described by covariantly constant sections of the Fock bundle and the bundle of hermitian operators over the phase space with a flat connection defined by the nilpotent BVF-BRST operator. Perturbative calculation of the first non-trivial quantum correction to the Poisson brackets leads to the Chevalley cocycle known in deformation quantization. Consistency conditions lead to a topological quantization condition with metaplectic anomaly.

Quantum group symmetry of the quantum Hall effect on non-flat surfaces

NASA Astrophysics Data System (ADS)

Alimohammadi, M.; Shafei Deh Abad, A.

1996-02-01

After showing that the magnetic translation operators are not the symmetries of the quantum Hall effect (QHE) on non-flat surfaces, we show that another set of operators which leads to the quantum group symmetries for some of these surfaces exists. As a first example we show that the su(2) symmetry of the QHE on a sphere leads to 0305-4470/29/3/010/img6(2) algebra in the equator. We explain this result by a contraction of su(2). Second, with the help of the symmetry operators of QHE on the Poincaré upper half plane, we will show that the ground-state wavefunctions form a representation of the 0305-4470/29/3/010/img6(2) algebra.

Quantum computing and probability.

PubMed

Ferry, David K

2009-11-25

Over the past two decades, quantum computing has become a popular and promising approach to trying to solve computationally difficult problems. Missing in many descriptions of quantum computing is just how probability enters into the process. Here, we discuss some simple examples of how uncertainty and probability enter, and how this and the ideas of quantum computing challenge our interpretations of quantum mechanics. It is found that this uncertainty can lead to intrinsic decoherence, and this raises challenges for error correction.

Testing Nonassociative Quantum Mechanics.

PubMed

Bojowald, Martin; Brahma, Suddhasattwa; Büyükçam, Umut

2015-11-27

The familiar concepts of state vectors and operators in quantum mechanics rely on associative products of observables. However, these notions do not apply to some exotic systems such as magnetic monopoles, which have long been known to lead to nonassociative algebras. Their quantum physics has remained obscure. This Letter presents the first derivation of potentially testable physical results in nonassociative quantum mechanics, based on effective potentials. They imply new effects which cannot be mimicked in usual quantum mechanics with standard magnetic fields.

Material platforms for spin-based photonic quantum technologies

NASA Astrophysics Data System (ADS)

Atatüre, Mete; Englund, Dirk; Vamivakas, Nick; Lee, Sang-Yun; Wrachtrup, Joerg

2018-05-01

A central goal in quantum optics and quantum information science is the development of quantum networks to generate entanglement between distributed quantum memories. Experimental progress relies on the quality and efficiency of the light-matter quantum interface connecting the quantum states of photons to internal states of quantum emitters. Quantum emitters in solids, which have properties resembling those of atoms and ions, offer an opportunity for realizing light-matter quantum interfaces in scalable and compact hardware. These quantum emitters require a material platform that enables stable spin and optical properties, as well as a robust manufacturing of quantum photonic circuits. Because no emitter system is yet perfect and different applications may require different properties, several light-matter quantum interfaces are being developed in various platforms. This Review highlights the progress in three leading material platforms: diamond, silicon carbide and atomically thin semiconductors.

Deducing the distribution of terminal electron-accepting processes in hydrologically diverse groundwater systems

USGS Publications Warehouse

Chapelle, Francis H.; McMahon, Peter B.; Dubrovsky, Neil M.; Fujii, Roger F.; Oaksford, Edward T.; Vroblesky, Don A.

1995-01-01

The distribution of microbially mediated terminal electron-accepting processes (TEAPs( was investigated in four hydrologically diverse groundwater systems by considering patterns of electron acceptor (nitrate, sulfate) consumption, intermediate product (hydrogen (H2)) concentrations, and final product (ferrous iron, sulfide, and methane) production. In each hydrologic system a determination of predominant TEAPs could be arrived at, but the level of confidence appropriate for each determination differed. In a portion of the lacustrine aquifer of the San Joaquin Valley, for example, all three indicators (sulfate concentrations decreasing, H2concentrations in the 1–2 nmol range, and sulfide concentrations increasing along flow paths identified sulfate reduction as the predominant TEAP, leading to a high degree of confidence in the determination. In portions of the Floridan aquifer and a petroleum hydrocarbon-contaminated aquifer, sulfate reduction and methanogenesis are indicated by production of sulfide and methane, and hydrogen oncentrations in the 1–4 nmol and 5–14 nmol range, respectively. However, because electron acceptor consumption could not be documented in these systems, less confidence is warranted in the TEAP determination. In the Black Creek aquifer, no pattern of sulfate consumption and sulfide production were observed, but H2 concentrations indicated sulfate reduction as the predominant TEAP. In this case, where just a single line of evidence is available, the least confidence in the TEAP diagnosis is justified. Because this methodology is based on measurable water chemistry parameters and upon the physiology of microbial electron transfer processes, it provides a better description of predominant redox processes in groundwater systems than more traditional Eh-based methods.

Effect of precursor and preparation method on manganese based activated carbon sorbents for removing H2S from hot coal gas.

PubMed

Wang, Jiancheng; Qiu, Biao; Han, Lina; Feng, Gang; Hu, Yongfeng; Chang, Liping; Bao, Weiren

2012-04-30

Activated carbon (AC) supported manganese oxide sorbents were prepared by the supercritical water impregnation (SCWI) using two different precursor of Mn(NO(3))(2) (SCW(N)) and Mn(Ac)(2)·4H(2)O (SCW(A)). Their capacities of removing H(2)S from coal gas were evaluated and compared to the sorbents prepared by the pore volume impregnation (PVI) method. The structure and composition of different sorbents were characterized by XRD, SEM, TEM, XPS and XANES techniques. It is found that the precursor of active component plays the crucial role and SCW(N) sorbents show much better sulfidation performance than the SCW(A) sorbents. This is because the Mn(3)O(4) active phase of the SCW(N) sorbents are well dispersed on the AC support, while the Mn(2)SiO(4)-like species in the SCW(A) sorbent can be formed and seriously aggregated. The SCW(N) sorbents with 2.80% and 5.60% manganese are favorable for the sulfidation reaction, since the Mn species are better dispersed on the SCW(N) sorbents than those on the PV(N) sorbents and results in the better sulfidation performance of the SCW(N) sorbents. As the Mn content increases to 11.20%, the metal oxide particles on AC supports aggregate seriously, which leads to poorer sulfidation performance of the SCW(N)11.20% sorbents than that of the PV(N)11.20% sorbents. Copyright © 2012 Elsevier B.V. All rights reserved.

An innovative coupling between column leaching and oxygen consumption tests to assess behavior of contaminated marine dredged sediments.

PubMed

Couvidat, Julien; Benzaazoua, Mostafa; Chatain, Vincent; Zhang, Fan; Bouzahzah, Hassan

2015-07-01

Contaminated dredged sediments are often considered hazardous wastes, so they have to be adequately managed to avoid leaching of pollutants. The mobility of inorganic contaminants is a major concern. Metal sulfides (mainly framboïdal pyrite, copper, and zinc sulfides) have been investigated in this study as an important reactive metal-bearing phase sensitive to atmospheric oxygen action. An oxygen consumption test (OC-Test) has been adapted to assess the reactivity of dredged sediments when exposed to atmospheric oxygen. An experimental column set-up has been developed allowing the coupling between leaching and oxygen consumption test to investigate the reactivity of the sediment. This reactivity, which consisted of sulfide oxidation, was found to occur for saturation degree between 60 and 90 % and until the 20th testing week, through significant sulfates releases. These latter were assumed to come from sulfide oxidation in the first step of the test, then probably from gypsum dissolution. Confrontation results of OC-Test and leachate quality shows that Cu was well correlated to sulfates releases, which in turn, leads to Ca and Mg dissolution (buffer effect). Cu, and mostly Zn, was associated to organic matter, phyllosilicates, and other minerals through organo-clay complexes. This research confirmed that the OC-Test, originally developed for mine tailings, could be a useful tool in the dredged sediment field which can allow for intrinsic characterization of reactivity of a material suspected to readily reacting with oxygen and for better understanding of geochemical processes that affect pollutants behavior, conversion, and transfer in the environment.

Hydrogen sulfide ameliorates aging-associated changes in the kidney.

PubMed

Lee, Hak Joo; Feliers, Denis; Barnes, Jeffrey L; Oh, Sae; Choudhury, Goutam Ghosh; Diaz, Vivian; Galvan, Veronica; Strong, Randy; Nelson, James; Salmon, Adam; Kevil, Christopher G; Kasinath, Balakuntalam S

2018-04-01

Aging is associated with replacement of normal kidney parenchyma by fibrosis. Because hydrogen sulfide (H 2 S) ameliorates kidney fibrosis in disease models, we examined its status in the aging kidney. In the first study, we examined kidney cortical H 2 S metabolism and signaling pathways related to synthesis of proteins including matrix proteins in young and old male C57BL/6 mice. In old mice, increase in renal cortical content of matrix protein involved in fibrosis was associated with decreased H 2 S generation and AMPK activity, and activation of insulin receptor (IR)/IRS-2-Akt-mTORC1-mRNA translation signaling axis that can lead to increase in protein synthesis. In the second study, we randomized 18-19 month-old male C57BL/6 mice to receive 30 μmol/L sodium hydrosulfide (NaHS) in drinking water vs. water alone (control) for 5 months. Administration of NaHS increased plasma free sulfide levels. NaHS inhibited the increase in kidney cortical content of matrix proteins involved in fibrosis and ameliorated glomerulosclerosis. NaHS restored AMPK activity and inhibited activation of IR/IRS-2-Akt-mTORC1-mRNA translation axis. NaHS inhibited age-related increase in kidney cortical content of p21, IL-1β, and IL-6, components of the senescence-associated secretory phenotype. NaHS abolished increase in urinary albumin excretion seen in control mice and reduced serum cystatin C levels suggesting improved glomerular clearance function. We conclude that aging-induced changes in the kidney are associated with H 2 S deficiency. Administration of H 2 S ameliorates aging-induced kidney changes probably by inhibiting signaling pathways leading to matrix protein synthesis.

Mechanistic study of the rubber-brass adhesion interphase

NASA Astrophysics Data System (ADS)

Ashirgade, Akshay

Brass-plated steel tire cords form an essential strengthening component of a radial automobile tire. Adhesion between rubber compound and brass-plated steel tire cord is crucial in governing the overall performance of tires. The rubber-brass interfacial adhesion is influenced by the chemical composition and thickness of the interfacial layer. It has been shown that the interfacial layer consists mainly of sulfides and oxides of copper and zinc. This thesis discusses the effect of changes in the chemical composition and the structure of the interfacial layers due to addition of adhesion promoter resins. Grazing incidence X-Ray Diffraction (GIXRD) experiments were run on sulfidized polished brass coupons previously bonded to six experimental rubber compounds. It was confirmed that heat and humidity conditions lead to physical and chemical changes of the rubber-steel tire cord interfacial layer, closely related to the degree of rubber-brass adhesion. Morphological transformation of the interfacial layer led to loss of adhesion after aging. The adhesion promoter resins inhibit unfavorable morphological changes in the interfacial layer thus stabilizing it during aging and prolonging failure. Tire cord adhesion tests illustrated that the one-component resins improved adhesion after aging using a rubber compound with lower cobalt loading. Based on the acquired diffraction profiles, these resins were also found to impede crystallization of the sulfide layer after aging leading to improved adhesion. Secondary Ion Mass Spectrometry (SIMS) depth profiles, SEM micrographs and AFM images strongly corroborated the findings from GIXRD. FTIR was utilized in a novel way to understand the degradation mechanism due to aging. A model for rubber and interfacial layer degradation is proposed to illustrate the effect of aging and the one-component resins. This interfacial analysis adds valuable new information to our understanding of the complex nature of the rubber-brass bonding mechanism.

Diffractive paths for weak localization in quantum billiards

NASA Astrophysics Data System (ADS)

Březinová, Iva; Stampfer, Christoph; Wirtz, Ludger; Rotter, Stefan; Burgdörfer, Joachim

2008-04-01

We study the weak-localization effect in quantum transport through a clean ballistic cavity with regular classical dynamics. We address the question which paths account for the suppression of conductance through a system where disorder and chaos are absent. By exploiting both quantum and semiclassical methods, we unambiguously identify paths that are diffractively backscattered into the cavity (when approaching the lead mouths from the cavity interior) to play a key role. Diffractive scattering couples transmitted and reflected paths and is thus essential to reproduce the weak-localization peak in reflection and the corresponding antipeak in transmission. A comparison of semiclassical calculations featuring these diffractive paths yields good agreement with full quantum calculations and experimental data. Our theory provides system-specific predictions for the quantum regime of few open lead modes and can be expected to be relevant also for mixed as well as chaotic systems.

Precise Control of Quantum Confinement in Cesium Lead Halide Perovskite Quantum Dots via Thermodynamic Equilibrium.

PubMed

Dong, Yitong; Qiao, Tian; Kim, Doyun; Parobek, David; Rossi, Daniel; Son, Dong Hee

2018-05-09

Cesium lead halide (CsPbX 3 ) nanocrystals have emerged as a new family of materials that can outperform the existing semiconductor nanocrystals due to their superb optical and charge-transport properties. However, the lack of a robust method for producing quantum dots with controlled size and high ensemble uniformity has been one of the major obstacles in exploring the useful properties of excitons in zero-dimensional nanostructures of CsPbX 3 . Here, we report a new synthesis approach that enables the precise control of the size based on the equilibrium rather than kinetics, producing CsPbX 3 quantum dots nearly free of heterogeneous broadening in their exciton luminescence. The high level of size control and ensemble uniformity achieved here will open the door to harnessing the benefits of excitons in CsPbX 3 quantum dots for photonic and energy-harvesting applications.

Hot-electron transfer in quantum-dot heterojunction films.

PubMed

Grimaldi, Gianluca; Crisp, Ryan W; Ten Brinck, Stephanie; Zapata, Felipe; van Ouwendorp, Michiko; Renaud, Nicolas; Kirkwood, Nicholas; Evers, Wiel H; Kinge, Sachin; Infante, Ivan; Siebbeles, Laurens D A; Houtepen, Arjan J

2018-06-13

Thermalization losses limit the photon-to-power conversion of solar cells at the high-energy side of the solar spectrum, as electrons quickly lose their energy relaxing to the band edge. Hot-electron transfer could reduce these losses. Here, we demonstrate fast and efficient hot-electron transfer between lead selenide and cadmium selenide quantum dots assembled in a quantum-dot heterojunction solid. In this system, the energy structure of the absorber material and of the electron extracting material can be easily tuned via a variation of quantum-dot size, allowing us to tailor the energetics of the transfer process for device applications. The efficiency of the transfer process increases with excitation energy as a result of the more favorable competition between hot-electron transfer and electron cooling. The experimental picture is supported by time-domain density functional theory calculations, showing that electron density is transferred from lead selenide to cadmium selenide quantum dots on the sub-picosecond timescale.

Cloud Quantum Computing of an Atomic Nucleus

NASA Astrophysics Data System (ADS)

Dumitrescu, E. F.; McCaskey, A. J.; Hagen, G.; Jansen, G. R.; Morris, T. D.; Papenbrock, T.; Pooser, R. C.; Dean, D. J.; Lougovski, P.

2018-05-01

We report a quantum simulation of the deuteron binding energy on quantum processors accessed via cloud servers. We use a Hamiltonian from pionless effective field theory at leading order. We design a low-depth version of the unitary coupled-cluster ansatz, use the variational quantum eigensolver algorithm, and compute the binding energy to within a few percent. Our work is the first step towards scalable nuclear structure computations on a quantum processor via the cloud, and it sheds light on how to map scientific computing applications onto nascent quantum devices.

Cloud Quantum Computing of an Atomic Nucleus

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

Dumitrescu, Eugene F.; McCaskey, Alex J.; Hagen, Gaute

Here, we report a quantum simulation of the deuteron binding energy on quantum processors accessed via cloud servers. We use a Hamiltonian from pionless effective field theory at leading order. We design a low-depth version of the unitary coupled-cluster ansatz, use the variational quantum eigensolver algorithm, and compute the binding energy to within a few percent. Our work is the first step towards scalable nuclear structure computations on a quantum processor via the cloud, and it sheds light on how to map scientific computing applications onto nascent quantum devices.

Cloud Quantum Computing of an Atomic Nucleus.

PubMed

Dumitrescu, E F; McCaskey, A J; Hagen, G; Jansen, G R; Morris, T D; Papenbrock, T; Pooser, R C; Dean, D J; Lougovski, P

2018-05-25

We report a quantum simulation of the deuteron binding energy on quantum processors accessed via cloud servers. We use a Hamiltonian from pionless effective field theory at leading order. We design a low-depth version of the unitary coupled-cluster ansatz, use the variational quantum eigensolver algorithm, and compute the binding energy to within a few percent. Our work is the first step towards scalable nuclear structure computations on a quantum processor via the cloud, and it sheds light on how to map scientific computing applications onto nascent quantum devices.

Cloud Quantum Computing of an Atomic Nucleus

DOE PAGES

Dumitrescu, Eugene F.; McCaskey, Alex J.; Hagen, Gaute; ...

2018-05-23

Here, we report a quantum simulation of the deuteron binding energy on quantum processors accessed via cloud servers. We use a Hamiltonian from pionless effective field theory at leading order. We design a low-depth version of the unitary coupled-cluster ansatz, use the variational quantum eigensolver algorithm, and compute the binding energy to within a few percent. Our work is the first step towards scalable nuclear structure computations on a quantum processor via the cloud, and it sheds light on how to map scientific computing applications onto nascent quantum devices.

The European quantum technologies flagship programme

NASA Astrophysics Data System (ADS)

Riedel, Max F.; Binosi, Daniele; Thew, Rob; Calarco, Tommaso

2017-09-01

Quantum technologies, such as quantum communication, computation, simulation as well as sensors and metrology, address and manipulate individual quantum states and make use of superposition and entanglement. Both companies and governments have realised the high disruptive potential of this technology. Consequently, the European Commission has announced an ambitious flagship programme to start in 2018. Here, we sum up the history leading to the quantum technologies flagship programme and outline its envisioned goals and structure. We also give an overview of the strategic research agenda for quantum communication, which the flagship will pursue during its 10-year runtime.

Polymer Based Molecular Composites. Volume 171. Materials Research Society Symposium Proceedings Held in Boston, Massachusetts on 27-30 November 1989

DTIC Science & Technology

1990-09-01

231 Harry L. Frisch PART V: IONOMERS/STRUCTURE SMALL ANGLE X - RAY SCATTERING ON POLY(ETHYLENE-METHACRYLIC ACID) LEAD AND LEAD SULFIDE IONOMERS 237...E.J. Kramer, R.J. Composto, R.S. Stein, T.P. Russell, G.P. Felcher, A. Mansour, and A. Karim * td:tt Papet Vil X - RAY REFLECTIVITY AND FLUORESCENCE...Sammann DETERMINATION OF PARTICLE SIZE OF A DISPERSED PHASE BY SMALL-ANGLE X - RAY SCATTERING 413 Frank C. Wilson *Invited Paper ix SYNTHESIS AND

Sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1985-01-01

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

Experimental simulations of sulfide formation in the solar nebula.

PubMed

Lauretta, D S; Lodders, K; Fegley, B

1997-07-18

Sulfurization of meteoritic metal in H2S-H2 gas produced three different sulfides: monosulfide solid solution [(Fe,Ni)1-xS], pentlandite [(Fe,Ni)9-xS8], and a phosphorus-rich sulfide. The composition of the remnant metal was unchanged. These results are contrary to theoretical predictions that sulfide formation in the solar nebula produced troilite (FeS) and enriched the remaining metal in nickel. The experimental sulfides are chemically and morphologically similar to sulfide grains in the matrix of the Alais (class CI) carbonaceous chondrite, suggesting that these meteoritic sulfides may be condensates from the solar nebula.

Hydrogen sulfide emission in sewer networks: a two-phase modeling approach to the sulfur cycle.

PubMed

Yongsiri, C; Vollertsen, J; Hvitved-Jacobsen, T

2004-01-01

Wherever transport of anaerobic wastewater occurs, potential problems associated with hydrogen sulfide in relation to odor nuisance, health risk and corrosion exist. Improved understanding of prediction of hydrogen sulfide emission into the sewer atmosphere is needed for better evaluation of such problems in sewer networks. A two-phase model for emission of hydrogen sulfide along stretches of gravity sewers is presented to estimate the occurrence of both sulfide in the water phase and hydrogen sulfide in the sewer atmosphere. The model takes into account air-water mass transfer of hydrogen sulfide and interactions with other processes in the sulfur cycle. Various emission scenarios are simulated to illustrate the release characteristics of hydrogen sulfide.

Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.

2004-01-01

Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

Sulfide intrusion in the tropical seagrasses Thalassia testudinum and Syringodium filiforme

NASA Astrophysics Data System (ADS)

Holmer, Marianne; Pedersen, Ole; Krause-Jensen, Dorte; Olesen, Birgit; Hedegård Petersen, Malene; Schopmeyer, Stephanie; Koch, Marguerite; Lomstein, Bente Aa.; Jensen, Henning S.

2009-11-01

Sulfur and oxygen dynamics in the seagrasses Thalassia testudinum and Syringodium filiforme and their sediments were studied in the US Virgin Islands (USVI) in order to explore sulfide intrusion into tropical seagrasses. Four study sites were selected based on the iron concentration in sediments and on proximity to anthropogenic nutrient sources. Meadow characteristics (shoot density, above- and below-ground biomass, nutrient content) were sampled along with sediment biogeochemistry. Sulfide intrusion was high in T. testudinum, as up to 96% of total sulfur in the plant was derived from sediment-derived sulfides. The sulfide intrusion was negatively correlated to the turnover of sulfides in the sediments regulated by both plant parameters and sediment sulfur pools. Sediment iron content played an indirect role by affecting sulfide turnover rates. Leaf production was negatively correlated with sulfide intrusion suggesting that active growth reduced sulfide intrusion. Sulfide intrusion was lower in S. filiforme (up to 44%) compared to T. testudinum consistent with a higher internal nighttime oxygen concentrations found for S. filiforme. When S. filiforme can take advantage of its ability to maintain high internal oxygen concentrations, as was the case on the USVI, it could increase its success in colonizing unvegetated disturbed sediments with potentially high sulfide concentrations.

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

PubMed Central

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-01-01

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions. PMID:26512669

Nanostructured metal sulfides for energy storage

NASA Astrophysics Data System (ADS)

Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

2014-08-01

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

Simultaneous sulfide removal, nitrification, and electricity generation in a microbial fuel cell equipped with an oxic cathode.

PubMed

Bao, Renbing; Zhang, Shaohui; Zhao, Li; Zhong, Liuxiang

2017-02-01

With sulfide as an anodic electron donor and ammonium as a cathodic substrate, the feasibility of simultaneous sulfide removal, nitrification, and electricity generation was investigated in a microbial fuel cell (MFC) equipped with an oxic cathode. Successful simultaneous sulfide removal, nitrification, and electricity generation in this MFC were achieved in 35 days, with the sulfide and ammonium removal percent of 92.7 ± 1.4 and 96.4 ± 0.3%, respectively. The maximum power density increased, but the internal resistance decreased with the increase of feeding sulfide concentration from 62.9 ± 0.3 to 238.5 ± 0.2 mg S/L. Stable ammonium removal with complete nitrification, preparing for future denitrification, was obtained throughout the current study. Sulfide removal loading significantly increased with the increase of feeding sulfide concentration at each external resistance, but no significant correlation between sulfide removal loading and external resistance was found at each feeding sulfide concentration. The charge recovery and anodic coulombic efficiency (CE) significantly decreased with the increase of external resistance. High feeding sulfide concentration led to low anodic CE. Granular sulfur deposition was found on the anode graphite fiber. The appropriate feeding sulfide concentration for sulfide removal and sulfur deposition was deemed to be 178.0 ± 1.7 mg S/L, achieving a sulfur deposition percent of 69.7 ± 0.6%.

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

NASA Astrophysics Data System (ADS)

Holwell, David A.; Keays, Reid R.; McDonald, Iain; Williams, Megan R.

2015-12-01

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu-PGE-Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190-700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu-Ni-PGE sulfides which require very high R factors, and settling of sulfide liquids.

Formation and Evolution of the Continental Lithospheric Mantle: Perspectives From Radiogenic Isotopes of Silicate and Sulfide Inclusions in Macrodiamonds

NASA Astrophysics Data System (ADS)

Shirey, S. B.; Richardson, S. H.

2007-12-01

Silicate and sulfide inclusions that occur in diamonds comprise the oldest (>3 Ga), deepest (>140 km) samples of mantle-derived minerals available for study. Their relevance to the evolution of the continental lithosphere is clear because terrestrial macrodiamonds are confined to regions of the Earth with continental lithospheric mantle keels. The goals of analytical work on inclusions in diamond are to obtain paragenesis constraints, radiogenic ages, and initial isotopic compositions. The purpose is to place diamond formation episodes into the broader framework of the geological processes that create and modify the continental lithosphere and to relate the source of the C and N in diamond-forming fluids to understanding the Earth's C and N cycles in the Archean. Although sulfide and silicate inclusions rarely occur in the same diamond, they both can be grouped according to their geochemical similarity with the chief rock types that comprise the mantle keel: peridotite and eclogite. Silicate inclusions are classified as harzburgitic (depleted; olivine > Fo91, garnet Cr2O3 > 3 wt% and CaO from 0 to 5 wt%), lherzolitic (fertile), or eclogitic (basaltic; garnet Cr2O3 < 2 wt% and CaO from 3 to 15 wt%, clinopyroxene with higher Na2O, Al2O3, and FeO); they are amenable for trace element study by SIMS and for Sm-Nd and Rb-Sr analysis by conventional P-TIMS after grouping by mineralogical similarity. Sulfide inclusions (chiefly FeS with lesser Ni, Cu, and Co) are classified as peridotitic (Ni > 14 wt%; Os > 2 ppm) versus eclogitic (Ni < 10 wt%; Os < 200 ppb); single sulfides are amenable for S isotopic study by SIMS or TIMS, and Re-Os analysis by N-TIMS. Work on inclusions in diamonds depends on the distribution of mined, diamond-bearing kimberlites, and the generosity of mining companies because of the extreme rarity of inclusions in suites of mostly gem-quality diamonds. Most isotopic work has been on the Kaapvaal-Zimbabwe craton with lesser work on the Slave, Siberian, and Australian cratons. Sm-Nd ages on silicate suites and Re-Os ages on sulfide suites confirm diamond formation from the Mesoarchean though the Neoproterozoic. Most important are the systematics across cratons in the context of crustal geology that lead to generalities about craton evolution. Inclusion suites date mantle keels as Mesoarchean and clearly point to subduction as the major process to form the earliest continental nuclei and to amalgamate the cratons in their present form. This is evident from the elevated initial Os isotopic compositions in 3.5 Ga Slave (Panda) and 2.9 Ga Kaapvaal (Kimberley) sulfides, the low Sm/Nd and elevated initial Sr isotopic compositions of 3.4 Ga Kaapvaal (Kimberley) harzburgitic garnets, the preponderance of 2.9 Ga eclogitic sulfides in every western Kaapvaal craton locality, and the occurrence of surficial, volcanogenic S in Kaapvaal (Orapa) sulfides. The continental lithosphere was accessible to melts and fluids from the asthenosphere throughout the Proterozoic as evident from silicate and sulfide inclusion suites of 0.9 to 2.0 Ga age in every locality studied in the Kaapvaal craton. The correspondence of silicate inclusion type with current seismic velocity structure of the Kaapvaal mantle keel shows that its structure is at least Bushveld age (2 Ga) and due to compositional differences. Seismic velocity structures of continental mantle keels may be more a function of their geologic history than current temperature distribution.

One-dimensional organic lead halide perovskites with efficient bluish white-light emission

NASA Astrophysics Data System (ADS)

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-01

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2-]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials.

One-dimensional organic lead halide perovskites with efficient bluish white-light emission

PubMed Central

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-01

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2−]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials. PMID:28051092

One-dimensional organic lead halide perovskites with efficient bluish white-light emission.

PubMed

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C; van de Burgt, Lambertus J; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-04

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C 4 N 2 H 14 PbBr 4 , in which the edge sharing octahedral lead bromide chains [PbBr 4   2- ] ∞ are surrounded by the organic cations C 4 N 2 H 14   2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials.

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

Dawson, P., E-mail: philip.dawson@manchester.ac.uk; Schulz, S.; Oliver, R. A.

In this paper, we compare and contrast the experimental data and the theoretical predictions of the low temperature optical properties of polar and nonpolar InGaN/GaN quantum well structures. In both types of structure, the optical properties at low temperatures are governed by the effects of carrier localisation. In polar structures, the effect of the in-built electric field leads to electrons being mainly localised at well width fluctuations, whereas holes are localised at regions within the quantum wells, where the random In distribution leads to local minima in potential energy. This leads to a system of independently localised electrons and holes.more » In nonpolar quantum wells, the nature of the hole localisation is essentially the same as the polar case but the electrons are now coulombically bound to the holes forming localised excitons. These localisation mechanisms are compatible with the large photoluminescence linewidths of the polar and nonpolar quantum wells as well as the different time scales and form of the radiative recombination decay curves.« less

Quantum cellular automata and free quantum field theory

NASA Astrophysics Data System (ADS)

D'Ariano, Giacomo Mauro; Perinotti, Paolo

2017-02-01

In a series of recent papers [1-4] it has been shown how free quantum field theory can be derived without using mechanical primitives (including space-time, special relativity, quantization rules, etc.), but only considering the easiest quantum algorithm encompassing a countable set of quantum systems whose network of interactions satisfies the simple principles of unitarity, homogeneity, locality, and isotropy. This has opened the route to extending the axiomatic information-theoretic derivation of the quantum theory of abstract systems [5, 6] to include quantum field theory. The inherent discrete nature of the informational axiomatization leads to an extension of quantum field theory to a quantum cellular automata theory, where the usual field theory is recovered in a regime where the discrete structure of the automata cannot be probed. A simple heuristic argument sets the scale of discreteness to the Planck scale, and the customary physical regime where discreteness is not visible is the relativistic one of small wavevectors. In this paper we provide a thorough derivation from principles that in the most general case the graph of the quantum cellular automaton is the Cayley graph of a finitely presented group, and showing how for the case corresponding to Euclidean emergent space (where the group resorts to an Abelian one) the automata leads to Weyl, Dirac and Maxwell field dynamics in the relativistic limit. We conclude with some perspectives towards the more general scenario of non-linear automata for interacting quantum field theory.

Free Quantum Field Theory from Quantum Cellular Automata

NASA Astrophysics Data System (ADS)

Bisio, Alessandro; D'Ariano, Giacomo Mauro; Perinotti, Paolo; Tosini, Alessandro

2015-10-01

After leading to a new axiomatic derivation of quantum theory (see D'Ariano et al. in Found Phys, 2015), the new informational paradigm is entering the domain of quantum field theory, suggesting a quantum automata framework that can be regarded as an extension of quantum field theory to including an hypothetical Planck scale, and with the usual quantum field theory recovered in the relativistic limit of small wave-vectors. Being derived from simple principles (linearity, unitarity, locality, homogeneity, isotropy, and minimality of dimension), the automata theory is quantum ab-initio, and does not assume Lorentz covariance and mechanical notions. Being discrete it can describe localized states and measurements (unmanageable by quantum field theory), solving all the issues plaguing field theory originated from the continuum. These features make the theory an ideal framework for quantum gravity, with relativistic covariance and space-time emergent solely from the interactions, and not assumed a priori. The paper presents a synthetic derivation of the automata theory, showing how the principles lead to a description in terms of a quantum automaton over a Cayley graph of a group. Restricting to Abelian groups we show how the automata recover the Weyl, Dirac and Maxwell dynamics in the relativistic limit. We conclude with some new routes about the more general scenario of non-Abelian Cayley graphs. The phenomenology arising from the automata theory in the ultra-relativistic domain and the analysis of corresponding distorted Lorentz covariance is reviewed in Bisio et al. (Found Phys 2015, in this same issue).

Sulfide and whole rock Re-Os systematics of eclogite and pyroxenite xenoliths from the Slave Craton, Canada

NASA Astrophysics Data System (ADS)

Aulbach, Sonja; Creaser, Robert A.; Pearson, Norm J.; Simonetti, Stefanie S.; Heaman, Larry M.; Griffin, William L.; Stachel, Thomas

2009-06-01

We characterized single sulfides in eclogite and pyroxenite xenoliths from the Diavik kimberlites (central Slave Craton, Canada) with regard to their petrography, major-element composition and Re-Os isotope systematics. Together with trace-element and Re-Os isotope compositions of whole rocks, these data allow identification of the major Re-Os host phases and provide constraints on the origin(s) of sulfides in these samples. The majority of sulfide minerals contain 8 to 28 at.% Ni, with intragranular sulfides having on average significantly lower contents (~ 6 at.%) than intergranular sulfides (~ 12 at.%). These high Ni-sulfides are not in equilibrium with an eclogitic assemblage and were likely introduced from a peridotitic source subsequent to eclogite formation. In contrast, their Re-Os abundances and Re/Os ratios (average ~ 825 ppb, 190 ppb and 10, respectively) overlap those of primary eclogitic sulfides. These conflicting compositional characteristics may document open-system disequilibrium processes accompanying the introduction of sulfides into eclogites. The general association of high 187Os/ 188Os with high 187Re/ 188Os of sulfides in three low-temperature eclogite xenoliths suggests that the addition is not young. In contrast, sulfides in a high-temperature eclogite plot on a ~ 90 Ma errorchron with radiogenic initial 187Os/ 188Os, perhaps indicative of young introduction of sulfides from a deep enriched source. Sulfides in a single pyroxenite xenolith have Ni, Re and Os contents intermediate between pristine eclogitic and peridotitic sulfides, and correlated Re-Os isotope systematics defining an age of 1.84 ± 0.14 Ga with a radiogenic 187Os/ 188Os i (0.16 ± 0.01). The age and 187Os/ 188Os i are identical to those obtained for eclogitic sulfide inclusions in diamonds from Diavik, thus supporting a link between eclogite and pyroxenite formation. Several eclogite and pyroxenite whole rocks show evidence for addition of secondary sulfides, but many plot on Paleoproterozoic Re-Os age arrays - particularly so at low Re/Os - coincident with previously determined ages using Lu-Hf and Pb-Pb techniques. They may represent sulfide-poor varieties that did not suffer secondary sulfide addition and that may be best suited to yielding meaningful Re-Os ages.

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

PubMed

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

2012-10-01

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

The Evolution of Sulfide Tolerance in the Cyanobacteria

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Understanding how the function of extant microorganisms has recorded both their evolutionary histories and their past interactions with the environment is a stated goal of astrobiology. We are taking a multidisciplinary approach to investigate the diversification of sulfide tolerance mechanisms in the cyanobacteria, which vary both in their degree of exposure to sulfide and in their capacity to tolerate this inhibitor of photosynthetic electron transport. Since conditions were very reducing during the first part of Earth's history and detrital sulfides have been found in Archean sediments, mechanisms conferring sulfide tolerance may have been important for the evolutionary success of the ancestors of extant cyanobacteria. Two tolerance mechanisms have been identified in this group: (1) resistance of photosystem II, the principal target of sulfide toxicity; and (2) maintenance of the ability to fix carbon despite photosystem II inhibition by utilizing sulfide as an electron donor in photosystem I - dependent, anoxygenic photosynthesis. We are presently collecting comparative data on aspects of sulfide physiology for laboratory clones isolated from a variety of habitats. These data will be analyzed within a phylogenetic framework inferred from molecular sequence data collected for these clones to test how frequently different mechanisms of tolerance have evolved and which tolerance mechanism evolved first. In addition, by analyzing these physiological data together with environmental sulfide data collected from our research sites using microelectrodes, we can also test whether the breadth of an organism's sulfide tolerance can be predicted from the magnitude of variation in environmental sulfide concentration it has experienced in its recent evolutionary past and whether greater average sulfide concentration and/or temporal variability in sulfide favors the evolution of a particular mechanism of sulfide tolerance.

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

PubMed Central

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

2015-01-01

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

Sulfide chemiluminescence detection

DOEpatents

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

1985-11-26

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

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1987-01-01

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

Electrochemical hydrogen sulfide biosensors.

PubMed

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

2016-02-21

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

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

USGS Publications Warehouse

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

1993-01-01

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

Adaptation of cyanobacteria to the sulfide-rich microenvironment of black band disease of coral.

PubMed

Myers, Jamie L; Richardson, Laurie L

2009-02-01

Black band disease (BBD) is a cyanobacteria-dominated microbial mat that migrates across living coral colonies lysing coral tissue and leaving behind exposed coral skeleton. The mat is sulfide-rich due to the presence of sulfate-reducing bacteria, integral members of the BBD microbial community, and the sulfide they produce is lethal to corals. The effect of sulfide, normally toxic to cyanobacteria, on the photosynthetic capabilities of five BBD cyanobacterial isolates of the genera Geitlerinema (3), Leptolyngbya (1), and Oscillatoria (1) and six non-BBD cyanobacteria of the genera Leptolyngbya (3), Pseudanabaena (2), and Phormidium (1) was examined. Photosynthetic experiments were performed by measuring the photoincorporation of [(14)C] NaHCO(3) under the following conditions: (1) aerobic (no sulfide), (2) anaerobic with 0.5 mM sulfide, and (3) anaerobic with 0.5 mM sulfide and 10 microM 3-(3',4'-dichlorophenyl)-1,1-dimethylurea (DCMU). All five BBD cyanobacterial isolates tolerated sulfide by conducting sulfide-resistant oxygenic photosynthesis. Five of the non-BBD cyanobacterial isolates did not tolerate sulfide, although one Pseudanabaena isolate continued to photosynthesize in the presence of sulfide at a considerably reduced rate. None of the isolates conducted anoxygenic photosynthesis with sulfide as an electron donor. This is the first report on the physiology of a culture of Oscillatoria sp. found globally in BBD.

Velocity of action of oxygen, hydrogen sulfide, and halogens on metals

NASA Technical Reports Server (NTRS)

Tammann, Gustav; Koster, Werner

1952-01-01

This report discusses a method of determining the rate of surface oxidation of a metal by the change in the color of the surface film produced by reactions with oxygen, chlorine, or iodine. The metals studied included iron, nickel, copper, zinc, cadmium, tin, lead, cobalt, and manganese. Tables are given for surface film thickness versus color for various times.

Microbial Remains in Middle Proterozoic Rocks of Northern Australia

NASA Technical Reports Server (NTRS)

Astafieva, Marina; Rozanov, Alexei Yu.; Hoover, Richard B.; Vickers-Rich, P.; Wilde, A.

2004-01-01

Investigation of the samples of the McArthur River complex ore deposit, one of the most zinc-lead m i n d provinces in the world, brings us to conclusion about the possibility of the biogenic origin of sulfides in McArthur River ore deposit and to make suppositions about the formation of the studied rocks in the photic zone of sea.

X-ray structural analysis of two-dimensional assembling lead sulfide nanocrystals of different sizes

NASA Astrophysics Data System (ADS)

Ushakova, Elena V.; Golubkov, Valery V.; Litvin, Aleksandr P.; Parfenov, Peter S.; Cherevkov, Sergei A.; Fedorov, Anatoly V.; Baranov, Alexander V.

2016-08-01

We report on the structural investigation of self-organized assemblies of PbS nanocrystals (NCs) of different sizes, which were deposited on a glass substrate or embedded in a porous matrix. Regardless of the NC size and the type of the substrate and matrix, the assemblies were ordered in two-dimensional superlattices with densely packed NCs.

On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone

NASA Astrophysics Data System (ADS)

Theberge, Stephen M.; Luther, George W.; Farrenkopf, Anna M.

Free hydrogen sulfide was not detected in the oxygen minimum zone (OMZ) of the Arabian Sea during legs D1 (September 1992) and D3 (October-November 1992) of the Netherlands Indian Ocean Programme (NIOP). However, sulfide complexed to metals was detected by cathodic stripping square wave voltammetry at 2 nM or less throughout the water column. A slight increase in sulfide was measured in the OMZ relative to the surface waters and may be related to sulfur release from organic matter during decomposition. Sulfide complexes are of two general types at low concentrations of metal and sulfide. First, metals such as Mn, Fe, Co and Ni form complexes with bisulfide ion (HS -) that are kinetically labile to dissociation and are reactive. Second, metals such as Cu and Zn form multinuclear complexes with sulfide (S 2-) that are kinetically inert to dissociation; thus, they are less reactive than free (bi)sulfide and the labile metal bisulfide complexes. Zinc and copper sulfide complexes are important in allowing hydrogen sulfide to persist in seawater which contains measurable oxygen.

Pumped spin and charge currents from applying a microwave field to a quantum dot between two magnetic leads

NASA Astrophysics Data System (ADS)

Zhou, Yun-Qing; Wang, Rui-Qiang; Sheng, L.; Wang, Baigeng; Xing, D. Y.

2008-10-01

The evolution-operator approach is applied to studying photon-electron-pumping effects on a quantum dot connected to two magnetic leads in the presence of both via-dot and over-dot tunneling channels. It is found that a microwave field applied to the quantum dot may give rise to charge and spin pumpings at zero-bias voltage for asymmetric magnetic junctions. More interestingly, a pure spin current can be pumped for symmetric magnetic junctions in the antiparallel magnetization configuration, providing an idea for the design of spin batteries.

Spin relaxation in quantum dots due to electron exchange with leads.

PubMed

Vorontsov, A B; Vavilov, M G

2008-11-28

We calculate spin relaxation rates in lateral quantum dot systems due to electron exchange between dots and leads. Using rate equations, we develop a theoretical description of the experimentally observed electric current in the spin blockade regime of double quantum dots. A single expression fits the entire current profile and describes the structure of both the conduction peaks and the suppressed ("valley") region. Extrinsic rates calculated here have to be taken into account for accurate extraction of intrinsic relaxation rates due to the spin-orbit and hyperfine spin scattering mechanisms from spin blockade measurements.

Experimental Estimation of Entanglement at the Quantum Limit

NASA Astrophysics Data System (ADS)

Brida, Giorgio; Degiovanni, Ivo Pietro; Florio, Angela; Genovese, Marco; Giorda, Paolo; Meda, Alice; Paris, Matteo G. A.; Shurupov, Alexander

2010-03-01

Entanglement is the central resource of quantum information processing and the precise characterization of entangled states is a crucial issue for the development of quantum technologies. This leads to the necessity of a precise, experimental feasible measure of entanglement. Nevertheless, such measurements are limited both from experimental uncertainties and intrinsic quantum bounds. Here we present an experiment where the amount of entanglement of a family of two-qubit mixed photon states is estimated with the ultimate precision allowed by quantum mechanics.

Activation mechanism of ammonium ions on sulfidation of malachite (-201) surface by DFT study

NASA Astrophysics Data System (ADS)

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

2017-07-01

The activation mechanism of ammonium ions on the sulfidation of malachite (-201) was determined by density functional theory (DFT) calculations. Results of DFT calculations indicated that interlayer sulfidation occurs during the sulfidation process of malachite (-201). The absorption of both the ammonium ion and sulfide ion on the malachite (-201) surface is stronger than that of sulfur ion. After sulfidation was activated with ammonium ion, the Cu 3d orbital peak is closer to the Fermi level and characterized by a stronger peak value. Therefore, the addition of ammonium ions activated the sulfidation of malachite (-201), thereby improving the flotation performance.

Anti-inflammatory and cytoprotective properties of hydrogen sulfide.

PubMed

Gemici, Burcu; Wallace, John L

2015-01-01

Hydrogen sulfide is an endogenous gaseous mediator that plays important roles in many physiological processes in microbes, plants, and animals. This chapter focuses on the important roles of hydrogen sulfide in protecting tissues against injury, promoting the repair of damage, and downregulating the inflammatory responses. The chapter focuses largely, but not exclusively, on these roles of hydrogen sulfide in the gastrointestinal tract. Hydrogen sulfide is produced throughout the gastrointestinal tract, and it contributes to maintenance of mucosal integrity. Suppression of hydrogen sulfide synthesis renders the tissue more susceptible to injury and it impairs repair. In contrast, administration of hydrogen sulfide donors can increase resistance to injury and accelerate repair. Hydrogen sulfide synthesis is rapidly and dramatically enhanced in the gastrointestinal tract after injury is induced. These increases occur specifically at the site of tissue injury. Hydrogen sulfide also plays an important role in promoting resolution of inflammation, and restoration of normal tissue function. In recent years, these beneficial actions of hydrogen sulfide have provided the basis for development of novel hydrogen sulfide-releasing drugs. Nonsteroidal anti-inflammatory drugs that release small amounts of hydrogen sulfide are among the most advanced of the hydrogen sulfide-based drugs. Unlike the parent drugs, these modified drugs do not cause injury in the gastrointestinal tract, and do not interfere with healing of preexisting damage. Because of the increased safety profile of these drugs, they can be used in circumstances in which the toxicity of the parent drug would normally limit their use, such as in chemoprevention of cancer. © 2015 Elsevier Inc. All rights reserved.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

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

1987-01-06

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

Quantum biology of the retina.

PubMed

Sia, Paul Ikgan; Luiten, André N; Stace, Thomas M; Wood, John Pm; Casson, Robert J

2014-08-01

The emerging field of quantum biology has led to a greater understanding of biological processes at the microscopic level. There is recent evidence to suggest that non-trivial quantum features such as entanglement, tunnelling and coherence have evolved in living systems. These quantum features are particularly evident in supersensitive light-harvesting systems such as in photosynthesis and photoreceptors. A biomimetic strategy utilizing biological quantum phenomena might allow new advances in the field of quantum engineering, particularly in quantum information systems. In addition, a better understanding of quantum biological features may lead to novel medical diagnostic and therapeutic developments. In the present review, we discuss the role of quantum physics in biological systems with an emphasis on the retina. © 2014 Royal Australian and New Zealand College of Ophthalmologists.

Synthesis of Zn-In-S Quantum Dots with Tunable Composition and Optical Properties.

PubMed

Wang, Xianliang; Damasco, Jossana; Shao, Wei; Ke, Yujie; Swihart, Mark T

2016-03-03

II-III-VI semiconductors are of interest due to their chemical stability and composition-tunable optical properties. Here, we report a methodology for the synthesis of monodisperse zinc-indium-sulfide (ZIS) alloy quantum dots (QDs, mean diameter from ∼2 to 3.5 nm) with an In content substantially below that of the stoichiometric ZnIn2 S4 compound. The effects of indium incorporation on the size, lattice constant, and optical properties of ZIS QDs are elucidated. In contrast to previous reports, we employ sulfur dissolved in oleic acid as the sulfur donor rather than thioacetamide (TAA). The size of the ZIS QDs and their crystal lattice constant increased with increasing In incorporation, but they maintained the cubic sphalerite phase of ZnS, rather than the hexagonal phase typical of ZnIn2 S4 . The QDs' absorbance onset at UV wavelengths red-shifts with increasing In content and the accompanying increase in NC size. The ZIS NCs and related materials, whose synthesis is enabled by the approach presented here, provide new opportunities to apply II-III-VI semiconductors in solution-processed UV optoelectronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local Gate Control of a Carbon Nanotube Double Quantum Dot

DTIC Science & Technology

2016-04-04

Nanotube Double Quantum Dot N. Mason,*† M. J. Biercuk,* C. M. Marcus† We have measured carbon nanotube quantum dots with multiple electro- static gates and...computation. Carbon nanotubes have been considered lead- ing candidates for nanoscale electronic applica- tions (1, 2). Previous measurements of nano- tube...electronics have shown electron confine- ment (quantum dot) effects such as single- electron charging and energy-level quantization (3–5). Nanotube

Engineering of lead chalcogenide nanostructures for carrier multiplication: Core/shell, 1D, and 2D

NASA Astrophysics Data System (ADS)

Lin, Qianglu

Near infrared emitting semiconductors have been used widely in industry especially in solar-cell fabrications. The efficiency of single junction solar-cell can reach the Shockley-Queisser limit by using optimum band gap material such as silicon and cadmium telluride. The theoretical efficiency can be further enhanced through carrier multiplication, in which a high energy photon is absorbed and more than one electron-hole pair can be generated, reaching more than 100% quantum efficiency in the high energy region of sunlight. The realization of more than unity external quantum efficiency in lead selenide quantum dots solar cell has motivated vast investigation on lowering the carrier multiplication threshold and further improving the efficiency. This dissertation focuses on synthesis of lead chalcogenide nanostructures for their optical spectroscopy studies. PbSe/CdSe core/shell quantum dots were synthesized by cation exchange to obtain thick shells (up to 14 monolayers) for studies of visible and near infrared dual band emissions and carrier multiplication efficiency. By examining the reaction mechanism, a thermodynamic and a kinetic model are introduced to explain the vacancy driven cation exchange. As indicated by the effective mass model, PbSe/CdSe core/shell quantum dots has quasi-type-II band alignment, possessing electron delocalized through the entire quantum dot and hole localized in the core, which breaks down the symmetry of energy levels in the conduction and valence band, leading to hot-hole-assisted efficient multi-exciton generation and a lower carrier multiplication threshold to the theoretical value. For further investigation of carrier multiplication study, PbTe, possessing the highest efficiency among lead chalcogenides due to slow intraband cooling, is synthesized in one-dimensional and two-dimensional nanostructures. By using dodecanethiol as the surfactant, PbTe NRs can be prepared with high uniformity in width and resulted in fine quantum confinement features. The reaction can be explained by a soft-template assisted process, in which the lamellar lead-thiolate precursor transforms into rod-shape micelle in the existence of telluride anions by electrostatic attraction. Fine tuning the reaction condition by changing the solvent to oleylamine, lead telluride nanowires with length up to 200 nm can be prepared, which bundled together because of the strong dipole-dipole attraction between nanowires. Decreasing the amount of surfactant dodecanethiol in the synthesis produces lead telluride nanorings, which formed by attaching four small particles together, leaving the center void. To prepare two-dimensional nanoplatelets, mixture ligands containing two amines with different carbon chain length were used, which initiate oriented attachment of the nanoparticles to form square-shape nanoplatelets. By further adopting stronger binding ligands such as phosphonic acid, PbTe nanoplatelets with micrometer lateral dimension were prepared with extremely sharp near infrared photoluminescence (less than 40 meV), which has never be achieved in quantum dots and other nanostructures.

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

NASA Astrophysics Data System (ADS)

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

We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on storage onboard ship even though they were filtered (0.2 μm) and handled to exclude oxygen contamination. Chemical additives such as formaldehyde, glutaraldehyde, hydroxylamine and ascorbic acid prevented or retarded the sulfide loss. Thiosulfate and azide did not inhibit sulfide loss. These studies suggest an anaerobic chemical oxidation of sulfide rather than a biological oxidation on stored and filtered samples.

A comparison of the optical properties of InGaN/GaN multiple quantum well structures grown with and without Si-doped InGaN prelayers

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

Davies, M. J., E-mail: Matthew.Davies-2@Manchester.ac.uk; Hammersley, S.; Dawson, P.

In this paper, we report on a detailed spectroscopic study of the optical properties of InGaN/GaN multiple quantum well structures, both with and without a Si-doped InGaN prelayer. In photoluminescence and photoluminescence excitation spectroscopy, a 2nd emission band, occurring at a higher energy, was identified in the spectrum of the multiple quantum well structure containing the InGaN prelayer, originating from the first quantum well in the stack. Band structure calculations revealed that a reduction in the resultant electric field occurred in the quantum well immediately adjacent to the InGaN prelayer, therefore leading to a reduction in the strength of themore » quantum confined Stark effect in this quantum well. The partial suppression of the quantum confined Stark effect in this quantum well led to a modified (higher) emission energy and increased radiative recombination rate. Therefore, we ascribed the origin of the high energy emission band to recombination from the 1st quantum well in the structure. Study of the temperature dependent recombination dynamics of both samples showed that the decay time measured across the spectrum was strongly influenced by the 1st quantum well in the stack (in the sample containing the prelayer) leading to a shorter average room temperature lifetime in this sample. The room temperature internal quantum efficiency of the prelayer containing sample was found to be higher than the reference sample (36% compared to 25%) which was thus attributed to the faster radiative recombination rate of the 1st quantum well providing a recombination pathway that is more competitive with non-radiative recombination processes.« less