(Table T1) Dissolved sulfide concentration and d34S of dissolved sulfate and sulfide in pore waters of ODP Leg 204

We report dissolved sulfide sulfur concentrations and the sulfur isotopic composition of dissolved sulfate and sulfide in pore waters from sediments collected during Ocean Drilling Program Leg 204. Porewater sulfate is depleted rapidly as the depth to the sulfate/methane interface (SMI) occurs between 4.5 and 11 meters below seafloor at flank and basin locations. Dissolved sulfide concentration reaches values as high as 11.3 mM in Hole 1251E. Otherwise, peak sulfide concentrations lie between 3.2 and 6.1 mM and occur immediately above the SMI. The sulfur isotopic composition of interstitial sulfate generally becomes enriched in 34S with increasing sediment depth. Peak d34S-SO4 values occur just above the SMI and reach up to 53.1 per mil Vienna Canyon Diablo Troilite (VCDT) in Hole 1247B. d34S-Sigma HS values generally parallel the trend of d34S-SO4 values but are more depleted in 34S relative to sulfate, with values from -12.7 per mil to 19.3 per mil VCDT. Curvilinear sulfate profiles and carbon isotopic composition of total dissolved carbon dioxide at flank and basin sites strongly suggest that sulfate depletion is controlled by oxidation of sedimentary organic matter, despite the presence of methane gas hydrates in underlying sediments. Preliminary data from sulfur species are consistent with this interpretation for Leg 204 sediments at sites not located on or near the crest of Hydrate Ridge.

Oxidation and tensile behavior of ferritic/martensitic steels after exposure to lead-bismuth eutectic

Two ferritic/martensitic steels, T91 steel and newly developed SIMP steel, were subject to tensile test after being oxidized in the liquid lead-bismuth eutectic (LBE) at 873 K for 500 h, 1000 h and 2000 h. Tensile tests were also carried out on the steels only thermally aged at 873 K. The result shows that thermal aging has no effect. Exposure to LBE at 873 K leads to a slight decrease in strength, but a large decrease in elongation when tested at 873 K. When tested at 873 K after 2000 h exposure, the tensile strength of T91 decreases slightly, and elongation from 39% to 21%. For SIMP, the decreases are slightly and from 44% to 28%, for tensile strength and elongation, respectively. The room temperature strength has slightly larger percentage reductions after the LBE exposure, but the elongation changes little.

Deterministic Switching in Bismuth Ferrite Nanoislands

We report deterministic selection of polarization variant in bismuth BiFeO3 nanoislands via a two-step scanning probe microscopy procedure. The polarization orientation in a nanoisland is toggled to the desired variant after a reset operation by scanning a conductive atomic force probe in contact over the surface while a bias is applied. The final polarization variant is determined by the direction of the inhomogeneous in-plane trailing field associated with the moving probe tip. This work provides the framework for better control of switching in rhombohedral ferroelectrics and for a deeper under- standing of exchange coupling in multiferroic nanoscale hetero- structures toward the realization of magnetoelectric devices.

Concrete deterioration due to sulfide-bearing aggregates

Dans la région de Trois-Rivières (Québec, Canada), plus de 1 000 bâtiments résidentiels et commerciaux montrent de graves problèmes de détérioration du béton. Les problèmes de détérioration sont liés à l’oxydation des sulfures de fer incorporés dans le granulat utilisé pour la confection du béton. Ce projet de doctorat vise à mieux comprendre les mécanismes responsables de la détérioration de béton incorporant des granulats contenant des sulfures de fer, et ce afin de développer une méthodologie pour évaluer efficacement la réactivité potentielle de ce type de granulats. Un examen pétrographique détaillé de carottes de béton extraites de fondations résidentielles montrant différents degré d’endommagement a été réalisé. Le granulat problématique contenant des sulfures de fer a été identifié comme un gabbro à hypersthène incorporant différentes proportions (selon les différentes localisations dans les deux carrières d’origine) de pyrrhotite, pyrite, chalcopyrite et pentlandite. Les produits de réaction secondaires observés dans les échantillons dégradés comprennent des formes minérales de "rouille", gypse, ettringite et thaumasite. Ces observations ont permis de déterminer qu’en présence d’eau et d’oxygène, la pyrrhotite s’oxyde pour former des oxyhydroxides de fer et de l’acide sulfurique qui provoquent une attaque aux sulfates dans le béton. Tout d’abord, la fiabilité de l’approche chimique proposée dans la norme européenne NF EN 12 620, qui consiste à mesurer la teneur en soufre total (ST,% en masse) dans le granulat pour détecter la présence (ou non) de sulfures de fer, a été évaluée de façon critique. Environ 50% (21/43) des granulats testés, représentant une variété de types de roches/lithologies, a montré une ST > 0,10%, montrant qu’une proportion importante de types de roches ne contient pas une quantité notable de sulfure, qui, pour la plupart d’entre eux, sont susceptibles d’être inoffensifs dans le béton. Ces types de roches/granulats nécessiteraient toutefois d’autres tests pour identifier la présence potentielle de pyrrhotite compte tenu de la limite de ST de 0,10 % proposée dans les normes européennes. Basé sur une revue exhaustive de la littérature et de nombreuses analyses de laboratoire, un test accéléré d’expansion sur barres de mortier divisé en deux phases a ensuite été développé pour reproduire, en laboratoire, les mécanismes de détérioration observés à Trois-Rivières. Le test consiste en un conditionnement de 90 jours à 80°C/80% RH, avec 2 cycles de mouillage de trois heures chacun, par semaine, dans une solution d’hypochlorite de sodium (eau de javel) à 6% (Phase I), suivi d’une période pouvant atteindre 90 jours de conditionnement à 4°C/100 % HR (Phase II). Les granulats ayant un potentiel d’oxydation ont présenté une expansion de 0,10 % au cours de la Phase I, tandis que la formation potentielle de thaumasite est détectée par le regain rapide de l’expansion suivi par la destruction des échantillons durant la Phase II. Un test de consommation d’oxygène a également été modifié à partir d’un test de Drainage Minier Acide, afin d’évaluer quantitativement le potentiel d’oxydation des sulfures de fer incorporés dans les granulats à béton. Cette technique mesure le taux de consommation d’oxygène dans la partie supérieure d’un cylindre fermé contenant une couche de matériau compacté afin de déterminer son potentiel d’oxydation. Des paramètres optimisés pour évaluer le potentiel d’oxydation des granulats comprennent une taille de particule inférieure à 150 μm, saturation à 40 %, un rapport de 10 cm d’épaisseur de granulat par 10 cm de dégagement et trois heures d’essai à 22ᵒC. Les résultats obtenus montrent que le test est capable de discriminer les granulats contenant des sulfures de fer des granulats de contrôle (sans sulfures de fer) avec un seuil limite fixé à 5% d’oxygène consommé. Finalement, un protocole d’évaluation capable d’estimer les effets néfastes potentiels des granulats à béton incorporant des sulfures de fer a été proposé. Le protocole est divisé en 3 grandes phases: (1) mesure de la teneur en soufre total, (2) évaluation de la consommation d’oxygène, et (3) un test accéléré d’expansion sur barres de mortier. Des limites provisoires sont proposées pour chaque phase du protocole, qui doivent être encore validées par la mise à l’essai d’un plus large éventail de granulats.

Molecular Mechanism of the Response to Hydrogen Sulfide in C. elegans

Thesis (Ph.D.)--University of Washington, 2016-08

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and delta Fe-57/54 Observations

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9 degrees 50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (RXAS) and X-ray diffraction (mu XRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe -bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of delta Fe-57 values up to 6 parts per thousand. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

Preliminary structure-activity relationship studies on some novel s-substituted aliphatic analogues of 5-{1-[(4- chlorophenyl) sulfonyl]-3-piperidinyl}-1, 3, 4-oxadiazol-2-yl sulfide

Purpose: To study the structure-activity relationships of synthetic multifunctional sulfides through evaluation of lipoxygenase and anti-bacterial activities. Methods: S-substituted derivatives of the parent compound 5-(1-(4-chlorophenylsulfonyl) piperidin-3- yl)-1, 3, 4-oxadiazole-2-thiol were synthesized through reaction with different saturated and unsaturated alkyl halides in DMF medium, with NaH catalyst. Spectral characterization of each derivative was carried out with respect to IR, 1H - NMR, 13C - NMR and EI - MS. The lipoxygenase inhibitory and antibacterial activities of the derivatives were determined using standard procedures. Results: Compound 5e exhibited higher lipoxygenase inhibitory potential than the standard (Baicalein®), with % inhibition of 94.71 ± 0.45 and IC50 of 20.72 ± 0.34 μmoles/L. Compound 5b showed significant antibacterial potential against all the bacterial strains with % inhibition ranging from 62.04 ± 2.78, 69.49 ± 0.41, 63.38 ± 1.97 and 59.70 ± 3.70 to 78.32 ± 0.41, while MIC ranged from 8.18 ± 2.00, 10.60 ± 1.83, 10.84 ± 3.00, 9.81 ± 1.86 and 11.73 ± 5.00 μmoles/L for S. typhi, E. coli, P. aeruginosa, B. subtilis and S. aureus, respectively. Compounds 5d, 5e and 5g showed good antibacterial activity against S. typhi and B. subtilis bacterial strains. Conclusion: The results suggest that compound 5e bearing n-pentyl group is a potent lipoxygenase inhibitor, while compound 5b with n-propyl substitution is a strong antibacterial agent. In addition, compounds 5d, 5e and 5g bearing n-butyl, n-pentyl and n-octyl groups, respectively, are good antibacterial agents against S. typhi and B. subtilis.

SELECTED CHEMOAUTOTROPHIC PROCESSES IN WASTEWATER TREATMENT: LOW TEMPERATURE NITRIFICATION INHIBITION BY AN AZO DYE AND BIOFILTRATION FOR ODOR CONTROL OF HYDROGEN SULFIDE

Biochemical processes by chemoautotrophs such as nitrifiers and sulfide and iron oxidizers are used extensively in wastewater treatment. The research described in this dissertation involved the study of two selected biological processes utilized in wastewater treatment mediated by chemoautotrophic bacteria: nitrification (biological removal of ammonia and nitrogen) and hydrogen sulfide (H2S) removal from odorous air using biofiltration. A municipal wastewater treatment plant (WWTP) receiving industrial dyeing discharge containing the azo dye, acid black 1 (AB1) failed to meet discharge limits, especially during the winter. Dyeing discharge mixed with domestic sewage was fed to sequencing batch reactors at 22oC and 7oC. Complete nitrification failure occurred at 7oC with more rapid nitrification failure as the dye concentration increased; slight nitrification inhibition occurred at 22oC. Dye-bearing wastewater reduced chemical oxygen demand (COD) removal at 7oC and 22oC, increased i effluent total suspended solids (TSS) at 7oC, and reduced activated sludge quality at 7oC. Decreasing AB1 loading resulted in partial nitrification recovery. Eliminating the dye-bearing discharge to the full-scale WWTP led to improved performance bringing the WWTP into regulatory compliance. BiofilterTM, a dynamic model describing the biofiltration processes for hydrogen sulfide removal from odorous air emissions, was calibrated and validated using pilot- and full-scale biofilter data. In addition, the model predicted the trend of the measured data under field conditions of changing input concentration and low effluent concentrations. The model demonstrated that increasing gas residence time and temperature and decreasing influent concentration decreases effluent concentration. Model simulations also showed that longer residence times are required to treat loading spikes. BiofilterTM was also used in the preliminary design of a full-scale biofilter for the removal of H2S from odorous air. Model simulations illustrated that plots of effluent concentration as a function of residence time or bed area were useful to characterize and design biofilters. Also, decreasing temperature significantly increased the effluent concentration. Model simulations showed that at a given temperature, a biofilter cannot reduce H2S emissions below a minimum value, no matter how large the biofilter.

Hydrogen sulfide:a novel mechanism for the vascular protection by resveratrol under oxidative stress in mouse aorta

Reactive oxygen species (ROS) decreases bioavailability of nitric oxide (NO) and impairs NO-dependent relaxations. Like NO, hydrogen sulfide (H2S) is an antioxidant and vasodilator; however, the effect of ROS on H2S-induced relaxations is unknown. Here we investigated whether ROS altered the effect of H2S on vascular tone in mouse aorta and determined whether resveratrol (RVT) protects it via H2S. Pyrogallol induced ROS formation. It also decreased H2S formation and relaxation induced by l-cysteine and in mouse aorta. Pyrogallol did not alter sodium hydrogensulfide (NaHS)-induced relaxation suggesting that the pyrogallol effect on l-cysteine relaxations was due to endogenous H2S formation. RVT inhibited ROS formation, enhanced l-cysteine-induced relaxations and increased H2S level in aortas exposed to pyrogallol suggesting that RVT protects against "H2S-dysfunctions" by inducing H2S formation. Indeed, H2S synthesis inhibitor AOAA inhibited the protective effects of RVT. RVT had no effect on Ach-induced relaxation that is NO dependent and the stimulatory effect of RVT on H2S-dependent relaxation was also independent of NO. These results demonstrate that oxidative stress impairs endogenous H2S-induced relaxations and RVT offers protection by inducing H2S suggesting that targeting endogenous H2S pathway may prevent vascular dysfunctions associated by oxidative stress.

Bagasse Fractionation by the Soda Process

The soda process was the first chemical pulping method and was patented in 1845. Soda pulping led to kraft pulping, which involves the combined use of sodium hydroxide and sodium sulfide. Today, kraft pulping dominates the chemical pulping industry. However, about 10% of the total chemical pulp produced in the world is made using non-wood material, such as bagasse and wheat straw. The soda process is the preferred method of chemical pulping of non-wood materials, because it is considered to be economically viable on a small scale and for bagasse is compatible with sugarcane processing. With recent developments, the soda process can be designed to produce minimal effluent discharge and the fouling of evaporators by silica precipitation. The aim of this work is to produce bagasse fibres suitable for papermaking and allied applications and to produce sulfur-free lignin for use in specialty applications. A preliminary economic analysis of the soda process for producing commodity silica, lignin and pulp for papermaking is presented.