Calculation of resonances and product state distributions for the unimolecular dissociation of H2S

Resonance phenomena associated with the unimolecular dissociation of H2S --> SH + H have been investigated quantum mechanically by the Lanczos homogeneous filter diagonalization method using a newly developed potential energy surface (J. Chem. Phys. 2001, 114, 320). Resonance energies, widths (rates), and product state distributions have been obtained. Both dissociation rates and product state distributions of SH show, strong fluctuations, indicating that the dissociation of H2S is essentially irregular. Statistical analysis of neighboring level spacing and width distributions also confirms this behavior. The dissociation rates and product state distributions are compared to the predictions of quantum phase space theory.

Estudo da influência do material inorgânico na formação de H2S e HCl durante a co-gasificação de CDR com carvão

O objectivo principal deste trabalho relaciona-se com a compreensão dos mecanismos de formação de H2S e HCl durante a co-gasificação de C.D.R com carvão. A presença de material inorgânico nas cinzas dos combustíveis utilizados poderá ter alguma influência na formação e subsequentes reacções de H2S e HCl, tornando-se importante compreender qual a extensão da influência destes materiais na formação destas espécies, encaradas como contaminantes do gás produzido. A utilização de misturas de C.D.R. com carvão em gasificação poderá contribuir para a redução das quantidades de resíduos depositadas em aterro. Sendo a gasificação um processo menos poluente do que a incineração, a gasificação destes materiais poderá traduzir-se num menor impacto ambiental. Os C.D.R. são materiais heterogéneos e portanto as quantidades de S, Cl e material inorgânico poderão variar tornando relevante o estudo de potenciais sinergias entre os C.D.R. e o carvão com o objectivo de 1) minimizar a emissão de poluentes gasosos, 2) minimizar a quantidade de cinza produzida e 3) aproveitar o material inorgânico, que pode desempenhar actividade catalítica conduzindo à redução da formação de H2S e HCl. Com este estudo foi determinada uma aparente relação linear entre os teores de enxofre nos combustíveis e a formação de H2S, sendo que no entanto a forma sob a qual o enxofre se encontra nos combustíveis poderá desempenhar um importante papel na conversão do enxofre em H2S. No caso do HCl, a referida relação não pareceu ser tão clara. Foi igualmente determinado que maiores temperaturas de operação promovem a formação de H2S, ao mesmo tempo que reduzem a formação de HCl, e que enquanto o aumento da quantidade de oxigénio poderá conduzir à redução da formação de H2S, não terá impacto significativo na formação de HCl. No que diz respeito aos metais foi verificado que Ca, Fe e Zn terão um papel importante na redução da formação de H2S e HCl, enquanto que K e Na terão apenas influência na formação de HCl e o Al e a Si, não afectaram nem a formação de H2S nem a de HCl.

Validación y cuantificación de sulfuros de hidrógeno (H2S) en agua intersticial de sedimentos marinos recientes

Para la validación del método analítico de cuantificación de sulfuros en aguas intersticiales se analizaron varios parámetros: la especificidad, determinándose que el único compuesto formado es el azul de metileno con absorbancia máxima a 670 nm; la linealidad en intervalo de 3 a 36 μM (y= 0,0319 x +0,0142) con coeficiente de regresión 0,9983; la repetitividad obteniéndose promedio de 0,1043% y CV de 5,0811. La reproducibilidad se analizó con la prueba t de Student, determinándose que t calculado H2S en el agua intersticial varían, siendo importante la presencia de Zona de Mínimo de Oxígeno (ZMO).

Characterization of magmatic sulfur in the Aegean island arc by means of the δ34S values of fumarolic H2S, elemental S, and hydrothermal gypsum from Nisyros and Milos islands

A delta(34)S value of +6.3 +/- 1.5% was estimated for the rhyodacitic degassing magma present underneath the hydrothermal system of Nisyros, based on the S isotope ratios of H2S in fumarolic vapors. This value was estimated by modeling the irreversible water-rock mass transfers occurring during the generation of the hydrothermal liquid which separates these fumarolic vapors. The S isotope ratio of the rhyodacitic degassing magma of Nisyros is consistent with fractional crystallization of a parent basaltic magma with an initial delta(34)S value of +4% (+/-at least 1.5%). This positive value could be explained by mantle contamination due to by either transference of fluids derived from subducted materials or involvement of altered oceanic crust, whereas contribution of biogenic sulfides from sediments seems to be negligible or nil. This conclusion agrees with the lack of N-2 and CO2 from thermal decomposition of organic matter contained in subducted sediments, which is a characteristic of the whole Aegean arc system. Since hydrothermal S at Milos and Santorini has isotope ratios similar to those determined at Nisyros, it seems likely that common controlling processes are active throughout the Aegean island arc. (C) 2002 Elsevier, Science B.V. All rights reserved.

Laite- ja työturvallisuus H2S-tiloissa

Tässä työssä selvitettiin, millä tavoin räjähdysvaarallisten työtilojen työturvallisuuteen voidaan vaikuttaa ja miten turvallisuutta pidetään yllä. Työssä selvitettiin, mitä vaatimuksia räjähdysvaaralliset tilat asettavat laite- ja työturvallisuudelle. Työn lähtökohdaksi otettiin ilmanvaihdon vaikutus sisäilman olosuhteisiin ja samalla selvitettiin, mitä muutoksia räjähdysvaarallisten aineiden käyttö teollisuuden tuotantoprosesseissa aiheuttaa ilmanvaihdossa. Räjähdysvaarallisten tilojen suunnittelua ohjailevat säädökset, lait ja direktiivit. Johdonmukaisen suunnittelulla ja säädöksiä noudattamalla pystytään toteuttamaan turvallinen työympäristö. Räjähdysvaarallista tilaa päästiin tarkastelemaan Talvivaaran Kaivososakeyhtiö Oyj:n metallien talteenottolaitoksella. Työssä haluttiin tutkia rakennuksen työturvallisuutta ja työskentelyolosuhteita. Tutkimuskohteena olleessa reaktorihallissa tehtiin ilmanvaihdon suorituskyvyn mittauksia. Tarkoituksena oli myös tehdä rikkivedyn pitoisuus mittauksia, mutta Talvivaaran tuotannon viivästyessä, pitoisuus mittaukset jätettiin tämän diplomityön ulkopuolelle. Talvivaaraan reaktorirakennuksen olosuhteita ja turvallisuutta tarkasteltiin lähemmin teoreettisten laskelmien avulla. Laskelmien ja mittaustulosten perusteella reaktorirakennuksen ilmanvaihdon suorituskyky todettiin riittäväksi ja toiminta työturvalliseksi. Riskin arvioinnin perusteella reaktorirakennuksen riskitason katsotaan olevan siedettävä.

Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases

One of the main challenges in the development of metal-oxide gas sensors is enhancement of selectivity to a particular gas. Currently, two general approaches exist for enhancing the selective properties of sensors. The first one is aimed at preparing a material that is specifically sensitive to one compound and has low or zero cross-sensitivity to other compounds that may be present in the working atmosphere. To do this, the optimal temperature, doping elements, and their concentrations are investigated. Nonetheless, it is usually very difficult to achieve an absolutely selective metal oxide gas sensor in practice. Another approach is based on the preparation of materials for discrimination between several analyte in a mixture. It is impossible to do this by using one sensor signal. Therefore, it is usually done either by modulation of sensor temperature or by using sensor arrays. The present work focus on the characterization of n-type semiconducting metal oxides like Tungsten oxide (WO3), Zinc Oxide (ZnO) and Indium oxide (In2O3) for the gas sensing purpose. For the purpose of gas sensing thick as well as thin films were fabricated. Two different gases, NO2 and H2S gases were selected in order to study the gas sensing behaviour of these metal oxides. To study the problem associated with selectivity the metal oxides were doped with metals and the gas sensing characteristics were investigated. The present thesis is entitled “Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases” and consists of six chapters.

Caracterización de la exposición ocupacional a los gases, dióxido de azufre (so2), sulfuro de hidrógeno (h2s), y monóxido de carbono (co), y la percepción de salud de los trabajadores, en una empresa del sector hidrocarburo en Colombia

En el proceso de extracción de petróleo (crudo) deben realizarse tratamientos físicos y químicos en estaciones de recolección del hidrocarburo con el fin de garantizar su calidad antes de su entrega para el transporte y comercialización. Para la realización de esta actividad el personal operativo requerido (operadores) debe realizar diferentes actividades, tales como ronda operacional, verificación de sistemas de almacenamiento del crudo, agua residual del proceso e insumos químicos utilizados en su tratamiento y manipulación de facilidades en las estaciones de recolección, entre otras. Como resultados de las actividades rutinarias los operadores están expuestos a factores de riesgo químico asociados a gases y vapores orgánicos generados en los procesos de tratamiento del crudo. En el presente trabajo se realizaron mediciones de calidad de aire e higiene industrial en diferentes estaciones tratamiento de crudo, con el propósito de evaluar los niveles de exposición de los operadores a gases y vapores de hidrocarburos durante el proceso de tratamiento de crudo y dar respuesta a la siguiente pregunta: ¿existe relación entre la exposición ocupacional, las emisiones atmosféricas de gases (SO2, CO, H2S) y la percepción de afectación de la salud de los trabajadores que se encuentran expuestos durante la actividad laboral, en una empresa del sector de hidrocarburos? Se realizó un estudio de corte transversal, mediante la aplicación de cuestionarios sobre las condiciones de trabajo y de salud a 30 trabajadores que laboran en una estación de tratamiento de crudo de una compañía del sector de hidrocarburos. Los operadores objeto de estudio laboran en turnos rotativos, han estado vinculados con la compañía por más de dos años y tienen contrato directo, adicionalmente, se identificaron los factores de riesgos ambientales y ocupacionales para el grupo de trabajadores y se realizó una revisión de los informes de medición de higiene industrial y de calidad de aire de las estaciones donde labora el personal seleccionado con el fin de establecer si los resultados se relacionan. Los resultados obtenidos indican que el 100% de los trabajadores son de género masculino y se desempeñan en cargos de operadores, recorredores de pozos de crudo y supervisores. El 97% de los operadores tiene más de cuarenta años de edad y el 80% de los mismos ha laborado por más de 6 años en la compañía. Acerca de la percepción de los trabajadores sobre su estado de salud el 90% afirma que su salud es buena, el 97% respondió que no presenta problemas respiratorios, el 23% manifiesta que presenta trastornos dermatológicos y el 27% indican que presenta dolor de cabeza constante. De la revisión de los informes de calidad de aire disponibles se encontró que las mediciones de Dióxido de Azufre SO2, Monóxido de Carbono CO se encuentran dentro del rango definido como el de menor impacto para la salud humana. De los datos del informe se puede concluir que la calidad del aire es buena en el 100% de las áreas de influencia de las estaciones de tratamiento de crudo. Según los informes de higiene industrial el 34% de las instalaciones presenta concentraciones de Sulfuro de Hidrógeno (H2S) en el límite permisible para exposiciones crónicas en un promedio ponderado de tiempo (TLV-TWA) y el límite permisible para exposiciones agudas en un límite de exposición a corto plazo (TLV-STEL). Solo el 37% de los trabajadores objeto de este estudio percibe el riesgo por la exposición a factores de riesgo químicos y son claramente consientes que se encuentran expuestos a estos riesgos por la manipulación de productos químicos y exposición a sustancias químicas producto de sus actividades rutinarias, el 73% no percibe el riesgo de exposición por su actividad laboral. Se recomienda que la compañía fortalezca su esquema de vigilancia para generar alternativas que eleven los niveles de consciencia del riesgo del trabajador. Los factores de riesgo ambiental y ocupacional, de los gases y vapores generados se deben al proceso de tratamiento de crudo, están mutuamente relacionados dado que al generarse una emisión y/o escape no controlado como consecuencia se tiene una afectación directa al medio ambiente y a los trabajadores.

Inducible hydrogen sulfide synthesis in chondrocytes and mesenchymal progenitor cells: is H2S a novel cytoprotective mediator in the inflamed joint?

Hydrogen sulfide (H(2)S) has recently been proposed as an endogenous mediator of inflammation and is present in human synovial fluid. This study determined whether primary human articular chondrocytes (HACs) and mesenchymal progenitor cells (MPCs) could synthesize H(2)S in response to pro-inflammatory cytokines relevant to human arthropathies, and to determine the cellular responses to endogenous and pharmacological H(2)S. HACs and MPCs were exposed to IL-1β, IL-6, TNF-α and lipopolysaccharide (LPS). The expression and enzymatic activity of the H(2)S synthesizing enzymes cystathionine-β-synthase (CBS) and cystathionine-γ-lyase (CSE) were determined by Western blot and zinc-trap spectrophotometry, respectively. Cellular oxidative stress was induced by H(2)O(2), the peroxynitrite donor SIN-1 and 4-hydroxynonenal (4-HNE). Cell death was assessed by 3-(4,5-dimethyl-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and lactate dehydrogenase (LDH) assays. Mitochondrial membrane potential (DCm) was determined in situ by flow cytometry. Endogenous H(2) S synthesis was inhibited by siRNA-mediated knockdown of CSE and CBS and pharmacological inhibitors D,L-propargylglycine and aminoxyacetate, respectively. Exogenous H(2)S was generated using GYY4137. Under basal conditions HACs and MPCs expressed CBS and CSE and synthesized H(2)S in a CBS-dependent manner, whereas CSE expression and activity was induced by treatment of cells with IL-1β, TNF-α, IL-6 or LPS. Oxidative stress-induced cell death was significantly inhibited by GYY4137 treatment but increased by pharmacological inhibition of H(2)S synthesis or by CBS/CSE-siRNA treatment. These data suggest CSE is an inducible source of H(2)S in cultured HACs and MPCs. H(2)S may represent a novel endogenous mechanism of cytoprotection in the inflamed joint, suggesting a potential opportunity for therapeutic intervention.

Key bioactive reaction products of the NO/H2S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide (H2S) signaling pathways are intimately intertwined, with mutual attenuation or potentiation of biological responses in the cardiovascular system and elsewhere. The chemical basis of this interaction is elusive. Moreover, polysulfides recently emerged as potential mediators of H2S/sulfide signaling, but their biosynthesis and relationship to NO remain enigmatic. We sought to characterize the nature, chemical biology, and bioactivity of key reaction products formed in the NO/sulfide system. At physiological pH, we find that NO and sulfide form a network of cascading chemical reactions that generate radical intermediates as well as anionic and uncharged solutes, with accumulation of three major products: nitrosopersulfide (SSNO−), polysulfides, and dinitrososulfite N-nitrosohydroxylamine-N-sulfonate (SULFI/NO), each with a distinct chemical biology and in vitro and in vivo bioactivity. SSNO− is resistant to thiols and cyanolysis, efficiently donates both sulfane sulfur and NO, and potently lowers blood pressure. Polysulfides are both intermediates and products of SSNO− synthesis/decomposition, and they also decrease blood pressure and enhance arterial compliance. SULFI/NO is a weak combined NO/nitroxyl donor that releases mainly N2O on decomposition; although it affects blood pressure only mildly, it markedly increases cardiac contractility, and formation of its precursor sulfite likely contributes to NO scavenging. Our results unveil an unexpectedly rich network of coupled chemical reactions between NO and H2S/sulfide, suggesting that the bioactivity of either transmitter is governed by concomitant formation of polysulfides and anionic S/N-hybrid species. This conceptual framework would seem to offer ample opportunities for the modulation of fundamental biological processes governed by redox switching and sulfur trafficking.

Influência da temperatura e da presença de H2S no comportamento mecânico e eletroquímico do aço API 5CT grau P110 em água do mar sintética

o presente trabalho teve por objetivo estudar o comportamento de um aço de alta resistência e baixa liga (com amostras de composição aproximada de 0,4% C, 0,6% Cr e 0,4% Mo), da classe API scr PIlO, utilizado na perfuração de petróleo offshore, frente a processos de fragilização causados pelo meio. Água do mar sintética foi utilizada como meio, com intuito de padronizar, em laboratório, as condições a que o material fica submetido na prática. Buscou-se avaliar e comparar o comportamento mecânico do material pela modificação dos parâmetros: temperatura, potencial aplicado ao material, e o efeito da presença ou ausência de H2S na solução. Para isso, foram realizados ensaios de tração pelo método de baixa taxa de deformação (da ordem de 10-6S-I), obtendo-se as curvas tensão x deformação nas diferentes situações ensaiadas, comparadas com as obtidas em óleo mineral. Análises fratográficas também foram utilizadas como forma de caracterizar os processos de fragilização. Além disso, estudou-se o comportamento eletroquímico do material nas diferentes condições através de ensaios de polarização potenciostáticos. Com isso, pode-se determinar quais as condições mais danosas e de maior risco para a utilização do material e em quais delas o seu uso é seguro. O aço estudado apresentou-se susceptível a processos de fragilização e todos os parâmetros analisados mostraram-se importantes no estudo desses processos.

Evaluation of the zinox and zeolite materials as adsorbents to remove H2S from natural gas

MELO, Dulce Maria de Araújo et al. Evaluation of the Zinox and Zeolite materials as adsorbents to remove H2S from natural gas. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, Estados Unidos, v. 272, p. 32-36, 2006.

Avaliação da dolomita funcionalizada para remoção de H2S em gás natural

The natural gas is an alternative source of energy which is found underground in porous and permeable rocks and being associated or not to the oil. Its basic composition includes methane, other hydrocarbon and compounds such as carbon dioxide, nitrogen, sulphidric gas, mercaptans, water and solid particles. In this work, the dolomite mineral, a double carbonate of calcium and magnesium whose the chemical formula is CaMg(CO3)2, was evaluated as adsorbent material. The material was characterized by granulometric analysis, X-ray fluorescence, X-ray diffraction, thermogravimetric analysis, differential thermal analysis, specific surface area, porosity, scanning electronic microscopy and infrared spectroscopy. Then the material was functionalized with diethanolamine (dolomite+diethanolamine) and diisopropylamine (dolomite+diisopropylamine). The results indicated that the adsorbents presented appropriate physiochemical characteristics for H2S adsorption. The adsorption tests were accomplished in a system coupled to a gas chromatograph and the H2S monitoring in the output of the system was accomplished by a pulsed flame photometric detector (PFPD). The adsorbents presented a significant adsorption capacity. Among the analyzed adsorbents, the dolomite+diethanolamine presented the best capacity of adsorption. The breakthrough curves obtained proved the efficiency of this process

Avaliação e modelagem da absorção de H2S do gás natural em coluna de leito estagnado

Natural gas, although basically composed by light hydrocarbons, also presents contaminant gases in its composition, such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). The H2S, which commonly occurs in oil and gas exploration and production activities, causes damages in oil and natural gas pipelines. Consequently, the removal of hydrogen sulfide gas will result in an important reduction in operating costs. Also, it is essential to consider the better quality of the oil to be processed in the refinery, thus resulting in benefits in economic, environmental and social areas. All this facts demonstrate the need for the development and improvement in hydrogen sulfide scavengers. Currently, the oil industry uses several processes for hydrogen sulfide removal from natural gas. However, these processes produce amine derivatives which can cause damage in distillation towers, can cause clogging of pipelines by formation of insoluble precipitates, and also produce residues with great environmental impact. Therefore, it is of great importance the obtaining of a stable system, in inorganic or organic reaction media, able to remove hydrogen sulfide without formation of by-products that can affect the quality and cost of natural gas processing, transport, and distribution steps. Seeking the study, evaluation and modeling of mass transfer and kinetics of hydrogen removal, in this study it was used an absorption column packed with Raschig rings, where the natural gas, with H2S as contaminant, passed through an aqueous solution of inorganic compounds as stagnant liquid, being this contaminant gas absorbed by the liquid phase. This absorption column was coupled with a H2S detection system, with interface with a computer. The data and the model equations were solved by the least squares method, modified by Levemberg-Marquardt. In this study, in addition to the water, it were used the following solutions: sodium hydroxide, potassium permanganate, ferric chloride, copper sulfate, zinc chloride, potassium chromate, and manganese sulfate, all at low concentrations (»10 ppm). These solutions were used looking for the evaluation of the interference between absorption physical and chemical parameters, or even to get a better mass transfer coefficient, as in mixing reactors and absorption columns operating in counterflow. In this context, the evaluation of H2S removal arises as a valuable procedure for the treatment of natural gas and destination of process by-products. The study of the obtained absorption curves makes possible to determine the mass transfer predominant stage in the involved processes, the mass transfer volumetric coefficients, and the equilibrium concentrations. It was also performed a kinetic study. The obtained results showed that the H2S removal kinetics is greater for NaOH. Considering that the study was performed at low concentrations of chemical reagents, it was possible to check the effect of secondary reactions in the other chemicals, especially in the case of KMnO4, which shows that your by-product, MnO2, acts in H2S absorption process. In addition, CuSO4 and FeCl3 also demonstrated to have good efficiency in H2S removal

Estudo da mistura comercial dolomita-quartzo, dopada com Hg(I), Cd(II) e Cr(III), para adsorção de H2S

The present work was to carry out a study on the adsorption of hydrogen sulfide (H2S) in arrays synthesized from a commercial clay mineral formed by a mixture of dolomite and quartz. To produce the ion exchange matrix were made using aqueous solutions of salts of cobalt II chloride hexahydrate (CoCl2.6H2O) II cadmium nitrate tetrahydrate (Cd (NO3)2.4H2O) I mercuric chloride (HgCl) nitrate and chromium III pentahydrate (Cr (NO3)3.5H2O). The arrays were subjected to hydrogen sulphide gas passage for one hour. To check the amount of gas adsorbed was used gravimetric process. The best result was in the adsorption matrix doped with cadmium and the solution retained for a longer time than the largest amount of H2S was the cobalt matrix. The matrix unmodified exhibited poor adsorption capacity. The characterization of the matrices were used XRD, XRF and IV. Mother with cadmium showed a high capacity in ion exchange, because the percentage of cadmium increased from 0% to 81.38% by replacing atoms of calcium and silicon which increased from 96.54% to 17.56% and 15, 72% to 0.32%, respectively, but also the best performance in adsorption of H2S adsorbing 11.89507 mg per gram of matrix