Made available in DSpace on 2014-12-17T14:06:45Z (GMT). No. of bitstreams: 1 RosaneMPBO.pdf: 98647 bytes, checksum: ef6407a549134b95288d059aac5174a4 (MD5) Previous issue date: 2008-05-02 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / 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 / O g?s natural ? uma fonte de energia alternativa encontrada no subsolo em rochas porosas e perme?veis, podendo estar associado ou n?o ao petr?leo. Sua composi??o b?sica inclui metano, outros hidrocarbonetos e compostos tais como o di?xido de carbono, nitrog?nio, g?s sulf?drico, mercaptanas, ?gua e part?culas s?lidas. Neste trabalho, o mineral dolomita, um carbonato duplo de c?lcio e magn?sio de f?rmula qu?mica CaMg(CO3)2, foi avaliado como material adsorvente. O material foi caracterizado atrav?s de an?lise granulom?trica, fluoresc?ncia de raios X, difra??o de raios X, an?lise termogravim?trica, an?lise t?rmica diferencial, ?rea de superf?cie espec?fica, porosidade, microscopia eletr?nica de varredura, espectroscopia de absor??o na regi?o do infravermelho e, posteriormente, foi funcionalizado com dietanolamina (dolomita+dietanolamina) e diisopropilamina (dolomita+diisopropilamina). Os resultados indicaram que os adsorventes apresentavam caracter?sticas f?sico-qu?micas adequadas para adsor??o de H2S. Os ensaios de adsor??o foram realizados em um sistema acoplado a um cromat?grafo a g?s e o monitoramento do H2S na sa?da do sistema foi realizado por um detector fotom?trico de chama pulsante (PFPD). Os adsorventes apresentaram uma capacidade de adsor??o significativa. Dentre os adsorventes analisados, a dolomita+dietanolamina apresentou melhor capacidade de adsor??o, as curvas de ruptura obtidas comprovaram a efici?ncia deste processo

Ce travail de thèse a porté sur l’impact de traces d’oxygène sur la corrosion de fer pur ou d’acier en milieu H 2 S, ainsi que sur le chargement en hydrogène. Trois axes de recherche ont été suivis.Une première partie est consacrée à la chimie de la réaction H 2 S+O 2 . Nous avons d’abord identifié dans la littérature les chemins réactionnels possibles de la réaction H2S+O2 , et les méthodes d’analyse des espèces S-O en solution. Nous avons ensuite utilisé des méthodes thermodynamiques pour prédire les espèces les plus stables, qui ont été validées par des essais expérimentaux. Il ressort de cette analyse que les principaux produits solubles de la réaction H2S+O2 sont les ions sulfate, thiosulfate etsulfite, ainsi que les ions H + . La décroissance continue du pH de la solution d’essai dans un système corrosif en milieu H2S peut être un indicateur d’une pollution par l’oxygène.La seconde partie utilise des méthodes électrochimiques pour étudier les phénomènes de corrosion et de formation de dépôts en présence ou en absence d’oxygène. La vitesse de corrosion est systématiquement plus grande en présence de O2 . Un modèle d’impédance a été developpé pour l’étude de l’évolution de l’interface métal/électrolyte, et ce modèle est en accord avec la littérature et est validé par l’évaluation de la vitesse de corrosion par perte de masse.Enfin, la troisième partie est consacrée au chargement en hydrogène dans le fer pur ou dans un acier pétrolier de type X65. En absence de pollution par l’oxygène, on observe des rendements très proches de 100 % entre le courant de perméation et le courant de corrosion estimé à partir des mesures d’impédance, et ce sur plusieurs semaines. En présence d’O2 , ce rendement est systématiquement beaucoup plus faible. Par ailleurs, quelques tests menés sur l’acier pétrolier montrent également un effet important de l’oxygène sur le caractère plus ou moins protecteur du dépôt, qui n’avait pas été observé sur système modèle utilisant du fer pur / The work in this thesis presents the effect of trace concentrations of oxygen (O2 ) on corrosion and hydrogen uptake of pure iron/steel in H2S-media. Three main avenues of research were conducted.The first part is concerned with the reaction chemistry between dissolved H2S and O2. A literature review is presented, identifying a number of reaction pathways associated with the dissolved H2S and O2 reaction as well as analytical methods used to measure the resulting S-O reaction products. Subsequently, thermodynamic calculations allow for the prediction of the most stable species indissolved H2S -O2 solutions, later confirmed using spectroscopic and chromatographic methods. Such techniques reveal that the principal soluble reaction products are sulfate, thiosulfate and sulfite anions,as well as hydronium ions. From pH monitoring, a continuous rise in acidity of an H2S solution can be an indication of O2 ingress.Secondly, electrochemical methods are used to explore corrosion phenomena and deposit formation in the presence and absence of O2 pollution. Corrosion rates in the presence of O2 are reproducibly much higher if compared against those in the system lacking O2 . An electrochemical impedance spectroscopy model has been developed to study the evolution of the metal / electrolyte interface over time, which is validated using weight loss corrosion rate measurements, and represents impedance data reported in the literature on similar systems.Finally, the third part is devoted to hydrogen uptake in pure iron and petroleum industry sour-grade steel (X65). In the absence of O2 pollution, permeation efficiency yields close to 100% are observed between the permeation current and the corrosion current estimated from the impedance measurements over a period of several weeks. In the presence of O2 , however, this yield is reproducibly far lower. Moreover, some tests conducted on X65 also show a significant effect of O2 on the quite protective nature of the deposit, not observed on the model system using pure iron

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A precipitaÃÃo de Ãons metÃlicos com sulfeto à um processo importante no tratamento Ãguas residuÃrias oriundas de efluentes industriais de acabamento metÃlico. Sobretudo, por ser uma alternativa viÃvel para a recuperaÃÃo e reutilizaÃÃo de metais jà que o controle de pH a torna seletiva. O presente trabalho estudou a precipitaÃÃo seletiva de Cu2+, Zn2+ e Ni2+ utilizando H2S(g) gerado pela hidrÃlise da Tioacetamida. Os estudos foram realizados em escala laboratorial em duas etapas. Na primeira etapa, foram realizados estudos monoelementar para cada Ãon (100 mg.L-1), sendo inicialmente investigado os seguintes parÃmetros: montagem do sistema reacional, faixa de pH (2,0 a 6,0) e tempo de exposiÃÃo ao gÃs H2S (de 30 a 150 minutos). O estudo mostrou que o Cu2+ precipita imediatamente quando à exposto ao H2S(g) e em qualquer valor de pH testados alcanÃando 99,9% de remoÃÃo. Para o Zn2+ a precipitaÃÃo foi preferencial quando o pH ficou entre 4,0 e 5,0, e o tempo de exposiÃÃo ideal foi de 60 min, para que a precipitaÃÃo fosse acima de 95,0%. O pH influenciou todo o processo de precipitaÃÃo dos Ãons, sendo mais influente para o Ni2+, iniciando sua precipitaÃÃo em pH 6,0, e apÃs 4 ciclos de 30 min, somando um tempo de exposiÃÃo de 120 min para que a sua remoÃÃo fosse acima de 90%. Na segunda etapa, foram realizados estudos de mistura binÃria e ternÃria dos Ãons a partir dos valores de pH e tempo de exposiÃÃo encontrados pelo estudo individual. Em resumo, os resultados obtidos nos experimentos feitos com a mistura dos Ãons corresponderam aos resultados obtidos no estudo de metal simples, fixando o valor de pH 2,0 para precipitaÃÃo do Cu2+, pH entre 4,0 e 5,0 para precipitaÃÃo do Zn2+ e pH = 6,0 para precipitaÃÃo do Ni2+. Para os sistemas Cu2+-Zn2+ e Cu2+-Ni2+ os resultados mostraram pouca interferÃncia de um Ãon na precipitaÃÃo do outro, sendo possÃvel a separaÃÃo de ambos e precipitaÃÃo acima de 90%. Por outro lado para o estudo do sistema Zn+2-Ni +2 foi constatado que o controle rÃgido de pH à determinante para separar sulfetos metÃlicos com pKps muito prÃximos, obtendo 90% de remoÃÃo para ambos. Os resultados envolvendo a separaÃÃo fracionada do sistema Cu2+-Zn2+-Ni2+ foram satisfatÃrios, nÃo necessitando do uso de agentes complexantes e sim o controle rÃgido de pH. / The precipitation of metal sulfides is an important process to treat wastewater coming from industrial effluents from metal finishing Mostly because it is a viable alternative for the recovery and reuse of metals by controlling the pH becomes selective. This work studied the selective precipitation.of Cu2+, Zn2+-and Ni2+ using H2S(g) provided by the hydrolysis of thioacetamide. The studies were conducted in laboratory scale and in two steps. Firstly, studies were performed for each single metal ion (100 mg.L-1) were initially investigated the following parameters: setting up a reaction system, the pH range (0,5 a 6,0) and exposure time (30 -150 minutes). The studies showed that Cu2+ easily precipitated in the first 30 min at all pH values tested reaching 99,9% of removal. For the Zn2+ precipitation is preferred when the pH was between4.0 and 5.0, and optimum exposure time was 60 min, so that the precipitation was greater than 95.0%. The pH has influenced the process ion precipitation, and most influential for the Ni2+, starting from their precipitation at pH 6.0, and after 4 times of 30 min, adding an exposure time of 120 min so that its removal should be above 90%. In the second step, studies were conducted in binary and ternary mixture of ions from the values of pH and exposure time for individual study found. In summary, the results obtained in experiments conducted with the mixture of the ions correspond to the results obtained in the study of single metal, setting the pH value of 2.0 to precipitation of Cu2+, pH between 4.0 and 5.0 for precipitation of Zn2+ and pH = 6,0 for precipitation of Ni2+. For systems Cu2+ and Zn2+, Cu2+ and Ni2+ results showed little interference of an ion in the precipitation of another, with the possible separation and precipitation of both above 90%. In addition to the study of the system Zn2+- Ni2+ was found that the rigid control of pH is critical to separate metallic sulfides pKps very close to getting 90% removal for both. The results involving the fractional separation system Cu2+, Zn2+ e Ni2+ were satisfactory and does not require the use of complexing agents, but the drive control of pH.

Dans le cadre de ces travaux, il a clairement été établi que l’hydrogène piégé ou diffusible pouvait avoir une forte influence sur les propriétés mécaniques des matériaux. Cependant, cet effet varie de façon importante en fonction de leur microstructure, leur composition chimique et leur traitement thermique. En effet, les aciers martensitiques trempés/revenus dédiés à des tubes pour des milieux sous-service présentent, de par leur structure, différents types de pièges tels que les dislocations, les joints de grains, les précipités, les inclusions, les lacunes et d’autres interfaces qui jouent un rôle important dans les mécanismes endommageants. Ces aciers de haute résistance mécanique, lorsqu’ils sont soumis à des contraintes mécaniques et à un environnement agressif (qui dépend de la pression en H2S et du pH de la solution) peuvent rompre à cause du phénomène de Sulphide Stress Cracking (SSC). Ce dernier est une forme de fragilisation par l’hydrogène (FPH) qui inclut un amorçage de fissure suivi d’une étape de propagation conduisant à la rupture, dont la contribution de l’hydrogène reste encore mal comprise. En parallèle de l’impact de la microstructure de l’acier, les champs de contrainte et déformation subis par le matériau modifient les effets induits par l’hydrogène. C’est pourquoi un montage de perméation sous contrainte a été utilisé afin de pouvoir réaliser des essais mécaniques jusqu’à rupture sous flux d’hydrogène et les comparer au comportement du matériau lorsque celui-ci est sollicité à l’air ou dans un environnement H2S. Ainsi, l’impact sur le comportement mécanique du flux d’hydrogène mais également de son piégeage peut être étudié. Dans ce cadre, des éprouvettes plates et axisymétriques, lisses et entaillées ont été employées. Les informations expérimentales obtenues dans ce travail ont servi à alimenter un modèle numérique qui a permis de caractériser localement l’état mécanique et les concentrations d’hydrogène piégé et diffusible dans le matériau. Ceci a rendu possible la définition d’un critère local de rupture. / The findings of this work established that the diffusible and trapped hydrogen could have a strong influence on the mechanical properties of materials. However, this effect varies significantly with the materials’ microstructure, chemical composition, and heat treatment. Due to their structure, quenched and tempered martensitic steels (developed for tubes suitable for sour service environments) have different types of traps such as dislocations, grain boundaries, precipitates, inclusions, vacancies and other interfaces that play an important role in the damage mechanisms. These high strength steels may break due to Sulphide Stress Cracking (SSC) if subjected to mechanical stress and an aggressive environment (which depends on the H2S partial pressure and pH solution). This phenomenon is a form of hydrogen embrittlement (HE) that includes a crack initiation followed by a propagation step leading to failure. However the hydrogen contribution is still insufficiently understood. In addition to the impact of the microstructure on the steel, the stress and the deformation fields in the material also modify the effects induced by hydrogen. To investigate this event, electrochemical permeation tests under stress were used to perform mechanical tests under hydrogen flux until failure is reached. The results were compared to those mechanically loaded in air or in a H2S environment. This enabled the examination of the impact of the hydrogen flux and trapping on the mechanical behavior of martensitic steel. In this framework, flat and axisymmetric, smooth and notched specimens were employed. Experimental data obtained in this work were used to provide a numerical model that enables the locally characterization of the mechanical condition and the concentrations of trapped and diffusible hydrogen in the material. These outcomes enabled us to determine a local failure criterion.

Ce travail de thèse s’inscrit dans le contexte de la désulfuration par absorption des gaz utilisables dans des technologies émergentes comme les piles à combustible ou le procédé Fischer-Tropsch. Cette purification peut être réalisée à des températures modérées (200-300°C) sans régénération d'échantillon. L’absence de traitements à haute température permet d'envisager l'utilisation des solides nanostructurés qui devraient montrer naturellement une réactivité élevée. En fonction du schéma précis du procédé, on pourra être amené à éliminer des molécules de nature différente : H2S ou des molécules réfractaires comme mercaptans ou thiophènes. Pour répondre à ces exigences, la thèse s'est déroulée en deux parties. Dans la première partie des échantillons à base de nanoparticules de ZnO pur et dopé (M0,03Zn0,97O, M=Fe, Co, Ni, Cu) ont été préparés, caractérisés et leur réactivité vis-à-vis d’H2S a été étudiée. Il a été trouvé que le cuivre est le dopant qui permet d’améliorer le plus les performances de l’échantillon. L'étude du mécanisme de sulfuration par MET, DRX in situ et XPS a permis de conclure que la diffusion des ions O2- à travers la couche de ZnS est l'étape limitante de la sulfuration. Son accélération en présence de cuivre serait due à la formation d'une solution solide Cu2S-ZnS riche en lacunes anioniques. La deuxième partie du travail a été consacrée à l'élimination du thiophène. Un nouveau solide nanocomposite 2,8NiO-H1,8Ni0,6(OH)MoO4 a été mis au point. Sa structure ouverte sous forme de feuillets et sa capacité à se réduire facilement en présence d’H2 créent des conditions propices pour l'interaction avec le thiophène et permettent ainsi d'augmenter considérablement sa vitesse de sulfuration en comparaison avec l'échantillon classique à base de Ni/ZnO. Sa haute réactivité avec le thiophène en fait un excellent candidat pour éliminer les traces d’autres espèces sulfurées (COS, CS2, mercaptans). / This work focuses on the desulfurization by absorption of gases which can be used inemerging technologies such as fuel cells or Fischer-Tropsch process. This purification canbe achieved at low temperatures (200-300°C) without regeneration of the sorbent. Theabsence of high temperature treatment allow to use nanostructured solids wich can normallymust exibit higher reactivity. Depending on the process chosen, we will have to eliminatemolecules of different nature : H2S or molecules like mercaptans or thiophene. To answerthese requirements, the thesis work consisted of two parts. In the first part, nanoparticles ofpure and doped ZnO (M0,03Zn0,97O, M=Fe,Co,Ni,Cu) were synthesized and characterized,and their reactivity towards H2S was investigated. It was found that copper is the dopandwhich allow to improve considerably the performances of the sorbent. The study ofsulfidation mechanism by TEM, in situ XRD and XPS allow to conclude that diffusion ofO2- ions trough the ZnS layer is the rate limiting step of sulfidation. The acceleration in thepresence of copper may be due to formation of a solid solution Cu2S-ZnS rich in anionicvacancies. The aim of the second part of this work was to eliminate thiophene. A newnanocomposite solid 2,8NiO-H1,8Ni0,6(OH)MoO4 was prepared. Its layered open structureand its ability to be easily reduced create favorable conditions for interactions withthiophene, and in this way, allow to increase considerably its sulfidation rate (in comparisonwith the sulfidation rate of the classical sample Ni/ZnO). Its high reactivity with thiophenemakes it an excellent candidate for the elimination of other sulfure containing molecules(COS, CS2, mercaptans).

Hydrogen Sulfide (H2S) is a harmful gas produced during petroleum extraction that leads to corrosion of drilling tools and pipelines. However, a H2S-scavenging liquid compound, when added to pipelines, interacts with liquids that absorbed H2S to create a non-corrosive bi-product. The interaction is associated with the mixing of gases and liquids. This thesis is a study on the effect of superficial gas and liquid velocities on the scavenger's efficiency. This study employs two experimental setups designed to simulate the mixing of gases and liquids within pipelines. A high pressure closed loop was designed and fabricated to determine the influence of gas, liquid velocities and liquid volume on the scavenger's efficiency. All experiments were conducted in this high pressure loop with a thousand feet of coiled tubing to simulate the horizontal section of the pipeline that runs along the ocean floor from the reservoir. This provided practical understanding to petroleum companies to make a better forecast of how the scavenger used in eliminating the H2S, is affected in the process of transporting the liquids and gases from the reservoir to the surface. For an adequate analysis, experiments on four liquid and four gas velocities ranging from 0.2m/s to 0.5m/s and 0.4m/s to 1.1m/s respectively were conducted. Results in this study indicated that increases in superficial gas velocity at low superficial liquid velocity decreases the scavenger efficiency while the opposite is seen at high superficial liquid velocity. In addition, the H2S mass absorption was not a function of liquid volume as would be seen in static reservoirs but more of a function of superficial liquid and gas velocities. With the scavenger interacting with the liquid absorbed H2S, it was expected that the efficiency would increase with the increase in volume but in this study this was not the case. The second experiment is a flow visualization loop which was designed to understand the flow regimes at high pressures. This was done by constructing four 25ft section hoses together with four foot long breaks for visualization. This provided a more fundamental study of the fluid's behavior inside the pipelines allowing for the creation of appropriate flow regime maps in air-water flow. A hundred experiments for two different pressures were conducted at the 25ft location. At high pressures, the flow regime map appeared to shift the transition zones.

Emission of odorous and gaseous compounds such as hydrogen sulphide (H2S) from livestock facilities can be a major impediment to its daily operations and potential expansion. Occupational and environmental concerns require the control of H2S emissions. A treatment approach used in the oil industry in which nitrite and/or molybdate are used as metabolic inhibitors to control the production of H2S in oil reservoirs was shown to be effective in controlling H2S emissions from swine manure.<p> The addition of nitrite and molybdate to swine manure was investigated in closed laboratory scale systems and then evaluated in semi-pilot scale open systems and in specifically designed chambers aiming to simulate an actual swine barn. The effect of manure age (extent of storage) on H2S emissions and the levels of nitrite and molybdate required for effective control of these emissions were assessed. Laboratory scale tests showed that emission of H2S was dependent on manure age. Fresh manure emitted the highest level of H2S and the level of emission decreased as manure age (1-6 months) increased. With fresh 1, 3, and 6-month old manures average H2S concentration in the headspace gas of the closed systems were 4856b460, 3431b208, 1037b98 ppm, and non-detectable (<0.4 ppm), respectively. This translated to lower levels of nitrite or molybdate required to control H2S emission with increase in manure age. When compared to molybdate, the addition of nitrite initially led to lower levels of H2S but its effect was only temporary and not as persistent as molybdate. In the semi-pilot and room scale tests H2S levels emitted from untreated fresh manure (831¡Ó26 ppm and 88.4 ppm, respectively), were significantly lower than those observed in the laboratory system (4856¡Ó460 ppm). Moreover, the levels of molybdate required to control the emission of H2S were much lower in both the semi-pilot system and in the room scale chamber than in the closed system (0.1-0.25 mM as opposed to 2 mM).<p> Small scale land application of manure treated with 0.1 mM molybdate did not raise the level of molybdenum in the soil that could cause potential toxicity to plants and animals. No major differences in the nutrient properties of the soils exposed to the treated and untreated manure were observed. Finally, a preliminary feasibility study of this treatment approach showed that the cost associated with this control approach was less than 1% of the total production cost.

Emission of odorous and gaseous compounds such as hydrogen sulphide (H2S) from livestock facilities can be a major impediment to its daily operations and potential expansion. Occupational and environmental concerns require the control of H2S emissions. A treatment approach used in the oil industry in which nitrite and/or molybdate are used as metabolic inhibitors to control the production of H2S in oil reservoirs was shown to be effective in controlling H2S emissions from swine manure.<p> The addition of nitrite and molybdate to swine manure was investigated in closed laboratory scale systems and then evaluated in semi-pilot scale open systems and in specifically designed chambers aiming to simulate an actual swine barn. The effect of manure age (extent of storage) on H2S emissions and the levels of nitrite and molybdate required for effective control of these emissions were assessed. Laboratory scale tests showed that emission of H2S was dependent on manure age. Fresh manure emitted the highest level of H2S and the level of emission decreased as manure age (1-6 months) increased. With fresh 1, 3, and 6-month old manures average H2S concentration in the headspace gas of the closed systems were 4856b460, 3431b208, 1037b98 ppm, and non-detectable (<0.4 ppm), respectively. This translated to lower levels of nitrite or molybdate required to control H2S emission with increase in manure age. When compared to molybdate, the addition of nitrite initially led to lower levels of H2S but its effect was only temporary and not as persistent as molybdate. In the semi-pilot and room scale tests H2S levels emitted from untreated fresh manure (831¡Ó26 ppm and 88.4 ppm, respectively), were significantly lower than those observed in the laboratory system (4856¡Ó460 ppm). Moreover, the levels of molybdate required to control the emission of H2S were much lower in both the semi-pilot system and in the room scale chamber than in the closed system (0.1-0.25 mM as opposed to 2 mM).<p> Small scale land application of manure treated with 0.1 mM molybdate did not raise the level of molybdenum in the soil that could cause potential toxicity to plants and animals. No major differences in the nutrient properties of the soils exposed to the treated and untreated manure were observed. Finally, a preliminary feasibility study of this treatment approach showed that the cost associated with this control approach was less than 1% of the total production cost.

Forest rings are large features common in Ontario’s boreal forests that comprise circular topographic depressions in carbonate mineral soil that are filled with peat. This thesis documents differences in peat and soil chemistry along transects across the “Bean” and “Thorn North” rings, which are centered on accumulations of CH4 and H2S, respectively. Within the mineral soil, ring edges are characterized by strong negative anomalies in pH, ORP and carbonate, as well as positive anomalies of Al, Fe and Mn in the results of aqua regia and hydroxylamine-hydrochloride digestions. Within the peat, positive carbonate and pH anomalies are recorded. This antithetic relationship suggests vertical migration of carbonate species from clay to peat. An inverse relationship exists between ORP, versus redox inferred from aqua regia. Strong ORP lows occur where oxidized products show highest concentrations. This is interpreted to reflect the proliferation of autotrophic organisms occupying the strong redox gradient at the ring edge.

Hydrogen sulfide (H2S) is an endogenous gasotransmitter that regulates vascular function and blood pressure, and also protects the heart from injury associated with myocardial infarction (MI). The mitochondrial enzyme thiosulfate sulfurtransferase (TST) has a putative role in the breakdown of H2S but its role in the cardiovascular system is unknown. I hypothesised that TST reduces cardiovascular H2S availability and that inhibiting TST activity may therefore ameliorate cardiovascular pathology. In the heart, TST was expressed by cardiomyocytes and vascular smooth muscle cells. Tst-/- mice all survived to adulthood and had normal cardiac structure and function. Cardiac and hepatic H2S breakdown rates were reduced and H2S levels were higher in the blood of Tst-/- mice. However, in heart tissue, protein levels for the H2S-activated Nrf2 downstream targets, thioredoxin (Trx1) and heme oxygenase-1 (HO-1) were comparable. In contrast, protein levels for the cardiac specific H2S-synthetic enzyme, cystathionine gamma lyase (CSE) was reduced, suggesting a homeostatic negative feedback mechanism to maintain H2S at non-toxic levels. Respiration, measured using an oxygen-sensing electrode was normal in isolated mitochondria from whole Tst-/- compared to control C57BL6 hearts. Endothelial nitric oxide synthase (eNOS) protein expression was lower in Tst-/- hearts, highlighting potential cross talk between H2S and nitric oxide (NO) signalling. TST was expressed in whole aorta homogenates and in isolated endothelial cells from aorta and small intramuscular vessels of the hindlimb from C57BL/6N control mice. Myography and western blotting revealed a greater influence of NO in aorta from Tst-/- mice that was associated with increased phosphorylation of the activating serine1177 residue of eNOS (PeNOSSer1177). NO plays a lesser role in resistance arteries, but in comparison to control vessels, small mesenteric vessels from Tst-/- mice was more reliant on small and intermediate calcium activated potassium channels for relaxation. Tst-/- mice were normotensive, despite this alteration in the regulation of vascular tone. However, metabolic cage experiments identified that Tst-/- mice presented with diuresis, polydipsia, and increased urinary electrolyte excretion of sodium, potassium and chloride, possibly to compensate for increased vascular tone in order to maintain stable blood pressure. To investigate the role of TST in regulating the response to pathological challenge, MI was induced by coronary artery ligation (CAL). In control mice, gene expression of CSE was downregulated by 2 days after CAL, but TST expression was 12-fold increased, suggesting regulation of H2S bioavailability during the acute MI-healing phase. Tst-/- male mice had a 40% greater incidence of cardiac rupture during infarct healing and surviving Tst-/- mice had greater left ventricular dilatation and impaired function compared to controls. Ex vivo, isolated perfused hearts from Tst-/- mice were more susceptible to ischaemia/ reperfusion injury, suggesting an additional role of TST in determining cardiomyocyte susceptibility to injury. In conclusion, these data indicate that cardiovascular H2S bioavailability is regulated through degradation by TST. The data presented here provide evidence for significant tissue specific crosstalk between H2S synthetic and degradative mechanisms and between H2S and other local regulatory mechanisms, including ion channels and NOS. We infer TST has a physiological role in the kidney where its loss leads to changes in renal electrolyte and water handling, although other compensatory mechanisms prevent a change in blood pressure. Under conditions of pathological challenge following MI, loss of TST is detrimental, illustrating its key role in removal of H2S. The data refute the original hypothesis that TST inhibition would be protective against cardiovascular pathology. Further studies in mice with tissue specific deletion of TST are now required to more fully reveal the cardiovascular role of TST.