973 resultados para Hazardous Substances


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"3/94"--P [4] of cover.

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Arsenic has been classified as a group I carcinogen. It has been ranked number one in the CERCLA priority list of hazardous substances due to its frequency, toxicity and potential for human exposure. Paradoxically, arsenic has been employed as a successful chemotherapeutic agent for acute promyelocytic leukemia and has found some success in multiple myeloma. Since arsenic toxicity and efficacy is species dependent, a speciation method, based on the complementary use of reverse phase and cation exchange chromatography, was developed. Inductively coupled plasma mass spectrometer (ICP-MS), as an element specific detector, and electrospray ionization mass spectrometer (ESI-MS), as a molecule specific detector, were employed. Low detection limits in the µg. L−1 range on the ICP-MS and mg. L−1 range on the ESI-MS were obtained. The developed methods were validated against each other through the use of a Deming plot. With the developed speciation method, the effects of both pH on the stability of As species and reduced glutathione (GSH) concentration on the formation and stability of arsenic glutathione complexes were studied. To identify arsenicals in multiple myeloma (MM) cell lines post arsenic trioxide (ATO) and darinaparsin (DAR) incubation, an extraction method based on the use of ultrasonic probe was developed. Extraction tools and solvents were evaluated and the effect of GSH concentration on the quantitation of arsenic glutathione (As-GSH) complexes in MM cell extracts was studied. The developed method was employed for the identification of metabolites in DAR incubated cell lines where the effect of extraction pH, DAR incubation concentration and incubation time on the relative distribution of the As metabolites was assessed. A new arsenic species, dimethyarsinothioyl glutathione (DMMTA V-GS), a pentavalent thiolated arsenical, was identified in the cell extracts through the use of liquid chromatography tandem mass spectrometry. The formation of the new metabolite in the extracts was dependent on the decomposition of s-dimethylarsino glutathione (DMA(GS)). These results have major implications in both the medical and toxicological fields of As because they involve the metabolism of a chemotherapeutic agent and the role sulfur compounds play in this mechanism.

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Spent hydroprocessing catalysts (HPCs) are solid wastes generated in refinery industries and typically contain various hazardous metals, such as Co, Ni, and Mo. These wastes cannot be discharged into the environment due to strict regulations and require proper treatment to remove the hazardous substances. Various options have been proposed and developed for spent catalysts treatment; however, hydrometallurgical processes are considered efficient, cost-effective and environmentally-friendly methods of metal extraction, and have been widely employed for different metal uptake from aqueous leachates of secondary materials. Although there are a large number of studies on hazardous metal extraction from aqueous solutions of various spent catalysts, little information is available on Co, Ni, and Mo removal from spent NiMo hydroprocessing catalysts. In the current study, a solvent extraction process was applied to the spent HPC to specifically remove Co, Ni, and Mo. The spent HPC is dissolved in an acid solution and then the metals are extracted using three different extractants, two of which were aminebased and one which was a quaternary ammonium salt. The main aim of this study was to develop a hydrometallurgical method to remove, and ultimately be able to recover, Co, Ni, and Mo from the spent HPCs produced at the petrochemical plant in Come By Chance, Newfoundland and Labrador. The specific objectives of the study were: (1) characterization of the spent catalyst and the acidic leachate, (2) identifying the most efficient leaching agent to dissolve the metals from the spent catalyst; (3) development of a solvent extraction procedure using the amine-based extractants Alamine308, Alamine336 and the quaternary ammonium salt, Aliquat336 in toluene to remove Co, Ni, and Mo from the spent catalyst; (4) selection of the best reagent for Co, Ni, and Mo extraction based on the required contact time, required extractant concentration, as well as organic:aqueous ratio; and (5) evaluation of the extraction conditions and optimization of the metal extraction process using the Design Expert® software. For the present study, a Central Composite Design (CCD) method was applied as the main method to design the experiments, evaluate the effect of each parameter, provide a statistical model, and optimize the extraction process. Three parameters were considered as the most significant factors affecting the process efficiency: (i) extractant concentration, (ii) the organic:aqueous ratio, and (iii) contact time. Metal extraction efficiencies were calculated based on ICP analysis of the pre- and post–leachates, and the process optimization was conducted with the aid of the Design Expert® software. The obtained results showed that Alamine308 can be considered to be the most effective and suitable extractant for spent HPC examined in the study. Alamine308 is capable of removing all three metals to the maximum amounts. Aliquat336 was found to be not as effective, especially for Ni extraction; however, it is able to separate all of these metals within the first 10 min, unlike Alamine336, which required more than 35 min to do so. Based on the results of this study, a cost-effective and environmentally-friendly solventextraction process was achieved to remove Co, Ni, and Mo from the spent HPCs in a short amount of time and with the low extractant concentration required. This method can be tested and implemented for other hazardous metals from other secondary materials as well. Further investigation may be required; however, the results of this study can be a guide for future research on similar metal extraction processes.

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The capacity of dry protonated calcium alginate beads to sorb metals from an industrial effluent was studied and compared with a commercial ion-exchange resin (Lewatit TP 207). Both sorbents decreased zinc, nickel, iron and calcium concentrations in the effluent, and released sodium during treatment. Alginate beads removed lower amounts of heavy metals than the resin, but exhibited faster uptake kinetics. Zinc desorption from the sorbents was achieved in 30 minutes using 0.1 M HCl or 0.1 M H(2)SO(4). Desorption ratios with these acids varied between 90 and 100% for alginate, and 98 to 100% for the ion-exchange resin. Reusability tests with HCl showed that alginate beads can stand acid desorption and recover binding capacity. Overall, the comparison of dry protonated alginate beads with the resin supports the potential of the biosorbent for the treatment of industrial effluents.

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Natural events are a widely recognized hazard for industrial sites where relevant quantities of hazardous substances are handled, due to the possible generation of cascading events resulting in severe technological accidents (Natech scenarios). Natural events may damage storage and process equipment containing hazardous substances, that may be released leading to major accident scenarios called Natech events. The need to assess the risk associated with Natech scenarios is growing and methodologies were developed to allow the quantification of Natech risk, considering both point sources and linear sources as pipelines. A key element of these procedures is the use of vulnerability models providing an estimation of the damage probability of equipment or pipeline segment as a result of the impact of the natural event. Therefore, the first aim of the PhD project was to outline the state of the art of vulnerability models for equipment and pipelines subject to natural events such as floods, earthquakes, and wind. Moreover, the present PhD project also aimed at the development of new vulnerability models in order to fill some gaps in literature. In particular, a vulnerability model for vertical equipment subject to wind and to flood were developed. Finally, in order to improve the calculation of Natech risk for linear sources an original methodology was developed for Natech quantitative risk assessment methodology for pipelines subject to earthquakes. Overall, the results obtained are a step forward in the quantitative risk assessment of Natech accidents. The tools developed open the way to the inclusion of new equipment in the analysis of Natech events, and the methodology for the assessment of linear risk sources as pipelines provides an important tool for a more accurate and comprehensive assessment of Natech risk.

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This research investigated expertise in hazardous substance risk assessment (HSRA). Competent pro-active risk assessment is needed to prevent occupational ill-health caused by hazardous substance exposure occurring in the future. In recent years there has been a strong demand for HSRA expertise and a shortage of expert practitioners. The discipline of Occupational Hygiene was identified as the key repository of knowledge and skills for HSRA and one objective of this research was to develop a method to elicit this expertise from experienced occupational hygienists. In the study of generic expertise, many methods of knowledge elicitation (KE) have been investigated, since this has been relevant to the development of 'expert systems' (thinking computers). Here, knowledge needed to be elicited from human experts, and this stage was often a bottleneck in system development, since experts could not explain the basis of their expertise. At an intermediate stage, information collected was used to structure a basic model of hazardous substance risk assessment activity (HSRA Model B) and this formed the basis of tape transcript analysis in the main study with derivation of a 'classification' and a 'performance matrix'. The study aimed to elicit the expertise of occupational hygienists and compare their performance with other health and safety professionals (occupational health physicians, occupational health nurses, health and safety practitioners and trainee health and safety inspectors), as evaluated using the matrix. As a group, the hygienists performed best in the exercise, and this group were particularly good at process elicitation and at recommending specific control measures, although the other groups also performed well in selected aspects of the matrix and the work provided useful findings and insights. From the research, two models of HSRA have been derived, an HSRA aid, together with a novel videotape KE technique and interesting research findings. The implications of this are discussed with respect to future training of HS professionals and wider application of the videotape KE method.

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Polymeric nanoparticles have been developed for several applications, among them as carrier system of pesticides. However, few studies have investigated the fate of these materials in the environment in relation to colloidal stability and toxicity. In nature, humic substances are the main agents responsible for complexation with metals and organic compounds, as well as responsible for the dynamics of these nanoparticles in aquatic and terrestrial environments. In this context, the evaluation of the influence of aquatic humic substances (AHS) on the colloidal stability and toxicity of polymeric nanoparticles of chitosan/tripolyphosphate with or without paraquat was performed. In this study, the nanoparticles were prepared by the ionic gelation method and characterized by size distribution measurements (DLS and NTA), zeta potential, infrared and fluorescence spectroscopy. Allium cepa genotoxicity studies and ecotoxicity assays with the alga Pseudokirchneriella subcapitata were used to investigate the effect of aquatic humic substances (AHS) on the toxicity of this delivery system. No changes were observed in the physical-chemical stability of the nanoparticles due to the presence of AHS using DLS and NTA techniques. However some evidence of interaction between the nanoparticles and AHS was observed by infrared and fluorescence spectroscopies. The ecotoxicity and genotoxicity assays showed that humic substances can decrease the toxic effects of nanoparticles containing paraquat. These results are interesting because they are important for understanding the interaction of these nanostructured carrier systems with species present in aquatic ecosystems such as humic substances, and in this way, opening new perspectives for studies on the dynamics of these carrier systems in the ecosystem.

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Aims: To determine the prevalence of hazardous drinking and alcohol-related negative consequences in New Zealand tertiary students, and to identify predictors of hazardous drinking across a 6-month period. Methods: A total of 1480 tertiary students living in halls of residence was surveyed at the start of the academic year, and a subsample of 967 students was followed up 6 months later. Questionnaire items included quantity and frequency of drinking, alcohol-related problems, use of other substances, and the Alcohol Use Disorders Identification Test (AUDIT). Drinking at follow-up was modelled using demographic characteristics, mental well-being, other substance use, alcohol-related problems, and hall drinking norms, measured at baseline. Results: Among drinkers, mean (+/- SD) weekly consumption was 243 +/- 241 and 135 +/- 157 g of ethanol for males and females respectively. The majority of male (60.0%) and female (58.2%) drinkers typically consumed more than national safe drinking guidelines. Mean (+/- SD) AUDIT scores were 10.9 +/- 7.6 for males and 7.6 +/- 5.9 for females. After controlling for AUDIT scores at baseline, increased AUDIT scores at follow-up were higher with lower age, Maori ethnicity, smoking, cannabis use, high levels of alcohol-related negative consequences, and higher levels of drinking in the student's hall of residence. Conclusions: Hazardous drinking is widespread and persistent among students living in the halls of residence. There is a need for university alcohol policies and intervention approaches among New Zealand tertiary students.

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L’objectif principal du présent mémoire réside dans l’exploration des liens concomitants existant entre les trois dimensions de l’épuisement professionnel telles que définies par Maslach (1981) et la consommation de substances psychoactives, plus précisément au niveau de la consommation épisodique excessive et hebdomadaire à risque d’alcool et de la consommation de médicaments psychotropes. À partir d’un échantillon composé de 1809 travailleurs provenant de 83 milieux de travail québécois, des profils-types correspondant à des formes particulières de comorbidité de santé mentale au travail sont identifiés grâce à la méthode d’analyse en classes latentes. Ainsi quatre profils-types sont dégagés: un premier regroupant les individus dits «sains», dont les scores aux différentes dimensions de l’épuisement professionnel sont faibles et dont la consommation de substances psychoactives est modérée; deux autres correspondant à des formes intermédiaires de risques; et un quatrième rassemblant des travailleurs dits «fragiles» dont les scores pour chacune des dimensions de l’épuisement professionnel se situent dans le quintile le plus élevé et dont les probabilités de consommation de substances psychoactives sont grandes. De plus, cette recherche s’est penchée sur l’identification de facteurs de risque et de protection associés à chacun des profils-types. À cet effet, les résultats des analyses corroborent la plupart des associations retrouvées au sein de la littérature quant aux facteurs du travail (composantes des modèles du stress professionnel de Karasek et Theorell (1990) ainsi que de Siegrist (1990)), hors travail (statut matrimonial, obligations parentales, revenu du ménage) et certaines caractéristiques individuelles (âge et genre). De faibles récompenses et un fort degré de surinvestissement de la part de l’individu se révèlent être des facteurs de risque particulièrement significatifs pour les formes intermédiaires et à risque de comorbidité de la santé mentale au travail. Dans une moindre mesure, une faible utilisation des compétences, des demandes psychologiques élevées, un soutien social inadéquat et le jeune âge expliquent une part de la variation observée entre les différents profils-types. Enfin, les résultats soutiennent une conceptualisation tridimensionnelle de l’épuisement professionnel.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)