As partículas atmosféricas com diâmetro aerodinâmico menor que 10 µm são classificadas por MP10. Essas partículas podem ser subdivididas em partículas grossas (entre 2,5 e 10 &#181;m) e finas (< 2,5 &#181;m), sendo que as últimas apresentam poder de penetração maior no organismo, podendo atingir os alvéolos pulmonares. O objetivo deste trabalho foi estudar espécies solúveis em água no material particulado MP10, coletado na Cidade Universitária (São Paulo-SP) durante o ano de 2003, como também, investigar a variação sazonal destas espécies na atmosfera de São Paulo, caracterizando as principais fontes de emissões existentes no sítio de estudo, tais como possíveis formações de espécies secundárias e influências de transporte de massas de ar. As amostras foram coletadas no Instituto de Astronomia, Geofísica e Ciências Atmosféricas da USP, utilizando filtros de fibra de quartzo e um amostrador de grande volume. A amostragem ocorreu a cada quinze dias, entre os meses de abril/2003 e maio/2004 (n=28), sendo realizadas também duas amostragens durante dias consecutivos, uma ocorrendo em março/2003 (n=5) e outra em julho/2003 (n=10). Esses dois períodos correspondem a estudos de casos, no qual o primeiro é caracterizado pela ocorrência de precipitação nos dias amostrados, enquanto, o segundo representa dias de ausência de precipitação, característicos do inverno na região de estudo. O tempo de amostragem foi de 24 horas. A extração da fração solúveis em água foi feita por via aquosa e a quantificação por cromatografia de íons. O inverno/2003 representou a estação de maior concentração média de MP10 e também das espécies estudadas, entretanto, considerando o intervalo de concentração obtido em cada estação, no outono/2003 foram encontrados valores de MP10 tão elevados quanto no inverno/2003. Nenhuma amostra apresentou concentração de material particulado acima do limite recomendado pela legislação brasileira (150 µg m-3), porém, considerando o limite de MP10 recomendado pela Organização Mundial de Saúde (50 µg m-3), apenas a primavera/2003 e o verão 2003/2004 não apresentaram amostras acima deste limite. O sulfato representou a espécie mais abundante da fração solúvel em água do MP10, não apresentando grandes variações ao longo das estações do ano. A razão entre os ácidos fórmico e acético mostrou que as reações fotoquímicas contribuem mais intensamente para a presença destas espécies na atmosfera do sítio estudado. O estudo das trajetórias de massas de ar e também as correlações entre as espécies mostraram que o sítio de estudo recebe influência de aerossóis marinhos e também de locais provenientes de queima de biomassa. / PM10 is classified by the atmospheric particulate matter that present the diameter smaller than 10 µm. These particles may be divided in the coarse fraction (diameter between 2,5 and 10 µm) and fine fraction (<2,5 µm). The fine fraction presents high power penetration in the human organism. The objective of this study was to determinate the water-soluble ions in the PM10 collected in the Cidade Universitária (São Paulo, SP) during 2003 year and to investigate the seasonal variation of these species, characterizing the principal emissions sources in the studied site, secondary reaction and air mass transport. Samples were collected in the Instituto de Astronomia, Geofísica e Ciências Atmosféricas of USP, using the high volume sample and fiber quartz filter. The sampling occurred every 15 days, between April/2003 and May/2004 (n=28). It was done two sampling in consecutive days, during March/2003 (n=5) and July (n=10). The first period was characterizing by occurrence of precipitation during the sample days and the second period was characterizing by absence of precipitation. The sample time was 24 hours. The extraction of the water soluble ions was done using water and the quantification by ions chromatography. The winter/2003 presented the highest average concentration of PM10 and of the studied species. However, considering the range of the concentration, the autumn/2003 presented PM10 concentration as high as winter/2003. It was not noticed concentrations of PM10 above that established by Brazilian laws (150 µg m-3), but considering the limit of PM10 established by World Health Organization (50 µg m-3), only spring/2003 and summer 2003/2004 did not present concentration highest than this limit. Sulfate was the more abundant studied species. The concentration of that ion did not present variation each season of the year. The ratio between formic acid and acetic acid showed that the photochemical reaction is the principal responsible for the presence of these acids in the atmosphere of studied site. The study of back mass trajectories and the correlation between same species showed that the São Paulo receive influence of marine aerosol by air mass transported and aerosols by region of the biomass burning, too.

O presente trabalho consistiu no desenvolvimento de metodologia simples e de baixo custo para determinação de gás carbônico da atmosféra. O CO2 é absorvido em solução aquosa de NaOH, 10-4M e, a solução resultante é adicionado NaCl para concentração final de 1,0M. A seguir, titula-se com ácido clorídrico 10-3M, potenciometricamente. A fim de se evitar interferência de íons carbonato possivelmente existentes na solução original de NaOH. Uma alíquota desta é titulada préviamente antes da absorção de CO2, constituindo o \"branco\". A solução de hidróxido de sódio e carbonato é titulada a seguir e, considera-se a diferença do volume no ponto final da solução do branco e da amostra; a avaliação é efetuada segundo Gran II, estudado por Pressinotti (9). Foram efetuados estudos experimentais de introdução do gás carbônico em solução de hidróxido de sódio. Estudaram-se os métodos com o uso de: a - com o uso de bomba misturadora; b - com o uso de frascos lavadores; c - com o uso de injeção com seringa em frasco plástico. Esta última mostrou ser simples e rápida para o processo. / This work deals with the development of a simple and low cost methodology the determination of carbonic gas in the atmosphere. The CO2 is absorved in aqueous solution of NaOH 10-4; M and, to t he resulting solution, NaCl is added to a concentratian of 1.0M and the potentiometric titration is done with HCl 10-3; M solution. To avoid the interference of carbonate ions in the original NaOH solution, an aliquot of the NaOH solution is previously titrated just before the absorption af CO2; this previous titration is the \"blank\". The final solulion of NaOH and carbonate ions is titrated and one measures the diference of the volume at the end point of the \"blank\" and the sample itself. The is made by Gran II method according to Pressinotti (9). Studies about introdution of CO2 in the solution of NaOH were made.The following methods were studied: a - by mixer bomb; b - by the cylindrical vessel bubble absorber; c - by the use of syringe injection. This last one showed to be extremaly simple and of low cost.

Visando a determinação de baixas concentrações de H2O2, HSO3- e Hidroximetanosulfonato (HMS) em água de chuva, desenvolveu-se novos métodos amperométricos em fluxo com detecção em eletrodo de gota pendente de mercúrio. A determinação analítica de H2O2 baseou-se na sua oxidação (reversível) em meio alcalino (NaOH 11mM), no potencial de -0,07V vs Ag/AgCI, em célula de fluxo adaptada a polarógrafo comercial. O limite de detecção foi 0,1 &#181;M. Para obter melhor seletividade, utilizou-se medidas diferenciais com e sem adição da enzima catalase. Para o HSO3- mostrou-se mais favorável sua redução a -0,8V, em meio ácido (tampão de HAc/Ac· 12/12mM). A interferência do oxigênio dissolvido foi eliminada por desgaseificação contínua com nova versão de dispositivo anteriormente desenvolvido. A corrente residual foi determinada mascarando o sinal do HSO3- por adição de HCHO. O HM:S foi determinado indiretamente. Após sua decomposição em HSO3- e HCHO, em pH em tomo de 12, reverteu-se o pH do fluxo para meio ácido e procedeu-se a determinação do HSO3- liberado. Aplicou-se as metodologias desenvolvidas às amostras de água de chuva, durante período de 12 meses. Foram observadas variações das concentrações das referidas espécies químicas em diversos eventos de precipitações, acompanhando-se o ciclo das estações climáticas e a intensidade da radiação solar. As concentrações de H2O2 variaram entre 0,3 a 34&#181;M, HSO3- não foi encontrado no período, enquanto HMS apresentou concentrações entre 0,1 e 1,5&#181;M. / Aiming the detennination of traces of H2O2, HSO3- an hydroximethanesulfonate (HMS) in rain water, a new flow method was developed, with amperometric detection at the hanging mercury drop electrode. The analytical detennination of H2O2 was based on its (reversible) oxidation in alkaline mediwn (NaOH 11 mM), by fitting a new flow adapter to a commercial multimode stand with the electrode operated as HMDE at -0.07V versus Ag/AgCl. Detection limit was 0.1&#181;M. To increase selectivity, differential measurements were done by subtracting the residual current after destruction of the analyte with the enzyme catalase. For the determination of HSO3-, results were more favorable for its reduction at -0.8V in acidic medium (HAc/Ac-) buffer, 12mM/12mM). The residual current was determined by masking the HSO3- signal with HCHO. HMS was determined indirectly. After its decomposition in alkaline medium (pH around 12) into SO3-2 and HCHO, the pH is lowered to 1.5 before detection of the HSO3-. Interference of oxygen was overcome by in-line degassing with a new two channel version of a previously described vacuum operated permeation device. The new methods were applied to rain samples collected during a one year period. Concentration of H2O2 ranged from 0.3 to 34&#181;M. HSO3- was not detected during the period and HMS appeared at concentrations between 0.1 to 1.5&#181;M. Although difficult to interpret, the results show correlation with intensity of solar radiation and, less clearly, with the seasons of the year.

Esta pesquisa se propõe a investigar as representações sociais acerca do termo \"Química Ambiental\" entre estudantes iniciantes (segundo semestre) e depois de quatro anos em andamento nos cursos de Bacharelado em Química Ambiental e Licenciatura em Química do Instituto de Química da Universidade de São Paulo. Adotamos como referencial de investigação a Teoria das Representações Sociais e como metodologia a técnica da associação livre de palavras associada à elaboração de um texto. Os resultados foram analisados através da freqüência e ordem média de evocação das palavras para delinear o núcleo central da representação social, além dos elementos periféricos. Nos textos são identificadas unidades de análise que são utilizadas para construção de mapas cognitivos. A associação das palavras mais evocadas com as leituras dos mapas cognitivos para cada aluno proporcionou a construção de um mapa conceitual representativo da visão sobre \"Química Ambiental\" para cada uma das turmas analisadas. De uma forma geral, os iniciantes tanto da Licenciatura em Química como da Química Ambiental apresentaram uma visão naturalista de meio ambiente e também revelaram uma concepção de Educação Ambiental sobre o ambiente, em que bastaria munir as pessoas com informações e fatos relacionados aos problemas ambientais para resolvê-los. Os estudantes iniciantes de ambos os cursos apresentaram uma concepção preservacionista do meio ambiente, sendo mais enfatizada a necessidade de conscientização das pessoas pelos licenciandos. Por outro lado, os bacharelandos em Química Ambiental fazem bastante menção à pesquisa com vistas ao tratamento da poluição e uma visão de remediação é predominante. A diferença entre as representações sociais verificadas entre os alunos das duas modalidades podem estar relacionadas, em parte, à representação social dos alunos sobre o seu papel enquanto profissionais nos aspectos que envolvem a Química Ambiental. Os alunos concluintes representam a Química Ambiental ainda com idéias preservacionistas. Um aspecto positivo, porém, é o aparecimento da idéia de Química Verde em ambos os grupos. As idéias centrais apresentadas pelos estudantes iniciantes em ambos os cursos incluem poluição, meio ambiente, reciclagem, e preservação. Essas mesmas idéias estavam presentes também no grupo de concluintes, o que significa que poderiam ser consideradas constituintes do núcleo central da representação, e que se mantém durante os cursos. Entretanto, foi possível notar a emergência de um elemento periférico de destaque: a Química Verde, que pode ser considerado representativo do amadurecimento do conhecimento técnico dos alunos ao longo do curso de graduação, podendo ser visto como incorporado ao flexível sistema periférico. / This research aims to investigate social representations of environmental chemistry among chemistry student-teachers and environmental chemistry majors from the Institute of Chemistry at the University of São Paulo. Two groups were considered: students enrolled in the second and in the eighth semesters of their respective courses, in order to investigate changes over time. The Theory of Social Representations was adopted as the theoretical reference for this study. The methodology included the technique of free evocation of words, as well as the writing of a text. Results were analyzed considering the frequency and the word evocation mean order, to define the central core and the peripheral elements of the social representation for each group of students. Analysis units were identified in the texts and were used to construct cognitive maps. The association between the most evocated words and individual cognitive maps resulted in a collective conceptual map for each group. Freshmen students from both investigated majors presented a naturalist view of the environment, and a conception of environmental education that can be described as \"about the environment\", in which it would be enough to provide people with information and facts related to the environment to address environmental problems. A preservationist view of the environment was also dominant in both groups, and the need to enhance awareness of people towards environmental issues is specially emphasized by the student-teachers. On the other hand, environmental chemistry majors lay emphasis on the relation between environmental chemistry and research on pollution treatment, and the remediation view is prevalent. The differences between social representations verified in both groups can be partially related to the roles as regard to environmental chemistry within the different professions. Students in the eighth semesters of their respective courses still present strong influence from a preservationist view of the environment. A positive aspect that can be stressed is the rising of ideas related to Green Chemistry in both groups. Representations of freshmen students show a central core founded upon the ideas of pollution, environment, recycling and preservation. The social representation for the group of advanced students rests on the very same ideas. This means that these ideas can be considered as part of the central core of the representation and are maintained during the courses. However, it was possible to notice the incorporation of the peripheral idea associated to Green Chemistry during the undergraduate courses. This can be considered as a result of a growth on technical knowledge which is incorporated to the flexible peripheral elements of the social representations

Desreguladores Endócrinos (DE) é um termo dado a todos agentes ou substâncias químicas que promovem alterações no sistema endócrino e hormonal dos seres vivos. Estes compostos são encontrados em quantidades escalares micrométricas ou até mesmo nanométricas, em várias matrizes ambientais aquáticas, oriundos dos mais diferentes meios, notavelmente, dos esgotos das residenciais, industriais e agropecuário. Bem como, são derivados químicos antropogênicos, provenientes de pesticidas, plásticos, detergentes, lacas, tintas e ainda estão presentes em cosméticos, medicamentos e alimentos, dentre outros. Neste trabalho estudouse a degradação eletroquímica e fotoquímica do DE conservante parabeno, denominado etilparabeno. A degradação eletroquímica se deu por meio da técnica a potencial controlado, denominada cronoamperometria, enquanto que a fotoquímica se deu por meio das técnicas fotólise, fotocatálise e eletrofotocatálise. Dedicou-se a técnica eletrofotocatalitica uma maior atenção, pois atribui-se a ela a possibilidade de agir de forma extremamente eficaz na degradação de poluentes orgânicos. O agente catalítico utilizado no revestimento das superfícies dos eletrodos foi, o dióxido de titânio (TiO2), depositado por técnicas distintas, tanto para a formação dos nanotubos, quanto para aderência das nanopartículas de TiO2@SiO2 ao substrato. Nas técnicas fotocatálise e eletrofotocatálise estudou-se comparativamente a eficiência dos eletrodos revestidos de nanopartículas (CNP), nanotubos (CNT) e nanotubos revestidos com nanopartículas de TiO2@SiO2 (CNT/P). As degradações do etilparabeno foram acompanhadas por espectrofotometria na região do UV-Vis, cromatografia líquida de alta eficiência (CLAE) e espectrometria de massas (MS) Os resultados da degradação fotoquímico e eletroquímico do etilparabeno foram abordados em termos qualitativos por meio de cromatogramas e quantitativos por meio das propriedades da lei cinética das reações, constante da velocidade (k) e tempo de meia vida (t1/2). Por fim, os produtos da degradação foram identificados por meio de espectroscopia de massas MS e COT onde por meio destes resultados foi sugerido um mecanismo para a reação eletrofotocatalitica utilizando o catalisador CNT/P e ainda, testou-se o seu grau de toxidade por meio do teste fitotóxico com sementes de lactuca sativa (alface lisa). / Desreguladore Endocrine (DE) is a term given to all agents or chemicals that promote changes in the endocrine and hormonal system of living thing. These chemicals are found in scalar quantities (micrometer or even nanometric) in various aquatic environmental matrices, deriving from different means, notably from residential sewage, industrial and agricultural and are derived from anthropogenic chemicals from pesticides, plastics , detergents, lacquers, paints, is still present in cosmetics, medicines and food, among others. In this work we studied the electrochemical and photochemical degradation of DE ethylparaben preservative. Electrochemical degradation occurred through the controlled potential technique, called chronoamperometry, while the photochemical was through the photolysis, photocatalysis and electro photocatalysis techniques, while the later received more attention due to better performance. The catalyst used on the surface electrode coating was titanium dioxide (TiO2), deposited by three different techniques, for both the formation of nanotubes, both of TiO2 and for the adhesion of the nanoparticles of TiO2@SiO2 to the substrate. The photocatalysis and electro photocatalysis technique were studied comparing the effectiveness of coated electrodes nanoparticles (CNP), nanotubes (CNT) and nanotubes coated with nanoparticles of TiO2@SiO2 (CNT/P). The ethylparaben degradations were accompanied by spectrophotometrically in the UV-Vis region, high-performance liquid chromatography (HPLC) and mass spectrometry (MS). The results of electrochemical and photochemical degradation of ethylparaben were discussed in qualitative terms by chromatograms and quantitative kinetic law by means of the properties of reaction, rate constant (k) and half-life (t1/2). Finally, the degradation products were identified by mass spectroscopy MS and also tested for its degree of toxicity by the test phytotoxic seed Lactuca sativa (butter lettuce).

Many modern products, especially electronic goods, are protected by brominated flame retardants (BFR). Some of the most common flame retardants are polybrominated diphenylethers (PBDE), tetrabromobisphenol-A (TBBP-A) and hexabromocyclododecane (HBCD). These compounds have been found in environmental samples and shown to have physiological effects on experimental animals. This thesis considers end-of-life aspects of brominated flame retardants. When spread in the environment, these compounds may be degraded into other forms. For example, if sludge contaminated with PBDE is used as an agricultural fertilizer, the PBDE could be degraded by sunlight to species of PBDE with lower degree of bromination and, to some extent, also form polybrominated dibenzofurans (PBDF). In addition, PBDF and polybrominated dibenzo-p-dioxins (PBDD) are formed during combustion of brominated flame retardants. When waste products with brominated flame retardants are co-combusted with household waste or other chlorinated fuel, polybrominated- chlorinated dibenzo-p-dioxins (PBCDD) and polybrominated- chlorinated dibenzofurans (PBCDF)will be formed. The bromin/chlorine composition of dioxins and furans is dependent on the bromine/chlorine ratio in the fuel, but the types of brominated flame retardants that are being combusted is less important. In the studies reported here, bromine levels higher than "normal" for household waste has been used. The results show that there is a pronounced increase in total dioxin levels in fluegas when when bromine is present, implying that waste containing brominated flame retardants should only be incinerated at combustion plants with effecient air pollution control devices.

Exposure to arsenic (As) in water, the ubiquitous toxin that poses adverse health risks to tens of millions, is the result of both anthropogenic and geochemical mobilization. Despite recent publicity and an increased public awareness, the dangers associated with arsenic exposure rank among the top priorities of public health agencies globally. Existing sequestration applications mainly include reductions and adsorption with zero-valent metals and their oxides. The performance of adsorption media is known to preferentially favor aqueous As(V) over As(III) due to the charge of the dissolved oxyanion. Magnetic nanoparticles (MNP) have been the focus of multidisciplinary research efforts for the removal of aqueous toxic metals and metalloids since they can be magnetically separated from the treated water. This improves isolation and allows for regeneration of the MNP, reducing cost and resource consumption. This research is focused on As(III & V) sequestration through the use of synthetic ligands N,N’bis(2-mercaptoethyl)isophthalamide (abbreviated BDTH2) and 2,2’- (isophthaloybis(azanaediyl))bis-3-mercaptopropanoic acid (abbreviated ABDTH2). Additionally, As(III) sequestration with ABDTH2 functionalized on silica core-shell MNP (ABDTH2 MNP), magnetite MNP (ABDTH2@MNP), and commercial silica beads (ABDTH2 Si60) is demonstrated. Both BDTH2 and ABDTH2are effective precipitation agents for the removal of As(III) through the formation of S-As covalent bonds. ABDTH2MNP reduced a 200 ppb As(III) batch solution to below 10 ppb at pH 5,7, and 9. Additionally, complete removal was achieved in the presence of anions at concentrations of 200, 500, and 1000 ppb. This system was evaluated for the removal of total arsenic from industrial solutions accumulated during the production of renewable biogas in landfills. Direct precipitation with BDTH2 and ABDTH2 was inhibited by the complex matrix. However, batch removal with ABDTH2@MNP was effective in removing 82% of the inorganic arsenic. Sequestration of arsenic and speciation from these industrial solutions remains a challenge.

Atmospheric aerosols play an important role in climate by scattering and absorbing radiation and by serving as cloud condensation nuclei. An aerosol’s optical or nucleation properties are driven by its chemical composition. Chemical aging of aerosols by atmospheric oxidants, such as ozone, alters the physiochemical properties of aerosol to become more hygroscopic, light absorbing, and viscous during transport. However the mechanism of these transformations is poorly understood. While ozone is a protective and beneficial atmospheric gas in the stratosphere, it is a potent greenhouse gas in the troposphere that traps heat near the Earth’s surface. It also impacts human heath by irritating the respiratory tract and exacerbating cardiovascular diseases. Additionally, ozone can alter the ecosystem through oxidizing plant foliage which can lead to deforestation and crop losses as well. Both gases and aerosols in the troposphere can react with ozone directly and indirectly with hydroxyl radicals. While daytime aging is thought to be primarily driven by photochemical processes and hydroxyl radicals, ozone is thought to be a key player in nighttime or dark aging processes that can alter the physicochemical properties of aerosols. Measured concentrations of trace gases and aged aerosol components in the field are higher than values predicted based on laboratory studies and computer simulations. Consequently, new experimental approaches are needed to narrow the gaps between observations and mechanistic understandings. In this dissertation, a plume of microdroplets was generated by pneumatically assisted aerosolization and then exposed to a flow of ozone before entering a mass spectrometer. This surface-specific technique allowed for the real-time analysis of reaction products and intermediates at the air-water interface. This work explores the in situ oxidation of iodide, a component of sea spray aerosols, by 0.05 – 13.00 ppmv ozone to explore how heterogeneous oxidation could enhance the production of reactive iodide species. Methods to study the reaction channels and intermediates were also established to not only determine a mechanism of iodide oxidation by ozone, but to enable the study of more complex systems. The developed approach was then applied to examine the oxidation of catechol and its substituted cousins, a family of compounds selected to model biomass burning and combustion emissions, at the air-water interface. While literature suggested that the primary mechanism of catechol oxidation by ozone would be the cleavage of the C1-C2 bond, it was determined that this was only a minor pathway. An indirect oxidation channel dominated heterogeneous processes at the air-water interface, giving rise to hydroxyl and semiquinone radicals that recombine to produce polyhydroxylated aromatics and quinones. This new mechanism of aging represents an overlooked channel by which brown, light-absorbing carbon aerosols are produced in the atmosphere. In addition, the work investigates how reactions on solid particulate aerosols proceed under variable relative humidity. Thin films were developed alongside a novel flow-through reactor to study of how aerosols are transformed by ozone and hydroxyl radicals when exposed to 50 ppbv - 800 ppmv of ozone. This system was employed to probe how catechol reacts with ozone under variable relative humidity. Further work was undertaken to model the adsorption process at the air-solid interface under variable humidity, permitting the estimation of the reactive uptake of ozone by the film at concentrations (50-200 ppbv) seen in rural and urban areas. Together, these results provide an increased understanding of how heterogeneous oxidation of aerosols contributes to aerosol aging processes as well as free radical production in the troposphere.

Iron oxides and arsenic are prevalent in the environment. With the increase interest in the use of iron oxide nanoparticles (IONPs) for contaminant remediation and the high toxicity of arsenic, it is crucial that we evaluate the interactions between IONPs and arsenic. The goal was to understand the environmental behavior of IONPs in regards to their particle size, aggregation and stability, and to determine how this behavior influences IONPs-arsenic interactions. A variety of dispersion techniques were investigated to disperse bare commercial IONPs. Vortex was able to disperse commercial hematite nanoparticles into unstable dispersions with particles in the micrometer size range while probe ultrasonication dispersed the particles into stable dispersions of nanometer size ranges for a prolonged period of time. Using probe ultrasonication and vortex to prepare IONPs suspensions of different particle sizes, the adsorption of arsenite and arsenate to bare hematite nanoparticles and hematite aggregates were investigated. To understand the difference in the adsorptive behavior, adsorption kinetics and isotherm parameters were determined. Both arsenite and arsenate were capable of adsorbing to hematite nanoparticles and hematite aggregates but the rate and capacity of adsorption is dependent upon the hematite particle size, the stability of the dispersion and the type of sorbed arsenic species. Once arsenic was adsorbed onto the hematite surface, both iron and arsenic can undergo redox transformation both microbially and photochemically and these processes can be intertwined. Arsenic speciation studies in the presence of hematite particles were performed and the effect of light on the redox process was preliminary quantified. The redox behavior of arsenite and arsenate were different depending on the hematite particle size, the stability of the suspension and the presence of environmental factors such as microbes and light. The results from this study are important and have significant environmental implications as arsenic mobility and bioavailability can be affected by its adsorption to hematite particles and by its surface mediated redox transformation. Moreover, this study furthers our understanding on how the particle size influences the interactions between IONPs and arsenic thereby clarifying the role of IONPs in the biogeochemical cycling of arsenic.

Development and application of target and non-target techniques for routine analysis, identification of transformation products, and characterization of unknown compounds in water matrices using liquid-chromatography high-resolution mass spectrometry (HRMS) were explored in this dissertation. A novel analytical method based on online-SPE-LC-HRMS was developed for the detection of 18 drugs of abuse (DOAs) in raw sewage water from a college campus. Results showed the presence of 14 DOAs for which amphetamine and 11-nor-9-carcoxy-THC (THC metabolite) were the most prevalent and had the highest potential consumption rates. A second study dedicated to the identification of transformation products (TPs) generated from DOAs was conducted using a combination of HR-MS/MS and metabolic identification and structural elucidation software. Findings confirmed the presence of multiple phase I and II DOA TPs (n=35) in raw sewage influents. Concentrations of all TPs were estimated based on the parent DOAs response factors, and used to calculate the percent mole fraction contributions of each TP to the parent concentrations. High abundance and frequency (compared to the parent drug) was determined for 9 of the TPs coming from drugs like oxycodone, morphine, codeine, methadone, LSD, cocaine, and MDEA. Non-target analysis using HRMS was explored as a tool to characterize, and compare a series of interconnected water matrices along a river system. Several thousands of formulae were generated using automated heuristic rules from the full-scan acquisition at 140,000 resolution. Samples were part of a trajectory covering upstream, effluent, effluent mixing zone, downstream, drinking water intake, and treated drinking water locations. Graphical representations of the data were used to evaluate commonalities among the system. Using this approach, a total of 64 recalcitrant components were identified throughout the samples downstream of the effluent release point. Using a combination of MS/MS and computer-aid software techniques 4 out of the 64 compounds were tentatively confirmed. In addition, comparison of drinking water intake and finalized treated drinking water sites showed the presence of 1,152 chemical entities that were common to both locations; and 1,857 that were unique to the treated drinking water. Therefore, this non-target technique could be used to identify the potential formation of treatment byproducts.