A presença de resíduos de fármacos em águas superficiais e de abastecimento público tem preocupado a comunidade científica devido principalmente à sua persistência na água e aos efeitos adversos causados à comunidade aquática e aos possíveis riscos à saúde humana. Dentre os fármacos comumente identificados em águas de abastecimento público, encontram-se os anti-inflamatórios, como o diclofenaco (DCF), um dos fármacos mais consumidos no Brasil e no mundo. Nesse contexto, o presente trabalho, teve como objetivo principal estudar a eficiência das etapas de tratamento de água em ciclo completo (coagulação, floculação, sedimentação, filtração em areia e desinfecção com cloro) com e sem pré-oxidação com cloro e com dióxido de cloro e adsorção em carvão ativado granular (CAG) na remoção de DCF. Também foram determinados os trialometanos (THM) e identificados os principais subprodutos do DCF formados na oxidação com cloro e dióxido de cloro. Para a determinação do DCF nas amostras de água antes e após as etapas de tratamento de água foram desenvolvidos e validados métodos analíticos de extração em fase sólida (SPE) e cromatográfico por cromatografia líquida de alta eficiência (HPLC) com detecção no ultravioleta (UV). A validação do método foi feita de acordo com a resolução n&ordm; 899 de 2003 da Agência Nacional de Vigilância Sanitária (ANVISA), considerando os requisitos para métodos bioanalíticos. Os procedimentos analíticos empregados foram efetivos e confiáveis para a identificação e quantificação do DCF nas amostras de água antes e após os processos de tratamento de água. Os ensaios de tratamento de água foram feitos em equipamento de reatores estáticos (jarteste) e filtros de escala laboratorial empregando-se água de poço artesiano não clorada preparada com substâncias húmicas aquáticas (SHA) para conferir cor verdadeira de 20 uH, caulinita para conferir turbidez de 70 uT e fortificada com 1 mg L-1 de DCF. Os resultados indicaram que as etapas de coagulação com sulfato de alumínio, floculação, sedimentação e filtração em areia não removeram o DCF. Nas etapas de préoxidação com cloro e dióxido de cloro e de pós-cloração houve remoção parcial do DCF, porém verificou-se a formação de subprodutos provenientes da oxidação do DCF. Dentre os THM, foi quantificado apenas o clorofórmio na etapa de pré-oxidação com cloro. Em geral, os resultados indicaram que o dióxido de cloro foi mais eficiente na redução do DCF e formou menos subprodutos. Entretanto, o tratamento em ciclo completo seguido da adsorção em CAG foi eficiente na remoção de DCF, com remoção maior que 99,7%. Os subprodutos formados na oxidação com cloro e dióxido identificados por cromatografia líquida acoplada a espectrometria de massas em série (LC-MS/MS) consistiram na descaboxilação/hidroxilação e substituição aromática de átomos de hidrogênio por cloro. Os subprodutos identificados na oxidação com cloro apresentaram as seguintes fórmulas moleculares: C14H11</subCl2NO3, C13H10Cl3N e C14H10Cl3NO2. Com o dióxido de cloro foi identificado o subproduto de fórmula molecular igual a C14H11Cl2NO3. / The presence of pharmaceutical residues in surface waters and in drinking water supply has concerned the scientific community, mainly in which regards their persistence in water, adverse effects on the aquatic community and possible risks to human health. Antiinflammatory drugs, as diclofenac (DCF), are among those drugs commonly identified in drinking water supply. In this context, the main objective of this study was to assess the efficiency of the different stages of the conventional drinking water treatment (coagulation, flocculation, sedimentation, sand filtration and chlorine disinfection) with and without preoxidation with chlorine and chlorine dioxide and adsorption on granular activated carbon (GAC) in the removal of DCF. The trihalomethanes (THMs) were also determined and the main by-products of DCF formed by oxidation with chlorine dioxide and chlorine were identified. For the DCF determination in water samples before and after water treatment stages analytical methods of solid phase extraction (SPE) and chromatographic method by high performance liquid chromatography (HPLC) with detection in the ultraviolet (UV) were developed and validated. The method validation was based on Resolution n&ordm; 899 of the 2003 of the Brazilian National Health Surveillance Agency (ANVISA), considering the requirements for bioanalytical methods. The analytical procedures used were effective and reliable for the identification and quantification of DCF in the water samples before and after the water treatment stages. The water treatment tests were carried out in jar test equipment and filters on laboratory scale employing non chlorinated water of artesian well prepared with aquatic humic substances (AHS) to yield 20 uH true color, kaolin turbidity of 70 NTU and DCF concentration of 1 mg L-1. The results indicated that the stages of coagulation with aluminum sulphate, flocculation, sedimentation and filtration sand did not remove DCF. In the stages of pre-oxidation with chlorine and chlorine dioxide and chlorine disinfection the DCF was partially removed, however by-products were formed from the DCF oxidation. Among the THMs, only chloroform was quantified in the pre-oxidation with chlorine. In general, the results showed that chlorine dioxide was more effective to reduce the DCF and fewer by-products were formed. Nevertheless, the complete cycle treatment followed by GAC adsorption was effective to remove DCF (&gt; 99.7%. removal). The by-products of the oxidation of DCF with chlorine and chlorine dioxide identified by liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) consisted in the descaboxylation/hydroxylation and aromatic substitution of hydrogen atoms by chlorine. The compounds identified in the oxidation with chlorine showed the following molecular formulas: C14H11</subCl2NO3, C13H10Cl3N e C14H10Cl3NO2. The by-product identified using chlorine dioxide was C14H11Cl2NO3.

Halogen chemistry plays an important role in spring time ozone and mercury depletion events (ODEs and MDEs) and may efficiently oxidize hydrocarbons such as the important greenhouse gas methane (CH4) in the polar marine boundary layer. This thesis presents a detailed study of bromine and chlorine chemistry in the Arctic boundary layer based on measurements of bromine and chlorine containing species using chemical ionization mass spectrometry (CIMS). The capability of CIMS to accurately measure bromine oxide (BrO) was demonstrated. The first direct measurements of hypobromous acid (HOBr) were achieved. Conditions that likely favor bromine activation (e.g. high wind speeds) was presented. To advance the understanding of bromine recycling, a time dependent model was built to simulate the bromine speciation. Unexpected high levels of molecular chlorine (Cl2) were observed at Barrow, AK, which had a large impact on methane oxidation and could contribute to ozone loss and mercury oxidation at Barrow, AK. Moreover, BrO levels observed at Summit, Greenland did not explain the under prediction of hydroxyl radical (OH). However, the enhanced OH was found to be coincident with elevated reactive gaseous mercury (RGM). In addition, airborne BrO measurements were found to be generally consistent with airborne observations of soluble bromide based on the response factors of mist chamber to the bromine species and bromine chemical mechanisms.

A laser flash photolysis resonance fluorescence (LFP-RF) technique has been employed to study the kinetics of the reactions of methylvinyl ketone (MVK) with atomic bromine (Br) and atomic chlorine (Cl) as a function of temperature (203 755 K) and pressure (12 600 Torr) in nitrogen bath gas. The results of this study are also compared to published kinetics studies for similar reactions. Over the temperature range 200 K < T < 250 K for the reaction of Br with MVK, measured rate coefficients were pressure dependent suggesting the formation of an adduct. The adduct undergoes dissociation on the time scale of the experiments (< 0.1 s) and establishes an equilibrium between Br, MVK, and MVK Br. At temperatures above 298 K no reaction of Br with MVK was observed. Similarly, over the temperature range 405 K < T < 510 K, the reaction of Cl with MVK shows similar kinetics to that of Br and MVK suggesting an equilibrium is established. Equilibrium constants for adduct dissociation and formation are determined for the forward and reverse rate coefficients in both reactions. Second and third-law analyses are carried out to obtain information about the thermochemistry of the equilibrium reactions for Br with MVK and Cl with MVK. Adduct bond strengths of Br and Cl reactions with MVK are reported and compared to reactions with other unsaturated species. Ab initio calculations for these reactions are also presented in this study. Excellent agreement is observed between theory and experiment. Additionally, a reaction of Cl with MVK was observed over the temperature ranges 600 K < T < 760 K and 210 K < T < 365 K. At the lower temperatures, measured rate coefficients are also pressure dependent, however, the adduct remained stable. At the highest temperatures, the measured rate coefficients were pressure independent, suggesting hydrogen abstraction as the dominant reaction pathway. Energetics obtained from ab initio calculations suggest that only abstraction of the methyl hydrogen is likely to occur at a measurable rate in the temperature range investigated.

Diss. (sammanfattning) Linköping : Linköpings universitet, 2004. / Härtill 5 uppsatser.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-23T13:02:45Z No. of bitstreams: 1 GEORGE ANTONIO BELMINO DA SILVA - DISSERTAÇÃO (PPGECA) 2017.pdf: 2397938 bytes, checksum: a59c1724d1e23040d6b147ffa3ccfb8e (MD5) / Made available in DSpace on 2018-08-23T13:02:45Z (GMT). No. of bitstreams: 1 GEORGE ANTONIO BELMINO DA SILVA - DISSERTAÇÃO (PPGECA) 2017.pdf: 2397938 bytes, checksum: a59c1724d1e23040d6b147ffa3ccfb8e (MD5) Previous issue date: 2017-08 / O objetivo deste trabalho é simular o decaimento de cloro residual livre em reservatórios de distribuição de diferentes capacidades e modos de operação do sistema integrado de abastecimento de água da cidade de Campina Grande, Paraíba. Foram determinados coeficientes cinéticos de decaimento com base em modelos de 1ª ordem, 1ª ordem paralela, 1ª ordem limitada e ordem n, sendo verificado que o modelo de 1ª ordem paralela apresentou o melhor ajuste e a melhor aplicação para o sistema. Para a simulação do comportamento do cloro residual livre foi empregado o software EPANET 2.0 considerando cenários construídos sobre diferentes abordagens de reações do desinfetante. Os resultados mostraram que, embora tenha sido verificada conformidade com a Portaria 2914/2011 do Ministério da Saúde, mesmo para reservatórios em série e distantes do reservatório inicial de água tratada, o processo de degradação de cloro residual livre no sistema como um todo é intenso. / The aim of this work is to simulate the decay of free residual chlorine in distribution reservoirs of different capacities and operation modes in the integrated water supply system of the city of Campina Grande, Paraíba state, northeast Brazil. Kinetic coefficients of chlorine decay were determined based on models of 1st order, parallel 1st order, limited 1st order and nth order. It was verified that the parallel 1st order model presented the best fit and application for the system. For the simulation of free residual chlorine behavior, EPANET 2.0 software was used, considering scenarios constructed on different approaches of disinfectant reactions. Results showed that, although it was verified compliance with the standards of Brazilian Ministry of Health Ordinance 2914/2011, even for reservoirs in series and distant from the initial treated water reservoir, the process of free residual chlorine degradation in the system as a whole is intense.

No Brasil, a desinfecção e oxidação da água, para o consumo humano, são usualmente realizadas com a adição de cloro nas formas de gás cloro e hipoclorito de sódio. Estudos recentes tem demonstrado que a oxidação e desinfecção da água com o cloro podem ocasionar a formação de trialometanos e outros subprodutos clorados. Alguns destes subprodutos são substâncias carcinogênicas. Neste trabalho estudou-se a influência das substâncias húmicas (SH) extraídas da turfa, com diferentes massas moleculares, na formação de trialometanos e outros subprodutos clorados em decorrência do uso do cloro e dióxido de cloro na etapa de oxidação da água. As frações das SH utilizadas neste trabalho foram caracterizadas por análise elementar, ultravioleta visível, ressonância magnética nuclear de C13 (RMN de C13), ressonância paramagnética nuclear eletrônica (EPR) e infravermelho. Estas caracterizações demonstraram que a fração de menor massa molecular (30-100 KDa), obtidas por ultrafiltração (UF), apresentou um menor grau de condensação de grupamentos aromáticos em relação as frações de SH de massa molecular menor que 0,45 &#956m e maior do que 100 KDa. Nas análises realizadas por RMN de C13 e análise elementar, constatou-se que a fração de SH de massa molecular entre 30-100 KDa, apresentou uma maior porcentagem de grupos contendo oxigênio. Após as caracterizações das SH, preparou-se três tipos de água, com cor 100 +/ - 5 uH, adicionando-se as diferentes frações de SH na água separadamente. A seguir foram realizados ensaios no equipamento jarteste, para a determinação das dosagens dos oxidantes cloro e dióxido de cloro os quais foram utilizadas nos ensaios de formação dos subprodutos clorados. Estes ensaios foram realizados variando-se as dosagens do oxidante em função do tempo de reação. As concentrações dos oxidantes determinadas foram de 7,0 mg/L para o cloro e de 1,0 mg/L para o dióxido de cloro. Na realização dos ensaios de formação dos subprodutos clorados, considerou-se o tempo de reação em função da dosagem dos oxidantes cloro e dióxido de cloro que foram determinadas anteriormente nos ensaios de demanda. Os subprodutos clorados, formados, foram quantificados utilizando-se a técnica de cromatografia gasosa com detector de captura de elétrons. O método utilizado foi o do padrão interno. O clorofórmio foi o subproduto majoritário, nos ensaios realizados com todas as frações. Na oxidação da água com o cloro, ocorreu a formação de um maior número de subprodutos clorados em relação aos ensaios realizados com oxidante dióxido de cloro. Nos ensaios realizados com a água preparada com SH de menor tamanho molecular ocorreu uma maior concentração dos subprodutos clorados formados, especialmente para o clorofórmio. / In Brazil, the disinfection and oxidation of drinking water is usually done by the addition of chlorine gas and sodium hypochloride forms. Recent studies have demonstrated that disinfection and oxidation of water using chlorine can cause the formation of trihalomethane and others chlorine by-products, which are carcinogenic substances. In this present work, it has been studied the influence of the humic substance (SH) extracted from peat soil, with different molecular size, in the formation of trihalomethane and others chlorine by-products as results of the use of chlorine and chlorine dioxide in the water oxidation step. The SH fractions used in this were characterized by elemental analysis, visible ultraviolet, C13 nuclear magnetic resonance (C13 NMR), electron paramagnetic resonance (EPR) and infrared spectroscopy. Such characterization showed that the fractions with smaller molecular size (30-100 KDa), obtained by ultrafiltration (UF), presented a smaller degree of aromatic groups condensation with respect to fractions of SH molecular size smaller than 0,45 &#956m and higher than 100 KDa. C13 NMR and elemental analysis were also used. SH fraction of molecular size between 30-100 KDa presented higher percentage of groups containing oxygen. After characterizations of SH, water was prepared with 100 +/- 5 uH color, with separated addition of different fractions of SH in the water. Tests in the jartest equipment were realized for the determination of dosages of chlorine and chlorine dioxide oxidants, which were utilized in the test of formation of chlorine by-products. These tests were performed studying the oxidation dosage in function of the reaction time. The oxidant concentrations were 7.0 mg/L for the chlorine and 1.0 mg/L for chlorine dioxide. Formation of chlorine by-products was tested considering the reaction of time with respect to the oxidants dosage of chlorine and oxidant chlorine, previously determined. The chlorine by-products resultant were quantified using the gas chromatography with detector of electron capture technique GC-ECD. The method utilized was the addition of internal standard. In the water oxidation by chlorine an higher number of chlorine by-products occurred in comparison of the test performed with chlorine dioxide. In the test performed with the water prepared with SH of smallest molecular size a highest concentration of resultant by-products occurred, specially by chloroform.

Metallic bronze-Co-Ag alloys ranging from1-90 µm have been discovered in bomb and lava vesicles from the mafic volcanoes of Kilauea in Hawaii and Vesuvius, Stromboli and Etna in Italy. It is inferred that the metals for these alloys were transported (in part) as chloride complexes, and that the metal ratios in the alloys may be a function of S/Cl. Alloy compositions in each system are extremely heterogeneous with Co concentrations from 1% to 94%, Cu from 2% to 89%, Sn from 1% to 22% and Ag from 0.5% to 42%. Maximum abundances (in wt%) of other trace or minor elements are, Fe (3.0), Zn (0.11), As (0.50), Pd (0.05), Pt (0.05), Au (0.05), Hg (0.10) and Pb (.13) Spot analyses and element maps of alloy grains reveal that three major exsolved components exist. They are bronze, Co, and Ag. Kilauean alloys are dominantly Cu-Sn (bronze) with little Co and Ag while a systematic decrease in the bronze component and an increase in Co occurs in grains from Stromboli to Etna to Vesuvius. Element maps show a covariance of Cu and Sn while Co and Ag concentrations vary independently. Element maps of the alloys also reveal that chlorides are occasionally present in the same vesicles as the alloys. Sulphur content of the metal alloys rarely exceed about 0.4 wt%. Electron back-scatter diffraction (EBSD) was employed for lattice characterization of the exsolved phases and shows a FCC structure for the Cu-Sn section of the alloys. Cu-Sn alloys high in Sn are successfully indexed using the Cu6Sn5 pattern (hexagonal), even though the Sn:Cu ratio of our alloys is considerably lower than 5:6. Cu-Sn alloys containing significant subequal amounts of Co and Fe (≈5 wt% each) indexes as body-centered cubic (BCC). The presence of alloys suggests metal transport as complexes in a vapor phase before being reduced to native metals. Our current model for the origin of the alloys suggests that the metals are transported to vesicles as chlorides and then deposited as sulfides and/or native metals. Oxidation and removal of most of the S then occurs. This data suggests that in some circumstances Cu-Sn-Co and Ag are readily partitioned into escaping magmatic volatiles during quenching of mafic magma. Further examination into vesicle-hosted alloys may confirm that the ratio of Cu, Ag, Au, Zn, and Pb in vesicles reflects the ratio of available metals present in the magma and in subsequent ore deposits.

Water disinfection systems utilizing electrolytically generated copper:silver ions (200:20 to 400:40 ug/L) and low levels of free chlorine (0.1 to 0.4 mg/L) were evaluated at room (21-23°C) and elevated (39-40°C) temperatures in filtered well water (pH 7.3) for their efficacy in inactivating Legionella pneumophila (ATCC 33155). A contact time of 24 hr was necessary for copper:silver (400:40 ug/L) to achieve a 3 log₁₀ reduction in bacterial numbers at room temperature. As the copper:silver concentration increased to 800:80 ug/L (K = 7.50 x 10⁻³ log₁₀ reduction/min), the inactivation rate significantly (p ≤ 0.05) increased. In water systems at room temperature with and without copper:silver (400:40 ug/L), the inactivation rates significantly increased as the free chlorine concentration increased from 0.1 mg/L (K = 0.397 log₁₀ reduction/min) to 0.4 mg/L (K = 1.047 log₁₀ reduction/min). All disinfection systems, regardless of temperature or free chlorine concentration, showed increased inactivation rates when 400:40 ug/L copper:silver was added; however, this trend was significant only at 0.4 mg/L free chlorine.

The research addresses two groups of reactions: chlorine atom reactions with fluorinated propenes and methyl amines. Most of the reactions were studied over a range of temperature and pressure with the goals of (i) assessing the potential importance of the reactions in atmospheric chemistry and (ii) obtaining kinetic and thermochemical information of fundamental physical–chemical interest. In the studies reported herein, laser flash photolysis (LFP) was coupled with time resolved atomic resonance fluorescence (RF) spectroscopic detection of chlorine atoms to investigate chlorine atom kinetics.

The Chlorine-Ammonia Process was developed recently as a preoxidation process to minimize the formation of bromate during ozonation of the waters containing a significant bromide concentration. Chlorine is added first, followed by ammonia 5-10 minutes later, with the goal of sequestering bromide in monobromamine before the subsequent ozonation step. The goal of this research was to improve the Chlorine-Ammonia Process by introducing a very short prechlorination step (i.e., 30 seconds before addition of ammonia) to minimize overall disinfection by-product formation. Also, in this strategy, formation of a powerful halogenating agent, HOBr, is minimized and bromochloramine (NHBrCl) is used predominantly instead of monobromamine to sequester bromide during ozonation. To support this improved approach to bromide sequestration, this study examined the formation and decay of bromochloramine as a function of operating conditions, such as pH and Cl2/N ratio, and refined a chemical kinetic model to predict haloamine concentrations over time. Two natural organic matter (NOM) sources were used in this study (Lake Austin, Texas and Claremore Lake, Oklahoma) to study the effect of NOM on monochloramine and total chlorine decay after 30 seconds of prechlorination. The rate of the reaction between haloamines and fast and slow sites on the NOM was estimated. A kinetics model was developed to model total chlorine decay after a short prechlorination time. The model is based on the Unified Haloamine Kinetic Model developed by Pope (2006). Pope`s model failed to model the initial monochloramine concentration after 30 seconds prechlorination time as well as the monochloramine and total chlorine decay over time. The modified model shows an excellent prediction of monochloramine and total chlorine decay after 30 seconds prechlorination time at pH range of 6.5-8.0 and over a carbonate buffer concentration range of 2-10 mM. The model includes a new bromochloramine decay scheme via the reaction with monochloramine and with itself. In addition, new rate constants for the reaction of HOCl with bromide ion and reaction of HOBr with monochloramine were added. The hypobromous acid formation rate was found to be an acid-catalyzed reaction, which confirms the finding of Kumar et al. (1987). A new value of the acid catalysis effect of hydrogen ion was estimated. New terms were introduced to the hyprobromous acid formation rate including the acid catalysis effect of bicarbonate, carbonic acid, and ammonium ion. In addition, the reaction of HOBr with monochloramine to form bromochloramine was found to be an acid-catalyzed reaction, and a new value of the rate constant was estimated. / text