Thesis (M.S.)--University of Michigan, 1971.

Nos últimos anos, os processos oxidativos avançados (POAs) têm emergido como métodos potencialmente poderosos para transformar poluentes orgânicos recalcitrantes em substâncias menos tóxicas. O presente trabalho visa estudar a degradação de clorofenóis 2,4-diclorofenol (2,4-DCF) e pentaclorofenol (PCF) em solução aquosa por meio do processo foto-Fenton. Os experimentos foram realizados em um reator fotoquímico, em regime batelada, com recirculação e admissão contínua de peróxido de hidrogênio. Os efeitos das concentrações iniciais de clorofenóis, H2O2 e Fe(II), bem como, da potência da lâmpada de vapor de mercúrio, foram estudados a partir de um planejamento experimental Doehlert em multiplos níveis e analisados segundo a metodologia de superfícies de respostas. A foto-oxidação foi monitorada por medidas da concentração de carbono orgânico total (TOC) e do espectro de absorção da solução ao longo do tempo e, em alguns casos, medidas de toxicidade por meio de bioensaios com Artemia sp. Os resultados dos experimentos realizados com 2,4-DCF evidenciaram degradação gradativa, com remoções de TOC superiores a 99%, após 1 hora de tratamento, além de remoção de toxicidade, mesmo para altas concentrações iniciais do poluente (até ca. 415 mgC L-1). Nos experimentos realizados com PCF observouse decaimento inicial de TOC bastante rápido (15 minutos), o que sugere que a degradação dos clorofenóis torna-se mais rápida com o aumento do número de átomos de cloro ligados ao anel aromático. Foi removida mais da metade do TOC inicial por volta de 30 minutos de reação, obtendo-se remoções de até 90,8% ao final do tratamento. Por outro lado, comparado ao 2,4-DCF, no caso do PCF observou-se redução acentuada da taxa de remoção de TOC após esse tempo, o que pode ser explicado a partir da maior concentração de íons cloreto em solução, da formação de complexo estável desses íons com Fe(III) e de espécies geradas a partir de reações envolvendo esse complexo. No conjunto, os resultados comprovam a viabilidade do processo foto-Fenton para remediação de efluentes aquosos contendo clorofenóis. / In recent years, advanced oxidation processes (AOP) have emerged as potentially powerful methods to transforming organic pollutants into harmless substances. The present work aims to study the degradation of chlorophenols (2,4-dichlorophenol and pentachlorophenol) in aqueous solution by the photo-Fenton process. The experiments were conducted in a batch recycle photochemical reactor with continuous feed of hydrogen peroxide solution. The effects of the initial concentrations of chlorophenols, H2O2, and Fe(II), as well as of the electric power of mercury vapor lamp, were studied by means of a Doehlert multivariate experimental design at multiple levels. Experimental results were analyzed according to the response surface methodology. In order to characterize the degradation of the pollutant, time-measurements of the total organic carbon concentration (TOC) as well as the absorbance spectra of the solution, were carried out. In some cases toxicity bioassays were carried out with Artemia sp. The results obtained from experiments with 2,4-dichlorophenol showed a gradual degradation, with more than 99% of TOC removals after 1 hour of treatment, along with toxicity removal, even for high initial pollutant concentrations (ca. 415 mgC L-1). In the case of pentachlorophenol, a fast initial TOC decrease (around 15 minutes) was observed, suggesting that chlorophenols degradation becomes faster with the increment of chloro atoms number bounded to the aromatic ring. More than a half of the initial TOC was removed around 30 minutes of reaction, rising 90.8% of TOC removal at the end of the treatment. In the other hand, comparing to 2,4-DCF, for PCF a marked reduction of the maximum rate of TOC removal after that time. This can be explained by higher concentrations of chloride ions in the solution, for the formation of stable complexes with Fe(III) ion and resulting species in reaction involving such complexes. As a whole, the results confirm the effectiveness of the photo-Fenton process for the remediation of aqueous solutions containing chlorophenols.

Neste trabalho foram preparados eletrodos de óxidos de composição nominal Ti/RuyTi(1-y-x)SnxO2 por decomposição térmica (400 °C) via três rotas diferentes: Método Tradicional empregando-se precursores inorgânicos dissolvidos em Isopropanol (MT/ISO) e em solução de HCl 1:1 (v/v) (MT/HCl) e, Método dos Precursores Poliméricos (MPP). Os recobrimentos de óxidos foram caracterizados por Microscopia Eletrônica de Varredura, análises de Energia Dispersiva de raios X e Difração de Raios X. A caracterização eletroquímica dos eletrodos foi feita por estudos de potencial em circuito aberto, tempo de vida útil e voltametria cíclica na ausência e na presença do poluente selecionado como modelo, o 4-clorofenol. Eletrólises do 4-clorofenol e de seus principais subprodutos foram realizadas em uma célula de fluxo tipo filtro-prensa e monitoradas por análises de Cromatografia Líquida de Alta Eficiência, Carbono Orgânico Total e íons cloreto em solução, além de testes bacteriológicos de toxicidade. Os resultados mostram que o método de preparação influencia na morfologia e na composição dos eletrodos, mas não afeta o tamanho dos cristalitos. Apesar das características distintas, MT/ISO e MPP são adequados para o preparo desses eletrodos pois evitam perdas dos componentes e proporcionam recobrimentos de estabilidade eletroquímica bastante apropriada frente às condições drásticas de eletrólise, viabilizando assim a aplicação destes eletrodos na degradação de poluentes orgânicos. Além disso, todos os eletrodos investigados são muito promissores para a degradação eletroquímica de clorofenóis, pois apresentam excelente atividade para o consumo do 4-clorofenol. Independente da composição e do método de preparação do eletrodo, os subprodutos formados na eletrooxidação de 4-clorofenol são: hidroquinona, benzoquinona, cloro-hidroquinona e 4-clorocatecol, além dos ácidos oxálico, maleico, málico, succínico e malônico. Embora a mineralização completa do poluente não tenha sido atingida, a toxicidade das soluções após o término das eletrólises diminui consideravelmente, visto que tanto o composto orgânico de partida quanto os subprodutos aromáticos formados são degradados com excelente eficiência, sobretudo quando se utilizam ânodos preparados por MT/ISO. / In this work oxides electrodes of nominal composition Ti/RuyTi(1-y-x)SnxO2 were prepared by thermal decomposition (400 °C) by three different routes: Traditional Method using inorganic precursors dissolved in either Isopropanol (MT/ISO) or a solution of HCl 1:1 (v/v) (MT/HCl) and the Polymeric Precursors Method (MPP).Oxides coatings were characterized by Scanning Electron Microscopy, Energy Dispersive X ray analyses and X ray Diffraction. The electrochemical characterization of the electrodes was performed by studies of potential in open circuit, service lifetime, and cyclic voltammetry in the absence and in the presence of the model pollutant 4-chlorophenol. Electrolyses of 4-chlorophenol and its main by-products were accomplished in filter-press flow cell and monitored by High Performance Liquid Chromatography, Total Organic Carbon, and analyses of chloride ions in solution, besides bacteriological toxicity tests. Results show that the preparation method influences the morphology and composition of the electrodes, but it does not affect the crystallite size. In spite of their different characteristics, MT/ISO and MPP are appropriate methods for the preparation of these electrodes because they avoid the loss of components and provide electrochemically stable coatings before the drastic conditions of electrolysis. Therefore, these electrodes can be applied in the degradation of organic pollutants. Furthermore, all the investigated electrodes are very promising for the electrochemical degradation of chlorophenols, because they present excellent activity regarding the consumption of 4-chlorophenol. Independent of the composition and the preparation method of the electrode, the by-products formed in the electrooxidation of 4-chlorophenol are hydroquinone, benzoquinone, chlorohydroquinone, and 4-chlorocatechol, as well as oxalic, maleic, malic, succinic, and malonic acids. Although the complete mineralization of the pollutant has not been reached, the toxicity of the solutions decreases considerably after the end of the electrolyses. This is because both the initial organic compound and the aromatic by-products formed in the electrolyses are degraded with excellent efficiency, especially when the anodes prepared by MT/ISO are employed.

Content: The restriction of certain dangerous substances according to REACH (Registration, Evaluation, Authorisation of Chemicals as well as the Restricted Substances Lists (RSL) requirements promoted by various renowned brands obliges tanneries to everyday more numerous analysis with undesired conflictual situations on false positive tests results. This situation is worsened by the voluntary reduction of requested detection limits far below the levels recommended by the accepted ISO methods. On this context, ISO 17070:2015 was extended in its current version from the determination of pentachlorophenol to tetrachlorophenol, trichlorophenol, dichlorophenol and monochlorophenol isomers. Some brands also included under this technique the ortho phenyl phenol (OPP) analysis, requesting a quantification limit below 1 mg/kg for all analytes. The present paper proposes a new HPLC-DAD-MS direct method for the verification of chlorophenols positive cases, and its extension to leather chemicals analysis, as well as the discrimination among false positive cases and real positive ones. The paper also illustrates case studies reporting differences in the quantification of the said analytes and the chlorophenol scission in different analytical conditions. Take-Away: False positives verification of the presence of chlorophenols. Quicker method respect to the current ISO 17070:2015 standard. Method reliable on Leather chemicls chlorophenos research. Generation of chlorophenols from certain AOX substances.

No description available.

No description available.

In this final thesis, an existing method for analysis of chlorophenols (CP) in bottom sediments has been updated and adjusted for analysis of chlorophenols in soil. The covalent bonds between the chlorophenols and the soil matrix were broken through basic hydrolysis and the chlorophenols were then separated from the water phase through addition of sulphuric acid followed by ether extraction. The chromatography was improved through extractive acetylation of the chlorophenols. The updated method was then applied on soil samples from a contaminated area (a former sawmill in Hyttsjö, Östergötland, Sweden). The analyse was preformed by GC/MS with respect to 2-MonoCP, 4-MonoCP, 2,4-DiCP, 2,6-DiCP, 2,4,6-TriCP, 2,3,4,6-TetraCP and pentachlorophenol (PCP). Contamination of chlorophenols in nature can be explained by the former use of wood preservative chemicals based on chlorophenols. In the 1960s and the 1970s these chemicals were used in Sweden, but due to their toxicity they were banned by the Swedish government in 1978. In Hyttsjö a pentachlorophenol-based product named Santobrite was used for several years. The concentration of PCP in the soil samples from Hyttsjö varied from 0.2->1.8 ng/mg dry substance. 2,3,4,6- Tetrachlorophenol was also detected in some of the soil samples.

Aerobic biodegradation kinetics of 4-Chlorophenol (4-CP) and 2,4-Dichlorophenol (2,4-DCP) by acclimated mixed cultures were examined separately and in mixture using batch and sequencing batch reactors (SBRs). Biodegradation abilities of acclimated mixed cultures were also compared with those of isolated pure species. Complete degradation of chlorophenols and high COD removal efficiencies were observed throughout the SBRs operation. During the degradation of 4-CP, 5-chloro-2-hydroxymuconic semialdehyde, (the -meta cleavage product of 4-CP), accumulated but was subsequently removed completely. Chlorophenol degradation rates increased with increasing chlorophenols concentration in the feed of the SBRs. Gradually decreasing feed peptone concentration did not adversely affect chlorophenol degradation profiles in SBRs. Only competent biomass was thought to be responsible for chlorophenol degradation due to required unique metabolic pathways. It was assumed that the fraction of competent biomass (specialist biomass) is equal to COD basis fraction of chlorophenols in the feed of the reactors as competent biomass grows on chlorophenols only. Models developed using this assumption agreed well with experimental data. The performance of a two stage rotating biological contactor (RBC) was also evaluated for the treatment of synthetic wastewater containing peptone, 4-CP and 2,4-DCP at 5 rpm. High chlorophenols (&gt / 98%) and COD (&gt / 94%) removals were achieved throughout the reactor operation up to 1000 mg/L 4-CP and 500 mg/L 2,4-DCP in the feed. Results showed that RBC is more resistant than suspended growth reactors to high chlorophenols load. The change of dominant species during the operation of SBRs and RBC was also followed using API 20NE identification kits.

Attualmente il gusto di tappo è uno dei problemi più gravi per il settore enologico e sugheriero. I principali composti responsabili di questo difetto sono i policloroanisoli, tra cui in particolare il 2,4,6-tricloroanisolo (TCA),che si formano dai corrispondenti precursori fenolici. La ricerca ha preso in esame vari aspetti:-studio dell'impatto sensoriale del TCA in diversi tipi di vino;-ottimizzazione di metodi di estrazione e analisi di policlorofenoli e policloroanisoli nel sughero e nel vino;-studio della microflora presente nel sughero in base alla capacità di degradare i policlorofenoli. I risultati hanno mostrato che l'uso di un unico valore soglia per la percezione del TCA nei vini non sembra idoneo; i metodi messi a punto sono risultati adeguati per la determinazione di clorofenoli e cloroanisoli; i microrganismi hanno presentato una capacità di produrre TCA differente a seconda del ceppo utilizzato. / Today cork taint is one of most serious problems for wine and cork industries. The primary compounds considered responsible for this defect are chloroanisoles, especially 2,4,6-trichloroanisole (TCA), that are produced from their phenolic precursors. The PhD work was carried out studying different aspects of this subject: -effect of wine style on the perception of TCA;-optimization of extraction and analysis methods to determine chlorophenols and chloroanisoles in wine and cork; biodegradation ability of mould isolated from cork to produce TCA from TCP. The results showed that the use of generic threshold values for all wines does not seem to be accurate enough; methods optimized are adequate to detect chlorophenols and chloroanisoles; micro-organisms tested can produce TCA from TCP.

<p>In this final thesis, an existing method for analysis of chlorophenols (CP) in bottom sediments has been updated and adjusted for analysis of chlorophenols in soil. The covalent bonds between the chlorophenols and the soil matrix were broken through basic hydrolysis and the chlorophenols were then separated from the water phase through addition of sulphuric acid followed by ether extraction. The chromatography was improved through extractive acetylation of the chlorophenols.</p><p>The updated method was then applied on soil samples from a contaminated area (a former sawmill in Hyttsjö, Östergötland, Sweden).</p><p>The analyse was preformed by GC/MS with respect to 2-MonoCP, 4-MonoCP, 2,4-DiCP, 2,6-DiCP, 2,4,6-TriCP, 2,3,4,6-TetraCP and pentachlorophenol (PCP).</p><p>Contamination of chlorophenols in nature can be explained by the former use of wood preservative chemicals based on chlorophenols. In the 1960s and the 1970s these chemicals were used in Sweden, but due to their toxicity they were banned by the Swedish government in 1978.</p><p>In Hyttsjö a pentachlorophenol-based product named Santobrite was used for several years. The concentration of PCP in the soil samples from Hyttsjö varied from 0.2->1.8 ng/mg dry substance. 2,3,4,6- Tetrachlorophenol was also detected in some of the soil samples.</p>