<p>This thesis describes some new methods for analysis oforganic trace components from air and water by gaschromatography. The work is particularly focused on thedevelopment of new technologies for analyte enrichment, usingsorbent-based concepts. Short lengths of open tubular columnswere examined for their potential use as denuders.Polydimethylsiloxane-based stationary phases as well as anadsorbent-based column were evaluated in an equilibrium mode oftrapping. For the analytes selected, detection levels in theppb range were obtained (Paper I).</p><p>A new, fully automated set-up for analysis of organic tracecomponents in aqueous samples has been developed (Paper II).The work combines specific advantages of the solid phase microextraction (SPME) technology and stir bar sorptive extractionconcept. Ultra trace components, down to 0.1 ppt could bedetected. Finally a simple method for preparation a new type ofultra thick film open tubular trap is described (Paper III).The traps are characterized by an irregular coating, and it wasdemonstrated that the performance characteristics of thesetraps were practically as good as of traps with a smooth,regular coating. The technology can be utilized in many areas,e.g. environmental monitoring, process analysis and otherfields dealing with analysis of trace organic volatiles ingaseous samples.</p><p><b>Keywords:</b>Organic trace components, volatiles, denuders,sorbent trapping, thick film trapping, open tubular traps,SPME, automation, water analysis, gas analysis, environmentalanalysis.</p>

Ph.D. (Zoology) / The study concept was derived following an information requirement related to the need for the development of a scientifically sound technique to minimize illegal entries at major South African freshwater fishing tournaments. The hypothesis was that fish that are in equilibrium with the environment that they live in should reflect the chemistry of that environment. Therefore it would be possible to chemically link the fish to a specific impoundment and identify whether the fish are indeed from that impoundment or whether they were brought there to be illegally entered at a fishing tournament. The project area consisted of selected lakes within the Vaal, Mgeni, Crocodile (West) and Olifants River catchments in South Africa. The catchments were chosen to contain major sport fishing lakes and to have different sizes, different sources of pollution, different underlying geological compositions and different climates. Soil analyses data from the regional geochemical mapping program of the Council for Geoscience as well as lake sediment and lake water analyses were used to trace chemical elements during weathering, erosion and deposition. This was done to identify unique characteristics that are able to distinguish between water and sediment from individual lakes. It was found that Rb, Sr, Ba, Cu, Ni,Th, Pb, Sc, K, Mg and Ca could be effectively used as single elements or element ratios to distinguish between lakes. Large variation in sediment compositions within individual lakes limited this distinction. Anomalous catchment soil concentrations related to the underlying geology or anthropogenic contamination can however be traced to lake sediments. Rare earth elements are not uniformly distributed in lake sediments or lake waters and sampling localities should be carefully considered when comparing lakes. Leachable soil sulphate distribution patterns from coal mining areas above Lake Witbank and Lake Middelburg extend downstream through Lake Loskop to Lake Arabie (Flag Boshielo). Leachable fluoride, abundant in the Pilanesberg Alkaline Complex extends northwards along rivers draining the complex. The mineralogy of lake sediments was also compared with the major element composition of these sediments as well as with the anion composition of lake water. Genetic rock classification diagrams could be used effectively to show correlations between catchment soil and lake sediment samples both in terms of mineralogy and chemistry. Lake water and fish tissue samples were collected and analysed to investigate the link between element concentrations in lake water and otolith, fin spine, muscle, liver and gill tissues. Using the Sr/Ca elemental ratio, a species-specific correlation was identified between lake water, otolith, spine and gill tissue samples. The best discrimination between fish species was achieved using a Na/Ca versus Mg/Ca elemental ratio diagram of gill tissues. The best discrimination between fish from different lakes was achieved using a Ba/Mg versus Sr/Mg elemental ratio diagram for spine tissue. Sediments from most lakes in the project area showed elevated Hg values during the dry season as well as elevated Hg levels in sediments from the deeper/central part of these lakes. Lake Sterkfontein has a low sediment Hg concentration but contains fish with the highest Hg tissue concentration in the project area. When comparing the Hg distribution in fish muscle and spine tissue from the project area there is a better correlation with species than with location. The Sr isotope ratio of lake water shows a remarkable correlation with the Sr isotope ratio of fish from the same lake. Analytical data showed that fish within a specific lake all have the same Sr isotope ratio in their spines regardless of species, age, sex and condition. The Sr isotope ratio of water generally increases with distance from the source within tertiary catchments and is determined by the prevalent geology of the formations being weathered. In large rivers like the Vaal River where pollution also plays a role the pattern is much more complicated. The Pb isotopic composition of soil samples from Pretoria and the surrounding areas correspond well to the major underlying geological units. Superimposed on this pattern is an anomalous anthropogenic Pb component possibly related to leaded fuel, which extends from the Pretoria city center northwards along the road and railway networks. Water and sediments from Lake Bon Accord and Lake Marais also contain this anthropogenic signature. The hypothesis that fish, which are in equilibrium with the environment that they live in, should reflect the chemistry of that environment, is therefore not rejected since the results of analysing lake water and fish tissues from 23 South African lakes, within 4 major catchments showed definite correlations. Comparing single elements is the least effective method of establishing such correlations. Comparing elemental ratios is a much better method, while comparing isotope ratios is the most effective method.

A research report submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science in Engineering. August, 2017 / The foremost aim of potable water treatment is to produce water that does not pose a health risk when consumed and/or otherwise used. Nevertheless, research has established that the quality of treated water deteriorates during distribution. The nature and extent of this deterioration varies from system to system and from time to time. The aim of this research study was to monitor the parameters that are known to significantly affect biostability and biofilm formation potential in drinking water distribution systems. Biweekly water samples were collected from thirteen sites, across a section of Johannesburg Water’s network, between September 2015 and August 2016. All samples were assayed for a suite of fifteen water quality parameters using standard methods. Heightened temperature, dearth of chlorine residuals, availability of biodegradable dissolved organic carbon (BDOC), and advanced water age all engendered the loss of biostability (instability). Biostability controlling parameters varied seasonally and spatially. Samples collected during spring and summer, in general, were most likely to be characterized by instability than samples collected during winter and autumn. Samples collected from sites RW80, RW81, RW82, RW83, RW104 and RW253 were more prone to instability compared to samples from other sites. From the results, it is clear that chlorine residuals ought to be kept above 0.2 mg/l, and, BDOC below 0.3mg/l to prevent the loss of heterotrophic stability in distributed water. BDOC concentrations can be decreased by, flushing the pipes, cleaning reservoirs regularly and by further treating feed water before distributing. Booster disinfection can be relied upon to ensure that chlorine residuals are maintained throughout the network. Apart from potential health risks, biological instability and biofilm growth can result in non-compliance with regulations. / MT2018

A oferta de água vem se tornando cada vez mais diminuta à medida que a população, a indústria e a agricultura se expandem. A contaminação dos mananciais gerada pelo descarte de efluentes domésticos e industriais leva a eutrofização, processo pela qual grande aporte de nutrientes, particularmente fosfatos, leva ao crescimento excessivo de algas. As cianobactérias são microrganismos procariontes, que vivem nos ambientes mais adversos. A floração dessas algas quando presente em mananciais destinados ao consumo humano gera sérios problemas à saúde humana, pois algumas dessas algas podem gerar toxinas, conhecidas como hepatotoxinas, neurotoxinas e dermatotoxinas, de acordo com sua ação farmacológica. Dentre as hepatotoxinas encontramos a microcistina, um heptapeptídeo cíclico que pode levar à morte em horas ou dias. O objetivo desse estudo foi viabilizar a técnica HPLC, já proposta por outros autores, para quantificar microcistinas-LR em reservatórios de água, em escala empresarial para ser implementada em laboratórios de análise de águas. Para o desenvolvimento da técnica, foram utilizadas amostras de uma lagoa com floração de Microcystis. Para determinar a eficiência da técnica cromatográfica, foram realizados estudos com outro método, através do kit ELISA. Nessa etapa do trabalho, verificou-se que a técnica HPLC é mais sensível e viável para a quantificação das microcistinas. Nos experimentos realizados com a cromatografia líquida, observou-se que a coluna C-18 LiChrosorb (25 cm) 7 Sm utilizada no método, e o solvente metanol apresentaram grande influência nos resultados. À medida que os experimentos foram executados, verificou-se o decréscimo da sensibilidade da coluna. Os resultados foram satisfatórios apenas após a limpeza realizada na coluna, onde os padrões apresentaram uma curva de correlação igual a 0,92. Este fato leva a concluir que as colunas precisam ser renovadas para análises mais sensíveis, como no caso das microcistinas. As amostras extraídas com metanol apresentaram resultados relevantes, isto é, quanto maior a concentração de metanol utilizado na extração, maior a concentração de microcistina-LR obtida nos resultados, concluindo o metanol ser o solvente apropriado para a extração. Por fim, conclui-se que o método desenvolvido é viável, apresentando algumas dificuldades para sua implantação em escala empresarial. / The water supply has been decreasing more and more as the population, industry and agriculture expand. The contamination of the water sources generated by the domestic and industrial effluents discharges leads to the eutrophization, process where the large presence of nutrients, particularly phosphates, causes excessive increase of algae. The cyanobacteria are procaryote microorganisms which live in the most diverse environments. The florescence of the algae when present in sources directed to human consumption generates serious problems to the human health, for some of them may produce toxins known as hepatotoxins, neurotoxins and dermotoxins, according to their pharmacological action. Among the hepatotoxins, the microcystin, a cyclic heptapeptide that can lead to death in hours or days, is found. The objective of this study was to make feasible the use of the HPLC technique, already proposed by other authors, to quantify microcystins-LR in water reservoirs, in enterprise scale to be implemented in water analysis laboratories. In order to develop the technique, samples of water from a pond with Microcystis florescence were utilized. To evaluate the efficiency of the chromatographic technique, studies were performed with another method, through the ELISA kit. In this phase of the work, it was verified that the HPLC technique is the most sensible and viable for the quantification of the microcystins. It was observed, in the experiments performed with the liquid chromatography, that the column C-18 LiChrosorb (25 cm) 7 Sm utilized in the method and the methanol solvent presented great influence in the results. As the experiments were realized, the decrease of the sensibility of the column was verified. The results were satisfactory only after the column being cleaned, when the patterns presented a curve of correlation equal to 0.92. This fact leads to the conclusion that the columns need to be renewed for more sensible analysis, like in the case of the microcystins. The samples extracted with methanol presented relevant results, that is, the greater the concentration of the methanol utilized, the higher the concentration of microcystin-LR obtained in the results, leading to the conclusion that methanol was the solvent adequate to the extraction. Finally, it was concluded that the method developed is feasible, presenting some difficulties concerning its implantation in enterprise scale.

A fluoretação da água de abastecimento público é um método muito eficiente, mas para ser eficaz, tem que acontecer de forma contínua e ininterrupta, dentro das normas e padrão de potabilidade. O objetivo deste estudo foi avaliar se a quantidade de flúor usada na água de abastecimento público das 10 cidades tocantinenses mais populosas, todas com mais de 20 mil habitantes, encontram-se dentro das normas estabelecidas por portarias e consenso técnico relacionados ao assunto. Pesquisou-se os municípios de Palmas, Porto Nacional, Paraiso do Tocantins, Tocantinópolis, Gurupi, Guaraí, Dianópolis, Colinas do Tocantins, Araguaína e Araguatins, durante 3 meses distintos, entre os meses de maio a agosto de 2017. Um questionário elaborado para avaliar o processo de fluoretação da água foi respondido pelos responsáveis pela fiscalização da água no estado do Tocantins. Além disso, amostras de água, foram coletadas mensalmente, em vários pontos das cidades, contendo amostras de todas as estações de tratamento de água do município. As amostras foram analisadas por laboratório externo e a análise laboratorial do íon flúor foi realizada pelo método eletrométrico. Observou-se que 80,2% das amostras analisadas encontravam-se inadequadas, onde 8 em cada 10 amostras não estão no padrão adequado de menor risco a fluorose dentária e maior proteção contra a cárie dentária. Também, concluiu-se que o estado não possui legislação específica sobre o assunto, mesmo a temperatura local oscilando a valores tão peculiares. Esses dados demonstram a necessidade de se estabelecer uma portaria estadual de fluoretação e um programa de heterocontrole nas cidades pesquisadas, a fim de garantir à população os benefícios do flúor no controle e na prevenção da cárie dental e evitar agravos como fluorose dentária. / Fluoridation of public water supply is a very efficient method, but to be effective, it has to happen continuously and uninterrupted, within the norms and standard of potability. The objective of this study was to evaluate if the amount of fluoride used in public water supply in the 10 most populous towns of Tocantins, with more than 20 thousand inhabitants, are within the norms established by ordinances and technical consensus related to the subject. The municipalities of Palmas, Porto Nacional, Paraiso do Tocantins, Tocantinópolis, Gurupi, Guaraí, Dianópolis, Colinas do Tocantins, Araguaína and Araguatins were surveyed for 3 months between May and August 2017. A questionnaire was prepared for to evaluate the process of water those responsible for water control in the state of Tocantins answered fluoridation. In addition, water samples were collected monthly at various points in the cities, containing samples from all municipal water treatment plants. The samples were analyzed by external laboratory and the laboratory analysis of the fluorine ion was performed by the electrometric method. It was observed that 80.2% of the analyzed samples were inadequate, where 8 out of 10 samples were not in the appropriate standard of lower risk of dental fluorosis and greater protection against dental caries. In addition, it was concluded that the state has no specific legislation on the subject, even local temperature oscillating at such peculiar values. These data demonstrate the need to establish a state regulation of fluoridation and a program of heterocontrol in the cities surveyed, in order to guarantee to the population the benefits of fluoride in the control and prevention of dental caries and to avoid diseases such as dental fluorosis.

Esta tese descreve o desenvolvimento de metodologias eletroanalíticas, em especial a voltametria de onda quadrada com o eletrodo de gota pendente de Hg, para determinação de atrazina em águas de rios do Estados de São Paulo e em amostras de solo. A exatidão das metodologias foi avaliada por comparação com HPLC e estudos de recuperação. Inicialmente desenvolveu-se o método em modo estático, no qual a maior sensibilidade foi obtida em pH 2 e freqüência de 400 Hz, com limites de detecção e determinação de 2 e 10 microgramas L-1, respectivamente. O estudo do comportamento eletroquímico revelou que a atrazina comporta-se reversivelmente em altas freqüências de onda quadrada. Dentre os metabólitos da atrazina, a desetilatrazina e desiosopropilatrazina, também são eletroativas nas condições estudadas, sendo possíveis interferentes, ao contrário da hidroxiatrazina e didealquilatrazina. Sistemas em fluxo contínuo e de injeção seqüencial foram desenvolvidos para determinação de atrazina em extrato de solo e águas naturais, bem como em estudos de adsorção. Em águas, os limites de detecção e determinação obtidos por injeção seqüencial foram de 4,5 e 15 microgramas L-1. Estudos de adsorção revelaram que atrazina liga-se mais fortemente a solos em meios ácidos. As metodologias em fluxo permitiram um significativo aumento da velocidade analítica e economia de reagentes, automatizando as determinações. / This thesis describes the development of electroanalytical methodologies, especially the square wave voltammetry with the hanging mercury drop electrode, for determination of the herbicide atrazine in river waters of the São Paulo state and soil samples. The accuracy of the methodologies was evaluated by comparison with HPLC and recovery studies. Initially, a stationary method was developed, in which the highest sensitivity was attained at pH 2 and at frequency of 400 Hz, with detection and quantification limits of 2 and 10 micrograms L-1, respectively. The electrochemical behavior of atrazine was reversible at the higher square wave frequencies. Among the atrazine metabolites, deethylatrazine and deisopropylatrazine are also electroactive under the studied conditions, being possible interferences, contrary to hydroxyatrazine and didealkylatrazine. Continuous flow and sequential injection systems were developed for determination of atrazine in soil extracts and natural waters, as well as in adsorption studies. In waters, the detection and quantification limits attained by sequential injection were 4.5 and 15 micrograms L-1. Adsorption studies showed that atrazine binds more strongly to soil in acidic media. The flow analysis methodologies lead to significant increase in the sampling throughput and reagent saving, automating the determinations.

No description available.

<p>Water is the most consumed foodstuff around the world. Therefore it is very important to analyze possible faecal contamination of water, and Enterococci are an indicator for that. They are also used as an indicator for possible faecal contamination in food. Normally you find Enterococci in the intestines of humans and animals, but Enterococci can also give infections like urinary tract infection.</p><p>In this study, varying number of colonies and colours of Enterococci on different media were evaluated. The purpose was to investigate if three different methods would give the same numbers of colonies. Another interesting perspective was to investigate if one medium could be used for two methods. Membrane filter techniques and surface spreading techniques were used to detect Enterococci. These methods were compared with a most probable number method.</p><p>None of the strains showed an optimal result on all media, however one medium, ChromoCult, showed good results for all investigated strains.</p>

Water is the most consumed foodstuff around the world. Therefore it is very important to analyze possible faecal contamination of water, and Enterococci are an indicator for that. They are also used as an indicator for possible faecal contamination in food. Normally you find Enterococci in the intestines of humans and animals, but Enterococci can also give infections like urinary tract infection. In this study, varying number of colonies and colours of Enterococci on different media were evaluated. The purpose was to investigate if three different methods would give the same numbers of colonies. Another interesting perspective was to investigate if one medium could be used for two methods. Membrane filter techniques and surface spreading techniques were used to detect Enterococci. These methods were compared with a most probable number method. None of the strains showed an optimal result on all media, however one medium, ChromoCult, showed good results for all investigated strains.

14.8-MeV neutrons from a Cockcroft-Walton type accelerator/neutron generator have been used to irradiate particulate and ionic samples prepared from river water. Five-minute irradiations were performed in a flux of order 109 neutrons/cm2/sec at target position. Gamma-ray spectra resulting from the activated products were recorded with a spectrometer system consisting of a high resolution Ge(Li) detector (2.5% efficiency at 1330 keV) and multichannel analyzer. Trace elements present in the samples were identified by the characteristic gamma-ray energies and half lives associated with the decay products. Standards of known concentration were used to make relative determinations of the quantities of trace elements present in the water. Elements observed in samples with parts per million concentrations include Al, Ba, Ca, Cl, Cr, Fe, K, Mg, Na, Si, and Sr. Sensitivities for elements not observed in the water samples were also determined for As, Cd, Hg, Ni, Ti, Zn, and Zr.Ball State UniversityMuncie, IN 47306