Advanced oxidation processes (AOPs) are commonly used for the destruction of persistent trace organic contaminants (TOrCs) that survive conventional wastewater treatment processes. Three types of AOPs, UV/H2O2, sunlight photolysis and photo-Fenton are experimentally investigated and mathematically quantified to anticipate the fate of TOrCs during oxidation processes, specifically addressing the significant effect of reaction by-products and water matrix on oxidation efficiencies. Hydrogen peroxide UV photolysis is among the most widely used AOPs for the destruction of TOrCs in waters destined for reuse. Previous kinetic models of UV/H2O2 focus on the dynamics of hydroxyl radical production and consumption, as well as the reaction of the target organic with hydroxyl radicals. In this work, we build a predictive kinetic model for the destruction of p-cresol by hydrogen peroxide photolysis based on a complete reaction mechanism that includes reactions of intermediates with hydroxyl radicals. The results show that development of a predictive kinetic model to evaluate process performance requires consideration of the complete reaction mechanism, including reactions of intermediates with hydroxyl radicals. Applying the model to an annular flow-through reactor with reflecting walls, the model mathematically demonstrates that the wall reflectivity significantly enhances the rate of conversion of the target, accounting for the UV light reflection from the reacting walls, as well as the hydrodynamics of the annular flow. Direct and indirect sunlight photolysis is critically important in the breakdown of contaminants in effluent wastewater. The fate of a suite of TOrCs and estrogenic activity were investigated in an effluent-dependent stream. Some TOrCs, which are not sufficiently attenuated through biodegradation and soil adsorption were destructed obviously with distance of travel in the stream. Independent experiments, conducted in batch reactor with 17α-ethinylestradiol (EE2) spiked in effluent showed that attenuation of estrogenic compounds maybe due in part to indirect photolysis caused by formation of reactive species from sunlight absorption. Further investigation was conducted using selective probe compounds to characterize reactive species. And results showed that singlet oxygen generated from excited state of effluent organic matter was responsible for essentially all observed transformations of targets in the effluent in Tucson. To mathematically quantify the photo-Fenton AOP, a kinetic model is proposed for the photolysis of Fe3+ hydroxo complexes at low pH (pH ≤ 3.0). The model incorporates elementary reactions of the Fenton-like and UV/H2O2 system. Iron speciation and photochemical parameters, including the molar absorptivities of light-absorbing species and the quantum yields of Fe3+ and FeOH2+ hydrolysis are experimentally validated. However, the predicted, time-dependent Fe2+ concentrations during Fe3+ photolysis are much lower than measured. The possible missing elements in the model could be (i) quenching of OH radicals by unknown species, or/and (ii) shielding of Fe2+ by unknown compounds at the beginning of the process.

Each and every one of us is exposed to chemicals on a daily basis and contributes to the global issue of chemical pollution. Humankind has become heavily dependent on the use of man-made chemicals in order to sustain the increased quality of life that is generally seen globally. There is however a price to pay in that we generally live in a world that is polluted by anthropogenic chemicals. From the water we drink to the food we eat there will be some trace of chemical residues; you just need to look closely enough and/or know what you’re looking for. With many hundreds of thousands of man-made chemicals approved within Europe for use in various ways, it is no surprise that we come into daily contact with them. What is also important to understand is that the presence of a man-made chemical is not enough to establish whether it poses a risk to environmental or human health; it needs to be present in sufficient amounts to elicit an effect. Over the past 20 years the focus of my research been on understanding which chemicals we should be concerned with, which pose the greatest risk and why do they pose such a risk. This work is of major societal and scientific significance as it protects the world we live in whilst teaching us about the better regulation of the chemicals we have become so dependent. To understand the nature of my research it is important to understand that prior to the mid-nineteen nineties hazardous organic chemicals were typically restricted to lists comprising of a number of banned (and typically chlorinated) pesticides, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans and the antifouling biocide tributyltin (TBT). One of the major enigmas that faced environmental scientists at the time was that even though it was possible to quantify and monitor the presence of the above hazardous substances in the environment, they often didn´t explain the environmental quality measured though biological effects on organisms. Chemicals are globally regulated on an individual substance level and subsequently within the context of influencing these regulations, for the improved protection of environmental and human health, it is therefore essential to know which chemical contaminants are actually causing biological effects. It is also necessary to know the levels at which any organism will be exposed and what the consequences of these levels. My research subsequently became focused on two separate approaches; identifying which substances actually cause the biological effects unexplained by hazardous substances and evaluating the occurrence, environmental fate and ecotoxicity of those chemicals not routinely monitored or present on priority lists of hazardous substances; a group of chemical contaminants later termed contaminants of emerging concern (CECs). An effect-directed non-target approach A targeted approach to environmental analysis infers that we know exactly what we should be looking for. Whilst this is a suitable approach for chemicals that we suspect may be of concern, it does not help us understand which other contaminants may be present in the environment and potentially causing harm. When embryos of oysters exposed to estuarine surface waters developed deformities and this could not be attributable to the levels of priority hazardous substances a bioassay-directed non-target approach to environmental analysis was developed to identify chlorinated and alkylphenols as responsible [5, 6]. This approach has subsequently evolved into the approach termed effect-directed analysis (EDA) and is widely used globally for the identification of CECs. My own research has successfully applied the approach to identify for the first time a number of important environmental contaminants; steroidal androgens [10, 13, 14] as environmental contaminants, the phthalate ester bis(2-ethylhexyl)phthalate [10], cinnarizine, cholesta-4,6.dien-3-one [19], C1-C5 and C9 alkylphenols [21], petrogenic naphthenic acids [57] as environmental estrogen receptor agonists, C1-C5 and C9 alkylphenols [21], PAHs and petrogenic naphthenic acids [57] as androgen receptor antagonists and unresolved polar aromatic compounds as important environmental genotoxins [15]. Another focus of my effects-directed research has been identifying environmental contaminants that exert the same effects as dibenzo-p-dioxins and polychlorinated dibenzofurans in that they are aryl hydrocarbon receptor (AhR) agonists. Dioxin-like chemicals are ubiquitous in the environment and in addition to those that are routinely monitored there are a large number of other compounds that exert dioxin-like effects [26, 28, 32, 33, 37, 52, 64, 82, 93, 98, 99]. Better understanding of AhR agonists will in the long run help protect the environment and humans from a particularly hazardous group of chemicals. A targeted approach The early- to mid-nineteen nineties saw the widespread introduction of liquid chromatography coupled to mass spectrometry (LC-MS) to the environmental analytical toolbox. Robust instruments typically using electrospray and atmospheric pressure chemical ionisation were well suited to the analysis of the more polar CECs, such as alternative antifouling biocides to TBT, pharmaceuticals, personal care products, veterinary medicines, illicit drugs and rodenticides. Robust analytical methodology is key to my research [2, 4, 18, 31, 34, 35, 42, 49, 66, 69, 72, 73, 86, 94, 102] as it allows the better understanding of how contaminants behave and interact with the environment. Development of robust, specific and sensitive methods for the analysis of alternative antifouling biocides [2, 4] allowed for the first time an evaluation of their life-cycle from release at the paint surface, and the factors that influence this [3], their occurrence in the environment [7, 8, 12, 29], fate and behaviour [12, 16] and subsequent effects [36, 41]. Assessment of the environmental risks based upon these data showed that both Irgarol 1051 and diuron were a threat to freshwater and marine algae. The significance of this research is that it subsequently led to restrictions being placed on the use of Irgarol 1051 and diuron in antifouling products in a number of European countries [58] and an awareness of the hazards associated with the deliberate release of biocidal products into the environment [86]. Observations of human pharmaceutical residues in the chromatograms of wastewater effluent samples being analysed by EDA and reports of their occurrence in German wastewaters motivated the development of LC- tandem MS methods for the quantification of pharmaceutical residues in waste- and surface waters [18]. Pharmaceuticals, we showed, occur in treated wastewater effluents and marine and freshwater recipients [24, 25, 30, 42, 43, 51, 66] and that, to no great surprise, the per capita pharmaceutical loads from hospitals were greater than the general population [43, 51]. Other highlights include understanding the processes that occur within sewer systems and what influences pharmaceutical occurrence in the final treated effluent [59, 60, 81, 85, 105], all of which allow for a better assessment of the overall risk posed to the environment. Even though several hundred papers have been published on pharmaceuticals in the environment since my early work, this has almost exclusively been focused on the parent pharmaceutical ingredient in aqueous matrices from developed counties. To remedy this shortfall more recent work has focused on quantifying the proportion of pharmaceutical metabolites released as compared to the parent [66], pharmaceutical occurrence in sludges and sediments [69], as well as evaluating occurrence in less studied water cycles [101].

The aluminosilicate materials kaolinite, calcium montmorillonite and emathlite have been tested as solid sorbents for alkali vapour in controlled gaseous environments, in order to study their sorption characteristics. The study used pan pelletised and extruded pellets in single pellet and fixed bed reactor systems under gaseous environmental conditions containing water vapour, hydrogen chloride and nitrogen at a temperature of 850°C. The means of producing the pellets and the composition of the gaseous environment were shown to determine the sorption performance of the sorbent pellets. The physical properties of the pellet (particle size, total pore volume, surface area, crush strength) significantly affect the sorption effectiveness, while the formation of reaction products is dependent upon the sorbents' chemical composition and on the sorption conditions. Reaction products identified under the various sorption conditions indicated possible pathways for alkali capture. Hydrogen chloride mixtures were shown to cause a reverse of the sorption process for some sorbents. A leaching method for extracting sodium from treated pellets enabled the type of bonding to be determined but not necessarily the prime sorption mechanism. With the introduction of water vapour, some evidence was presented that the alkali sorption rate can change significantly. The previously reported effect of hydrogen chloride upon alkali capture by the sorbent material, calcium montmorillonite; shown by McLaughlin (1990) was confirmed and the effect was also investigated for emathlite and kaolinite. Reversibility depended upon the presence or absence of hydrogen chloride. Both water vapour and hydrogen chloride determine sorption activity and capacity. Likewise the structural characteristics of the pellet influences the sorption activity and capacity. The sorption process is not due to aluminosilicate reaction alone but also due to replacement mechanisms. Conclusions are drawn regarding mechanism and theoretical model proposed.

Soil contamination from petroleum spills is a frequent environmental problem in the world. It is obvious that petroleum exploration has contributed immensely to the economic growth of Nigeria, but over the last few decades, the Niger Delta of Nigeria has suffered grave human health risk and ecosystem degradation resulting from oil spillages, petroleum products leakages and other involuntary effluent discharges from oil exploration activities. This research seeks to develop and optimize GC-FID methods for the analysis of Petroleum hydrocarbons. Crude oil spillage contamination of soil from the Niger Delta was investigated 3 months after a crude oil-pipeline spillage. 47 Soil samples (300-500g) were collected at several points in the South-South Niger Delta. Control samples were taken from four unaffected sites within the vicinity of spillage with similar soil characteristics. Samples were collected at depths of 0-15 cm, 15-30 cm and 30-60 cm. The soil samples were prepared for analysis using solvent extraction methods, passed through column of sodium sulphate and Florisil® to aid in column performance, remove moisture and gross impurities. Samples were analysed using gas chromatography with a flame ionisation detector. Penetration and migration of C10-C26 and C26-C34 hydrocarbons through the soil layers were assessed by cluster analysis to determine the spatial distribution, penetration and chemical similarity of these compounds over the contaminated area. This information is a useful guide for bioremediation purpose. It was found that total petroleum hydrocarbon concentrations varied from 9-289 mgkg-1 topsoil, 8-318 mgkg-1 subsoil and 7-163 mgkg-1 at the greatest depth measured.The results show elevated levels of total hydrocarbon contents when compared with the reference sites. Drastic steps should be taken to carefully monitor and remediate the environment. Bioremediation with plants and micro-organisms is endorsed.

Aquaculture feeds, traditionally composed mainly of fishmeal and fish oil, currently represent the largest cost to fish farmers. With aquaculture growing at an average of 8.8% per year and limited supply of fishmeal and fish oil, suitable alternatives must be found. In addition to increasing sustainability and lowering production costs, the use of plant and/or animal ingredients has the potential to lower flesh levels of persistent organic pollutants (POPs) such as polychlorinated biphenyls. Fish oil and to a lesser extent fishmeal, are considered to be the largest source POPs in farmed fish. Using alternative feed ingredients however, can compromise fish growth and the flesh quality of the final product. Lipid sources including flaxseed oil, canola oil, poultry fat and the protein sources canola protein concentrate, soy protein concentrate and poultry by-product meal were examined as alternatives to fish oil and fishmeal in one on-farm field study and one laboratory feeding trial with Atlantic salmon (Salmon salar) and two laboratory feeding trials conducted on sablefish (Anoplopoma fimbria), a relatively new marine aquaculture species. The nutritive value of the alternative ingredients was assessed on the basis of fish growth performance, proximate composition, fatty acid composition and apparent digestibility coefficients. Sensory attributes were evaluated in the sablefish studies while flesh POP levels were determined in both species. The use of alternative dietary lipids showed no negative effects on fish performance. However replacement of fishmeal with plant proteins in some cases, negatively affected fish growth. Flesh levels of persistent organic pollutants were significantly decreased (p<0.05) with the use of alternative dietary lipids, and flesh levels of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) were also depressed. Activated carbon treated anchovy oil and finishing diets were examined in the Atlantic salmon laboratory feeding trial and were effective at lowering flesh POP levels while providing high levels of EPA and DHA. The use of alternative feed ingredients will soon be inevitable in aquaculture feeds. The current research shows alternative lipids and proteins can be incorporated successfully in sablefish and Atlantic salmon feeds with minimal effects on fish growth and quality. / Land and Food Systems, Faculty of / Graduate

We have developed a regional mass balance model for the St. Lawrence River near Cornwall, Ontario that describes the fate and transport of mercury in three forms, elemental mercury (Hg0), divalent mercury (Hg2+), and methyl mercury (MeHg), in a five compartment environment (air, water, sediments, periphyton, and benthos). Our first objective was to construct a steady-state mass balance model to determine the dominant sources and sinks of mercury in this environment. Our second objective was to construct a dynamic mass balance model to predict and hindcast mercury concentrations in this environment. We compiled mercury concentrations, fluxes, and transformation rates from previous studies completed in this section of the river to develop the model in STELLA®. The inflow of mercury was the major source to this system, accounting for 0.42 mol month-1, or 95.5% of all mercury inputs, whereas outflow was 0.28 mol month-1, or 63.6% of all losses, and sediment deposition was 0.12 mol month-1, or 27.3% of all losses. The dynamic mass balance model provides estimated results that are consistent with measured data and predicts historical local industrial emissions to be approximately 400 kg year-1. Uncertainty estimates were greatest for advective fluxes in surface water, porewater, periphyton, and benthic invertebrates. This model is useful for predicting and hindcasting mercury concentrations in other aquatic environments because it contains the three main environmental compartments, all forms of mercury, and compartments (e.g. periphyton) not included in previous mercury multi-media models.

Orientador: Solange Cadore / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T20:30:04Z (GMT). No. of bitstreams: 1 Aranha_TaiseSuellendeCastroPorto_M.pdf: 1506809 bytes, checksum: 8eb73b125b97bd8ac0468a36f62aad43 (MD5) Previous issue date: 2015 / Resumo: O objetivo principal deste projeto de pesquisa consistiu em desenvolver e validar um método para a determinação de cádmio e chumbo, pela técnica de Espectrometria de Absorção Atômica com Forno de Grafite (GF AAS), nas matrizes rim e fígado de caprinos, ovinos e avestruz. Este trabalho justifica-se pela importância do monitoramento do teor de contaminantes inorgânicos em produtos alimentícios, uma vez que a exposição a estes pode afetar os seres humanos e os animais, devido ao seu potencial tóxico e seus efeitos cumulativos. Além disso, o controle de resíduos em alimentos também é relevante devido às exigências do mercado, como o atendimento às legislações vigentes para a comercialização interna e exportação de produtos. Para o preparo de amostra adotou-se a amostragem em suspensão, um método particularmente atrativo, uma vez que não requer um pré-tratamento químico agressivo, é menos susceptível a contaminação e perda do analito, além de que padrões aquosos podem ser usados para a calibração, facilitando as análises de rotina. Os fatores envolvidos nesta etapa, bem como os parâmetros instrumentais foram otimizados através de planejamentos experimentais. Desta forma, o preparo das amostras de carne foi conduzido à temperatura ambiente, a partir da hidratação de 500 mg da amostra (in natura ou liofilizada), seguida de solubilização com 500 ?L de TMAH 25% (m/v), e avolumando-se para 10,0 mL com água desionizada. As análises foram realizadas por Espectrometria de Absorção Atômica com Forno de Grafite, adotando-se temperaturas de pirólise e de atomização iguais a 500 e 1500 ºC, associadas ao uso de uma combinação de 5 ?g Pg(NO3)2 e 3 ?g de Mg(NO3)2 como modificador químico, para a determinação de Cd. Por sua vez, para a quantificação de Pb, empregaram-se temperaturas de pirólise e de atomização de 1000 e 2000 ºC, com 10 ?g Pg(NO3)2 + 6 ?g de Mg(NO3)2 como modificador químico combinado. Visando atender às legislações nacionais e internacionais, a validação do método foi conduzida em níveis de concentrações específicos, relacionados ao teor máximo de contaminantes (TMC), e os critérios de aceitabilidade das figuras de mérito seguiram as recomendações da comunidade européia (CE/657, CE/333) e do Mercosul (Mercosul/GMC/RES n. 57/94) / Abstract: The main objective of this project was to develop and validate a method for the determination of cadmium and lead, by Graphite Furnace Atomic Absorption Spectrometry (GF AAS), in caprines, ovines and ostrich kidney and liver. This work is justified by the importance of monitoring the content of inorganic contaminants in food products, since exposure to them can affect humans and animals due to their toxic potential and their cumulative effects. In addition, the residue control in food is also relevant for commercial reasons, such as attending the existing laws for internal commerce and for exportation. For sample preparation was adopted slurry sampling, a particularly attractive method because it does not require an aggressive chemical pretreatment, is less susceptible to contamination and loss of analyte, and aqueous standards can be used to calibration, facilitating the routine analysis. The factors involved in this treatment, as well as the instrumental parameters, were optimized using experimental designs. In the proposed method, 500 mg meat sample (fresh or lyophilized) was previously hydrated and treated using 500 ?L of tetramethylammonium hydroxide solution (TMAH) which provided stable and homogeneous slurry at room temperature in less than 10 min. The volume was brought up to 10 mL with deionized water. Analyses were performed by GF AAS, adopting pyrolysis and atomization temperatures equal to 500 and 1500 ° C, respectively, associated with the use of 5 ?g Pg(NO3)2 and 3 ?g de Mg(NO3)2 as a chemical modifier for the determination of cadmium. In turn, for the lead quantification, pyrolysis and atomization temperatures equal to 1000 and 2000 °C were employed, respectively, and as chemical modifier 10 ?g Pg(NO3)2 and 6 ?g de Mg(NO3)2, containing triton X-100, was used. In order to comply with national and international legislation, the method validation was conducted on specific concentrations levels, related to the maximum contaminants levels (ML), and the criteria of acceptability of figures of merits followed the European Community and MERCOSUL recommendations / Mestrado / Quimica Analitica / Mestra em Química

Contaminants of emerging concern (CECs) are an unregulated suite of constituents frequently detected in environmental waters, which possess the potential to cause a host of reproductive and developmental problems in humans and wildlife. Degradation pathways of several CECs are well-characterized in idealized laboratory settings, but CEC fate and transport in complex field settings is poorly understood. In the present study I use a multi-tracer solute injection to study and quantify physical transport and photodegradation in a wastewater effluent-impacted stream in Ankeny, Iowa. Conservative tracers are used to quantify physical transport processes in the stream. Use of reactive fluorescent tracers allows for isolation of the relative contribution of photodegradation within the system. Field data were used to calibrate a one-dimensional transport model, and forward modeling was then used to predict the transport of sulfamethoxazole, an antibiotic in the effluent which is susceptible to photolysis. Results show that accurate predictions of reactive CECs at the scale of stream reaches can be made using the fate and transport model based on field tracer studies. Results of this study demonstrate a framework that can be used to couple field tracer and laboratory CEC studies to accurately predict the transport and fate of CECs in streams.

Philosophiae Doctor - PhD / The increasing evidence of chemicals of emerging concern (CECs) in water bodies is causing major concern around the world because of their toxicological effects upon humans and aquatic organisms. The release of wastewater to the aquatic environment is most likely to introduce some trace levels of organic contaminants, some of which may be toxic, carcinogenic, or endocrine disruptors, as well as, persistent in the environment. These compounds are often persistent but not regularly monitored because they are mostly still excluded from environmental legislation. Their fate and persistence in the environment are not well understood. / 2022-02-24

Sediments of lotic and lentic water can be a reservoir of a number of contaminants, which can enter the aquatic ecosystem either due to the controlled discharge of waste water or leakage of various accidents or technological devices. Sediments can hereby affect not only the aquatic ecosystem, but also the terrestrial system in the case that they will be used as fertilizer or as a material for the recultivation. For this reason it is important to consider their potential ecotoxicity. Sediments were subjected to ecotoxicological bioassays and their potential ecotoxicity was assessed. The phytotoxicity assays on terrestrial plants Sinapis alba, Lactuca sativa and Allium cepa were used and the effects of aqueous extracts of sediments on the inhibition of growth their root were evaluated and the value of IC50 was determined. For the ecotoxicological assessment of sediments and determination of IC50 value also Lemna minor as a representative of aquatic plants was selected. For more objective assessment of the sediment ecotoxicity aquatic invertebrates as Artemia salina and Daphnia magna were selected and the value of LC50 or EC50 was determined.