Rozprawy doktorskie na temat „And contaminants”

La detección de contaminantes peligrosos requiere especial atención debido a su posible toxicidad, baja concentración en muestras reales y, en la mayoría de los casos, una imposibilidad de llevar a cabo la detección a través de un metodo tan específico como el inmunoensayo. Una de las estrategias orientadas a la fácil detección de compuestos nocivos es el uso de plataformas microfluídicas llamadas Lab-on-a-chip. En el Capítulo 3, una innovadora plataforma microfluídica en miniatura es desarrollada para la detección simultánea y extracción de polibromodifenil éteres (PBDEs). La plataforma consiste en un chip microfluídico de polidimetilosiloxano (PDMS) para el paso de la inmunoreacción, un chip de PDMS con un electrodo serigrafiado de carbono (SPCE) integrado para la detección, y un chip de PDMS-óxido de grafeno reducido (rGO) para la adsorción física y posterior eliminación de residuos de PBDE. La detección se basó en un inmunoensayo competitivo entre PBDE y PBDE modificado con Peroxidasa de Rábano Silvestre (HRP-PBDE) seguido de un monitoreo de oxidación enzimática de o-aminofenol (o-AP), utilizando voltamperometría de onda cuadrada y resolución anódica (SW-ASV). PBDE fue detectado con una buena sensibilidad y un límite de detección similar al obtenido a través de una prueba colorimétrica comercial (0.018 ppb), pero con la ventaja de utilizar volúmenes reactivos más bajos y un tiempo de análisis reducido. Con el objetivo de diseñar un sistema de detección apropiado para compuestos tóxicos como PBDEs, un compósito de óxido de grafeno reducido y PDMS ha sido desarrollado y optimizado para obtener mayor adsorción (basados en hidropobicidad e interacción π–π entre moléculas de rGO y PBDE) comparado con los PDMS sin modificación. Este sistema se puede aplicar perfectamente para detectar cualquier análito utilizando el inmunoensayo apropiado y facilitar el funcionamiento en matrices tan complejas como el agua marina. En el Capítulo 4 se desarrolla un dispositivo LOC para la preconcentración y la detección simultánea de metales pesados. Dicho dispositivo consta de un electrodo serigrafiado de carbono, un chip de PDMS y otro de GO-PDMS. El chip de GO-PDMS fue fabricado y los factores más esenciales fueron optimizados, incluidos la concentración de GO y aquella del curador de PDMS. Se descubrió que la habilidad de adsorción es inversamente proporcional a la concentración de curador de PDMS en el compósito y proporcional a la concentración de GO. El mecanismo de adsorción está basado en una reacción de complejación , donde grupos activos de oxígeno con cargas negativas se pueden enlazar con metales bivalentes como el Pb. La adsorción más alta fue obtenida en pH=7. El GO-PDMS tiene una capacidad relativamente grande de adsorción, ya que incluso las muestras que contienen niveles más altas que 500 ppb (mayores a 500 ppb) son totalmente adsorbidas, teniendo en cuenta que tal concentración es muy alta. El proceso de desorción ha sido también optimizado. Gracias a ello, metales que habían sido previamente adsorbidos se pueden liberar y detectar en voltamperometría de Onda Cuadrada y Resolución Anódica. El límite de detección de esta técnica (utilizando electrodos serigrafiados de carbono) fue de 0.5 ppb para el plomo (Pb). Esto significa que utilizando una plataforma de preconcentración GO-PDMS, se pueden cuantificar cantidades más bajas de Pb, ya que las muestras preconcentradas mostraron una corriente de hasta 30 veces más alta que las no preconcentradas. Esta plataforma se puede utilizar para la detección mejorada de metales pesados y también para su eliminación.
The detection of hazardous contaminants requires special attention due to their possible toxicity, low concentration in real samples and, in most cases, an impossibility to perform detection by using such a specific approach as immunoassay. One of the approaches taking an important step towards easier detection of hazardous compounds is the use of Lab-on-a-chip platform. In Chapter 3, a novel, miniaturized microfluidic platform for the simultaneous detection and removal of polybrominated diphenyl ethers (PBDEs) was developed. The platform consists of a polydimethylsiloxane (PDMS) microfluidic chip for the immunoreaction step, a PDMS chip with an integrated screen-printed electrode (SPCE) for detection, and a PDMS-reduced graphene oxide (rGO) chip for physical adsorption and subsequent removal of PBDE residues. The detection was based on competitive immunoassay-linked binding between PBDE and PBDE modified with horseradish peroxidase (HRP-PBDE) followed by the monitoring of enzymatic oxidation of o-aminophenol (o-AP) by using square wave anodic stripping voltammetry (SW-ASV). PBDE was detected with good sensitivity and a limit of detection similar to that obtained with a commercial colorimetric test (0.018 ppb), but with the advantage of using lower reagent volumes and a reduced analysis time. In order to design a detection system suitable for toxic compounds such as PBDEs, a reduced graphene oxide–PDMS composite has been developed and optimized to obtain increased adsorption (based on both the hydrophobicity and π–π stacking between rGO and PBDE molecules) compared to those of non-modified PDMS. This system can be easily applied to detect any analyte by using the appropriate immunoassay and it supports operation in such complex matrices as seawater. In Chapter 4, a LOC device for the simultaneous preconcentration and detection of heavy metals was developed. This device consists of a screen-printed carbon electrode, a PDMS chip, and a GO-PDMS chip. The GO-PDMS chip was fabricated and the most crucial factors were optimized, including the concentration of GO and the concentration of the curing agent. It was found that the adsorption ability is inversely proportional to the PDMS catalyser (curing agent) concentration in the composite and proportional to the GO concentration. The mechanism of adsorption is based on surface complexation, where oxygen active groups of negative charge can bind with such bivalent metals as Pb. The highest adsorption was obtained in pH=7. The GO-PDMS has a relatively big large adsorption capacity, as even the samples >500 ppb are nearly fully adsorbed, taking into account that such a concentration is very high. The desorption process was optimized as well. Thanks to this, previously adsorbed metals can be released and detected in square wave anodic stripping voltammetry. The limit of detection of this technique (using screen-printed electrodes) was 0.5 ppb for Pb. This means that by using a preconcentration GO-PDMS platform, a lower amount of Pb can be quantified because preconcentrated samples showed a current up to 30 times higher than that of non-preconcentrated one. This platform can be used for improved heavy metal sensing and also for its removal.

Els contaminants orgànics són substàncies químiques amb el potencial de causar efectes adversos al medi ambient i/o a la salut humana. Degut a l’ús cada cop més elevat de substàncies químiques i la seva emissió continuada al medi ambient, aquestes es poden considerar com a pseudo-persistents, convertint en una prioritat el monitoratge de la seva presència al medi ambient. Un dels aspectes que està suscitant una major preocupació es el control dels contaminants orgànics al medi aquàtic, ja que pot afectar de manera significativa a la seva qualitat. En aquest sentit, l'objectiu principal d'aquesta Tesi es el desenvolupament de metodologia analítica basada en la cromatografía líquida acoblada a l'espectrometría de masses en tandem, utilitzant un analitzador de triple quadrupol, per a la determinació de certs contaminants orgànics, tant prioritàris com emergents, en mostres d'aigua. Un cop la metodologia ha estat desenvolupada i validada, ha estat aplicada a l'analisi de mostres d'aigua del riu Ebre i a mostres recollides en una ETAP. D'aquesta manera s'ha pogut avaluar la presència d'aquests contaminants en aquestes aigües, així com l'efectivitat dels diferents tractaments aplicats en aquesta ETAP per a l'eliminació d'aquests contaminants.
Los contaminantes orgánicos son sustancias químicas con el potencial de causar efectos adversos al medio ambiente y / o la salud humana. Debido al uso cada vez más elevado de sustancias químicas y su emisión continuada al medio ambiente, estas se pueden considerar como pseudo-persistentes, convirtiendo en una prioridad el monitoreo de su presencia en el medio ambiente. Uno de los aspectos que está suscitando una mayor preocupación es el control de los contaminantes orgánicos en el medio acuático, ya que puede afectar de manera significativa a su calidad. En este sentido, el objetivo principal de esta Tesis es el desarrollo de metodología analítica basada en la cromatografía líquida acoplada a la espectrometría de masas en tándem, utilizando un analizador de triple cuadrupolo, para la determinación de ciertos contaminantes orgánicos, tanto prioritarios como emergentes, en muestras de agua. Una vez la metodología ha sido desarrollada y validada, ha sido aplicada al análisis de muestras de agua del río Ebro y en muestras recogidas en una ETAP. De esta manera se ha podido evaluar la presencia de estos contaminantes en estas aguas, así como la efectividad de los diferentes tratamientos aplicados en esta ETAP para la eliminación de estos contaminantes.
Organic pollutants are chemicals with the potential to cause adverse effects to the environment and / or human health. Due to the increasing use of chemical substances and their continuous release into the environment, these can be considered as pseudo-persistent, making monitoring their presence in the environment a priority. One of the aspects that is causing the greatest concern is the control of organic pollutants in the aquatic environment, as it can significantly affect its quality. In this sense, the main objective of this Thesis is the development of analytical methodology based on liquid chromatography coupled to tandem mass spectrometry, using a triple quadrupole analyzer, for the determination of certain organic pollutants, both priority and emerging, in water samples. Once the methodology has been developed and validated, it has been applied to the analysis of water samples from the Ebro river and in samples collected in an ETAP. In this way, the presence of these pollutants in these waters has been evaluated, as well as the effectiveness of the different treatments applied in this ETAP for the elimination of these pollutants.

Objetivo. Comparar a qualidade do ar externo com o ambiente interno das estações Clínicas e Praça da Sé do Metrô de São Paulo, quantificando e qualificando os contaminantes microbiológicos e atmosféricos. Propõe-se com este estudo promover o conhecimento de fatores sobre a qualidade do ar e das condições de higiene e saúde destes locais, contribuindo para a melhoria da qualidade de vida dos trabalhadores e usuários do sistema. Métodos. As amostras foram realizadas no período de Julho a Novembro de 2005. Os fungos foram coletados com o impactador de Andersen de um estágio com volume de aspiração de 28 l/min por um tempo de 10 minutos por amostra, e como meio de cultivo Agar Sabouraud Dextrose a 4 por cento . A quantificação e identificação foram feitas por meio de análises de lâminas do material microbiológico em microscópio óptico, coradas com azul de lactofenol. Para o dióxido de nitrogênio utilizou-se difusor passivo com trietanolamina como substância adsorvente e as análises foram realizadas por espectrofotometria. O difusor passivo para avaliação da concentração de benzeno é do tipo membrana, com carvão ativado como substância adsorvente e a análise por cromatografia gasosa. O tempo de exposição para estes amostradores foi de 30 dias. O PM10 foi medido com um monitor contínuo, com leitura direta. Foram instalados dois equipamentos em cada estação por um período de 7 dias. Resultados. Os estudos indicam a presença de fungos comuns com predominância para o Cladosporium sp (52 por cento ), Alternaria sp (17 por cento ) e Penicillium sp (13 por cento ) e em proporções semelhantes interna e externamente às estações. A concentração média de NO2 no interior das estações, foi de 73,9JPñ (VWHV YDORUHV Vão semelhantes às medições externas realizadas com o equipamento de Espectroscópia de Absorção por Diferencial Óptico (DOAS) e os valores medidos pela estação de monitoramento da CETESB, instalado na FSP/USP. Os valores viii máximos encontrados para o benzeno foram de 5,7JPñ QR LQWHULRU GDV estações e 6,2JPñQRDPELHQWHH[WHUQR230LQGLFRXYDORUHVHOHYDGRV sendo o valor médio, para a estação Clínicas de 312,4JPñ PHGLGRV QD SODWDIRUPDHJ/m³ no mezanino, na estação Praça da Sé verificamos a concentração de 150,9JPñ QD SODWDIRUPD GD OLQKD H JPñ QD plataforma da linha 3. Conclusões. O presente estudo possibilitou a avaliação e comparação dos níveis de poluição ambiental interno e externo às estações. A constatação da predominância de fungos comuns no ar não indica a ausência de riscos para a saúde humana, pois o seu impacto depende da suscetibilidade dos indivíduos expostos. A concentração de NO2 e benzeno encontradas no ambiente interno e externo são de mesma ordem de grandeza, o que indica que estes contaminantes têm a mesma fonte de origem. A alta concentração de PM10 representa uma maior preocupação. Para este contaminante deve-se avaliar a composição do material encontrado e seu grau de toxicidade
Objective. Compare the air quality outdoors with the indoors environment at Clínicas and Praça da Sé Stations of the São Paulo Subway, measuring the quantity and quality of the existing microbiological and atmospheric contaminants. The purpose of this study is to promote the knowledge of factors related to the air quality and the health and hygiene conditions in these places, contributing to the improvement of the quality of life of employees and users of the system. Methods. The samples were taken from July to November 2005. The fungi were taken by one-stage Andersen impactor with aspiration volume of 28 l/min for a period of 10 minutes per sample, making use of Agar Sabouraud Dextrose at 4 per cent for the culture. The quantification and identification are done by the analysis of slides with the microbiological material in an optical microscope, colored with lactofenol blue. For the nitrogen dioxide, a passive diffuser was used with triethanolamine as absorbing substance and the analysis was done by spectrophotometry, the passive diffuser used to evaluate the concentration of benzene is the membrane type with activated carbon as absorbing substance making use of gas chromatography analysis. The exposure period for these samplers was 30 days. The PM10 was measured with a continuous monitor, with direct reading. This equipment uses fibreoptic sensors for the identification of the size and concentration of the particles which are sucked by a diaphragm pump, passing through a measuring chamber which also measures the temperature and the air humidity. Two pieces of this equipment were installed in each station for a period of seven days. Results. The studies indicate the presence of ordinary fungi with the prevalence of Cladosporium sp (52 per cent ), Alternaria sp (17 per cent ) and Penicillium sp (13 per cent ) in similar proportions both indoors and outdoors. The indoor average concentration of NO2 was 69,5g/m³. These values are similar to the outdoor x results obtained with the equipment for Differential Optical Absorption Spectroscopy (DOAS) and the values measured by CETESB control station, located at FSP/USP. The values found for benzene ranged from 3,8 to 6,2g/m³, indicating an average of 5,0g/m³. The PM10 indicated high values with an average, at Clínicas Station, of 312,4 g/m³ measured in the platform and 243,9 g/m³ in the mezzanine. At Praça da Sé Station the concentration on the platforms was 150,9 g/m³ for line 1 and 124,2 g/m³ for line 3. Conclusions. The present study permitted the assessment and comparison of the environmental pollution levels inside and outside the stations. The verification of the predominance of common fungi in the air doesn\'t indicate the absence of risks for the human health, because it impact depends on the exposed individuals\' susceptibility. The concentration of NO2 and benzene found in the internal and external atmosphere are of same order of greatness, what indicates that these pollutants have the same origin source. The high concentration of PM10 represents a larger concern. This pollutant it should be evaluated the composition of the found material and his toxicity degree

ENGLISH SUMMARY:

In this work, the ozonation of emergent contaminants represented by pharmaceuticals (Sulfamethoxazole and Bezafibrate) and surfactants (Quaternary Ammonium Compounds) was studied. Results in terms of target compound degradation and mineralization along with the biodegradability and toxicity assessment of formed intermediates are presented. Moreover, a previous study about the suitability of the combination ozonation-Sequencing Batch Biofilm Reactor (SBBR), using the model compound 4-chlorophenol, is shown.

The preliminary runs aimed to assess the mineralization of 100 and 200 mg L-1 4-chlorophenol (4-CP) solutions by ozonation and ozonation-biological treatment (SBBR). The experimental results showed that with an ozone flow rate of 5.44 and 7.57 g h-1, 4-CP was completely removed from the solution in 15 and 30 minutes of ozonation, respectively. By the other hand, at the 4-CP abatement time, on average only 26 % of total organic carbon (TOC) removal was achieved. The biodegradability (BOD5/COD) of the pre-ozonated solutions increased from 0 until a range between 0.2-0.37. The combination of ozonation and aerobic biological treatment in an aerobic sequencing batch biofilm reactor (SBBR) gave an abatement of more than 90 % of the initial TOC.

The Quaternary Ammonium Compounds (QACs) ozonation was carried out in order to assess the mineralization potential of ozonation processes for this class of compounds. To perform this study, the QACs 16-BAC (Benzyl-dimethyl-hexadecylammonium-chloride) and 18-BAC (Benzyl-dimethyl-stearylammonium-chloride) were treated by ozonation at different O3 dosage. According to experimental results, from an initial TOC concentration of 50 mg L-1, 90 minutes of ozonation reached at most 50% of mineralization at the used conditions (ozone flow rate 7.57 g h-1). In order to observe the mineralization of QACs by means of photo-Fenton, the runs were carried out with the same QAC concentration used in ozonation runs. Besides, two different lamps were used (UV and Xe). According to experimental results, after 90 minutes of treatment, the photo-Fenton process achieved up to 80% of mineralization when the UV lamp was used. The efficiency of the photo-Fenton with Xe lamp was lower.

To carry out the study of the sulfamethoxazole (SMX) ozonation, 200 mg L-1 SMX solutions were treated by ozonation at different pH. Results showed that ozonation was proved to be an efficient method to degrade sulfamethoxazole. After 15 minutes of ozonation (corresponding dose = 0.4 g of ozone L-1), the complete antibiotic abatement was almost achieved with just 10 % of mineralization. The biodegradability and toxicity of the ozonation intermediates were also studied. A biodegradability enhancement (increment of BOD5/COD ratio) from 0 to 0.28 was observed after 60 min of ozonation. The acute toxicity of the intermediates was followed by the Microtox® test and the toxicity profile showed a slight acute toxicity increment in the first stage of ozonation. The second order kinetic constants for the ozonation of the SMX in an order of magnitude of 105 L mol-1 s-1 were also determined for pH 5 and 7.

Concerning the Bezafibrate (BZF) ozonation, the results showed that ozonation is an efficient method to degrade BZF: after 10 minutes of treatment (corresponding to a dose of 0.73 mmoles L-1 of ozone), the complete BZF abatement is achieved, starting from an initial concentration of 0.5 mmoles L-1. However, only a small part of the substrate is mineralized. The identification of main intermediates, attempted by HPLC-MS technique, indicates that the oxidation of BZF develops through both the hydroxylation of the aromatic ring and the attack of ozone on the unchlorinated aromatic one. The assessment of by-products biodegradability and acute toxicity demonstrates that ozonation is a suitable technique to improve the biodegradability and reduce the toxicity of waters containing BZF.

Obesity is a worldwide problem affecting both children and adults. Genetic, physiological, environmental, psychological, social and economic factors interact in varying degrees, influencing body weight and fat distribution and the progress of obesity. Moreover, some anthropogenic chemicals have proven to be endocrine disrupting chemicals (EDCs) with the potential to interfere with different actions of hormones in the body. EDCs may thereby disrupt homeostasis, modifying developmental, behavioral and immune functions in humans and animals, and also promoting adiposity. Because hormones generally act at low concentrations, small changes in the endocrine system may lead to extensive effects. Based on data from experimental and epidemiological studies this thesis elucidates the relationship between a large number of environmental contaminants and obesity. The experimental studies demonstrated that fructose supplementation in the drinking water resulted in unfavorable metabolic alterations such as a higher liver somatic index (LSI), an increase in plasma triglycerides and increased plasma levels of apo A-I. Fructose in combination with exposure to bisphenol A (BPA) increased liver fat content and plasma levels of apo A-I in juvenile female Fischer 344 rats. The experimental studies also showed that the retro-peritoneal fat, which in rats is a distinct fat depot easy to distinguish and dissect, correlated well with the measurements of total fat mass analyzed with MRI, and could therefore be used as a substitute for total fat mass in rats. The epidemiological studies showed that circulating levels of persistent organic pollutants (POPs) were related to fat mass measured by DXA. OCDD, HCB, TNC, DDE and the less chlorinated PCBs were positively related to fat mass, while the more highly chlorinated PCBs showed a negative association. Further, circulating levels of BPA were positively associated with levels of the hormones adiponectin and leptin, but negatively related with ghrelin, hormones which are involved in the regulation of hunger and satiety. However, serum BPA levels were not related to measures of fat mass in the elderly individuals in the PIVUS cohort. This thesis concludes that environmental contaminants such as BPA and POPs most likely are contributors, along with genetic, social and behavioral factors, to the development of obesity.

The contamination of foods with hydrocarbon mixtures migrating from food contact materials (FCM) was first observed for jute and sisal bags treated with batching oil in the 1990s. Since the millennium, the focus has shifted to printing inks and recycled cardboard packaging as most recognized sources for hydrocarbon contamination from FCM. Mineral oil containing printing inks can either release hydrocarbons directly from the printing of folding boxes into food or indirectly entering the recycling chain of cardboard material by printed products, such as newspapers. The contamination of dry foods with mineral oil hydrocarbons (MOH) from recycled fiber packaging has been reported to reach up to 100 mg/kg [1]. Using LC-GC-FID technique the MOH were categorized into mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The molecular mass, which is assumed to be toxicological relevant, is derived from the GC retention times of accumulated MOSH in human tissues and is limited to n C16 to n-C35 [2]. MOSH is the most significant contaminant of the human body reaching 1-10 g per person, which is of particular concern since a formation of microgranulomas (causing inflammatory reactions) in the liver was observed in rats fed with saturated hydrocarbons [3]. Furthermore, some MOAH are assumed to be genotoxic analogous to polycyclic aromatic hydrocarbons [3]. In the latest draft of a German ‘Mineral Oil Regulation’ the following limits for the migration of MOH from recycled fiber are proposed: for MOSH C16-20 4.0 mg/kg, MOSH C21-35 2.0 mg/kg and for MOAH 0.5 mg per kg food [4]. Functional barriers reducing the migration of undesirable compounds from recycled cardboards (such as MOH and other contaminants) could be a part of the solution for this issue. Supporting that approach in this study, the boxes of recycled cardboard featuring a barrier layer on the internal surface or an integrated adsorbent available early in 2014 were investigated for their efficiency in reducing migration of mineral oil hydrocarbons into dry food. A practice-oriented one-year storage test was performed with wheat flakes in seven configurations: a box of virgin fibers, two boxes of unprotected recycled cardboard, three cardboards with barrier layers (a flexo-printed polyacrylate layer, a polyvinyl alcohol coating and a multilayer involving polyester) and a cardboard containing activated carbon. The highest migration of MOH (C16-24) was observed in the boxes of unprotected recycled cardboard (MOSH: 11.4 mg/kg, MOAH: 2.4 mg/kg). Of the three investigated barrier layers only two reduced migration of MOH into food below the limits of the 3rd draft of the German mineral oil ordinance (2014) until the end of shelf life. The cardboard box involving active carbon as adsorbent prevented detectable migration of mineral oil hydrocarbons (<0.1 mg/kg). In the case of virgin fiber, which was virtually free of MOH (<1 mg/kg), migration close to the proposed limits was detected (C16-24, MOSH: 1.5 mg/kg, MOAH: 0.4 mg/kg). Therefore, it has been proven that the transport box (corrugated board) substantially contributed to the transfer of MOH into food. Plastic FCM can also release hydrocarbons, such as polyolefin oligomeric hydrocarbons (POH), into food. These POH are of synthetic nature and are formed during the polymerization process of polyolefins (150 – 3000 mg/kg in granulates of homo/hetero polymers involving ethylene and propylene). This group of synthetic contaminants contain also saturated hydrocarbons (POSH) analogous to mineral oils, but contrary no aromatic hydrocarbons. Further, a significant amount (10 – 50%) of monounsaturated hydrocarbons (POMH) was determined in the oligomeric fraction of polyolefins, which are not detectable in mineral oil products. Therefore, these POMH can be used as a marker for POH migration. A method based on two-dimensional high performance liquid chromatography on-line coupled to gas chromatography (on-line HPLC-HPLC-GC) was developed to enable the separate analysis of saturated, monounsaturated and aromatic hydrocarbons in extracts of packaging materials like polyolefins or paperboard and foods, repectively. It is an extension of the HPLC-GC method for MOSH and MOAH [1] using an additional argentation HPLC column, since normal-phase HPLC on silica gel did not preseparate saturated from monounsaturated hydrocarbons. Further, this method and comprehensive two-dimensional GC (GCxGC) was used to investigate the concentration of different oligomer types in polypropylene (PP) and polyethylene (PE) based sealing layers as well as their corresponding granulates. The analyzed sealing layers contained 180-995 mg/kg POSH and 90-435 mg/kg POMH (C16-35). Only in sealing layers involving low-density PE, oxidized polyolefin oligomers as well as cyclic oligomers (alkylated cyclopentanes and hexanes) have been detected. The transfer of POH (C16-35) from the investigated sealing layers into food can be substantial (>50%) and can reach more than 2 mg per kg food. The level of contamination depends on the oligomer content of the sealing layer, the fat content of the food, the processing temperature and the surface-volume ratio. Hot melt adhesives are widely utilized to glue cardboard boxes used as food packaging material. The analysed raw materials of hot melts mainly consisted of paraffinic waxes, hydrocarbon resins and polyolefins. The hydrocarbon resins, functioning as tackifiers, were the predominant source of hydrocarbons of sufficient volatility to migrate via gaseous phase into dry foods. The 18 hydrocarbon resins analyzed contained 8.2-118 g/kg saturated and up to 59 g/kg aromatic hydrocarbons (C16-24). These synthetic tackfier resins, especially the oligomers ≤C24, have been characterized structurally and migration into food was estimated using a food simulant and by the analysis of real food samples. About 0.5-1.5 % of the potentially migrating substances (C16 24) of a hot melt were found to be transferred into food under storage conditions, which can result in a food contamination of approximately 1 mg/kg food in this case. The order of magnitude depends on the absolute amount of potentially migrating substances from the hot melt, the hot melt surface, contact time, amount and type of foods.

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FAPESB
A cultura do tomate tem ocupado lugar de destaque em todo mundo. O aumento na produtividade da hortaliça provocou um aumento na utilização de insumos agroquímicos, fazendo-se necessário o monitoramento de elementos essenciais e elementos potencialmente contaminantes. Neste trabalho foram determinadas as concentrações de elementos essenciais e elementos potencialmente contaminantes em tomates das espécies caqui, itália e cereja, em cultivos convencional e orgânico, em fase inicial e final de maturação. As amostras foram coletadas em vários estabelecimentos da cidade de Salvador, Bahia, Brasil visando avaliar as diferenças nas concentrações entre os estágios de maturação, tipo de cultivo e espécie, no fruto inteiro e em suas partes (casca, polpa e semente). Os elementos estudados foram Al, Ba, Cd, Cu, Co, Cr, Fe, Mn, Ni, Pb, Sb, Se, Sn, Sr, V e Zn. Após otimização do procedimento de preparo, as amostras foram submetidas à digestão em forno de micro-ondas com cavidade, usando a mistura de 3,5 mL de ácido nítrico concentrado destilado, 3,5 mL de água ultra pura e 1,0 mL de peróxido de hidrogênio. Para determinação dos elementos foram empregadas as técnicas espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) e espectrometria de massas com plasma indutivamente acoplado (ICP-MS). Através dos resultados obtidos, foi possível comparar a concentração dos elementos estudados nos estágios de maturação, cultivo e espécies dos tomates analisados. Quanto ao estágio de maturação, os tomates em estágio final de maturação apresentaram maiores valores de concentração para a maioria dos elementos medidos, nas três espécies estudadas. Na comparação quanto ao tipo de cultivo, as amostras provenientes do manejo orgânico apresentaram maiores valores de micronutrientes e menores de elementos com potencial contaminante quando em comparação com as amostras de tomates oriundas de cultivo convencional. Em relação às diferentes espécies estudadas, observou-se que as amostras de tomate contribuem significativamente para a ingestão diária recomendada de Cr, Cu e Mn, sendo a espécie caqui a que mais contribui para a ingestão de Cu, a itália de Cr e a cereja de Mn. As concentrações dos elementos potencialmente tóxicos, encontradas para as amostras das três espécies de tomate, estão abaixo dos teores regulamentados pela ANVISA. Palavras-Chave: toma
Salvador

Aquesta Tesi Doctoral se centra en el desenvolupament de nous mètodes analítics per determinar diferents contaminants orgànics emergents, com ara productes farmacèutics de consum generalitzat, els medis iodat de contrast per a raigs-X (un altre grup de productes farmacèutics emprats en la medicina de diagnòstic), i un grup d'edulcorants d'alta intensitat en organismes aquàtics. Dues tècniques d'extracció (extracció mitjançant líquids pressuritzats i QuEChERS) van ser avaluades per extreure els compostos seleccionats i diferents neteges també van ser provades. La determinació es va realitzar mitjançant cromatografia de líquids acoblada a espectrometria de masses.D'altra banda, també es va dur a terme un estudi ecotoxicològic en l'espècie Gammarus pulex, on s' avaluà la toxicitat del triclosan en aquesta espècie i, a més a més, es van estudiar poblacions procedents de diferents ambients amb diferents graus de contaminació per determinar si la seva resistència era similar o no.
Esta tesis doctoral se centra en el desarrollo de nuevos métodos analíticos para determinar diferentes contaminantes orgánicos emergentes, como productos farmacéuticos de consumo generalizado, medios yodados de contraste para rayos-X (otro grupo de productos farmacéuticos empleados en medicina de diagnóstico) y un grupo de edulcorantes de alta intensidad en organismos acuáticos. Para ello se evaluaron dos técnicas de extracción (extracción con líquidos presurizados y QuEChERS) para extraer los compuestos seleccionados y también se ensayaron diferentes limpiezas. La determinación se realizó mediante cromatografía de líquidos acoplada a espectrometría de masas. Además, se realizó un estudio ecotoxicológico en la especie Gammarus pulex, donde se evaluó la toxicidad del triclosán para esta especie y, además, se estudiaron poblaciones procedentes de diferentes ambientes con diferentes grados de contaminación para determinar si su resistencia era similar o no.
This Doctoral Thesis focuses on the development of new analytical methods to determine different emerging organic contaminants such as pharmaceuticals of widespread consumption, iodinated X-ray contrast media (another group of pharmaceuticals employed in diagnostic medicine), and a group of high-intensity sweeteners, in aquatic organisms. To do so two extraction techniques (pressurised liquid extraction and QuEChERS) were evaluated to extract the selected compounds and different clean-ups were also tested. The determination was perfomed with liquid chromatography coupled with mass spectrometry. Moreover, another objective is to conduct an ecotoxicological study in the amphipod species Gammarus pulex, where the toxicity of triclosan to this species was evaluated. Moreover, populations that come from different environments with different degrees of pollution were evaluated in order to establish whether their resistance was similar or not.

Els contaminants emergents (ECs) són un ampli grup de compostos orgànics detectats en diversos compartiments ambientals que degut a la seva presència en el medi ambient i la seva difícil degradació han aixecat un gran interès en la comunitat científica. Tot i que la seva concentració normalment està compresa entre els ng/L i els μg/L, poden representar una amenaça per a la salut humana i el medi ambient ja que són excretats per la orina i els fems, ja sigui en forma de compost actiu o com a metabòlit, ja que no són completament assimilats. D’entre tots els emergents, els compostos disruptors endocrins (EDCs) i els principis actius dels fàrmacs (PhACs) generen especial preocupació. Està àmpliament acceptat que la seva principal font d’entrada al medi ambient és a través dels efluents de les plantes depuradores (WWTP), on els tractaments convencionals de llots actius no són capaços de degradar-ne la majoria, sent capaços d’arribar a les aigües superficials, subterrànies i, posteriorment, a l’aigua potable. Per tant, s’han de buscar tractaments alternatius. Un d’aquests tractaments podria ser l’ús de les microalgues aprofitant la seva capacitat pel tractament d’aigües residuals, eliminant els nutrients de l’aigua residual i la seva posterior conversió en biocombustibles. Aquesta tesi avalua diferents aspectes relacionats amb la degradació de contaminants emergents i tractament d’aigües amb microalgues. A més de l’estudi d’un dels principals colls d’ampolla dels sistemes de microalgues, la collita, que té l’avantatge de clarificar l’aigua residual tractada i concentrar la biomassa algal per a la seva conversió a biogàs. Tant, cultius purs com efluents de microalgues s’han considerat. Primerament, s’ha estudiat la degradació individual de dos compostos estrogènics. Aquests dos compostos estrogènics s’han introduït recentment a la llista de substàncies prioritàries de la directiva de l’aigua: 17α-etinileestradiol (EE2) i 17β- estradiol (E2). La seva degradació s’ha monitoritzat a partir dels cultius purs de Chlamydomonas reinhardtii i Pseudokirchneriella subcapitata a nivell de laboratori. Per tal d’obtenir més informació sobre els mecanismes de degradació s’ha fet la identificació dels productes de transformació. A més, la degradació d’una mescla de 10 fàrmacs (9 antibiòtics i un antidepressiu) s’ha avaluat en cultius purs de microalgues a escala laboratori. S’ha realitzat la identificació dels productes de transformació de tres PhACs seleccionats. Posteriorment, un dels antibiòtics, la ciprofloxacina, s’ha analitzat. Els seus mecanismes d’eliminació han estat estudiats en sistemes algals, tant en reactors a escala laboratori com en escala pilot. Per altra banda, s’ha dissenyat un fotobioreactor (PBR) d’algues tractant aigua residual urbana i en operació durant 6 mesos. S’ha monitoritzat el seu seguiment i s’han provat diferents condicions d’operació. A més, un cop a l’estat estacionari l’eliminació de PhACs s’ha estimat i s’ha caracteritzat la població microbiana. També s’ha estudiat l’eliminació del compost estrogènic E2 en el PBR. En aquesta tesi també es remarca la importància de la collita de microalgues. Tres tècniques de collita (i.e., sedimentació natural, coagulació-floculació i la tècnica innovadora de co-pel·letització utilitzant el fong Trametes versicolor) s’han aplicat en dos efluents reals de microalgues i a una suspensió pura de Chlamydomonas reinhardtii. Finalment, s’ha dut a terme la metanització de biomassa exhausta. Abans del procés de digestió anaeròbia, per tal de solubilitzar la paret cel·lular les algues han estat sotmeses a un pretractament enzimàtic. S’han provat enzims específics i no específics, així com l’efecte combinat utilitzant una mescla d’enzims. Aquest estudi es completa amb la valorització de biomassa fúngica que prové del tractament d’efluents.
Emerging contaminants (ECs) are a wide range of organic compounds detected in many environmental compartments that have raised an increasing interest in the scientific community due to their ubiquitous presence in the environment and their difficult degradation. Even though their environmental concentration is usually in the range of ng/L to μg/L, they still represent a threat to human health and environment since they are excreted with urine and faeces either as active substances or metabolites, because they are not completely assimilated. Among emerging contaminants, endocrine disrupting compounds (EDCs) and pharmaceutical active compounds (PhACs) are of major concern. It is widely accepted that the main source to the environment are the effluents of wastewater treatment plants (WWTP), where conventional activated sludge treatments are not able to degrade most of them being able to reach surface, groundwater and subsequently, drinking water. Therefore, alternative treatments should be found. One of those alternatives might be the use of microalgae by taking advantage of their capacity for wastewater treatment removing the nutrients contained in the wastewater and further microalgal biomass conversion into biofuels. The present thesis assesses different factors related to microalgal degradation of emerging contaminants and wastewater treatment. As well as the study of one of the major bottlenecks on microalgal systems, the harvesting, which has the advantage to clarify the treated wastewater and concentrate the microalgal biomass for further biogas production. Pure microalgal cultures and real microalgal effluents have been considered. First of all, individual degradation of two estrogenic compounds has been studied. The two estrogenic compounds evaluated have been recently incorporated in the priority substances in the Water Framework Directive: 17α-ethinylestradiol (EE2) and 17β- estradiol (E2). Their degradation by Chlamydomonas reinhardtii and Pseudokirchneriella subcapitata pure cultures at laboratory scale conditions has been monitored. To obtain further insights in the mechanism of degradation the transformation products have been identified. Moreover, the removal of a mixture of 10 PhACs (9 antibiotics and an antidepressant) has also been assessed in pure microalgal cultures at laboratory scale conditions. Transformation products from three chosen PhACs have been identified. One of the antibiotics, ciprofloxacin, was further evaluated. The removal mechanisms have been studied in real algal ponds in both, laboratory and pilot scale reactors. On the other hand, an algal photobioreactor (PBR) treating urban wastewater has been designed and operated during 6 months. Its performance has been monitored and different operating conditions have been tested. Furthermore, PhACs removal has been evaluated during the steady state and microbial diversity has been identified. The estrogenic compound E2 removal in the PBR has been studied. The importance of microalgal harvesting has been highlighted in the thesis. Three different harvesting techniques (i.e., natural sedimentation, coagulation-flocculation and the novel technique of co-pelletization using Trametes versicolor fungus) have been evaluated using two real microalgal effluents and a pure Chlamydomonas reinhardtii suspension. Finally, methanization of exhausted biomass has been conducted. Prior the anaerobic digestion process microalgal biomass has been submitted to an enzymatic pretreatment for its cell wall solubilisation. Specific and non-specific enzymes have been tested as well as the synergistic effects between an enzymatic mixture. The study is completed valorising fungal biomass coming from the treatment of effluents.

L’objectiu general d’aquesta tesi ha estat avaluar l’aplicabilitat de bioassajos específics i un bioassaig estandarditzat genèric en mostres de diferents matrius ambientals. D’aquesta manera es pretén complementar la informació obtinguda de les anàlisis químiques per tal de poder establir un millor diagnòstic ambiental. S’han analitzat diferents metalls i compostos orgànics en mostres dels diferents compartiments ambientals. Per avaluar l’ecotoxicitat de mostres d’aigua dolça, s’ha triat l’alga Pseudokirschneriella subcapitata, mentre que per mostres de sòl i residus orgànics, s’han escollit plantes d’interès agrícola com són Allium cepa, Raphanus sativus i Lolium perenne. Per últim, s’han realitzat tests in vitro de toxicitat humana per avaluar la toxicitat de les partícules PM10 de l’aire amb cultius de cèl•lules pulmonars (línia A549). En tots els casos, s’ha realitzat també un assaig ecotoxicològic amb el bacteri luminescent Vibrio fischeri, per avaluar la seva idoneïtat en les diferents matrius ambientals. Els resultats, han demostrat que l’aplicació de bioassajos específics en diferents matrius ambientals pot suposar una bona eina d’“screening” per completar la informació obtinguda de les anàlisis químiques que, realitzades de forma individual, poden estimar erròniament la toxicitat real de les mostres ambientals. S’ha observat que el bioassaig amb Vibrio fischeri ha mostrat bona complementarietat amb d’altres assajos més específics de cada matriu, a més de resultar molt sensible a la presència de contaminants en aigües i sediments fluvials, fangs de depuradora i partícules d’aire PM10.
El objetivo general de esta tesis ha sido evaluar la aplicación de bioensayos específicos y un bioensayo estandardizado genérico en distintas matrices ambientales. De este modo se pretende complementar la información obtenida con los análisis químicos para poder establecer un mejor diagnóstico ambiental. Se han analizado metales y compuestos orgánicos en muestras de distintos compartimentos ambientales. Para evaluar la ecotoxicidad de muestras de agua dulce se ha escogido el alga Pseudokirschneriella subcapitata, mientras que para muestras de suelos y residuos orgánicos se han escogido plantas de interés agrícola como son Allium cepa, Raphanus sativus y Lolium perenne. Por último, se han realizado tests in Vitro de toxicidad humana para evaluar la toxicidad de las partículas PM10 del aire, con cultivos de células pulmonares (línea A549). En todos los casos se ha realizado un ensayo ecotoxicológico con la bacteria luminescente Vibrio fischeri, para evaluar su idoneidad en las distintas matrices ambientales. Los resultados han demostrado que el uso de bioensayos específicos en distintas matrices ambientales puede suponer una buena herramienta de ‘’screening’’ para completar la información obtenida de los análisis químicos, que realizados de forma individual, pueden estimar erróneamente la toxicidad real de las muestras ambientales. Además, se ha observado que el bioensayo con Vibrio fischeri presenta buena complementariedad con otros ensayos más específicos de cada matriz ambiental, además de ser muy sensible a la presencia de contaminantes en aguas y sedimentos fluviales, lodos de depuradora y PM10 del aire.

4 pp.
This short fact sheet is taken from "Arizona Well Owner's Guide to Water Supply" currently in print. We plan to complete part 2 of this fact sheet by the end of July, 2009. Please note that the text has already been incorporated into the eXtension Community of Practice web page - - I am the author for the COP/Drinking Water group text on chemistry of naturally occurring water contaminants.
Arizona well water is often contaminated with elevated concentrations of naturally occurring constituents that are a human health concern. This short fact sheet is the first in a two-part series about what naturally occurring contaminants may be found in your water supply well and includes a brief discussion on environmental pollutants that originate from land use activities. If you own a well in Arizona, you have the sole responsibility for checking to see if your drinking water is contaminated. Arizona state law does not require private well owners to test or treat their water for purity. The second part of this series outlines what to sample for and how to understand your analytical results.

Chemical exposure in humans rarely consists of a single chemical. The everyday exposure is characterized by thousands of chemicals mainly present at low levels. Despite that fact, risk assessment of chemicals is carried out on a chemical-by-chemical basis although there is a consensus that this view is too simplistic. This thesis aims to validate a statistical method to study the impact of mixtures of contaminants and to use that method to investigate the associations between circulating levels of a large number of environmental contaminants and atherosclerosis and the metabolic syndrome in an elderly population. Contaminants measured in the circulation represented various classes, such as persistent organic pollutants, plastic-associated chemicals and metals. There was little co-variation among the contaminants and only two clusters of PCBs could be discerned. Gradient boosted CARTs were used to assess additive and multiplicative associations between atherosclerosis, as measured by the intima-media thickness (IMT) and the echogenicity of the intima-media complex (IM-GSM), and prevalent metabolic syndrome. Systolic blood pressure was the most important predictor of IMT while the influence of the contaminants was marginal. Three phthalate metabolites; MMP, MEHP and MIBP were strongly related to IM-GSM. A synergistic interaction was found for MMP and MIBP, and a small antagonistic interaction was found for MIBP and MEHP. Associations between the contaminants and prevalent metabolic syndrome were modest, but three pesticides; p,p’-DDE, hexachlorbenzene and trans-nonachlor along with PCBs 118 and 209 and mercury were the strongest predictors of prevalent metabolic syndrome. This thesis concludes that many contaminants need to be measured to get a clear picture of the exposure. Boosted CARTs are useful for uncovering interactions. Multiplicative and/or additive effects of certain contaminant mixtures were found for atherosclerosis or the metabolic syndrome.

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

El objetivo de esta tesis es el desarrollo de métodos analíticos para la determinación de un grupo de contaminantes emergentes entre los cuales se incluyen los fármacos y los compuestos de cuidado personal en lodos de depuradora.
Los métodos desarrollados se basan en la extracción presurizada con solventes (PLE) y, debido a la polaridad de estos contaminantes, la cromatografia de líquidos. Como técnicas de detección se han utilizado la espectrometría de masas (con quadrupolo y tiempo de vuelo como analizadores) y la espectrometría de masas en tandem (con triple quadrupolo como analizador) utilizando la interfase de electrospray.
A parte del desarrollo de los métodos para la determinación de fármacos, hormonas y compuestos de cuidado personal, se han analizado muestras de dos plantas de tratamiento de aguas residuales de la zona de Tarragona. Se han obtenido resultados de la presencia de estos compuestos en lodos de depuradora que hasta la fecha no existían sobre las muestras de esta zona.
The scope of this thesis is to develop analytical methods to determine a group of pharmaceuticals and personal care products included in the list of so called "emerging organic contaminants".
The methods are based on pressurized liquid extraction as extraction technique and due to the polarities of these contaminants, liquid chromatography was the selected separation technique. Because the low concentration of these contaminants in sewage sludge, sensitive and selective detection technique have to be used such as mass spectrometry (with quadruople or time of flight analyzers) and tandem mass spectrometry (with triple quadrupole analyzer) using in all cases the electrospray interface.
The methods developed have been used to monitor several groups of pharmaceuticals and personal care products from sewage sludge from two different sewage treatment plants. The samples have been collected in Tarragona, where no studies related to the control of these compounds have been done.

Aquesta tesi té com a objectiu desenvolupar biosensors per al monitoratge ambiental. Primer, s'ha desenvolupat un biosensor colorimètric basat en lateral flow strips (LFS) per a la detecció i quantificació d'Escherichia coli com a indicador fecal universal. En aquest cas, nanopartícules d'or (AuNP) s'utilitzen com a transductors òptics i anticossos policlonals com a elements de bioreconeixement per capturar, marcar i indicar la presència del bacteri. Paral·lelament, s'ha desenvolupat un sistema de filtració per millorar la sensibilitat dels LFS. L'optimització del flux de la mostra a través dels diferents materials s'ha realitzat mitjançant una tècnica innovadora basada en el seguiment del flux del bacteri bioluminescent Aliivibrio fischeri, similar en grandària i forma a E. coli. Finalment, aquests LFS s'han provat amb mostres d'aigua de rius i aigües residuals, mostrant una sensibilitat similar i bona reproductibilitat i selectivitat en tots els casos. En segon lloc, s'ha desenvolupat un biosensor de toxicitat bioluminescent per a la detecció i quantificació de pesticides en mostres d'aigua. En particular, Aliivibrio fischeri, un bacteri bioluminescent, s'ha utilitzat com a element de bioreconeixement i transductor perquè augmenta i disminueix la bioluminescència d'acord amb la concentració de compostos tòxics en les mostres d'aigua. A més, l'òxid de grafè (GO) s'ha utilitzat com un potenciador del creixement no específic per promoure el creixement bacterià i augmentar la sensibilitat del sistema al detectar parcialment la bioluminescència emesa per A. fischeri. La detecció i quantificació de la bioluminescència es va realitzar amb un telèfon mòbil que permet una avaluació de la toxicitat de l'aigua de forma portàtil, més barata, i més fàcil d'utilitzar que els estàndards en els laboratoris. En tercer lloc, s'ha desenvolupat una plataforma portàtil basada en un telèfon mòbil per a realitzar assajos que requereixen una detecció òptica, incloent assaigs colorimètrics, fluorescents i bioluminescents. Aquesta plataforma s'ha utilitzat per dur a terme i analitzar proves ELISA estàndard basades en resultats colorimètrics per a la detecció de la immunoglobulina humana i una proteïna del coronavirus. A més, el sistema permet realitzar un seguiment de l'agregació de AuNPs en funció del color de la solució. D'altra banda, la plataforma s'ha utilitzat per detectar i quantificar quantum dots (QD) i altres indicadors fluorescents (per exemple, fluoresceïna), i per a fer proves ELISA fluorescents basades en aquests transductors. A més, la plataforma permet realitzar lectures bioluminiscents amb aplicacions com l'anàlisi de la toxicitat de l'aigua. Finalment, la plataforma és útil per al cultiu de bacteris, mesuraments de terbolesa i detecció de resistència a antibiòtics.
Esta tesis tiene como objetivo desarrollar biosensores para el monitoreo ambiental. Primero, se ha desarrollado un biosensor colorimétrico basado en lateral flow strips (LFS) para la detección y cuantificación de Escherichia coli como indicador fecal universal. En este caso, nanopartículas de oro (AuNP) se utilizan como transductores ópticos y anticuerpos policlonales como elementos de bioreconocimiento para capturar, marcar e indicar la presencia de la bacteria. Paralelamente, se ha desarrollado un sistema de filtración para mejorar la sensibilidad de las LFS. La optimización del flujo de la muestra a través de los diferentes materiales ha realizado mediante una técnica innovadora basada en el seguimiento del flujo de la bacteria bioluminiscente Aliivibrio fischeri, similar en tamaño y forma a E. coli. Finalmente, estos LFB se han probado con muestras de agua de ríos y aguas residuales, mostrando una sensibilidad similar y buena reproducibilidad y selectividad en todos los casos. En segundo lugar, se ha desarrollado un biosensor de toxicidad bioluminiscente para la detección y cuantificación de pesticidas en muestras de agua. En particular, Aliivibrio fischeri, una bacteria bioluminiscente, se ha utilizado como elemento de bioreconocimiento y transductor porque aumenta y disminuye la bioluminiscencia de acuerdo con la concentración de compuestos tóxicos en las muestras de agua. Además, el óxido de grafeno (GO) se ha utilizado como un potenciador del crecimiento no específico para promover el crecimiento bacteriano y aumentar la sensibilidad del sistema al detectar parcialmente la bioluminiscencia emitida por A. fischeri. La detección y cuantificación de la bioluminiscencia se realizó con un teléfono móvil que permite una evaluación de la toxicidad del agua de forma portátil, más barata, y más fácil de usar que los estándares en los laboratorios. En tercer lugar, se ha desarrollado una plataforma portátil basada en un teléfono móvil para realizar ensayos que requieren una detección óptica, incluyendo ensayos colorimétricos, fluorescentes y bioluminiscentes. Esta plataforma se ha utilizado para llevar a cabo y analizar pruebas ELISA estándar basadas en resultados colorimétricos para la detección de la inmunoglobulina humana y una proteína del coronavirus. Además, el sistema permite realizar un seguimiento de la agregación de AuNPs en función del color de la solución. Por otro lado, la plataforma se ha utilizado para detectar y cuantificar quantum dots (QD) y otros indicadores fluorescentes (por ejemplo, fluoresceína), así como para realizar pruebas ELISA fluorescentes basadas en estos transductores. Además, la plataforma permite realizar lecturas bioluminiscentes con aplicaciones como el análisis de la toxicidad del agua. Finalmente, la plataforma es útil para el cultivo de bacterias, mediciones de turbidez y detección de resistencia a antibióticos.
This thesis aims to develop biosensing tools for environmental monitoring. First, a colorimetric lateral flow biosensor (LFB) has been developed for the detection and quantification of Escherichia coli as a universal fecal indicator. Gold nanoparticles (AuNPs) are used as optical transducers and polyclonal antibodies as the biorecognition elements to capture, tag and indicate the presence of the bacteria. In parallel, a filtration system has been developed to improve the sensitivity of the LFBs. The optimization of the flow properties of the different lateral flow materials has been done by an innovative technique based on the tracking of the flow of the bioluminescent bacteria Aliivibrio fischeri, similar in size and shape to E. coli. Eventually, these LFBs have been tested with river and sewage waters, showing similar sensitivity and good reproducibility and selectivity in all the cases. Second, a bioluminescent toxicity biosensor has been developed for the detection and quantification of pesticides in water samples. In particular, Aliivibrio fischeri, a bioluminescent bacteria, has been used as the biorecognition element and the transducer because it turns up and down bioluminescence according to the concentration of toxic compounds within the water samples. Besides, graphene-oxide (GO) has been used as a non-specific growth enhancer to promote bacterial growth and increase the sensitivity of the system by partially screening the bioluminescence emitted by A. fischeri. The detection and quantification of the bioluminescence has been performed by a smartphone that allows for a cheaper, more user friendly, and portable water toxicity assessment. Third, a smartphone-based portable platform has been developed for the performance of optical sensing, including colorimetric, fluorescent, and bioluminescent assays. This platform has been used to perform and read standard ELISA tests based on colorimetric outputs for human IgG and coronavirus detection. In addition, the system allows for tracking AuNPs aggregation based on the color output of the solution. On the other hand, the platform has been used to detect and quantify quantum dots (QDs) and other fluorescent reporters (i.e. fluorescein), as well as performing fluorescent ELISA tests based on these transducers. Next, the platform allows for bioluminescent readouts with applications in toxicity analysis. Eventually, the platform is suitable for bacteria culture, turbidity measurements, and drug screening for antibiotic resistances assessment.

2 pp.
Chemical contaminants occur in drinking water supplies throughout the United States, ranging from barely detectable amounts to levels that could possibly threaten human health. Determining the health effects of these contaminants is difficult, especially since researchers are still learning how chemicals react to the damaged cells. This publication addresses the issue of chemical contaminants in drinking water, topics include; acute and chronic health effects, setting standards, and treatment techniques.

The bioavailability of polycyclic aromatic hydrocarbons (PAHs) and chlorobiphenyls (CBs) in sediments is largely dependent on the freely dissolved concentration of these pollutants. However, measuring these is challenging, due to the low concentrations of lipophilic contaminants in the environment and their strong affinity for particles and for traditional sampling (filtration and centrifugation) equipment. An equilibrium passive sampling device made of silicone rubber was developed in this research to measure the freely dissolved concentrations of lipophilic contaminants and other parameters (water extractable proportions and sediment-water partition coefficients) that describe the availability of these contaminants in the environment. Equilibration between sampler and sediment for PAHs and CBs was found to be adequately achieved after 20 days shaking of a silicone rubber sampler in sediment slurry on an orbital shaker at 200 rpm. The reproducibility of uptake was better than 5 %. Silicone rubber-water partition coefficients for 34 PAHs and 32 CBs were measured in the laboratory using a co-solvent method using methanol as co solvent. Strong linear correlations of log sr w K , with octanol-water partition coefficients (log ow K ) ( log 0.97 log 0.01; 2 0.94 , K = K − r = sr w ow & log 1.17 log 1.82; 2 0.90 , K = K − r = sr w ow ) were found for PAHs and CBs, with a systematic difference in correlations observed for the different classes of compounds which was attributed to structural differences of the compounds. The silicone rubber samplers were then used to measure concentrations of PAHs in the pore water of sediments from the Fladen Ground of the North Sea, Loch Shell, Firth of Forth, Firth of Clyde, Loch Etive and Aberdeen Harbour in Scotland and the Vefsn fjord, Norway. A proportion of the PAHs were found to be unavailable for exchange into the aqueous phase, and this was reflected in the high log oc K measured in all the sediments studied. The sediment-water partition coefficients also correlated positively with the octanol-water partition coefficients. Accumulation of PAHs in Nereis virens from sediments was better predicted from literature bio concentration factors and pore water concentrations obtained using the silicone rubber samplers than from sediment concentrations traditionally used in risk assessments. Participation in an International Council for the Exploration of the Seas (ICES) passive sampling trial survey using silicone rubber in sediments and water is described, and demonstrated the potential of passive sampling in monitoring environmental pollution. The log BCF (bio concentration factor) for PAHs in mussels increased with increasing log ow K at both Loch Etive and Aberdeen Harbour locations, and could be used to estimate concentrations in mussels directly. The survey data also showed the use of silicone rubber in assessing the diffusive exchange of PAHs across sediment-water interfaces.

Within the last few decades, epidemiological evidence has linked exposure to air pollution, both its particles and its organic components, with cardiovascular disease (CVD) progression. CVD is a life long disease with the disruption of the endothelium being the inaugural event in this inflammatory process. The vascular endothelium is extremely susceptible to environmental insults given its tremendous surface area and that it is in constant contact with blood and components circulating within the blood, including xenobiotics. The endothelium is important as a barrier from blood constituents however, dysfunction of this barrier leads to the influx of lymphocytes and granulocytes that lead to the fatty build‐up characteristic of atherosclerosis. The studies presented in this dissertation tested the hypothesis that two unique environmental contaminants, alumina nanoparticles and benzo[a]pyrene (B[a]P), lead to increased endothelial cell dysfunction, characterized by increased adhesion molecule expression. Alumina nanoparticles induced vascular cell adhesion molecule‐1 (VCAM‐1), intercellular adhesion molecule‐1 (ICAM‐1), and E‐selectin (ELAM‐1), as well as increased monocyte adhesion to activated endothelium. Polystyrene nanoparticles did not elicit this response. B[a]P induced ICAM‐1 expression, but only after toxification by aryl hydrocarbon receptor (AhR) controlled enzymes. Silencing of either AhR or the membrane microdomains called caveolae attenuated the B[a]P‐induced ICAM‐1 response. It was also shown that the induction of ICAM‐1 occurred by signaling through MEK, p‐38 MAPK, and activator protein‐1 (AP‐1). These data provide a novel mechanism by which air pollutants like B[a]P may cause increased atherosclerosis and describe a new toxicant, alumina nanoparticles, as a possible threat for the development of inflammatory diseases, such as atherosclerosis. Little is known about dietary interventions capable of alleviating xenobiotic‐induced toxicity. Nutrition is an obtainable and inexpensive means of possible preventative therapy. With this in mind, it was also hypothesized that plant polyphenols, such as flavonoids, can down‐regulate B[a]P‐induced ICAM‐1. Selective flavonoids, containing both a 4’ B‐ring hydroxyl substitution and a 2‐3 C‐ring double bond, protected against B[a]P‐induced ICAM‐1 activation, however this protection did not correlate with the flavonoid’s antioxidant capacity.

Thesis: S.M., Massachusetts Institute of Technology, Department of Civil and Environmental Engineering, 2018.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 63-70).
The transport of biological, chemical, or particulate contaminants shapes disease transmission, chemical spills, climate, ecology, and bio-hazard risks. Yet, little is understood on the mechanisms controlling droplet formation and selection of droplet sizes and contamination levels from a contaminated water bulk. Bubbles play a critical role in shaping this transfer of chemicals, particulates, and biological organisms from water to air. They surface, and eventually burst, emitting myriads of droplets into the air. Despite recent progress in our understanding of bubble formation and bursting at the air-water interface, the factors selecting the loads that they carry and emit into the air remain unknown in part due to limitation in direct measurements. In this thesis, we discuss a method of direct visualization and quantification of particulates contained in contaminated bubble films at interfaces. The calibration of this method is key to progress in our understanding of particulate transport from water to air. In particular, although our method allows to reveal contaminants within films via the appearance of spots, the exact link between the size of such spots and the size of the original particles or organisms, their shape, wetting, and the size of the film remain unexplored. In this thesis, we performed a series of systematic measurements and calibrations using bacteria, particles, and rods of various sizes and wetting properties to calibrate the spot sizes observed on contaminated bubbles and films. We rationalized the dependencies observed using a combination of optical ray-tracing and modelling of film distortion in the presence of contaminant. Our results have important implications for in situ study of particles and bacterial communities within large scale complex interfaces.
by Jia Su.
S.M.

The accumulation of industrial contaminants in the natural environments have rapidly become a serious threat for human and animal life. Fortunately, there are microorganisms capable of degrading or transforming environmental contaminants. The present dissertation work aimed to understand the genomic basis of microbial degradation and resistance. The focus was the genomic study of the following bacteria: a) Pseudomonas fluorescens NCIMB 11764, a unique bacterium with specific enzymes that allow cyanide adaptation features. Potential cyanide degradation mechanisms found in this strain included nit1C cluster, and CNO complex. Potential cyanide tolerance genes found included cyanide insensitive oxidases, nitric oxide producing gene, and iron metabolism genes. b) Cupriavidus sp. strain SK-3 and strain SK-4. The genome of both bacteria presented the bph operon for polychlorinated biphenyl (PCB) degradation, but we found differences in the sequences of the genes. Those differences might indicate their preferences for different PCB substrates. c) Arsenic resistant bacterial communities observed in the Atacama Desert. Specific bacteria were found to thrive depending on the arsenic concentration. Examples were Bacteroidetes and Spirochaetes phyla whose proportions increased in the river with high arsenic concentrations. Also, DNA repair and replication metabolic functions seem to be necessary for resistance to arsenic contaminated environments. Our research give us insights on how bacteria communities, not just individually, can adapt and become resistant to the contaminants. The present dissertation work showed specific genes and mechanisms for degradation and resistance of contaminants that could contribute to develop new bioremediation strategies.

Doutoramento em Biologia
Os humanos estão permanentemente expostos a vários contaminantes ambientais que têm sido produzidos pela indústria química ao longo das últimas décadas. Para além do contacto direto com produtos onde estes contaminantes são aplicados, a exposição ocorre principalmente porque estes químicos se libertam destes materiais e acumulam-se no ambiente, tornando-se desta forma disponíveis para serem consumidos involuntariamente pelos humanos. Durante muito tempo a alimentação foi considerada como a principal via da exposição dos humanos a diversas classes de contaminantes, incluindo os poluentes orgânicos persistentes (POPs) e metais tóxicos. No entanto, a exposição através do pó em ambientes interiores surgiu como uma importante via de exposição, principalmente porque estes contaminantes se acumulam no pó e devido ao facto das pessoas passarem grande parte do seu tempo em ambientes interiores. Na presente tese, foi estudada a presença de várias classes de contaminantes ambientais em amostras de duplicados de dieta e amostras de pó doméstico, de forma a caracterizar a exposição dos humanos através da ingestão de alimentos e pó doméstico em Portugal, e a avaliar os riscos associados a esta exposição. Os contaminantes estudados incluem: retardantes de chama bromados (BFRs); retardantes de chama fosforados (PFRs); bifenilos policlorados (PCBs); pesticidas organoclorados (OCs); e os metais tóxicos chumbo (Pb) e cádmio (Cd). Os níveis de BFRs, PCBs, OCs, Pb e Cd foram determinados em amostras de duplicados de dieta fornecidas por voluntários da comunidade académica da Universidade de Aveiro. No que diz respeito aos compostos orgânicos, as concentrações obtidas foram baixas. Os BFRs foram detetados em poucas amostras de dieta, sendo que o mais detetado foi o congénere BDE 209 (67%), enquanto os BFRs emergentes – 1,2-bis (2,4,6-tribromofenoxi) etano (BTBPE), decabromodifenill etano (DBDPE) – não foram detetados. Os PCBs e os OCs apresentaram as concentrações mais elevadas e foram detetados na maioria das amostras de duplicados de dieta analisadas, sendo que os diclorodifeniltricloroetanos (DDTs) e os hexaclorociclohexanos (HCHs) foram detetados em 100% das amostras. Os valores estimados das ingestões diárias foram baixos e abaixo dos valores de referência estabelecidos para a avaliação de risco em humanos. O Pb foi detetado em todas as amostras de duplicado de dieta e o seu consumo através da ingestão de alimentos foi associado a efeitos adversos para a saúde. Para 33% dos participantes a ingestão diária estimada (EDI) foi superior à dose de referência (bench mark dose level – BMDL) associada à doença renal crónica, e para um dos participantes a EDI foi 50% mais elevado do que a BMDL associada à pressão arterial sistólica elevada. A abordagem da margem de exposição (MOE - margin of exposure) foi aplicada e indicou que em pelo menos 3,3 e 26,7% dos participantes poderão surgir efeitos cardiovasculares e nefrotóxicos, respetivamente. As concentrações de Cd foram avaliadas em amostras de duplicados de dieta fornecidas por mulheres a trabalhar ou a estudar na Universidade de Aveiro. Este metal foi também detetado em todas as amostras analisadas e 35% das participantes apresentaram ingestões semanais estimadas (EWIs) mais elevadas do que a dose semanal tolerável estabelecida, sugerindo riscos de saúde elevados. No geral, os resultados obtidos através das análises feitas em amostra de duplicados de dieta demonstraram que a ingestão de alimentos é uma importante via de exposição aos contaminantes ambientais estudados. Os níveis de PFRs, BFRs and PCBs foram monitorizados em amostras de pó doméstico de casas de Aveiro e Coimbra. Estes compostos e os seus respetivos congéneres/isómeros foram detetados num grande número de amostras, sendo que os PFRs apresentaram as concentrações mais elevadas, seguidos dos BFRs e PCBs. Apesar das frequências de deteção elevadas, os EDIs foram inferiores às doses de referência (RfDs) estabelecidas. Os BFRs, PCBs, OCs foram também analisados em amostras de pó doméstico da Covilhã. Neste estudo, as amostras de pó foram recolhidas em casas de voluntários com asma e em casa de participantes sem asma. Os congéneres/isómeros dos contaminantes avaliados foram detetados na maioria das amostras, e o grupo de BFRs apresentou as concentrações mais altas, seguido de PCBs e DDTs. No entanto, para todos os contaminantes, as ingestões diárias foram inferiores às RfDs. Estes resultados confirmam que os PFRs, BFRs, PCBs e OCs estão omnipresentes nas casas Portuguesas, no entanto, o consumo diário dos contaminantes orgânicos através da ingestão de pó doméstico é baixo. Os resultados obtidos no âmbito desta tese permitiram descrever, pela primeira vez em Portugal, os níveis dos contaminantes selecionados em amostras de duplicados de dieta e pó doméstico. Estes resultados revelaram que o risco associado à ingestão de contaminantes orgânicos através da alimentação e do pó doméstico foram baixos, ao contrário do elevado risco associado à ingestão de Pb e Cd presentes nos alimentos.
Humans are permanently exposed to environmental contaminants which have been produced for decades and with numerous applications. Besides the direct contact with the consumer products in which these contaminants are applied, the exposure occurs mainly because these chemicals are released from those materials and accumulate in the environment being available for involuntary consumption. For a long time, diet has been considered the major human exposure route for several contaminants, including persistent organic pollutants (POPs) and toxic metals. However, the indoor exposure through dust emerged as important exposure route, mainly motivated by the fact that these contaminants accumulate in dust and because people in modern society spend much of their time indoors. In this thesis, several classes of environmental contaminants were analysed in duplicate diet samples and house dust in order to characterize the human exposure through the ingestion of food and the ingestion of house dust in Portugal and to access the associated risks. The contaminants studied include: brominated flame retardants (BFRs), phosphorus flame retardants (PFRs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs), and also the toxic metals lead (Pb) and cadmium (Cd). The levels of BFRs, PCBs, OCs, Pb and Cd were assessed in duplicate diet samples obtained from volunteers from the University of Aveiro community. Regarding the organic compounds the obtained levels were low. BFRs were detected in few duplicate diet samples, with the congener BDE 209 exhibiting the higher detection frequency (67%) while the emerging BFRs – 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE) – were not detected. PCBs and OCs exhibited higher levels and were detected in most analysed duplicate diet samples, with dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) being detected in 100% of the samples. The daily dietary intakes were estimated, being low and under the established guidance values for human risk assessment. Pb was detected in all duplicate diet samples and its dietary ingestion was associated with adverse health effects. For 33% of the participants, the estimated daily intakes (EDIs) were higher than the dietary intakes related to the bench mark dose level (BMDL) derived from chronic kidney disease, and for one participant the EDI was 50% higher than the BMDL derived from elevated systolic blood pressure. The margin of exposure approach (MOE) was applied and indicated that cardiovascular and nephrotoxic effects might likely occur in at least 3.3 and 26.7% of the participants, respectively. The concentrations of Cd were assessed in duplicate diet samples provided by women working or studying in University of Aveiro. This metal was also detected in all analysed samples and 35% of the participants exhibited estimated weekly intakes (EWIs) higher than the established tolerable weekly intake (TWI), suggesting increased health risks. Overall the results from the duplicate diet study demonstrate that the ingestion of food is an important pathway of exposure to these environmental contaminants. PFRs, BFRs and PCBs were monitored in house dust samples from two cities in central Portugal (Aveiro and Coimbra). These compounds and respective congeners/isomers were detected in a large number of samples, with PFRs exhibiting the highest concentrations followed by BFRs and PCBs. Despite their high detection frequencies, the EDIs were much lower than the established reference doses (RfDs). BFRs, PCBs and OCs were also analysed in house dust samples from Covilhã, Portugal. In this study, dust samples were collected from the houses of asthmatics and non-asthmatics participants. The contaminants congeners/isomers were detected in the majority of the dust samples, and the group of BFRs exhibited the higher concentrations, followed by PCBs and DDTs, however, the daily intakes were lower than the RfDs for all contaminants. These results confirm that PFRs, BFRs, PCBs and OCs are ubiquitously present in Portuguese households, however the daily intakes of these organic contaminants through house dust ingestion is low. The results obtained under the framework of this thesis allowed describing for the first time in Portugal the levels of the selected contaminants in duplicate diet samples and in house dust samples. The results disclosed that the risk associated with the ingestion of the organic contaminants through diet and house dust was low, which contrasts with the risk associated with the ingestion of Pb and Cd through diet.

Doctor of Philosophy
Department of Agronomy
Ganga M. Hettiarachchi
Urban soils may contain harmful levels of potentially toxic contaminants. These contaminants transfer to humans via two exposure pathways: direct transfer (soil-humans by soil ingestion, dermal exposure and inhalation) and food chain transfer (soil-plant-humans). Soil amendments alter the speciation of the contaminants in soils and thereby modify their bioavailability. The objectives of this research were to access the plant availability of lead (Pb), arsenic (As), and polycyclic aromatic hydrocarbons (PAHs); bioaccessibility and speciation of soil Pb, and As; and dermal absorption of soil PAHs in contaminated urban soils; and effectiveness of soil organic amendments on reducing contaminant bioavailability. Two field experiments were conducted in Kansas City, MO and Indianapolis, IN. Both sites had elevated concentrations of Pb in soils (Kansas City site: 30-380 mg kg⁻¹ and Indianapolis site: 200-700 mg kg⁻¹) . Indianapolis site’s soils also had elevated concentrations of As (40-100 mg kg⁻¹) and PAHs (benzo[a]pyrene: 1-10 mg kg⁻¹) . A control treatment (no-compost) and compost-types (leaf compost and/or composted biosolids, non-composted biosolids, mushroom compost) were used as treatments. A leafy vegetable, a fruiting vegetable and a root crop were grown for two growing seasons. The treatments were arranged in split-plot design (main plot factor: compost; sub-plot factor plant-type). An in vitro steady fluid experiment was conducted using human skins to examine the dermal transfer of soil PAHs. The concentrations of Pb, As, and PAHs in the vegetables were low, except Pb in root crops. Compost reduced the bioaccessibility of Pb, but did not change the bioaccessibility of As. Selected soil samples were analyzed for speciation of Pb using extended x-ray absorption fine structure spectroscopy. The predominant Pb species were Pb sorbed to Fe oxy(hydr)oxide and to organic C. Stable Pb phosphates (pyromorphite) was formed during the in vitro extraction. Dermal transfer experiments showed PAHs in the contaminated soils did not transfer through the skin. Stratum conium of the skin acted as a barrier for dermal transfer of soil PAHs. In general, the risk of food chain transfer of soil Pb, As, and PAHs were low in the studied sites and can be further reduced by compost addition. Bioaccessibility of Pb and As in urban soils were low. Dermal absorption of soil PAHs was insignificant.

In rivers, association of organic contaminants with dissolved organic carbon may limit freely dissolved or bioavailable fractions and toxicity of organic contaminants. Consequently, assessment of toxicity of organic contaminants on the basis of their total chemical concentrations may lead to overestimation of risks to organic contaminants. Therefore, to achieve reliable and accurate risks assessment for organic contaminants, determination of bioavailability is important. The influence of humic acid on the bioavailability of organic contaminants in rivers was studied, using three chemicals with different properties as model contaminants, which at the start of the study were detected in wastewater effluents. It was hypothesized that in the presence of dissolved organic carbon, a fraction of the total concentration of an organic contaminant would not be bioavailable in river water. Therefore, the aim of the study was to determine bioavailability and its impact on toxicity. Bioavailability in the presence of humic acid was determined chemically and using a yeast estrogen screen assay. The chemical method comprised solid-phase extraction and liquid chromatography-mass spectrometry to determine freely dissolved and the fraction of the chemicals associated with dissolved organic carbon. The results indicated increased binding to dissolved organic carbon with the hydrophobicity of the test compounds except for perfluorooctane sulfonate. The dissolved organic carbon-water partition coefficient for ethinylestradiol was determined to be Log KDOC 2.36. Log KDOC values of 4.15 and 4.41 at 10 and 100 mg/L humic acid, respectively, were derived for hexabromocyclododecane indicating greater binding than ethinylestradiol due to the more hydrophobic character. The yeast estrogen screen was used as a biological method to measure the effect of humic acid on the bioavailability of ethinylestradiol and a more hydrophobic compound, dichlorodiphenyltrichloroethane. Results of the yeast estrogen screen indicated that the presence of humic acid had no effect on bioavailability of either of the chemicals.

Civil Engineering
Ph.D.
There are many reports indicating the presence of emerging contaminants such as: estrogen hormones, 1,4-dioxane and perfluoro-octanoic acids in the natural environment. Estrogen hormones are considered important emerging class of contaminants due to their endocrine disrupting effects. These compounds are invariably found in the environment originating mostly from natural sources. Trace concentrations of estrogen hormones (low µg/L concentrations) have been detected in municipal wastewater treatment plants and observed in receiving water bodies. 1,4-Dioxane (C4H8O2) is used as an organic solvent and solvent stabilizer numerous in chemical processes. The United States Environmental Protection Agency (US-EPA) has recognized 1,4-dioxane as a toxic chemical and a possible human carcinogen. 1,4-dioxane has been detected as a contaminant in the natural environment, drinking water supplies, superfund sites, public groundwater sources in the United States, Canada and Japan at concentrations greater than the permissible standards. Perfluorinated chemicals such as perfluoro-octanoic acid (PFOA) and perfluorooctane-sulfonate (PFOS) have been manufactured for use in a variety of industrial and consumer applications. Due to their environmental persistence, PFOAs have been detected in surface waters at a number of locations at concentrations ranging from pg/L to ng/L. Elevated concentrations of PFOAs have been measured in surface and ground waters near specific point sources. Through this project, successful attempts have been made for the destruction of emerging contaminants using ultrasound. This study deals with the optimization of various process parameters for the destruction of estrogen hormones. The influence of process parameters such as power density, reactor geometry, power intensity, ultrasound amplitude, and external mixing was investigated. Artificial neural network (ANN) approach was used to describe the interactions between optimized parameters. The important findings obtained in the present work for the optimized estrogen degradation can help tackle the challenges of scale up such as operational optimization and energy consumption. The effect of process conditions such as pH and presence of oxidizing agents on the ultrasonic destruction of 1,4-dioxane and PFOA was studied. Acidic conditions favored the destruction of both the compounds. The presence of activated sulfate radicals enhanced the reaction rate kinetics. An innovative technology using electric potential and ultrasound for the removal organic contaminants was developed. The existence of organic contaminants in ionic form under certain process conditions has led to the development of this technology. Applying a low electric potential across the probe enhances the mass transfer of the contaminants into effective reaction zone, thereby enhancing the total destruction. A two-fold increase in the reaction rates was observed. This study shows ultrasound as an efficient and effective treatment technology for the destruction of emerging contaminants.
Temple University--Theses

Determination of low levels of chemicals unintentionally present in foods (trace contaminants) often requires extensive wet chemistry extraction and clean-up regimes prior to instrumental analysis and this is usually the bottleneck in analysis. In order to determine if levels pose a human health risk, rapid reliable methods are required that can unequivocally identify and quantify contaminants at trace levels. In particular, current methods for targeted food taint analysis have long extraction times and rapid screening methods such as direct headspace, do not provide the sensitivity required. In order to address the issues raised above, this study set out to review all aspects of sample preparation and the applicability of each technique for the determination of trace organic contaminants in foods. Following the review, solid-phase dynamic extraction (SPDE) was evaluated for the determination of example food contaminants furan and the BTEX compounds (benzene, toluene, ethyl benzene and 0, rn, and p-xylene). Stir bar sorptive extraction (SBSE) was also evaluated for the determination of furan, benzene and toluene. A SBSE method for the determination of furan in food and beverages was developed which gave the advantage of extraction at ambient temperature, (thus minimising potential formation) and was comparable to direct static headspace in performance and sensitivity. The use of SBSE was then evaluated for use as a generic screening method for compounds known to cause taints in foods. Twenty example compounds were chosen based on previously reported taints from a range of origins and included those most commonly investigated (such as halogenated phenols and anisoles). The optimised SBSE method was compared to the more established techniques, direct static headspace and steam distillation extraction using Likens Nickerson apparatus. The SBSE method provided an increase in sensitivity for most compounds and further improvements were demonstrated for more targeted analysis, using a GC-MS, GC-MS/MS and GC-HRMS instrumentation.

Orientador: Gisela de Aragão Umbuzeiro
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia
Made available in DSpace on 2018-08-21T02:00:16Z (GMT). No. of bitstreams: 1 Ribeiro_AlysonRogerio_M.pdf: 3701819 bytes, checksum: b2f0a69f435398e5de38f031d75649e3 (MD5) Previous issue date: 2012
Resumo: As planarias de água doce possuem vasta distribuição geográfica, plasticidade biologica, facilidade de cultivo em laboratório, sensibilidade a contaminantes diversos e capacidade regenerativa, por isso vem sendo utilizadas como organismos-teste em ensaios ecotoxicologicos. Porem, ainda não ha normatização internacional ou nacional que padronize esses ensaios. O objetivo deste trabalho foi verificar o potencial do uso de planarias de agua doce (Girardia tigrina) na avaliação de alguns contaminantes e amostras ambientais utilizando protocolos padronizados avaliando-se mortalidade e atraso na regeneração encefálica. Foram empregados 15 organismos por concentração-teste nos ensaios de mortalidade de filhotes (96h) e 20 planarias adultas regenerantes por concentração-teste nos ensaios de regeneração encefálica (120h). Avaliou-se cromo e zinco como substancias de referencia e empregou-se cobre, azo corante têxtil Disperse Red 1, herbicida atrazina, nanotubos de carbono de parede múltipla, alem de amostras da ETE Carioba e do Ribeirão dos Cristais. Carta controle com substancia de referencia foi realizada, sendo estabelecido um protocolo para o monitoramento da sensibilidade das culturas de G. trigrina. O zinco foi a substancia mais apropriada que o cromo, com a vantagem do ensaio de sensibilidade poder ser finalizado em 24h. Os métodos utilizados para realização do ensaio de regeneração encefálica e de mortalidade de filhotes foram eficazes para a observação de efeitos adversos das substancias analisadas. Todas as amostras testadas apresentaram toxicidade as planarias, exceto os nanotubos de carbono. Atraso na regeneração encefálica foi o endpoint mais sensível para os contaminantes avaliados. Os protocolos utilizados neste estudo podem ser utilizados como subsídios na elaboração futura de normas técnicas de testes ecotoxicologicos com planarias de agua doce
Abstract: Freshwater planarians are worldwide distributed, have biological plasticity and a unique body regenerative capacity. They are easily maintained under laboratorial conditions and are sensitive for several compounds. For these reasons they have been used in ecotoxicological testing although the lack of national or international guidelines. This research aimed to verify the potential use of freshwater planarians (Girardia tigrina) in mortality and regeneration delay endpoints to assess the toxicity of environmental contaminants using standardized protocols. The culture sensitivity of G. tigrina was monitored with zinc, which was the most suitable substance for this purpose, providing responses in only 24h. The adopted protocols for regeneration and mortality tests were efficient to assess the adverse effects of the chemical agents (copper, an azo textile dye, atrazine), carbon nanotubes and wastewater and water samples from Carioba WWTP and Cristais River. The regeneration test was the most sensitive endpoint and all analyzed substances showed toxicity for planarians, except carbon nanotubes. The methods adopted in this research can be used as basis for the development of a testing guideline using freshwater planarians
Mestrado
Tecnologia e Inovação
Mestre em Tecnologia

Emerging contaminants (ECs) are chemicals such as pharmaceuticals and personal care products that have been detected in various environmental matrices, including drinking water supplies at trace concentrations (ng/L-ug/L or ng/kg-ug/kg). Current wastewater treatment plant technology is largely ineffective at removing ECs. The objectives of this investigation were to: 1) determine the occurrence of ECs in private well water supplies in Montgomery and Roanoke County, VA 2) quantify the concentrations of three ECs in selected private water supplies; 3) examine the relationship between water quality constituents (nitrate, bacteria, pH and total dissolved solids) to EC occurrence in private water supplies; and 4) determine the ability of the MicroEvapTM, a novel wastewater treatment technology, to remove ECs from secondary wastewater effluent. In partnership with the Virginia Household Water Quality Program, 57 private water supplies were sampled and tested for the occurrence of 142 ECs and 43 other water quality constituents. Up to 73 ECs were detected in the sampled private water supplies. Higher numbers of ECs detected in the tested private water supplies were related with nitrate >1 mg/L, total dissolved solids >250 mg/L, and the presence of total coliform bacteria. Results indicate the MicroEvapTM technology had >99% removal effectiveness for all 26 tested ECs from three secondary wastewater effluent. With the increasing detection of ECs in water bodies, it is essential to understand the occurrence of ECs and environmental predictors of EC presence in different water matrices and continue to develop water treatment technology capable of treating wastewater for EC removal.
Master of Science

The remote sub-Arctic/Arctic environment has due to human activities become a sink for organohalogen contaminants (OHCs). These OHC include traditional contaminants such as polychlorinated biphenyls (PCBs), DDTs and technical mixtures of polybrominated diphenyl ethers (PBDEs), all included in the Stockholm Convention list of persistent organic pollutants (POPs). Other OHCs, currently under evaluation to be included among the POPs i.e. short chain chlorinated paraffins (SCCPs) and hexabromocyclododecane (HBCDD) are also found in these environments as well as a whole range of other OHCs. The main objective of this thesis is to increase the knowledge about the presence of OHCs in a high trophic Arctic shark species, the Greenland shark (Somniosus microcephalus). The Greenland shark is an opportunistic feeder, occasionally feeding at the top of the Arctic marine food chain. Furthermore may this species have a life span in excess of 100 years and is probably among the oldest of any fish species. These traits make the shark prone to accumulate elevated concentrations of OHCs. This has shown to be true for the Greenland sharks studied and most of the targeted OHCs were determined in the species. The highest concentrations were observed for the DDTs, ranging up to 26 μg/g fat. Other OHCs reported that are of special interest are SCCPs and brominated flame retardants used as replacement products to PBDEs; pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Also a range of OHCs whose origin is assumed to be natural, were shown to be present in Greenland sharks. This thesis is stressing the fact that even though the use of certain OHCs has been banned for decades they are still present at high concentrations in the deep waters of the Arctic. Therefore it is of major importance to continue to monitor the fate of traditional and emerging OHCs in the environment, and for this purpose the Greenland shark is an excellent species.
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Aquesta tesi doctoral es centra en el desenvolupament de mètodes analítics altament eficients i sensibles per a la determinació de contaminants orgànics en l’atmosfera, en pols domèstica i en aigües. Els mètodes analítics proposats es basen en la utilització de cromatografia de gasos amb diferent detectors (incloent espectrometria de masses i detecció de nitrogen amb chemiluminiscència) i diferent tractaments de mostra que minimitzen el consum de dissolvents orgànics en tot el procés analític. Els contaminants objecte de la recerca són: compostos orgànics volàtils, hidrocarburs aromàtics policíclics, ingredients presents en productes d’higiene personal, nicotina i nitrosamines. En aquesta tesi es caracteriza també la qualitat de l’aire i de l’aigua de la regió de Tarragona mitjançant l’anàlisi de diferents mostres ambientals i es realitza una estimació del risc per inhalació de determinats contaminants en la població al voltant del complex químic més important de la zona del Mediterrani.
This Doctoral Thesis focuses on the development of efficient and highly sensitive analytical methods for determining organic contaminants in atmospheric, aquatic and house dust samples. The proposed analytical methods are based on single and comprehensive gas chromatography followed by different detectors (including mass spectrometry and nitrogen chemiluminiscence detection) and different sample preparation methods that have the aim of minimising the consumption of organic solvents in the whole analytical process. The organic contaminants selected in this Thesis include several families of volatile organic compounds, polycyclic aromatic hydrocarbons and some emerging contaminants, such as personal care products, nicotine and N-nitrosamines. This Thesis also characterises the air and water quality of the Tarragona area through the analysis of several environmental samples and estimates the risk by inhalation of organic contaminants in people living around the largest chemical site of the Mediterranean.

In this research, the adsorptive capacities of kenaf in the forms of chopped whole stalk, chopped core, and bast materials were evaluated for the removal of lead, zinc, and toluene from contaminated synthetic waste streams using traditional adsorption isotherm techniques. The effect of surface oxidation using ozone was observed with respect to the adsorption of metals. Hydraulic conductivity experiments were conducted to evaluate the head loss associated with packing a column with kenaf fibers and to determine the suitability of its use in dynamic packed column systems. B.E.T. surface areas were determined as well. Under increasingly stringent regulatory requirements, even low level organic and inorganic contamination (under 100 ppm) in surface and ground waters must be treated. This study is part of an ongoing multi-year research effort aiming to develop a kenaf-based biosorptive process to improve treatment of contaminated aqueous streams at reduced costs and technical complexity.

2 pp.
This publication describes the common insects found in Arizona lettuce through the use of pictures. The insects include; lepidopterous larva, striped flea beetle, leafminer fly, leafminer mine, adult western flower thrips, winged adult aphid, false chinch bug, lygus bug, potato leafhopper, and threecornered alfalfa hopper.

In order to achieve the goals of 'Sustainable Development', alternative (secondary) materials are being increasingly used as bulk-fill aggregate within pavement construction as substitutes for traditional aggregates. This finds an end-use for stockpiles of industrial by-products (and hence the allowing the land on which they stand to be reclaimed for other uses) and protects finite, natural resources which they replace from over-extraction. Previously, there has been very little research concerned with the leaching of contaminants from alternative materials in pavement construction and the subsequent risks to water bodies from pavement drainage. It is this topic which is addressed here. Two flow regimes within a pavement have been studied in order to predict contaminant movement: (1) vertical flow through the aggregate and pavement and then vertically through the natural subgrade to ground water below and (2) horizontal flow through the aggregate to be discharged through pavement sides drains. Using these analyses a generic user-friendly risk assessment guide by which contractors may assess an aggregate prior to use is presented. A case-study is provided to illustrate some of the issues of concern. Guidelines in the risk assessment guide recommend the suitability of different physical parameters of a potential aggregate at a proposed pavement construction site for both water flow directions. If the subgrade at the site does not allow sorption by the soil to enable any contaminants in vertical flow to be below Water Quality Standards (WQS), the use of a geotextile clay liner to further increase sorption is recommended. If the concentrations of contaminants in water discharged from side drains is not below WQS for horizontal flow, guidelines determine whether the site rainfall and surface runoff allow sufficient dilution. In most situations alternative materials appear to be acceptable for use if pavement construction is on clay subgrades, with an exception of sites where the subgrades are shallower than those recommended or where they are close to areas of higher sensitivity, such as those in close proximity to protected groundwater.

This research investigates the removal of aromatic organic contaminants (nitrobenzene (NB), aniline (AN), paracetamol (PCT) and hydroquinone (HQ)) from aqueous systems. For NB, this study focusses on removal via both iron reduction and adsorption, while removal of the other three compounds is focussed purely on adsorption. The results demonstrate NB degradation using iron powder produces AN, with the rate decreasing under basic conditions, due to corrosive effects; it is established that the iron surface is essential to the degradation process. Initial NB concentration influences degradation, and pseudo-first order kinetics are observed for all systems studied. For the adsorption studies on all four species, non-functionalised Macronet MN200, acidic functionalised hyper-cross-linked polymeric resins MN500 and S957, and Granular Activated Carbon (GAC) were tested as sorbents. The results show the kinetics of adsorption, for all contaminants, follow pseudo-second order models with rates controlled by particle diffusion. For adsorption of NB, PCT and HQ, the equilibrium uptake capacities increase with decreasing acidic functionalisation of the sorbent surface; while the opposite trend was obtained for AN removal. The adsorption rate decreased as sorbent acidic capacity increased, for all sorbents, due to the inherent surface chemistry and smaller surface area of the acidic functionalised sorbents used. For equilibria study, the Freundlich equation fits the data most appropriately and adsorption of all contaminants onto the selected sorbents is a physical process. Adsorption of NB, AN, and PCT onto the studied sorbents is favourable, while it is moderately favourable for HQ. Leaching tendencies showed < 40% of all contaminants were leached from the sorbents with the higher leaching rates for the macroporous sorbents. Overall, the results obtained suggest polymeric resins as viable candidates for the removal of targeted aromatic substances from aqueous systems.

The endocrine system, specifically relating to sex hormones, and genetic material can be targets of environmental contaminants. Environmental contaminants in the Rio Grande region may originate from industrial or agricultural processes and growing populations lacking proper water and sewage infrastructure. Cliff (Petrochelidon pyrrhonota) and cave (P. fulva) swallows breeding near the Rio Grande were selected to monitor aromatase activity alterations and DNA damage. Swallows were sampled at six sites along the Rio Grande from Brownsville to Laredo, and a reference site (Somerville) 350 miles north of the Rio Grande. DNA damage, based on nuclear DNA content, was determined by flow cytometry. A significantly larger mean half peak coefficient of variation (HPCV) of DNA content in contaminated sites compared to a reference site reflects possible chromosomal damage. No detectable HPCV differences were observed in cave swallows among locations, notwithstanding the presence of mutagenic contaminants. Selenium may provide a protective role against genetic damage. However, cliff swallows from Laredo had significantly higher HPCV values than those from Somerville. DNA damage could be attributed to metals and polycyclic aromatic hydrocarbons released near Laredo. Brains and gonads, two estrogen-dependent organs, were tested for aromatase activity with a tritiated water method. Brain aromatase activity was higher, though not always statistically, for male cave and male and female cliff swallows. Dichlorodiphenyldichloroethylene (DDE) may play a role in the increased activity. Female cave swallows in Llano Grande appeared to have a greatly depressed brain aromatase activity, possibly attributed to past human use of toxaphene. Testicular and ovarian aromatase activity in cliff and cave swallows from Rio Grande was higher than in those from Somerville, though not always significantly. DDE, atrazine, sewage treatment plant contaminants (phthalates, alkylphenols, ethynylestradiol), metals, or other pollutants could play a role in the increased gonadal activity. Increased aromatase activity, in association with contaminants, may be easier to detect in testes of male birds which normally exhibit low levels of estrogen. Siterelated contaminants may be playing a role in DNA damage and aromatase alterations. This is the first known study which uses aromatase activity as an endocrine disruptor indicator in wild birds.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ
O Centro Tecnológico de Resíduos (CENTRES) é um exemplo de passivo ambiental localizado no município de Queimados, RJ. Neste local, toneladas de resíduos industriais foram armazenadas sem nenhum critério ou fiscalização. Os recipientes contendo rejeitos químicos sofreram vazamentos e ocasionaram o contato de metais tóxicos com o solo. Metais tóxicos no solo associam-se a diversos componentes orgânicos e inorgânicos, apresentando-se em diversas formas químicas que podem interferir na mobilidade destes metais no solo Este estudo visa observar a presença e a mobilidade dos metais Cádmio, Cromo, Cobre, Níquel, Chumbo e Zinco no solo do CENTRES. Para tal foram realizadas análises de caracterização do solo e extrações pseudototais e sequenciais em amostras de sete diferentes pontos da localidade mencionada. As análises físicas do solo foram realizadas segundo a metodologia da EMBRAPA (1997). As análises químicas para avaliação da concentração dos metais no solo e para fracionamento geoquímico foram realizadas com os métodos US EPA3051 e BCR, respectivamente. No método BCR as frações solúveis em ácido, redutível e oxidável, e residual são obtidas através de ataques químicos sucessivos. As análises de caracterização física mostraram um solo predominantemente franco-argiloarenoso, com pH variando entre 4,2 e 6,9 e baixa capacidade de troca de cátions. As análises de concentração de contaminantes mostraram solos com valores acima da recomendação sugerida pela Companhia de Tecnologia de Saneamento Ambiental (CETESB, 2005) e pela Resolução CONAMA (2009), com destaque para os pontos P5 e P6, que apresentaram altas concentrações de contaminantes. Dos sete pontos analisados, quatro estavam classificados como solos Classe 3 ou Classe 4 de acordo com CONAMA (2009), o que demonstra a gravidade da contaminação da área. O Fracionamento Geoquímico das amostras mostrou que em P1, P2, P5 e P6 os metais que apresentam maiores concentrações, encontram-se também na Fração Trocável do solo, ou seja, a Fração mais disponível ao ambiente. Em contrapartida, Zinco e Chumbo apresentaram altas concentrações na Fase Residual do solo.
Centro de Tecnológico de Resíduos (CENTRES) is an example of environmental liabilities in the town of Queimados, RJ. In this place, tons of industrial waste were stored without any discretion or supervision. The containers of chemical waste have suffered and caused leaks of toxic metals contact with the ground. Toxic metals in soil are associated with various organic and inorganic components, performing in various chemical forms that can interfere with the mobility of these metals in the soil. This study aims to observe the presence and mobility of metals Cadmium, Chromium, Copper, Nickel, Lead and zinc in soil from the center. For this analysis were performed to characterize the soil and pseudototais extractions and sequential samples from seven different points in the locality mentioned. The physical analysis of soil were performed using the methodology of EMBRAPA (1997). The chemical analysis to assess the concentration of metals in soil and geochemical fractionation methods were performed with the US EPA3051 and BCR, respectively. In BCR fractions soluble in acid, reducible and oxidizable, and residual are obtained by successive chemical attacks. The analysis of physical characterization showed a sandy-clay loam, with pH ranging between 4.2 and 6.9 and low cation exchange capacity. The analysis showed the concentration of contaminants in soil above the recommended values suggested by the Companhia de Tecnologia de Saneamento Ambiental (CETESB, 2005) and by CONAMA (2009), highlighting the points P5 and P6, which showed high concentrations of contaminants in area. Of the seven points analyzed, four were classified as Class 3 soils or Class 4 according to CONAMA (2009). The Geochemical fractionation of samples showed that in P1, P2, P5 and P6, the metals that have higher concentrations are also found in the exchangeable fraction of soil, the fraction most available to the environment. In contrast, zinc and lead concentrations were high in Residual Phase soil.