No description available.

Triclosan and triclocarban are antimicrobial compounds added to a variety of consumer products that are commonly detected in waste water effluent. The focus of this study was to determine whether the bioconcentration of these compounds in wetland plants and sediments exhibited species specific and site specific differences by collecting field samples from a constructed wetland in Denton, Texas. The study showed that species-specific differences in bioconcentration exist for triclosan and triclocarban. Site-specific differences in bioconcentration were observed for triclosan and triclocarban in roots tissues and sediments. These results suggest that species selection is important for optimizing the removal of triclosan and triclocarban in constructed wetlands and raises concerns about the long term exposure of wetland ecosystems to these compounds.

Cette thèse, intégrée dans le projet Cosmet’eau et la phase 4 du programme OPUR, apporte de nouveaux éclairages sur la dynamique des parabènes, du triclosan et du triclocarban en milieu urbain sous forte pression anthropique. Ces molécules sont des biocides couramment utilisés en tant que conservateur dans de très nombreux produits de consommation courante comme les cosmétiques, les produits alimentaires ou pharmaceutiques, les textiles, les produits d’entretien. En dépit de leur toxicité, ces molécules ne font l’objet d’aucun suivi réglementaire dans l’environnement. Aussi, ce travail porte sur la dynamique de ces micropolluants en milieu urbain : de leurs sources (à savoir les eaux grises et eaux vannes) jusqu’au milieu récepteur (amont-aval de l’agglomération parisienne par échantillonnage ponctuel et passif) en intégrant leur comportement en station d’épuration à l’échelle de l’ouvrage.Au niveau des sources, cinq types d’eau grise issus de douche, lavabo, lave-linge, lave-vaisselle et vaisselle manuelle ont été considérés. Une variabilité importante des concentrations au sein de chacune des eaux grises et entre les différents types d’eau grise a été observée. Cette variabilité est le reflet des pratiques de consommation des différents volontaires. Au final, les eaux des lave-linge et douche sont les plus contaminées. Pour les parabènes, le linge est la source majoritaire de contamination des eaux de lave-linge, dans le cas des eaux de douche, les personnes et les produits de soins corporels sont les principales sources de contamination.Depuis 2010, les flux quotidiens par habitant de ces molécules ont diminué significativement (d’un facteur compris entre 2 et 7 suivant la molécule). Cette diminution s’explique par (i) les changements de formulation des produits cosmétiques et (ii) l’apparition de nouvelles réglementations plus contraignantes.Le suivi du devenir en station d’épuration (sur Seine Centre), à l’échelle de l’ouvrage, a montré que le traitement primaire (décantation physico-chimique lamellaire) permet un abattement quasi-total du triclosan, les parabènes sont majoritairement éliminés lors de la biofiltration notamment au niveau du premier étage (Biofor). La généralisation d’un traitement tertiaire (du type Carboplus® suivi lors de ce travail) permettrait de réduire ces rejets.Les rejets urbains par temps de pluie (ici les déversoirs d’orage) constituent une source importante de contamination pour le milieu récepteur au regard des niveaux que nous avons observé. La combinaison des rejets des stations d’épuration, par temps sec et par temps de pluie, et des déversoirs d’orage contribue à augmenter les niveaux en parabènes, triclosan et triclocarban de la Seine comme le suivi de deux stations de mesure en amont et aval de l’agglomération parisienne l’a mis en évidence. Les échantillonneurs passifs sont des outils prometteurs pour déterminer la fraction biodisponible du TCS et du TCC. En effet, la méthode développée dans le cadre du projet Cosmet’eau a été appliquée avec succès à la Seine. / This Phd thesis is part of both the Cosmet’Eau project and the OPUR programme. It provides new insights into the dynamics of parabens, triclosan and triclocarban in urban areas under strong human pressure. These molecules are biocides commonly used as preservatives in a wide range of consumer products, such as cosmetics, food and pharmaceutical products, textiles and cleaning products. Despite their toxicity, these molecules are not subject to any regulatory monitoring in the environment. Also, this work deals with the dynamics of these micropollutants in urban areas: from their sources (namely gray water and sewage) to the receiving environment (upstream-downstream of the Parisian conurbation with punctual and passive sampling) along with their behavior at different stages of a wastewater treatment plant.At the source level, five types of greywater from shower, washbasin, washing machine, dishwasher and manual dish washing were considered. Significant variability in concentrations within each greywater and between different types of greywater was observed. This variability reflects the consumption practices of the different volunteers. Besides, the waters from washing machines and showers are the most contaminated. For parabens, clothes are the main source of contamination of washing machine waters, while in shower waters, people and personal care products are the main sources of contamination.Since 2010, per capita daily flows of these molecules have decreased significantly (by a factor between 2 and 7 depending on the molecule). This decrease can be explained by (i) changes in the formulation of cosmetic products and (ii) the emergence of new, more restrictive regulations. The monitoring of the fate in wastewater treatment plant (Seine Centre), at the scale of the device, showed that primary treatment (lamellar physico-chemical decantation) allows a quasi-total removal of triclosan, while parabens are predominantly eliminated during the biofiltration, at the level of the first stage (Biofor). The general use of a tertiary treatment (like Carboplus®, studied during this work) would reduce discharges to receiving waters of parabens, triclosan and triclocarban.Urban discharges during wet weather period (here combined sewer overfows) constitute a major source of contamination for the receiving waters with respect to the measured levels. The combination of sewage treatment plant discharges, during dry and wet weather periods, and combined sewer overfows contributes to increasing levels of parabens, triclosan and triclocarban in the Seine River, as the monitoring of two sites, upstream and downstream of the Paris conurbation, has highlighted it. Passive samplers are promising tools for determining the bioavailable fraction of TCS and TCC. Indeed, the method developed within the framework of the Cosmet'eau project has been successfully applied to the Seine

In the last decade emerging contaminants research has intensified in a bid to answer questions about fate, transport, and effects as these chemicals as they get released into the environment. The chemicals of interest were the antimicrobials; triclocarban (TCC) and triclosan (TCS), and a metabolite of triclosan, methyl triclosan (MTCS). This research was designed to answer the question: what is the fate of these chemicals once they are released from the waste water treatment plant into receiving streams. Three different assessment methods; field monitoring, in-situ experiments, and laboratory studies were used to answer the overall question. TCS, TCC, and MTCS levels were measured in surface water, sediment and the Asiatic clam Corbicula fluminea. Field studies were conducted using four sites at Pecan Creek, Denton TX. Levels of all three chemicals in clams were up to fives orders of magnitude the water concentrations but an order of magnitude lower than in sediment. Highest sediment levels of chemicals were measured in samples from the mouth of Pecan Creek (highest organic matter). TCC was the most and TCS was the least accumulated chemicals. In-situ and lab studies both indicated that uptake of these chemicals into the clams was very rapid and measurable within 24hours of exposure. The after clams were transferred into clean water most of the compounds were depurated within 14 days.

A crescente demanda por novos compostos químicos sintéticos para atender as necessidades médicas, agrícolas e industriais da população resultou no surgimento de novos contaminantes, denominados emergentes. Com a intensa utilização destes compostos em diversos produtos e o consequente aumento da concentração destes no meio ambiente, a população passou a estar exposta e sujeita aos seus possíveis efeitos deletérios. Os disruptores endócrinos fazem parte do grupo de contaminantes emergentes que tem a capacidade de interferir na ação natural dos hormônios por diferentes mecanismos, podendo agravar o quadro de doenças pré-existentes e causar diversos outros danos à saúde humana. Apesar de serem largamente utilizados na vida cotidiana, a regulamentação do uso desses compostos ainda é quase inexistente, aumentando a preocupação quanto à sua segurança. Comumente, os estudos de biomonitoramento humano para avaliar a exposição da população em geral são realizados utilizando amostras de sangue e urina. Neste sentido, o presente estudo teve como objetivo desenvolver um método alternativo para determinação simultânea de 17 compostos classificados como disruptores endócrinos: bisfenóis, parabenos, benzofenonas e triclocarban em saliva, empregando a microextração líquido-liquido dispersiva (DLLME) no preparo da amostra e cromatografia líquida de alta eficiência acoplada à espectrometria de massas (LC-MS/MS) para a determinação. Os seguintes parâmetros foram avaliados na otimização da DLLME: volume e tipo de solvente extrator e dispersor, força iônica, pH e agitação. Após a otimização, o processo de extração foi realizado adicionando-se 500 ?L de água deionizada à 500 ?L da amostra de saliva. Os solventes extrator e dispersor selecionados foram triclorometano e acetona, respectivamente (volume de 2 mL da mistura na proporção 1:3). Foi adicionada a etapa de agitação manual por dez segundos. As curvas de calibração de todos os analitos apresentaram linearidade, com coeficiente de correlação superiores a 0,99 no intervalo de concentração de 1-20 ng mL-1. O coeficiente de variação (CV) intra e interdias foram inferiores a 20% para o primeiro ponto da faixa linear e inferiores a 15% para as demais concentrações. O erro padrão relativo intra e interdias foram inferiores a 20% para o primeiro ponto da faixa linear e inferiores a 15% nas demais concentrações. Os limites de detecção (LOD) e de quantificação (LOQ) encontrados variaram de 0,01 - 0,15 ng mL-1 e 0,05 - 0,40 ng mL-1, respectivamente. Para avaliar a aplicabilidade do método, dez amostras de saliva foram analisadas e apresentaram concentrações detectáveis de bisfenol S (BPS), bisfenol AF (BPAF) e propilparabeno (PrP) ( <LOQ). O bisfenol A (BPA) e a benzofenona-3 (BP3) foram encontrados em concentrações que variaram entre 1,01-3,14 e 1,00-2,50 ng mL-1, respectivamente. O metilparabeno (MeP) foi detectado em todas as amostras, atingindo, nos níveis quantificáveis, a concentração de 17,8 ng mL-1. Portanto, o método aqui proposto é uma alternativa simples e rápida para estudos de biomonitoramento humano, capaz de determinar 17 analitos multi-classes simultaneamente com uso de baixo volume de solventes. / The growing demand of new synthetic chemical compounds to attend the medical, agricultural and industrial needs of the population has resulted in the emergence of new contaminants, known as emerging contaminants. The presence of these contaminants in several products, and its consequent concentration increase in the environment, exposed the population and subject them to possible deleterious effects. Endocrine disruptors are a group of these contaminants that have the ability to interfere at the natural action of hormones by different mechanisms, wich can worsen preexistent diseases and cause other damages to humam health. Despite the widely utilization of these compounds in everyday life, regulation of its use is almost non-existent, raising concerns about their safety. Mostly human biomonitoring studies to assess the exposure of the population are performed in urine and blood samples. In these sense, the present study aimed to develop an alternative method for simultaneous determination of 17 endocrine disrupting compounds: bisphenols, parabens, benzophenones and triclocarban in saliva, using dispersive liquid-liquid microextraction (DLLME) at sample preparation and high performance liquid chromatography coupled to mass spectrometry (LC-MS/MS) for determination. The evaluated parameters in the optimization of DLLME were: volume and type of extraction and disperser solvents, ionic strength, pH and agitation. After the optimization, the extraction procedure was performed by adding 500 ?L of deionized water to 500 ?L of saliva sample. The extraction and disperser solvents selected were trichloromethane and acetone, respectively (2 mL of the mixture in 1:3 ratio). The manual agitation for ten seconds. The matrix-matched calibration curves of all analytes were linear, with correlation coefficients higher than 0.99 in the range level of 1 - 20 ng mL-1. The intra and interday coefficient of variation (CV) was less than 20% for the first point of the linear range and less than 15% for the other concentrations. The intra and interday relative standard deviation (RSD) was less than 20% for the first point of the linear range and less than 15% for the other concentrations. The limits of detection (LOD) and quantification (LOQ) ranged from 0,01 - 0,15 ng mL-1 and 0,05 - 0,4 ng mL-1, respectively. To evaluate the applicability of the method, ten saliva samples were analyzed, showing detectable concentrations (<LOQ) of bisphenol S (BPS), bisphenol AF (BPAF) and propylparaben (PrP). Bisphenol A (BPA) and benzophenone-3 (BP3) were found in ranging concentrations from 1,01 - 3,14 and 1,00 - 2,50 ng mL-1, respectively. Methylparaben (MeP) was detected in all samples, reaching, at the quantifiable levels, the concentration of 17,8 ng mL-1. Thus, the proposed method is a simple and fast alternative for human biomonitoring studies, capable of determining 17 multi-class analytes simultaneously using low volume of solvent.

The presence of pharmaceuticals and personal care products (PPCPs) in the environment has become a matter of concern during the last decade. Increased production of PPCPs along with their increased use has led to release of these compounds in the environment via various routes. PPCPs includes large group of compounds including veterinary and human antibiotics, analgesics and anti-inflammatory drugs, psychiatric drugs, β-blockers, X-ray contrasts, and steroid hormones, etc. Many of the compounds used in PPCPs have been shown to possess adverse effects to living organisms and act as endocrine disrupting agents (ECDs). This dissertation includes the investigation of the occurrence of antibiotic compounds added to personal care product and the transformation of hormones used in pharmaceuticals such as contraceptives. The results obtained in this study can provide information on the fate and transformation of the studied compounds once released in the environment. An analytical method employing sonication extraction and HPLC-ESI-MS detection was developed. The developed method was used to detect antibiotic compounds triclosan (TCS) and triclocarban (TCC) in biosolids-applied soil and biosolids. Both TCS and TCC were detected at high concentrations in biosolids and at lower concentrations in biosolids-applied soil. TCS and TCC concentrations decreased in biosolids composts and in biosolids-applied soil collected at deeper depths. The developed method was able to provide efficient detection limits and reliable quantification of target compounds. A molecularly imprinted polymer (MIP) was synthesized to achieve efficient clean-up of TCS and TCC from biosolids-applied soil and biosolids samples using 4,4’- DBP-4-vp-EGDMA. The motivation behind this project was to be able to eliminate the use of expensive instruments such as LC-MS and employ easily available instruments such as LC-UV. The synthesized MIP was able to achieve efficient clean-up and allowed quantification and identification of TCS and TCC in a complex matrix. Transformation of hormones such as 17β-estradiol, estriol, ethynlestradiol, estrone and testosterone was studied by employing Fe (III)-saturated montmorillonite catalysts. The use of Fe (III) – saturated montmorillonite as a catalyst proved be to very efficient in transformation of the studied hormones. Complete removal of hormones was observed in aqueous environment. LC-UV was used for detection and quantification of hormones.

<div>Biosolids-based fertilizers are sold to the public to provide beneficial nutrients and organic matter for plant production. They are commonly applied to community gardens, municipal lands, reclamation projects, and golf courses. These fertilizers, however, may also contain a variety of trace organic contaminants, which can be persistent in the environment. Our work sought to quantify the persistence of biosolids contaminants in community garden soils. The commercial biosolids-based fertilizer, OCEANGRO®, was amended to two community garden soils to determine the first-order half-lives of four model contaminants: carbamazepine, miconazole, triclocarban, and triclosan. The criteria for their selection included biosolids occurrence, ecotoxicity, antimicrobial function, and knowledge gaps. Aerobic biosolids-amended soil microcosms were incubated at 22 ± 1 °C and approximately 80% field capacity. Sacrificial sampling occurred seven times over 180 days through multi-step solvent extractions. Detection and quantification were done on a high-performance liquid chromatograph tandem triple-quadrupole mass spectrometer. Results indicated that biosolids contaminants persist in soils with some having modeled half-lives in the hundreds of days. Additional analyses of solvent-spiked contaminant degradation and porewater desorption were performed to provide greater insight into possible limitations on resident biosolids contaminant degradation and to form a better comparative basis to previous literature. Solvent-spiked contaminants degraded more quickly than those resident within biosolids, which indicate that data using the former may underestimate persistence in real-world environments. The porewater analysis allowed for the desorption coefficient to be calculated for all four model resident contaminants. Disparities in the trends of these desorption coefficients and solvent-spiked degradation rates showed that desorption from the biosolids matrix may have been a limiting factor to resident degradation for only some of our four model contaminants. Nonetheless, the demonstrated persistence of these contaminants necessitates long-term thinking in relation to biosolids application. More work is needed on the potential hazards associated with biosolids use in public lands regarding ecotoxicity and antimicrobial resistance.</div>

Triclosan and triclocarban are antimicrobials found in numerous consumer products, while caffeine is the most commonly consumed stimulant by humans. This study was undertaken to determine the effects of triclosan, triclocarban, and caffeine on the development and physiology of amphibian larvae. LC50 values of triclosan and triclocarban were determined after 96 hours for three North American larval species: Acris crepitans blanchardii, Bufo woodhousii woodhousii, Rana sphenocephala, and for a common amphibian developmental model: Xenopus laevis. Amphibian larvae were most sensitive to triclosan and triclocarban exposure during early development based upon 96-hour LC50 values. Heart rates for X. laevis and North American larvae exposed to triclosan were variable throughout development. However, significantly lower heart rates were observed in all larvae exposed to triclocarban. Metabolic rates of X. laevis and R. sphenocephala larvae exposed to triclosan were significantly affected in larvae exposed to ½ LC50 and the LC50 concentration. Metabolic rates of X. laevis larvae exposed to triclocarban were significantly affected by exposure to ½ LC50 concentrations in three of four stages investigated. No significant differences were observed in North American larvae exposed to triclocarban. Tissue uptake, lipid uptake, tissue bioconcentration factor (BCF) and lipid BCF of triclosan and triclocarban were investigated in three developmental stages of X. laevis, and in one developmental stage of B. woodhousii woodhousii, and R. sphenocephala. For most tissue and lipid uptake values, a significant increase was observed as exposure concentration increased. Tissue and lipid BCF values were dependent upon both stage and species. Chronic and acute effects of caffeine were determined in X. laevis larvae. Acute 96-hour LC50 values in four developmental stages were > 75,000 ug L-1 caffeine and heart rates were significantly different at the two earliest developmental stages. Larvae chronically exposed to caffeine reached metamorphosis at the same time as controls. Changes in chronic heart rate were dependent upon stage of development and exposure concentration. This research indicates that the toxicity of amphibian larvae exposed to triclosan, triclocarban, and caffeine appears to be dependent upon species and developmental stage, with early developmental stages being most sensitive to contaminant exposure.

No description available.

Organic contaminants from industrial and/or domestic effluents may be harmful to humans directly or indirectly by degrading the quality of the aquatic environment. Consequently these contaminants must be reduced to levels that are not harmful to humans and the environment before disposal. Chemical, physical and biological methods exist for the removal of these pollutants from effluents. Among the available chemical methods, heterogeneous photocatalytic oxidation has been found particularly effective in removing a large number of persistent organics in water. In this study, photocatalytic degradation was explored for the removal of reactive azo-dye (textile dye), triclocarban (disinfectant), clopyralid (herbicide) and three endocrine disrupting compounds (EDCs) (estrone, 17ß-estradiol and 17α-ethinylestradiol) from synthetic effluents. The major factors affecting the photocatalytic processes including the initial concentration of the target compounds, the amount of catalyst, the light intensity, the type of catalyst, the electron acceptor, the irradiation time and the pH were studied. Other oxidation techniques including (O3, H2O2, UV) were also studied. Generally UV light is used in combination with titanium dioxide, as photocatalyst, to generate photoinduced charge separation leading to the creation of electron-hole pairs. The holes act as electron acceptors hence the oxidation of organics occur at these sites. These holes can also lead to the formation of hydroxyl radicals which are also effective oxidants capable of degrading the organics. The results obtained in this study indicated that photolysis (i.e. UV only) was found to have no effect on the degradation of reactive azo-dye (RO16). However, complete photocatalytic degradation of 20 mg/L (3.24×10-2 mM) RO16 was achieved in 20 minutes in the presence of 1g/L TiO2 Degussa P25 at pH 5.5. Comparison between various types of catalysts (i.e. Degussa P25, VP Aeroperl, Hombifine N) gave varied results but Degussa P25 was the most effective photocatalyst hence it was selected for this study. For RO16 the optimum catalyst concentration was 0.5 g/L TiO2 with initial concentration of 20 mg/L RO16. It was found that the disappearance of RO16 satisfactorily followed the pseudo first-order kinetics according to Langmuir-Hinshelwood (L-H) model. The rate constant was k= 0.0928 mol/min. Photodegradation of TCC was studied in 70%v acetonitrile: 30%v water solutions. UV light degraded TCC effectively and the reaction rates increased with decreasing initial concentration of TCC. UV/TiO2 gave unsatisfactory degradation of triclocarban (TCC) since only 36% were removed in 60 minutes with initial concentration of TCC 20 mg/L. The degradation of clopyralid and the EDCs was studied using three oxidation systems UV/TiO2, UV/H2O2 and O3. Complete degradation of clopyralid (3,6-DCP) was achieved with UV/TiO2 in about 90 minutes at an optimum catalyst concentration of 1g/L. Zero-order kinetics was found to describe the first stage of the photocatalytic reaction in the concentration range 0.078-0.521 mM. At pH 5 the rate constant was 2.09×10-6-4.32×10-7 M.s-1.Complete degradation of all the three EDCs was achieved with UV/H2O2 in 60 minutes at catalyst concentration of (2.94×10-2 M). On the other hand complete degradation of the EDCs was achieved in just 2 minutes with ozonation. For high concentration EDCs, TiO2/UV gave low efficiency of degradation as compared with ozone and H2O2/UV. First-order kinetics was found to describe the photocatalytic reaction of the EDCs. / Education Service Department of the Libyan Government