The difficulty of assessing risk of sediment-associated contaminant mixtures to benthic ecosystems is often attributed to understanding the bioavailable fraction of each contaminant. These issues have led to the development of the toxicity identification evaluation (TIE). Past pore water TIE testing on Illinois River sediments has indicated that ammonia was the primary contaminant. The current study, however, suggests that ammonia is no longer the primary contaminant of concern, but rather non-polar organics, including polycyclic aromatic hydrocarbons, are the primary cause for toxicity in the Illinois River Complex (IRC). Summer of 2007 testing showed that six out of the seven sites that proceeded to Phase I testing exhibited a significant increase in survival with the addition of the non-polar organic amendment powdered coconut charcoal (PCC), while zeolite (ammonia amendment) and Resin Tech SIR 300 (cationic metals amendment) did not significantly increase survival suggesting that non-polar organics are the source of toxicity. In addition, Phase II testing suggested that concentrations of PAHs were high enough to cause the observed toxicity, which confirmed the results of Phase I testing. Additional seasonal-based sampling (i.e., fall, winter, spring, and summer 2008) supported the summer findings, with little variation between toxicity and concentrations, with 46% of the sites being improved with the addition of PCC in Phase I testing. The results of Phase I and Phase II contradicted past pore water TIE studies as non-polar organics were suggested as the source of toxicity rather than ammonia. Thus, both pore water and whole sediment TIE methodologies were used on two selected sites. The results of this study suggested that discordance between the past pore water TIEs and the current whole sediment TIE were attributed to the methodologies and on a lesser note the test organisms used. The present study provides data that could be used in combination with previous work to more accurately characterize the sources and spatial trends of toxicity in Illinois River sediments for future risk assessment and mitigation. Furthermore, the present study showed that while TIE methodologies are a valuable tool in assessing risk associated with contaminants in aquatic system, further research in understanding the role that each TIE method may serve in risk assessment is also important.

Submitted by Luciana Sebin (lusebin@ufscar.br) on 2016-09-27T13:14:48Z No. of bitstreams: 1 TeseMAB.pdf: 527199 bytes, checksum: 9c17c3f72026e7aa20cc36238de2a00a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-27T19:53:19Z (GMT) No. of bitstreams: 1 TeseMAB.pdf: 527199 bytes, checksum: 9c17c3f72026e7aa20cc36238de2a00a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-27T19:53:27Z (GMT) No. of bitstreams: 1 TeseMAB.pdf: 527199 bytes, checksum: 9c17c3f72026e7aa20cc36238de2a00a (MD5) / Made available in DSpace on 2016-09-27T19:53:34Z (GMT). No. of bitstreams: 1 TeseMAB.pdf: 527199 bytes, checksum: 9c17c3f72026e7aa20cc36238de2a00a (MD5) Previous issue date: 2016-03-04 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Microalgae have been cultivated worldwide to obtain biomass for various applications. Nonetheless the production costs of microalgae is still high due to factors such as photobioreactors, water and nutrients to grow the organisms. In recent years the use of wastewaters of several origins for microalgal cultures have been studied. However wastewater generally are more complex than synthetic microalgae culture media. Their characteristics can vary over time and have associated microorganisms such as bacteria, fungi and yeasts. Vinasse is a wastewater generated in large volumes by the ethanol industry of Brazil and it is rich in nutrients and organic materials. The use of this effluent to support microalgae growth can reduce the microalgae production costs at the same time that it decreases the contaminant potential of the effluent through the incorporation of nutrients into biomass. The aim of this research was to evaluate the potential of the use of sugarcane vinasse as culture medium for the growth of the freshwater microalgae Chlorella vulgaris. C. vulgaris is a robust species commonly used in the treatment of effluents. Laboratory tests were initially conducted with two distinct vinasses, a conventional and an originating from a agroecological processing, at different concentrations. Based on these results the conventional vinasse was selected for more detailed studies that aimed at treating the vinasse in defined procedures known as Toxicity Identification Evaluation (TIE). Through such procedure, we attempted to answer why it is so difficult to grow microalgae in sugarcane vinasse and how could the microalgal production be increased in such a complex residue. The results showed that pH adjustment resulted in the highest Chlorella vulgaris biomass in vinasse, whereas the addition of EDTA, sodium thiosulfate and XAD-8 resin to remove specific compounds from the wastewater limited the microalgal final yield. The growth of C. vulgaris was higher at intermediate treated vinasse concentrations (30 - 70%). This demonstrated the possibility of using of this residue as a medium for microalgal cultivation. Once selected the ideal condition for C. vulgaris cultivation (30% vinasse and TIE pH=3.0), there was a screening of the microorganisms present in the vinasse and in non axenic cultures of microalgae after its inoculation with C. vulgaris. The microrganisms were isolated and characterized for indole acetic acid (IAA) production, nitrogen fixation and inorganic phosphate solubilization. The presence of heterotrophic microorganisms in the vinasse did not affect the microalgal production. We obtained promising results about future applications of these microorganisms as growth promoters in microalgal cultures. The biomass produced showed protein productivity of 15.57 mg L-1 day-1 and a decrease of nitrogen, sulfate, biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC) and total nitrogen (TN) contents in comparison with the initial vinasse was obtained. The results suggest the possibility of using vinasse as a medium for the cultivation of C. vulgaris, with decrease of the potential contaminant of the effluent and increase of biomass production when compared to synthetic culture medium. / Microalgas têm sido cultivadas no mundo todo visando obter biomassa para as mais diversas aplicações. No entanto, seu custo de produção é elevado, pois além de demandarem elevada quantidade de água, exigem nutrientes minerais para que possam crescer satisfatoriamente. A utilização de águas residuárias para cultivos microalgais tem merecido destaque uma vez que, simultaneamente à possibilidade de se reduzir os custos de produção algal, é possível reduzir o potencial eutrofizante e contaminante dos efluentes através da incorporação de nutrientes ali presentes à biomassa microalgal. No entanto, efluentes apresentam maior complexidade do que meios de cultura sintéticos, com características variáveis ao longo do tempo e maior presença de micro-organismos associados como bactérias, fungos e leveduras. O Brasil é o maior produtor mundial de etanol de cana-de-açúcar e a vinhaça é o principal subproduto dessa produção, sendo gerada na proporção de 10 - 12 L vinhaça/L etanol. A presença de nutrientes minerais na vinhaça indica seu uso como adubo vegetal, quer seja para microalgas, quer para vegetais vasculares. Entretanto, cultivar microalgas em vinhaça é ainda um desafio. Se, por um lado, em cultivos fotoautotróficos a coloração escura do efluente pode ser limitante, em cultivos heterotróficos a presença de contaminantes biológicos pode levar à competição por recursos e comprometer a qualidade da biomassa final. O objetivo deste trabalho foi avaliar o potencial de utilização de vinhaça de cana-de-açúcar como meio para o cultivo da microalga Chlorella vulgaris, uma espécie robusta usualmente empregada em tratamento de águas residuárias. Buscou-se desvendar qual constituinte da vinhaça a torna tão problemática aos cultivos microalgais e analisar as possibilidades de cultivo fotoautotrófico objetivando, sempre, maior rendimento de biomassa. Ensaios laboratoriais foram conduzidos inicialmente com duas vinhaças, uma convencional e uma oriunda de um processamento agroecológico, utilizando diferentes concentrações para o cultivo microalgal. Com base nesses resultados, selecionou-se a vinhaça convencional para intensificação dos estudos referentes à toxicidade deste efluente. Ensaios envolvendo avaliação e identificação da toxicidade (TIE) foram conduzidos através de uma série de manipulações físico-químicas da vinhaça, com objetivo de alterar a biodisponibilidade de determinados compostos e, consequentemente, aumentar a produção microalgal. Os resultados mostraram que, dentre os tratamentos, o ajuste de pH foi o principal responsável pelo maior crescimento de Clorella vulgaris quando cultivada em vinhaça, enquanto a adição de EDTA, tiossulfato de sódio e resina XAD-8 ao efluente limitou o crescimento microalgal. O crescimento de C. vulgaris foi maior em concentrações intermediárias de vinhaça (30 – 70%), demonstrando a possibilidade de utilização deste resíduo como meio para o cultivo microalgal. Selecionada a condição ideal de cultivo para C. vulgaris, realizou-se um rastreamento dos microorganismos presentes na vinhaça e nas culturas não axênicas da microalga, com isolamento e caracterização dos mesmos no tocante à produção de ácido indolacético (AIA), fixação de nitrogênio e solubilização de fosfato inorgânico. A presença de micro-organismos heterotróficos na vinhaça não comprometeu o crescimento microalgal e os resultados mostraram-se promissores quanto ao uso dos micro-organismos isolados como promotores de crescimento em cultivos microalgais. A biomassa produzida apresentou produtividade protéica de 15,57 mg L-1 dia-1, com diminuição dos teores de nitrogênio, sulfato, demanda bioquímica de oxigênio (DBO), demanda química de oxigênio (DQO), carbono orgânico total (COT) e nitrogênio total (NT) em relação à vinhaça inicial. Os resultados sugerem a possibilidade de uso de vinhaça como meio para o cultivo de C. vulgaris, com redução do potencial contaminante do efluente e aumento da biomassa produzida em relação ao meio de cultura sintético.

Orientadores: Cassiana Maria Reganhan-Coneglian, Gisela de Aragão Umbuzeiro / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-27T02:20:49Z (GMT). No. of bitstreams: 1 Spadotim_RegisFernando_M.pdf: 4096362 bytes, checksum: 0bd54b47a22f2ac240c18ef0d54ff13a (MD5) Previous issue date: 2015 / Resumo: O ribeirão Pires é o principal afluente do ribeirão Pinhal, manancial utilizado na captação de águas para distribuição à população de Limeira, SP. Estudos anteriores realizados na micro bacia do ribeirão Pinhal apontaram toxidade aguda apenas nas águas do ribeirão Pires, para o organismo-teste Ceriodaphnia dubia. Desta forma torna-se importante conhecer as fontes de contaminação, bem como seus contaminantes para assegurar água de qualidade para o município. No presente trabalho realizou-se a avaliação ecotoxicológica mediante testes de toxidade aguda e crônica de amostras de água superficial coletadas no ribeirão Pires, e identificação da toxidade utilizando o estudo de Avaliação e Identificação da Toxidade (AIT). O princípio desse método baseia-se no fracionamento das amostras por meio de uma série de processos físicos e químicos, objetivando eliminar ou separar grupos de compostos para verificação de seu potencial tóxico. Para realização do AIT utilizou-se os organismos-testes Ceriodaphnia dubia e Daphnia similis, mediante testes de toxidade aguda, após a manipulação das amostras verificou-se a redução significativa da toxicidade com tratamento em coluna C18 em pH 9 e quelação com EDTA. Estes tratamentos de AIT (Fase I) apontaram respectivamente, compostos orgânicos não polares, além de metais catiônicos como responsáveis pela toxidade aguda. Manipulações da Fase II utilizando espectrofotometria ICP-MS permitiram identificar o zinco em concentrações entre 270-1330 µg L-1. A caracterização e confirmação de compostos orgânicos nem sempre é necessária, visto que em alguns casos somente a classe dos compostos tóxicos pode fornecer informações suficientes para determinar o tratamento apropriado ou opções de controle da fonte da toxicidade. De acordo com os resultados obtidos nas análises, pode-se concluir que o zinco foi o principal agente responsável pela toxicidade das amostras coletadas no ribeirão Pires, para os organismos testados e a provável ocorrência de outros contaminantes / Abstract: The stream Pires is the main tributary of the stream Pinhal, source used in water catchment for distribution to the population of Limeira, SP. Previous studies in micro basin stream Pinhal pointed acute toxicity only in stream Pires of water to the organism Ceriodaphnia dubia. Thus it is important to know the sources of contamination and its contaminants to ensure quality water for the city. In the present work to review ecotoxicological by acute and chronic toxicity tests of surface water samples collected in the stream Pires and identification of toxicity study using the Toxicity Identification and Evaluation (TIE). The principle of this method is based on the fractionation of the samples through a series of physical and chemical processes in order to eliminate or separate groups of compounds to check their toxic potential. To perform the TIE was used the organism Ceriodaphnia dubia and Daphnia similis by acute toxicity tests after handling the samples there was a significant reduction in toxicity with treatment C18 column at pH 9 and chelation with EDTA. These treatments TIE (Phase I) indicated respectively nonpolar organic compounds, and cationic metal responsible for acute toxicity. Manipulations of Phase II using spectrometry ICP-MS permitted the identification zinc at concentrations of 270-1330 µg L-1. The characterization and confirmation of organic compounds is not always necessary because in some cases only the class of toxic compounds can provide sufficient information to determine the appropriate treatment or control options of the toxicity source. According to the analysis results, it can be concluded that zinc is the primary agent responsible for the toxicity of the samples collected in stream Pires for the tested organisms and the likely occurrence of other contaminants / Mestrado / Tecnologia e Inovação / Mestre em Tecnologia

The University of North Texas Stream Research Facility (UNTSRF) was designed to examine contaminant impacts on effluent-dominated stream ecosystems. Stream mesocosms, fed municipal effluent from the City of Denton, TX, Pecan Creek Water Reclamation Plant (PCWRP), were treated with 0, 15 or 140 µg/L cadmium for a 10-day study in August 2000. Laboratory toxicity test and stream macroinvertebrate responses indicated that cadmium bioavailability was reduced by constituents of effluent-dominated streams. The Biotic Ligand Model (BLM) for Cd was used to predict a 48 hour Cd EC50 for Ceriodaphnia dubia of 280 µg/L in these effluent-dominated streams. This value is higher that an EC50 of 38.3 µg/L Cd and a 7-day reproduction effect level of 3.3 µg/L Cd generated for C. dubia in reconstituted laboratory hard water. These results support use of a cadmium BLM for establishing site-specific acute water quality criteria in effluent-dominated streams. Although not affected by 15 µg/L treatments, organisms accumulated Cd in 15 µg/L treated streams. Hence, over longer exposure periods, Cd accumulation may increase and a no effect level may be lower than the observed 10-day no effect level of 15 µg/L. A toxicity identification evaluation procedure was utilized with in vitro and in vivo bioassays to identify estrogenic compounds in PCWRP effluent, previously identified to seasonally induce vitellogenin (VTG) in male fathead minnows. Steroids, nonylphenol ethoxylate metabolites, and other unidentified compounds were identified as causative effluent estrogens. These findings suggest that in vivo VTG bioassays should be used to confirm in vitro Yeast Estrogen Screening assay activity when effluents are fractionated or screened for estrogenicity. A subsequent 90-day cadmium study was initiated to assess long-term effluent and cadmium effects on fish endocrine function. Juvenile fathead minnows were placed in UNTSRF pool sections of replicate streams treated with 0, 5, 20 or 80 µg/L Cd. Male VTG was induced at each treatment level, indicating that PCWRP effluent was estrogenic during fall 2001. 20 and 80 µg/L Cd treatments reduced male circulating estradiol levels and critical swimming performance. Future studies are needed to assess impacts of environmental estrogen exposure on fish calcium metabolism and vertebral integrity.

With the advent of national storm water regulations, municipalities with populations greater than 100,000 are required to obtain National Pollutant Discharge Elimination System Permits (NPDES) for storm water discharges. In addition to the sampling required for the permit process, the City of Fort Worth contracted with the University of North Texas' Institute of Applied Sciences to conduct acute toxicity testing using Pimephales prcmelas and Ceriodaphnia dubia on storm water samples received from the Dallas/Fort Worth Metroplex. A Toxicity Identification Evaluation (TIE) was performed on four samples that exhibited acute toxicity to C. dubia. High levels of metals as well as diazinon were some of the probable toxicants found.