Native and naturalized California plant species were screened for their phytoremediation potential for the cleanup of soil contaminated with petroleum hydrocarbons (PHCs), poly-aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated dioxins/furans, and heavy metals. This screening was followed by controlled greenhouse experiments to further evaluate the phytoremediation potential of the best candidates. Field specimens and soils used for this study were collected from the former Energy Technology Engineering Center (ETEC) at the Santa Susana Field Laboratory in Southern California that was operated by the Department of Energy (DOE). Soils at this site contain all of the contaminants of interest (COIs). Nine plant species were screened in the field: Purple Needlegrass (Nassella pulchra), Blue Elderberry (Sambucus nigra), Laurel Sumac (Malosma laurina), Mule Fat (Baccharis salicifolia), Palmer’s Goldenbush (Ericameria palmeri), Summer Mustard (Hirschfeldia incana), Narrowleaf Milkweed (Asclepias fascicularis), Coyote Brush (Baccharis pilularis), and Thickleaf Yerba Santa (Eriodictyon crassifolium). In the field three samples of each species growing in contaminated soil and one of each species growing in uncontaminated soil were selected for harvesting and analysis. The roots, above ground plant tissue, and soil around the roots were sampled separately and analyzed for the COIs: PHCs, PAHs, PCBs, chlorinated dioxins/furans, and metals (which include mercury, silver, cadmium, and lead). All of the plants in the field appeared to generate compounds which result in higher measured PHC concentrations than those measured in the associated soil. The highest concentrations of PAHs in the roots were observed for Blue Elderberry (1740 ug/kg), Purple Needlegrass (703 ug/kg), and Yerba Santa (200 ug/kg). No uptake of PCBs was observed in the roots or foliage of any species. The highest concentrations of total chlorinated dioxins/furans in the roots were observed for Purple Needlegrass (2237 ng/kg), Blue Elderberry (1026 ng/kg), Palmer’s Goldenbush (432 ng/kg), and Yerba Santa (421 ng/kg). The highest concentrations of total chlorinated dioxins/furans in the foliage were observed for Yerba Santa (901 ng/kg), Palmer’s Goldenbush (757 ng/kg), and Purple Needlegrass (694 ng/kg). No uptake of mercury was observed in the roots or foliage of any species. The highest concentration of silver in the roots was observed for Laurel Sumac (7.34 mg/kg). Summer Mustard (SM) was the only species that showed uptake of silver into the foliage (0.405 mg/kg). The highest concentrations of cadmium in the roots and foliage were observed for Mule Fat (1.84 mg/kg and 3.64 mg/kg) and Coyote Brush (1.52 mg/kg and 2.12 mg/kg) and the greatest concentration of lead in the roots and foliage was observed for Purple Needlegrass (8.92 mg/kg and 1.17 mg/kg). Plants with a wide variety of observed contaminant uptake in the field were selected for a second phase of research in which three of the most promising species were grown in greenhouse microcosms to quantify the removal of contaminants from the soil. The three species selected based on preliminary results from the field study were Coyote Brush, Mule Fat, and Purple Needlegrass. Microcosms consisted of 2.17 kg of soil in 4-L glass jars with glass marbles for an underdrain. Plants were watered with deionized water and no leachate was collected. Five replicates of each microcosm type were created and incubated for 211 days with soil sampling at 85 and 211 days. Soil, plant roots/above ground tissue, and volatilization from the plants were analyzed for COIs to determine the mechanisms of phytoremediation. One set of microcosms was used to test the effect of addition of achelating agent (ethylenediaminetetraacetic acid) and another set was used to test the effect of fertilizer addition on phytoremediation potential. Three control treatments were tested: sterilized (gamma irradiation) soil planted with Purple Needlegrass, unplanted soil, and sterilized unplanted soil. None of the plant species demonstrated volatilization of COIs under these conditions. Volatilization of mercury was not tested for. The average PCB concentration (measured as Aroclor 1260) reductions in soils with Purple Needlegrass and chelated Coyote Brush were 49.4% and 51.4% respectively (p < 0.05). However, the sterilized unplanted control also had a decrease of Aroclor 1260 concentrations in the soil of 36.6% (p < 0.05). None of the species phytoextracted PCBs, so the mechanism of PCB remediation appears to be phytostimulation of the rhizosphere. Purple Needlegrass showed the greatest uptake of dioxins/furans into the foliage but did not appear to reduce the dioxin/furan concentrations in the soil. Coyote Brush, fertilized Coyote Brush, and Mule Fat also showed uptake of dioxins/furans into the roots and foliage. Only the Coyote Brush and fertilized Coyote Brush significantly (p = 0.036, p = 0.022) reduced the total dioxin/furan concentration in the soil (17.8% and 19.8% respectively). Coyote Brush may have stimulated microbes in the rhizosphere to better degrade the dioxins/furans. None of the plants were identified as hyper-accumulators of metals, and none of the soil metal concentrations significantly decreased in any of the microcosms. All of the metals (except mercury) were taken into the roots of plants to some degree, with Purple Needlegrass showing the most promise for metal extraction as it showed some of the highest concentrations of metals in roots and was the only species that contained mercury and silver in the foliage. This study suggests that there is some potential for phytoremediation of PCBs and chlorinated dioxins/furans. The results for petroleum hydrocarbons were inconclusive. Metal uptake was not substantial enough to lower metal concentrations in the soils. Thus phytoremediation of COIs at the site is limited and more aggressive forms of remediation may be required to reduce the concentrations of COIs quickly.

7 Abstract Groundwater flow and highly permeable zones in aquifers of eastern part of Bohemian Cretaceous Basin based on Litá area and surroundings In my thesis I deal with the character of highy permeable zones in marlstones and calcitic sandstones in east-bohemian synclines of the Czech Cretaceous Basin. My chosen area lies southwest of Nové M�sto nad Metují and within it lies Litá area, an important source of groundwater for Hradec Králové region. Groundwater in the area was contaminated in the 80's by chlorinated hydrocarbons. Based on a detailed field sampling of 23 boreholes and 4 sites of surface water performed in 2008 and on archival data on contaminant concentrations, I evaluate the character and relationships of groundwater from the boreholes. I grouped boreholes according to their chemical properties. In the second part of my thesis, I perform the analysis of the influence of faults on groundwater flow in a larger area of east-bohemian synclines. Results show that most yielding boreholes lie between fractures, not near them, which suggests the impermeable role of fractures. From available information I then try to answer the question of highly permeable zones of preferential groundwater flow. Based on the observed flow velocity,...

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This thesis estimates the spatial extent of chlorinated solvent contamination of the soil at the Naval Air Station, Dallas, then estimates the fate and transport of these contaminants, over time, using the Soil Transport and Fate database and the Vadose-Zone Interactive Processes (VIP) modeling software. Geostatistical analysis identifies two areas with serious chlorinated solvent contamination. Fate and transport modeling estimates that this contamination will degrade and disperse from the soil phase to below regulatory limits within one year, although there is a risk of groundwater contamination. Contaminants are estimated to persist in the water and air phases of the soil. Further sampling is recommended to confirm the results of this study.

Dans cette thèse, nous avons déterminé les mécanismes qui régissent l'efficacité des particules de fer zérovalent (ZVI) dans la dépollution des sols et des eaux souterraines. Dans les milieux contaminés par des polluants accepteurs d'électrons, le ZVI est injecté in situ sous forme de suspensions de particules micro et/ou nanométriques. La première étude a porté sur la caractérisation de poudres industrielles et de particules synthétisées au laboratoire à partir de thé vert. Afin de comparer la réactivité de l'ensemble des particules, un test en milieu fermé a été mis en oeuvre avec une solution de nitrate. Ce test a permis de différencier les particules en mettant en évidence des mécanismes réactionnels et des cinétiques de réduction qui dépendent du type de poudre utilisé. La seconde étude a porté sur la dégradation du chrome hexavalent (dans une matrice sol et eau) en combinant le ZVI à du thiosulfate de sodium. Les résultats ont été probants et ont mené au dimensionnement d'un pilote sur un site de Soléo Services. Enfin, deux cas de remédiation de sites pollués aux solvants chlorés ont été étudiés. Des expériences de laboratoire ont été menées pour expliquer l'impact des conditions opératoires sur l'efficacité du traitement / This thesis aims at a better understanding of mechanisms governing the efficiency of zerovalent iron (ZVI) particles in soil and groundwater remediation. In these processes ZVI is injected in situ as micro and/or nanoparticles slurry in areas contaminated by electron acceptor pollutants. At first, we characterized industrial powders and particles synthetized with green tea in the laboratory. In order to compare the reactivity of all the particles, a batch test has been carried out with nitrate solution. Differences in pathways and kinetic reduction have been exhibited. Secondly, we combined ZVI with sodium thiosulfate to investigate hexavalent chromium degradation (soil and water matrices). The results are conclusive and were used to design a pilot on a Soléo Services site.Finally, remediation cases of sites contaminated by chlorinated solvents have been investigated. Lab experiments have been run to explain the influence of operating conditions on the treatment efficacy

A contaminação da antiga Zona de Uso Predominantemente Industrial 131 (ZUPI 131) em Jurubatuba, São Paulo, levou ao estabelecimento de uma zona de restrição de uso da água subterrânea pelo Poder Público, sendo classificada posteriormente como uma área contaminada crítica. A falta de uma ferramenta que integre os dados ambientais dificulta o trabalho de gerenciamento do problema na escala de trabalho. O desenvolvimento desta ferramenta em SIG, objeto deste trabalho, contribui para a solução dessa demanda e apresenta um modelo conceitual da contaminação da ZUPI 131. O método de trabalho se mostrou adequado para superar as dificuldades de sistematização dos dados e a ferramenta apresentou bom desempenho. Contudo, não foram esgotadas todas as possibilidades de avaliação e processamento de dados, tampouco sua interpretação. A ferramenta possui caráter dinâmico, pode receber maior quantidade de dados e possibilitar novas interpretações e avanços na caracterização da contaminação. As operações espaciais realizadas permitiram identificar áreas prioritárias para futuras investigações; constatar a ausência de registros de informações pretéritas em metade dos empreendimentos; caracterizar rios e córregos como principais zonas de descarga dos aquíferos de porosidade intergranular (sedimentos e saprólito); caracterizar os principais locais de ocorrência de concentrações mais elevadas de solventes clorados; e identificar a existência de concentrações elevadas em alguns poços de abastecimento próximos às áreas que manipularam solventes clorados no passado. Todos esses achados contribuem para a gestão integrada da antiga ZUPI 131. / The contamination of the former industrial area 131 (ZUPI 131) at the Jurubatuba area, Sao Paulo, leaded to the demarcation of a groundwater restriction zone by the government authorities which classified the areas as critically contaminated. The lack of a Geographic Information System (GIS) to manage all the data poses many challenges to the problem in the work scale. The development of GIS tool brings new light to the former ZUPI 131 integrated management and its application resulted in a conceptual model of the contamination. The adopted method has proved to be able to deal with the data systematization issues and the tool had good performance, however the data evaluation and processing had just began as well as its interpretation. The tool is dynamic and more data can be imported enabling new interpretations and advances in the cha racterization of the contamination. Spatial operations have identified priority areas for future investigations such as; verify that half of the sites lack records of past land use; characterize the rivers and the streams as main discharge zones of the porous aquifers (sediments and saprolite); characterize the main hot spots of chlorinated solvents contamination; and identify the existence of high concentrations in some of the supply wells close to sites that manipulated chlorinated solvents in the past. All these findings contribute to the integrated management of the former ZUPI 131.

A proposta desta pesquisa foi avaliar a aplicação do processo oxidativo avançado (POA), peróxido de hidrogênio (\'H IND.2\'O IND.2\') e radiação ultravioleta (UV), como pós-tratamento de um reator anaeróbio utilizado para tratar efluentes de branqueamento de indústrias de celulose kraft. O principal objetivo do pós-tratamento químico foi aumentar a biodegradabilidade e a remoção de compostos recalcitrantes nos efluentes. O tratamento biológico foi realizado por meio de reator anaeróbio horizontal de leito fixo (RAHLF), em escala de bancada, seguido pelo tratamento \'H IND.2\'O IND.2\'/UV dos efluentes. As doses do agente oxidante variaram de 50 a 500 mg \'H IND.2\'O IND.2\'/L e as aplicações de energia pela lâmpada de radiação ultravioleta foram variadas, principalmente, de 3,8 a 15,0 kWh por \'M POT.3\' de efluente tratado. Desta forma, amostras de efluentes foram coletadas de duas indústrias brasileiras de celulose kraft branqueada, originando respectivamente duas fases experimentais. Na primeira fase, o RAHLF apresentou boa estabilidade de operação, obtendo adequadas eficiências de remoção de DQO (61 ± 3%), COT (69 ± 9%), \'DBO IND.5\' (90 ± 5%) e AOX (55 ± 14%). Todavia, não ocorreu boa remoção dos compostos de absorbância na \'UV IND.254\'. Além disso, houve aumento de constituintes da lignina do afluente para o efluente do RAHLF. Por sua vez, o pós-tratamento com \'H IND.2\'O IND.2\'/UV no efluente anaeróbio proporcionou eficiência de remoção variada nos parâmetros DQO (0 a 11%), \'UV IND.254\' (16 a 35%), lignina (0 a 29%) e AOX (23 a 54%). Em relação a melhoria da biodegradabilidade, todas as dosagens de \'H IND.2\'O IND.2\' estudadas promoveram aumento na relação \'DBO IND.5\'/DQO. Para uma relação \'DBO IND.5\'/DQO média inicial igual a 0,09, correspondente ao efluente do RAHLF, o maior aumento obtido foi de 131% aplicando 500 mg \'H IND.2\'O IND.2\'/L e 7,5 kWh/\'M POT.3\'. O tratamento conjugado biológico e químico foi necessário para atingir ao padrão europeu de emissão de AOX (< 0,4 kg AOX por tonelada de polpa de celulose seca produzida). Na segunda fase, o RAHLF apresentou alguns problemas operacionais, tais como entupimento nas conexões e quebras do reator de vidro, pelo possível aumento da carga orgânica volumétrica aplicada presente nos efluentes coletados na segunda indústria de celulose. O pós-tratamento com \'H IND.2\'O IND.2\'/UV mostrou menor desempenho nessa fase experimental, o que pode ser explicado também pelo maior teor de matéria orgânica residual, lignina, alcalinidade e íons cloretos ainda remanescentes nos efluentes tratados biologicamente. Visando complementar os estudos, testes em reatores aeróbios nos efluentes do RAHLF, tratados e não tratados pelos processos \'H IND.2\'O IND.2\'/UV, foram avaliados. Os resultados demonstraram que os melhores resultados (menor tempo de aeração necessário para atingir a mesma concentração dos parâmetros avaliados) foram alcançados pelos reatores que receberam efluentes previamente tratados pelo POA. Uma avaliação simplificada do custo operacional associado com a aplicação do tratamento \'H IND.2\'O IND.2\'/UV, em escala plena, indicou um custo de R$ 1,87 por \'M POT.3\' de efluente tratado. / The purpose of this research was to assess the application of the advanced oxidation processes (AOP), hydrogen peroxide (\'H IND.2\'O IND.2\') and ultraviolet radiation (UV), as post-treatment for an anaerobic reactor used to treat bleaching effluents from kraft pulp mills. The main objective of the chemical post-treatment was to increase the biodegradability and remove recalcitrant compounds from the wastewater. The biological treatment was performed in a fixed bed anaerobic horizontal reactor (FBAHR), in bench scale, followed by \'H IND.2\'O IND.2\'/UV treatment of the effluents. The oxidizer dosage varied from 50 to 500 mg \'H IND.2\'O IND.2\'/L while the energy applied by the UV lamp ranged, mainly, from 3.8 to 15.0 kWh per \'M POT.3\' of treated effluent. This way, wastewater samples were collected from two brazilian bleached kraft pulp mills thus the results were reported as two different experimental phases. In the first phase the FBAHR showed good operational stability and reached the expected removal efficiencies for COD (61 ± 3%), TOC (69 ± 9%), \'BOD IND.5\' (90 ± 5%) and AOX (55 ± 14%). However, the anaerobic treatment did not provide good removal of compounds indicated by \'UV IND.254\' absorbency. Furthermore, there was an increase of lignin from the affluent to effluent of the FBAHR. In its turn the \'H IND.2\'O IND.2\'/UV post-treatment provided a wide range of removal depending upon the dosage: COD (0 to 11%), \'UV IND.254\' (16 to 35%), lignin (0 to 29%) and AOX (23 to 54%). Regarding to the improvement in biodegradability, all dosages of \'H IND.2\'O IND.2\' applied in this work promoted an increase in the \'BOD IND.5\'/COD ratio. For an average initial \'BOD IND.5\'/COD ratio equal to 0.09, which corresponds to the FBAHR effluent, the greatest increase was 131% with 500 mg \'H IND.2\'O IND.2\'/L and 7.5 kWh/\'M POT.3\'. It was necessary to couple the anaerobic and the oxidative treatment to reach the current European allowable AOX emission load (< 0.4 kg AOX per ton of produced dried cellulose pulp). During the second phase of the experiments, the FBAHR had operational problems as plugging of the tubes and cracking of the reactor wall that may be partially attributed to the higher organic load applied, as the effluents from the second mill were stronger. The AOP post-treatment also had lower performance during this experimental phase, which may be explained by the higher concentration of the organic matter, lignin, alkalinity and chloride ions, still present in the biologically treated effluents. To complete the experiments samples from effluents of the FBAHR and AOP process were submitted to aerobic assays. By tests done in aerobic reactors in the FBAHR effluents, treated and non-treated by the processes \'H IND.2\'O IND.2\'/UV, it was verified that the best results, shorter aeration time requirement to reach the same concentration of the evaluated parameters, were obtained from reactors that received previously treated by AOP effluents. A simplified evaluation of the operational cost associated with the use of the tested AOP, in full scale, indicated a cost of R$ 1.87 per \'M POT.3\' of treated effluent.

Este estudo teve como objetivo avaliar o desempenho de 2 reatores anaeróbios de fluxo ascendente e manta de lodo (UASB), em escala de bancada, tratando licor negro diluído, durante 635 dias de operação contínua. Durante a Fase I os reatores foram alimentados com licor negro diluído, enriquecido com nutrientes essenciais, simulando os efluentes de uma indústria de pasta celulósica não branqueada. Durante a Fase II, um dos reatores foi alimentado com o mesmo substrato mais uma mistura de cinco compostos organoclorados, simulando os efluentes de uma indústria de pasta celulósica branqueada. O aumento da taxa de carregamento orgânico, na Fase I, de 0,40 kg DQO/dia m3 para 0,70 kg DQO/dia m3 não provocou diminuição da eficiência de remoção de DQO. Por outro lado, o aumento da taxa de carregamento hidráulico de 0,50 m3/dia m3 para 1,00 m3/dia m3 provocou diminuição de aproximadamente 10% na eficiência média de remoção de DQO no reator 1 e em torno de 12% no reator 2. A adição de 15,00 mg/L dos compostos organoclorados, não influenciou significativamente o desempenho do reator. A eficiência média de remoção de DQO na Fase II foi de 82% no reator de controle e de 79% no reator de tratamento. As eficiências médias de remoção dos compostos organoclorados foram de: 99,9% para o 2-clorofenol, 97,5% para o 2,4- diclorofenol, 95,8% para o 2,6-diclorofenol, 98,9% para o 2,4,6-triclorofenol e 92,8% para o tetraclorocatecol. / This research was conducted to assess the performance of two bench scale upflow anaerobic sludge blanket (UASB) reactors used for the treatment of diluted black liquor, over 635 days of continuous operation. During Phase I of the study both reactors were fed with the diluted black liquor enriched with essential nutrients. This substrate simulated the wastewater from unbleached cellulose pulp plant. Progressing in the research, during Phase II, one of the reactors was fed with the same substrate plus a mixture of five chlorinated organic compounds to simulate the wastewater from a bleached pulp plant. The increase in the organic loading rate, during Phase I, from 0.40 kg COD/m3.day to 0.70 kg COD/m3.day did not result in a decrease in the COD removal efficiency. On the other hand, the increase in the hydraulic loading rate from 0.50 m3/day.m3 to 1.00 m3/day.m3 resulted in a decrease of approximately 12 percent points in the average COD removal efficiency in the reactor 1 and approximately 12 percent points in the reactor 2. The addition of 15 mg/L of chlorinated organic compounds did not have a significant influence in the reactor performance in this research. The removal efficiency of COD during the second phase reached 82% in the control reactor and 79% in the treatment reactor. The average removal efficiencies for the chlorinated organic compounds were: 99.9% for 2-chlorophenol; 97.5% for the 2,4-dichlorophenol; 95.8% for the 2,6- dichlorophenol; 98.9% for the 2,4,6-trichlorophenol and 92.9% for the tetrachlorocatechol.