The industrial solvent trichloroethylene (TCE) and petroleum hydrocarbons (e.g., fuel oil) are among the most ubiquitous organic compounds found in subsurface contaminated environment. The developed treatment train system included the first stage of groundwater and surfactant flushing followed by the second stage of chemical oxidation such as potassium permanganate (KMnO4) and Fenton-like treatment. The third stage was the application of enhanced bioremediation for the further removal of residual contaminants after the first two treatment processes. The objectives of this study were to (1) assess the applicability of treatment train system for the remediation of organic compounds contaminated subsurface environment, (2) determine the optimal operational conditions of the three-stage treatment system, and (3) evaluate the effects of residual surfactant Simple GreenTM (SG) and hydrogen peroxide (H2O2) after chemical oxidation stage on the efficiency of bioremediation process. In this study, three different surfactants [SG, Triton X-100, and Tween 80] were evaluated in batch experiments for their feasibility on contaminants removal. Results from the surfactant biodegradation and microbial enumeration study indicate that SG was more biodegradable and was able to enhance the microbial activity of the intrinsic microorganisms. Thus, SG was applied in the following batch or column experiments of the treatment train system. Results from this study indicate that approximately 87.6% of TCE in the system (with initial concentration of 40 mg L-1) could be removed from the simulated dense non-aqueous-phase liquids (DNAPLs) system after groundwater flushing followed by biodegradable surfactant (1 g L-1 of SG) flushing, while the TCE concentrations dropped from 40 to 4.96 mg L-1 at the end of the flushing experiment. Moreover, approximately 10.7% of the remaining TCE could be removed from the system after the oxidation process using KMnO4 as the oxidant. Results from the oxidation process show that TCE was reduced from 4.96 to 0.69 mg L-1, and chloride concentation was increased from ND to 0.88 mg L-1 with the presence of 1 g L-1 of SG. The residual 1.7% of the TCE could be further remediated via the enhanced bioremediation stage, and the TCE concentrations dropped from 0.69 mg L-1 to below detection limit at the end of the bioremediation experiment. Results also indicate that the remaining KMnO4 had no significant inhibition on bacterial growth and TCE biodegradation. Thus, SG flushing and KMnO4 oxidation would not cause adverse effect on subsequent bioremediation process using intrinsic bacteria. Thus, complete TCE remediation was observed in this study using the three-stage treatment scheme. Results from the column experiment reveal that a complete TPH removal could be obtained after the application of three consecutive treatment processes. Results show that TPH concentration could be reduced from 50,000 mg kg-1 to below detection limit. This indicates that the treatment train system is a promising technology to remediate fuel-oil contaminated soils. Results from the column study indicate that approximate 80.3% of initial TPH in the soil could be removed after the SG [50 pore volumes (PVs)] followed by groundwater (30 PVs) flushing. The Fenton-like oxidation (with 6% of H2O2 addition) was able to remove another 15.0% of TPH. The observed first-order reaction rate constant of TPH oxidation was 2.74¡Ñ10-2 min-1, and the half-life was 25.3 min during the first 40 min of reaction. The residual 4.7% of the TPH could be further remediated via the aerobic bioremediation process. Thus, complete TPH removal was obtained in this study using the three-stage treatment scheme. The proposed treatment train system would be expected to provide a more efficient and cost-effective alternative to remediate chlorinated solvent and petroleum hydrocarbons contaminated sites.

O Parque Ecológico Tietê (PET), em Ermelino Matarazzo, a leste da região metropolitana de São Paulo, foi criado com o objetivo de preservar as várzeas do rio Tietê. Antes da criação do parque, a região foi palco de várias atividades antrópicas que levaram ao risco de contaminação do solo e águas subterrâneas. A recuperação iniciou-se com o plantio de espécies nativas, o que também promoveu a recolonização da fauna, composta essencialmente de espécies frugívoras. Dentre as espécies de plantas presentes no parque, a palmeira Jerivá (Syagrus romanzoffiana) é importante por sua ampla distribuição geográfica nos ecossistemas brasileiros. O presente estudo teve como objetivo compreender, através de coeficientes de prospecção biogeoquímicos, a interação entre os compartimentos solo, água subterrânea e planta, este último representado pela palmeira Jerivá. Os resultados indicaram que o Jerivá apresentou diferentes coeficientes de absorção entre suas folhas e pecíolos. O estudo também demonstrou que fatores como sazonalidade dentro de um período mínimo de um ano, idade e espécies de plantas devem ser levados em conta em abordagens biogeoquímicas. / The Tietê Ecological Park (PET) in Ermelino Matarazzo, east of the metropolitan area of São Paulo city, was created with the purpose of preserving the floodplains of the Tietê River. Prior to the establishment of the park, the region was scene of several anthropogenic activities which led to high risk of soil and groundwater contamination. Subsequent recovery of the degraded area was aimed through the planting of native plant species, which also promoted the recolonization of the area by the fauna, essentially composed of frugivorous species. Among the plant species introduced in the park, the Jerivá palm tree (Syagrus romanzoffiana) is important for its wide geographical distribution in Brazilian ecosystems. The current study aimed to understand, through biogeochemical prospecting coefficients, the interaction between soil compartments, underground water and plant, the latter represented by the Jerivá palm tree. The results indicated that Jerivá presented different absorption coefficients among its leaves and petioles. The study also demonstrated that factors like seasonality within a minimum period of one year, age and plant species must be taken into account in biogeochemical approaches.

台灣之石化產業欲著重於永續發展，就必須能落實企業社會責任，而環境議題(尤其是其中之土壤及地下水污染相關議題)是台灣石化產業在落實企業社會責任中最大的挑戰。 從石化產業之各利害關係人之角度(包括政府、社會、石化產業本身，供應鏈，資本市場等)分析，石化產業欲能在土壤及地下水污染領域落實企業社會責任，是需靠政府、社會、學術界及石化產業本身共同努力方能得之；政府及社會大眾可扮演監督、鼓勵及協助石化產業之角色；學術界可和石化產業共同研發相關技術或產品，共同創造經濟及分享經濟；石化產業本身亦可設置土壤及地下水污染專責人員或組織進行資訊揭露，並將企業社會責任內化及協助供應鏈做好土壤及地下水污染防治或整治工作。 目前台灣受土壤及地下水污染之場址有部分是石化產業相關之場址，若台灣之石化產業能在土壤及地下水污染領域落實企業社會責任，則對台灣的環境必定有正面的影響，而台灣石化產業之永續發展是指日可見的。

Submitted by Thelma Maria Ferreira (thelma_ferreira_geo@yahoo.com.br) on 2018-10-01T19:57:24Z No. of bitstreams: 1 DISSERTACAO_FERREIRA_TM.pdf: 2450841 bytes, checksum: 902acacd4fc1ad31e938c5742559f62e (MD5) / Rejected by Adriana Aparecida Puerta null (dripuerta@rc.unesp.br), reason: Prezada Thelma, O documento enviado para a coleção Campus Unesp Rio Claro foi recusado pelo(s) seguinte(s) motivo(s): - Agradecimentos: A Portaria nº 206, de 04/09/2018 Dispõe sobre obrigatoriedade de citação da CAPES nos agradecimentos da seguinte forma: "Art. 3º Deverão ser usadas as seguintes expressões, no idioma do trabalho: "O presente trabalho foi realizado com apoio da Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Código de Financiamento 001" Agradecemos a compreensão e aguardamos o envio do novo arquivo. Atenciosamente, Biblioteca Campus Rio Claro Repositório Institucional UNESP https://repositorio.unesp.br on 2018-10-02T11:42:08Z (GMT) / Submitted by Thelma Maria Ferreira (thelma_ferreira_geo@yahoo.com.br) on 2018-10-02T14:42:39Z No. of bitstreams: 2 DISSERTACAO_FERREIRA_TM.pdf: 2453303 bytes, checksum: 1fb9668aac7a92d7731e47a007d17c32 (MD5) DISSERTACAO_FERREIRA_TM.pdf: 2453303 bytes, checksum: 1fb9668aac7a92d7731e47a007d17c32 (MD5) / Approved for entry into archive by Adriana Aparecida Puerta null (dripuerta@rc.unesp.br) on 2018-10-02T18:53:41Z (GMT) No. of bitstreams: 1 ferreira_tm_me_rcla.pdf: 2453303 bytes, checksum: 1fb9668aac7a92d7731e47a007d17c32 (MD5) / Made available in DSpace on 2018-10-02T18:53:41Z (GMT). No. of bitstreams: 1 ferreira_tm_me_rcla.pdf: 2453303 bytes, checksum: 1fb9668aac7a92d7731e47a007d17c32 (MD5) Previous issue date: 2018-09-04 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / No processo industrial da produção sucroalcooleira um dos efluentes gerados é a vinhaça, que se destaca pelo grande volume com que é produzida e pelo alto potencial fertilizante, característica que possibilita seu aproveitamento em atividades agrícolas, no entanto, a vinhaça também possui alto poder poluente. Neste contexto, o uso da vinhaça na fertilização de cana-de-açúcar, embora seja uma prática aceita, deve ser realizado de forma controlada, sendo regulamentado no Estado de São Paulo pela Companhia Ambiental do Estado de São Paulo – CETESB através da Norma Técnica P4.231. Devido a composição da vinhaça ser muito variável não há como estabelecer doses fixas, assim, atualmente as dosagens de aplicação no solo são calculadas em função das necessidades da planta em relação ao potássio, sendo consideradas a capacidade de troca catiônica do solo e as concentrações de potássio no solo e na vinhaça. Todavia, além da oscilação composicional da vinhaça, seus efeitos sobre cada tipo de solo também são muito diversos, podendo modificar parâmetros hidráulicos do solo e, consequentemente, alterar a velocidade de percolação da água e dos contaminantes presentes na solução. Diante desta problemática, para avaliar o uso da dosagem calculada pela Norma P4.231 da CETESB, foram realizados ensaios laboratoriais de percolação a carga constante, em colunas com amostras de solo arenoso da Formação Rio Claro previamente infiltradas com as doses de 0 (testemunho), 55 (equivalente a dose máxima permitida pela CETESB), 80, 400 e 800 m3/ha. A aplicação destas doses permitiu a avaliação de seus efeitos nos parâmetros hidráulicos do solo estudado e a possível geração de diferentes graus de contaminação nos efluentes percolados, implicando um potencial risco para a água subterrânea e superficial. Os resultados obtidos indicam que com a aplicação das doses de 55 e 80 m3/ha houve um aumento na capacidade de retenção do solo, fator este positivo tanto para o aspecto fertilidade do solo quanto ao ambiental. Entretanto, com a aplicação de doses elevadas como as de 400 e 800 m3/ha observa-se uma queda progressiva na capacidade de retenção do solo, que implica em perdas por lixiviação e consequente aumento nas concentrações de sólidos totais dissolvidos, cloreto, fluoreto, acetato, carbono orgânico total, alumínio, ferro, manganês e zinco, que em algumas amostras apresentaram concentrações superiores aos valores de referência ambiental e de potabilidade adotados podendo, portanto, gerar riscos à qualidade do solo e da água subterrânea tornando-a imprópria para consumo humano. Quanto à condutividade hidráulica saturada, os valores obtidos para a coluna com 55 m3/ha foram muito similares aos obtidos na coluna sem aplicação de vinhaça, indicando que para o solo estudado esta dosagem não trouxe nenhuma alteração significativa, porém, com o aumento das dosagens houve redução gradual destes valores. Com base nos resultados obtidos para a configuração dos testes laboratoriais realizados, pode-se afirmar que, a aplicação de vinhaça na dose máxima estabelecida pela norma P4.231 CETESB (2015) não apresentou riscos à qualidade do solo estudado e da água subterrânea. / In the industrial production process of sugar and a lcohol, one of the effluents generated is vinasse, which stands out for the larg e volume produced and for the high fertilizing potential, allowing its use in agr icultural activities, however, the vinasse also has high pollution power. In this context, the use of vinasse in the fertilization of sugarcane, although it is an accepted practice, mus t be carried out in a controlled manner, being regulated in the State of São Paulo b y the Companhia Ambiental do Estado de São Paulo (CETESB) through Technical Stan dard P4. 231. Due to the composition of the vinasse being very variable, it is not possible to establish fixed doses, so, currently the dosages of application in the soil are calculated according to the needs of the plant in relation to potassium ion , considering the cation exchange capacity of the soil and the concentrations of pota ssium in soil and vinasse. In addition to the compositional oscillation of vinasse, its effects on each type of soil is also very diverse, being able to modify hydraulic p arameters of the soil and, consequently, to change the rate of percolation of the water and the contaminants present in the solution. In order to evaluate the u se of the dosage calculated by CETESB Standard P4.231, constant load percolation t ests were carried out in columns with samples of a sandy soil from the Rio C laro Formation previously infiltrated with the doses of 0 (control), 55 (equi valent to the maximum dose allowed by CETESB), 80, 400 and 800 m 3 /ha. The application of these doses allowed the evaluation of its effects on the hydraulic paramete rs of the studied soil and the possible generation of different degrees of contami nation in the percolated effluents implying a potential risk for groundwater and surfa ce water. The results indicated that for the doses of 55 and 80 m 3 /ha there was an increase in the retention capacity of soil, which is positive about the aspect of soil fe rtility as well as the environmental aspect. However the application of high doses such as 400 and 800 m 3 /ha, there is a progressive decrease in the soil retention capacity , which implies losses due to leaching and consequent increase in the concentrati ons of total dissolved solids, chloride, fluoride, acetate, total organic carbon, aluminum, iron, manganese and zinc, which in some samples presented concentrations high er than the values of potability and environmental reference adopted, what could gen erate risks to soil and groundwater quality. Regarding the saturated hydraulic conductivity, the values obtained for the column with 55 m 3 /ha dosage were very similar to those obtained in the control column, indicating that this dosage did not bring any significant change, but with the increase of the dosages there was grad ual reduction in those values. Based on the results obtained for the configuration of the laboratory tests carried out, it can be stated that the application of vinasse at the maximum dose established by standard P4.231 CETESB (2015) did not present risks to the quality of the studied soil and groundwater. / CAPES: 33004137036P9.

O Parque Ecológico Tietê (PET), em Ermelino Matarazzo, a leste da região metropolitana de São Paulo, foi criado com o objetivo de preservar as várzeas do rio Tietê. Antes da criação do parque, a região foi palco de várias atividades antrópicas que levaram ao risco de contaminação do solo e águas subterrâneas. A recuperação iniciou-se com o plantio de espécies nativas, o que também promoveu a recolonização da fauna, composta essencialmente de espécies frugívoras. Dentre as espécies de plantas presentes no parque, a palmeira Jerivá (Syagrus romanzoffiana) é importante por sua ampla distribuição geográfica nos ecossistemas brasileiros. O presente estudo teve como objetivo compreender, através de coeficientes de prospecção biogeoquímicos, a interação entre os compartimentos solo, água subterrânea e planta, este último representado pela palmeira Jerivá. Os resultados indicaram que o Jerivá apresentou diferentes coeficientes de absorção entre suas folhas e pecíolos. O estudo também demonstrou que fatores como sazonalidade dentro de um período mínimo de um ano, idade e espécies de plantas devem ser levados em conta em abordagens biogeoquímicas. / The Tietê Ecological Park (PET) in Ermelino Matarazzo, east of the metropolitan area of São Paulo city, was created with the purpose of preserving the floodplains of the Tietê River. Prior to the establishment of the park, the region was scene of several anthropogenic activities which led to high risk of soil and groundwater contamination. Subsequent recovery of the degraded area was aimed through the planting of native plant species, which also promoted the recolonization of the area by the fauna, essentially composed of frugivorous species. Among the plant species introduced in the park, the Jerivá palm tree (Syagrus romanzoffiana) is important for its wide geographical distribution in Brazilian ecosystems. The current study aimed to understand, through biogeochemical prospecting coefficients, the interaction between soil compartments, underground water and plant, the latter represented by the Jerivá palm tree. The results indicated that Jerivá presented different absorption coefficients among its leaves and petioles. The study also demonstrated that factors like seasonality within a minimum period of one year, age and plant species must be taken into account in biogeochemical approaches.