O óleo diesel é um dos derivados do petróleo mais consumidos no Brasil e responsável com grande número de áreas contaminadas. Enquanto há técnicas consagradas para a remoção do óleo diesel nas fases livre, vapor e dissolvida, as soluções para a remoção da fase residual ainda carecem de maior eficiência e/ou menor custo. Este trabalho mostra os resultados de uma investigação laboratorial da remoção de HPA de amostras indeformadas de um solo contaminado com óleo diesel por meio de ensaios de lavagem com soluções do surfactante Lauril Sulfato de Sódio (LSS) nas concentrações de 0,6, 1,5 e 3 CMC (concentração micelar crítica), seguido de um ensaio de respirometria para avaliar a capacidade de biodegradação aeróbia. Um equipamento foi desenvolvido especialmente para a realização dos ensaios de coluna utilizando os próprios anéis de amostragem. Os resultados mostraram que apenas na concentração de 3 CMC foi possível remover HPA em concentrações acima do limite de detecção da técnica analítica, e que essa remoção foi inferior a 7,6 % da massa residual no solo. Os resultados de respirometria mostraram que o solo sem a adição de surfactante degradou em média 1% do contaminante inicial, por semana. A influência da lavagem na biodegradação não demonstrou um comportamento regular e durou aproximadamente duas semanas. A biodegradação posterior ao período de influência do surfactante apresentou alta correlação linear com a concentração inicial de contaminante. / Diesel fuel is one of the most petroleum derivates consumed in Brazil and responsible with large numbers of contaminated areas. While there are consecrated techniques for the removal of diesel oil-free phases, vapor and dissolved, the solutions to remove the residual phase still need greater efficiency and/or lower cost. This work shows the results of a laboratory investigation of the removal of PAH undisturbed samples of soil contaminated with diesel oil by soil flushing tests with solutions of surfactant Sodium Lauryl Sulfate (SLS) at concentrations of 0,6, 1,5 and 3 CMC (critical micelle concentration), followed by a respirometric test to assess the ability of aerobic biodegradation. A device was developed specifically for the test column using their own sampling rings. The results showed that only the solution with 3 CMC concentration was able to remove PAH concentrations above the detection limit of the analytical technique, and that this removal was less than 7.6% of residual mass in the soil. The results showed in the soil respirometry without the addition of surfactant biodegraded on average 1% per week of the initial contaminant. The influence of flushing on the biodegradation has not established a regular pattern and lasted about two weeks. The biodegradation after the period of influence of the surfactant was highly correlated linearly with the initial concentration of contaminant.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A exploração, processamento, transporte, armazenamento e utilização do petróleo e seus derivados têm resultado em acidentes e vazamentos de proporções variadas e existe uma demanda crescente por soluções técnica, ambiental e economicamente viáveis. É nesse contexto que a fitorremediação ganha evidência e se mostra adequada por aliar um custo-benefício atraente. A fitorremediação utiliza espécies vegetais para extrair, conter, imobilizar ou degradar contaminantes do solo e da água. Além disso, a possibilidade de crescer espécies de valor comercial em solos contaminados que, de outra forma, não teriam qualquer uso, torna-se uma alternativa atraente. O presente trabalho tem por objetivo avaliar a capacidade de fitorremediação de Mentha x Villosa e as alterações fisiológicas e morfológicas em decorrência da contaminação dos solos por petróleo em quatro concentrações (0%, 2%, 4% e 6% p/p) com seis repetições. As variáveis analisadas foram: taxa de sobrevivência, biomassa total seca e fresca, dimensão foliar, densidade de estômatos e densidade de tricomas. Foram feitas análises de hidrcarbonetos totais de petróleo - HTPs presntes no solo no início do experimento e após 90 dias de cultivo. As plantas crescidas em solo contaminado tiveram uma taxa de sobrevivência de 100%. Houve uma tendência ao xeromorfismo nas plantas mantidas em solo contaminado. De acordo com a análise one-way ANOVA (Tukey, I.C. 95%), houve redução significativa da biomassa fresca em plantas crescidas na presença de petróleo em qualquer concentração quando compradas ao controle e, também, redução significativa entre as concentrações 2% versus 4% e 2% versus 6%. Entretanto plantas crescidas em 4% e em 6% não diferiam entre si. Como não houve diferença significativa da biomassa seca para nenhum par, conclui-se que as diferenças observadas em biomassa fresca decorrem da menor absorção e/ou retenção de água por plantas crescidas na presença de petróleo. A presença do petróleo em qualquer concentração resultou em aumento significativo da densidade dos estômatos quando comparada ao controle (0%), particularmente aos 90 dias. Entretanto, não houve diferença significativa entre as plantas crescidas em petróleo nas diferentes concentrações. Aos 30 dias observou-se aumento significativo da densidade dos tricomas apenas em plantas na concentração 6%, comparadas ao controle (0%) e às demais concentrações (2% e 4%). Aos 60 dias, um aumento significativo da densidade de tricomas foi observado em plantas crescidas em todas as concentrações de petróleo (2%, 4% e 6%), quando comparadas ao controle e aos 90 dias, tais diferenças foram mantidas. Mentha x Villosa mostrou ser uma planta com potencial para crescer em solo contaminado com petróleo, sendo que aos 90 dias foi observada uma remoção de 99,90% de HTPs no solo contaminado a 2% (p/p) e de 99,98% de remoção de HTPs no solo contaminado a 4% (p/p).

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2016-07-26T14:29:37Z No. of bitstreams: 1 2011 - Erica Souto Abreu Lima.pdf: 2820587 bytes, checksum: d25ffc37d1a7468d5bf9a15ae5e020b7 (MD5) / Made available in DSpace on 2016-07-26T14:29:37Z (GMT). No. of bitstreams: 1 2011 - Erica Souto Abreu Lima.pdf: 2820587 bytes, checksum: d25ffc37d1a7468d5bf9a15ae5e020b7 (MD5) Previous issue date: 2011-02-24 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior-CAPES / LIMA, Erica Souto Abreu. Dynamic of barium in soils treated with barite. 2011. 44p. Dissertation (Master Science in Agronomy, Soil Science) Instituto de Agronomia, Departamento de Solos, Universidade Federal Rural do Rio de Janeiro, Serop?dica, RJ, 2011. Barite is the natural mineral form of barium sulfate (BaSO4), which is used in drilling fluids for oil wells exploration. Although barium sulfate is poorly soluble, and therefore, not very bioavailable to plants and with low mobility, it is not know the magnitude of changes in its dynamics under reducing soil conditions. Thus, the main objective of the study was to evaluate if under extreme reduction conditions the solubilization and release of barium in the soil would occur, increasing risk of contamination to plants and groundwater. Two experiments were conducted in parallel, one in leaching columns and the other in pots, where rice was cultivated as a test plant. In both trials soil samples from an Udox soil were used. The installation of experiments followed a completely randomized design in factorial scheme (4 x 2) with four replications, i.e., composed of control and three levels of barium (100, 300, and 3000 mg kg-1), two moisture levels (at 70% of field capacity and saturated with the maintenance of a 5 cm layer of water), totaling 32 experimental units. The redox potential (Eh), and pH values to reach the Eh of -200 mV were monitored. After reaching these values a rainfall of 200 mm day-1 was simulated in the columns, and volumes of 200 mL were collected. The extract was divided into volumes of 200 mL, corresponding to 1/8 of the soil pore volume, and they were analyzed for levels of barium and other toxic metals. The rice (Oryza sativa L.) plants in the vases remained throughout the vegetative cycle up to about 4 months, when they were harvested and analyzed. The geochemical fractionation was also performed for the elements barium, manganese and iron, by the BCR method. The results showed that the addition of doses of barite in soil, and the condition of extreme reduction led to the increase of barium, iron and manganese in the highest labile fractions. Thereby promoting higher levels of barium in the leachate extract. Under these conditions, the plants showed growth and development reduction. However, the barium may not be the main cause of this reduction, which may be linked to iron toxicity and lower absorption of zinc, phosphorus and calcium. / A baritina ? a forma mineral natural de sulfato de b?rio (BaSO4), que ? amplamente utilizada nos flu?dos de po?os de prospec??o de petr?leo. Apesar do sulfato de b?rio ser pouco sol?vel, e consequentemente, pouco biodispon?vel para as plantas e de baixa mobilidade, n?o se conhece a magnitude das altera??es na sua din?mica em condi??es redutoras do solo. Diante disso, o objetivo principal do estudo foi avaliar se em condi??es de extrema redu??o ocorre o aumento da solubiliza??o e como conseq??ncia libera??o do b?rio no solo, potencializando o risco de contamina??o para as plantas e ?guas subterr?neas. Foram realizados dois experimentos em paralelo, sendo um em colunas de lixivia??o e o outro em vasos, onde foi cultivado arroz como planta teste. Em ambos os ensaios foram utilizadas amostras de terra coletadas de Latossolo Vermelho Amarelo. A instala??o dos experimentos seguiu o delineamento experimental inteiramente casualizado, em esquema fatorial (4 x 2) com 4 repeti??es, ou seja, composto por testemunha e tr?s doses de b?rio (100, 300 e 3000 mg kg-1), dois teores de umidade (70% CC e saturado com presen?a de l?mina de 5 cm), totalizando 32 unidades experimentais. Foram monitorados o potencial redox (Eh) e o pH, at? atingirem valores de Eh de -200 mV. Ap?s atingirem esses valores foi simulada uma precipita??o pluviom?trica de 200 mm dia-1 nas colunas, onde foram coletados volumes de 200 mL. O extrato foi dividido em volumes de 200 mL, que correspondem a 1/8 do volume de poro da coluna de solo, para em seguida serem analisados quanto aos teores de b?rio e outros metais considerados t?xicos. As plantas de arroz (Oryza sativa L.) foram cultivadas nos potes por todo o ciclo vegetativo (aproximadamente 4 meses) at? serem colhidas e analisadas. Tamb?m foi realizado o fracionamento geoqu?mico para os elementos b?rio, mangan?s e ferro pelo m?todo BCR. Os resultados obtidos evidenciaram que a adi??o das doses de baritina no solo e a condi??o de extrema redu??o, propiciaram o aumento de b?rio, ferro e mangan?s nas fra??es de maior labilidade. Promovendo, assim, maiores teores de b?rio no extrato lixiviado. Nessas condi??es, as plantas apresentaram redu??o no seu crescimento e desenvolvimento. Por?m o b?rio pode n?o ser o principal causador dessa redu??o, podendo esta estar ligada a toxicidade do ferro e a uma menor absor??o de zinco, f?sforo e c?lcio.

Estudos recentes constataram a existência de processos que permitem a atenuação natural dos contaminantes presentes nos lixiviados. O adequado entendimento destes processos pode originar benefícios possíveis de serem aplicados em aterros antigos, novos ou naqueles que ainda serão concebidos. O presente estudo avaliou o comportamento e a atenuação de contaminantes dos líxiviados no solo, por meio de experimento desenvolvido em colunas de percolação e, para a avaliação da atenuação este teste é indicado por refletir as condições naturais e as características adsortivas do solo, propiciando uma melhor simulação da atenuação. O lixiviado e o solo utilizados neste experimento são provenientes do aterro sanitário de São Carlos - SP. O solo utilizado foi caracterizado quanto à composição física, química, biológica e mineralógica para verificar o transporte do percolado nas colunas e a interação solo-contaminante. Na área do aterro foram feitas perfurações, ensaios de condutividade hidráulica e avaliação da geologia local, para conhecimento das características físicas, químicas, biológicas, mineralógicas e geológicas do solo in situ. Este foi classificado como arenoso, apresentando características físicas e químicas que não se enquadram nos parâmetros adequados para sua utilização em áreas de disposição de resíduos sólidos urbanos, pois, a capacidade de troca de cátions, superfície específica, potencial hidrogeniônico e classe textural arenosa, evidenciam que este solo possui deficiente capacidade de retenção e imobilização de contaminantes. Além disso, pela observação in situ, constata-se que a área de disposição de resíduos sólidos de São Carlos esta situado sobre rochas da Formação Botucatu, sendo que a mineralogia do solo presente no local é composta de quartzo, caulinita, goethita, hematita, gibsita e ilita. O ensaio de condutividade hidráulica indicou que o solo presente na base do Aterro sanitário não atende a valor de permeabilidade exigida por norma, o que poderá permitir a infiltração de água da chuva, aumentando a produção do lixiviado e sua movimentação no perfil, podendo atingir as águas subterrâneas. Assim, foram traçadas curvas características do transporte de contaminantes nas amostras efluentes monitoradas durante o processo de percolação, coletadas a cada 0,25 volume de poros até atingir 10,0 volume de poros percolados. As curvas características do transporte de contaminantes traçadas apresentaram baixas concentrações de Chumbo, Cádmio, Ferro, Zinco, Manganês, Cálcio, Magnésio, Cobre, Cromo nas amostras fluentes. Já o Sódio, Potássio, Cloro, Níquel e Alumínio foram preferencialmente percolados com o lixiviado, evidenciando a variação da faixa de concentração de cada elemento no percolado. Os perfis de concentração dos metais pesados mostraram que existe uma frente de contaminação. As curvas de retenção de metais no solo mostraram que a preferência de sorção apresentada pelos solos nas colunas foi : Cobre > Cádmio > Cálcio > Zinco > Magnésio > Potássio > Manganês > Fósforo > Ferro > Níquel > Alumínio. Cujos valores retidos no solo das colunas podem estar evidenciando a capacidade deste solo em reter contaminantes.O solo em questão apresentou baixo potencial para retenção dos contaminantes presentes no lixiviado, classificado como arenoso e, com características químicas que não se enquadram nos parâmetros adequados para sua utilização em áreas de disposição de resíduos sólidos urbanos. / Recent studies had found the existence of processes that allow a natural attenuation of the leachates\'s cotaminants. An adequate understanding of these processes may originate benefits, that may be applied in ancient, new or to be created landfills. This work evaluated the contaminant\'s behavior and attenuation, contaminants existing in soil\'s leaching, throughout an experiment developed in percolation columns. This is the indicated examination for evaluate the attenuation, because it reflects soil\'s natural conditions and adsorptive characteristics, providing a better simulation of it\'s attenuation. The leachate and the soil used in this experiment came from Sao Carlos-SP landfill. The used soil has been characterized as its mineralogical\'s and physical chemical-biological\'s composition, looking for the percolated\'s transportation inside the columns, and for the interaction soil-contaminant. The landfill\'s area has been several times drilled, tested as it\'s hydraulic conductivity and assessment of local geology, in order to know the physical, chemical, biological, mineralogical and geological in situ soil\'s characteristics. This, has been classified as sandy, and, by presenting chemical characteristics that does not reach the adequated value for utilization on solid urban wastes, due to the values of CTC, SE, pH, and the textural sandy class, what shows a deficient buffering capacity in retaining and immobilisating contaminants. By observation in situ, has been found that Sao Carlos\'s solids disposal waste is located over rocks from the Botucatu formation, and the mineralogy of it is composed of quartz, caulinith, goethith, hematith, gibsith an ilith. The hydraulic conductivity test has indicated that the soil in the base of the sanitary landfill does not reaches the permeability values required by the standards, what may allow rain water\'s infiltration, and raises the amount of leachate and it\'s movement onto the ground, and even the leachete to reach the underground waters. So, has been drawn the characteristics curves of the contaminant\'s transportation in the effluents samples found during the percolation process, collected by every 0,25 VP until it reaches 10,0 VP percolated. The characteristical curves of the contaminant\'s transportation drawn showed low concentrations in the effluent samples of Lead, Cadmium, Iron, Zinc, Manganese, Calcium, Magnesium, Cooper, Chromium. Also, Sodium, Potassium, Chlorine, Nickel and Aluminium had been preferencially percolated within the leachate, what evidentiates the variation in the range of concentrations of every percolated element. The concentration profiles from heavy metal\'s had shown that there is a front of contamination. The retention curves from the soil\'s retaining metal showed that the preferency for the sorption was: Cooper > Cadmium > Calcium > Zinc > Magnesium > Potassium > Manganese > Phosphorus > Iron > Nickel > Aluminium, whose values may point the soil\'s ability in retaining contaminants. The studied soil has presented low potential in retain contaminants from the leachete, and is characterized as sandy, and it\'s chemical features shall not be framed according the standards parameters to be utilized in solid urban waste\'s disposal.

The genotoxicity of energetic compounds (i.e., explosives) that are known to be present in contaminated soils at military training sites has not been extensively investigated. Thus, the Salmonella mutagenicity and Muta(TM)Mouse assays were employed as in vitro assays to examine the mutagenic activity of twelve explosive compounds, as well as three soil samples from Canadian Forces Base Petawawa. Salmonella analyses employed strains TA98 (frameshift mutations) and TA100 (base-pair substitution mutations), as well as the metabolically-enhanced YG1041 (TA98 background) and YG1042 (TA100 background), with and without exogenous metabolic activation (S9). For Salmonella analyses, the results indicate that ten of the explosive compounds were mutagenic, and consistently elicited direct-acting, base-pair substitution activity. All three soil samples were also observed to be mutagenic, eliciting direct-acting, frameshift activity. Mutagenic potencies were significantly higher on the metabolically-enhanced strains for all compounds and soil samples. For Muta(TM)Mouse analyses on FE1 cells, the results indicate that the majority of explosive compounds did not exhibit mutagenic activity. All three soil samples elicited significant positive responses (PET 1 and PET 3 without S9, and PET 2 with S9), and although there is some evidence of a concentration-related trend, the responses were weak. Correspondence of the mutagenic activity observed with the two assay systems, for both the explosive compounds and soil samples, was negligible. The differential response is likely due to differences in metabolic capacity between the two assay systems. Furthermore, it is likely that there are unidentified compounds present in these soil samples that are, at least in part, responsible for the observed mutagenic activity. Additional testing of other explosive compounds, as well as soil samples from other military training sites, using a variety of in vitro and in vivo assays, is warranted in order to reliably estimate mutagenic hazard and subsequently assess risk to human health.

The genotoxicity of energetic compounds (i.e., explosives) that are known to be present in contaminated soils at military training sites has not been extensively investigated. Thus, the Salmonella mutagenicity and Muta(TM)Mouse assays were employed as in vitro assays to examine the mutagenic activity of twelve explosive compounds, as well as three soil samples from Canadian Forces Base Petawawa. Salmonella analyses employed strains TA98 (frameshift mutations) and TA100 (base-pair substitution mutations), as well as the metabolically-enhanced YG1041 (TA98 background) and YG1042 (TA100 background), with and without exogenous metabolic activation (S9). For Salmonella analyses, the results indicate that ten of the explosive compounds were mutagenic, and consistently elicited direct-acting, base-pair substitution activity. All three soil samples were also observed to be mutagenic, eliciting direct-acting, frameshift activity. Mutagenic potencies were significantly higher on the metabolically-enhanced strains for all compounds and soil samples. For Muta(TM)Mouse analyses on FE1 cells, the results indicate that the majority of explosive compounds did not exhibit mutagenic activity. All three soil samples elicited significant positive responses (PET 1 and PET 3 without S9, and PET 2 with S9), and although there is some evidence of a concentration-related trend, the responses were weak. Correspondence of the mutagenic activity observed with the two assay systems, for both the explosive compounds and soil samples, was negligible. The differential response is likely due to differences in metabolic capacity between the two assay systems. Furthermore, it is likely that there are unidentified compounds present in these soil samples that are, at least in part, responsible for the observed mutagenic activity. Additional testing of other explosive compounds, as well as soil samples from other military training sites, using a variety of in vitro and in vivo assays, is warranted in order to reliably estimate mutagenic hazard and subsequently assess risk to human health.

Soil quality standards (SQSs) are one of the most important elements of management system for contaminated sites. In order to manage risks associated with soil contamination, risk based SQSs are used worldwide. However, in Turkey, the Soil Pollution Control Regulation in force was focusing mainly on the use of stabilized sludge on soil and was including standards for a limited number of parameters, mainly metals and some organic chemicals. Thus, existing SQSs were far away from providing common criteria for assessment of the soil quality. In this study, the aim was to develop human health risk based SQSs for Turkey. For derivation of risk based SQSs, the conceptual framework and technical infrastructure were established. SQSs were derived for 151 chemical substances and for three different land use types by incorporating generic site characteristics for Turkey. Since SQSs are highly sensitive to site conditions and chemical-specific data used in calculations, a Microsoft Excel based exposure model was developed as a technical tool. This tool serves for calculation of generic and site-specific SQSs and maintenance of the currency of the standards by allowing periodic update of data used in calculations. Besides, a hydrogeologic database was developed to provide information on the general soil and hydrogeologic characteristics that are used in derivation of SQSs. This database is ultimately, expected to serve for development of conceptual site models, sampling strategies, and derivation of dilution factors during risk assessment studies. As a result, this study presents a general perspective and approach for derivation of human health risk based SQSs. It is believed that the developed conceptual and technical infrastructure will contribute to contaminated site management and risk assessment studies conducted by the regulatory authorities and the other stakeholders in Turkey.

This research reports on an experimental and theoretical study of soil heating/air stripping and steam injection/vacuum extraction for remediation of MTBE and Diesel Contaminated Soils. Two one-dimensional mass transfer models were using to simulate the process of remediaction. Contaminant kinds(MTBE and Diesel)¡A contaminant concentration (152~13,912 mg/kg soil)¡Asoil temperature(38~120¢J)¡Asteam injection pressure(0.5~1.0 atm)¡A and the mass of steam used(0.379~0.730 kg/h)were employed as the experimental factors in this study. In soil heating/air stripping study, rising soil temperature will enhance the MTBE removed efficiency¡A it was shown in the concentration of effluent gas. Further, the flow rate at outlet of column was higher than that at inlet of column, it revealed MTBE transfers from liquid phase to gas phase and was removed by gas flow. The concentration of effluent gas curve in low initial MTBE concentration test was similar with high concentration test, but the mechanisms was quiet different¡Ait need advanced adsorption test to find the reasons. In medium initial MTBE concentration test¡Athe concentration of effluent gas curve showed linear shape. When using steam injection/vacuum extraction treating MTBE contaminated soil, it showed 90¢Mefficiency can be reached in one hour. In steam injection/vacuum extraction study, it showed higher initial diesel contaminant concentration¡Ahigher initial concentration of effluent gas. Further, in high initial diesel concentration test (13.912 g diesel/kg soil test and about 5g/ kg soil tests)¡Athe concentration of effluent gas curves had a dominant drop at early time in remediation, it revealed the injection steam flow was quiet large, so diesel didn¡¦t has enough time to transfer to gas phase, that the gas couldn¡¦t been saturation at outlet of column. But in low initial diesel concentration test (about 1 g diesel/kg soil tests), the concentration of effluent gas curves showed the typical NAPL remediation curve. The different with in high and low initial concentrations might from the complex composition of diesel. Because at the early time in remediaction of high initial diesel concentration, the low carbon numbers diesel could abundantly evaporate, it caused the high concentration of effluent gas. With the remediation time go by, the low carbon numbers diesel exhaust. So the main composition of effluent gas transfer to high carbon numbers diesel, that the concentration of effluent gas curve showed the slowly decline. For high initial diesel concentration test (13.912 g diesel/kg soil)¡A the efficiency was the highest (73.7¢M). For low initial diesel concentration test (about 1 g diesel/kg soil), the efficiency was the lost (about 20¢M). Further, the remediation of diesel contaminated soil exited a rapid removed period. Under the conditions of this study, the rapid removed period could remove more than 95¢Mcontaminant of diesel removed at hold remediation time. The experiment results also showed that larger the mass of steam injection, shorter the rapid removed period, and larger the steam injection pressure, longer the rapid removed period. When using soil heating/air stripping treating diesel contaminated soil, the removed efficiency was worse 10-20¢Mthan the same initial diesel contaminated concentration. In simulating remediation process, the prediction with the MTBE measured concentration yielded good agreement in NAPL model. But to get the better fit of diesel in NAPL model, it might set the ¡§could removed mass¡¨ to initial condition of model. In non-NAPL model, MTBE also showed good agreement with model, and the model enabled the prediction of the initial contaminant level in the soil.

The purpose of this study was to evaluate the treatment efficiency of phenol contaminated soils by electrokinetic (EK) process conducted in sand boxes (60 cm¡Ñ30 cm¡Ñ30 cm; L¡ÑW¡ÑH). The electric field strength, electrode polarity reverse, and Fenton reagent were employed as the experimental factors in this study to assess the variations of soil characteristics, potential difference, and residual phenol concentration distribution during a treatment period of 20 days and after the treatment. It was found that the anode reservoir pH decreased to around 2 and the cathode reservoir pH increased to approximately 12 after 2~3 days of treatment in the no electrode polarity reverse system. However, the variation of pH in the anode and cathode reservoirs was less obvious in the case with electrode polarity reverse. No matter a constant potential system or a constant current system was employed, a general trend of a lower pH at the anode reservoir and a higher pH at the cathode reservoir would be found. The acid front generated at the anode reservoir flushed across the soil specimen toward the cathode and the base front advanced toward the anode. However, in the central region of sand box, unsaturated and saturated soil specimen maintain neutral. For EK or EK-Fenton experiments, under the constant potential conditions, the potential difference relative to the cathode versus the distance from anode was found to have a linear relationship at the beginning of the electrical potential application. As the treatment time elapsed, the potential gradient became non-linear. Nevertheless, there was no remarked potential gradient change in the case with electrode polarity reverse. Although capillarity has resulted in an increase of the moisture content of unsaturated soil (from 25.34% to 30% after 20 days), electroosmotic (EO) flow was not obvious in the unsaturated zone. For the experiments with electrode polarity reverse, they had a much greater EO flow quantity, the electroosmotic permeability coefficients for constant potential and constant current systems were 6.42¡Ñ10-6 cm2/V¡Es and 9.47¡Ñ10-6 cm2/V¡Es, respectively. It was also found that the existence of contaminants did reduce the EO flow quantity. Regardless of the employment of a constant potential or constant current system, the maximum destruction and removal efficiency (DRE) of phenol was obtained for EK-Fenton process. The maximum DRE values of phenol for both constant potential and constant current systems were found to be 78.06% and 80.11%, respectively. However, the DRE of phenol was found to be much lower for the system with electrode polarity reverse. It was postulated that the destruction efficiency of phenol was less obvious than the removal efficiency in the electrode polarity reverse system. In addition, a frequent reverse of electrode polarity also resulted in a frequent change of EO flow direction. Thus, a flow hysteresis of phenol in the soil compartment was found.

Το πρόβλημα της ρύπανσης του εδάφους και του υδροφόρου ορίζοντα έχει πάρει ανησυχητικές διαστάσεις τις τελευταίες δεκαετίες. Η βιομηχανική ανάπτυξη πέρα απο τις θετικές συνέπειες που έχει για την ζωή των ανθρώπων, έχει δυστυχώς επιφέρει προβλήματα ρύπανσης του υπεδάφους και του υδροφόρου ορίζοντα με επικίνδυνες οργανικές ενώσεις. Η αλόγιστη και ανεύθυνη διαχείριση και διάθεση των αποβλήτων έχει αρνητικές και συχνά μη αντιστρεπτές συνέπειες για το οικοσύστημα και την δημόσια υγεία. Ανάμεσα στις μεθόδους για την αντιμετώπιση του προβλήματος της ρύπανσης του εδάφους και των υπογείων υδάτων, οι βιολογικές μέθοδοι κερδίζουν ολοένα έδαφος λόγω του χαμηλού κόστους, της αποτελεσματικότητας και του ελάχιστου αριθμού παραπροϊόντων. Οι βιολογικές μέθοδοι αποσκοπούν στην αποκατάσταση των εδαφών με την χρήση γηγενών μικροοργανισμών του εδάφους. Η κινητική ανάπτυξης των μικροοργανισμών στο έδαφος διαφέρει σημαντικά από την κινητική ανάπτυξης όταν οι μικροοργανισμοί αιωρούνται σε καλά αναδευόμενα περιβάλλοντα. Η συγκεκριμένη εργασία έχει σαν στόχο να μελετηθεί η κινητική ανάπτυξης ενός γηγενούς βακτηριακού πληθυσμού, του Pseudomonas fluorescens κατά την βιοαποδόμηση της φαινόλης σε κατάλληλη πειραματική διάταξη, χρησιμοποιώντας ως πρότυπο πορώδες μέσο πυριτική άμμο (SiO2) η οποία αποτελεί ένα από τα βασικότερα συστατικά του εδάφους. Η φαινόλη είναι μία αρωματική ένωση η οποία χρησιμοποιείται συχνά στην βιομηχανία για την παρασκευή χρωμάτων, πλαστικών και φαρμάκων. Εξαιτίας της ευρείας χρήσης της, συναντάται συχνά στο έδαφος και τον υδροφόρο ορίζοντα. Για τον σκοπό αυτό έγιναν αρχικά πειράματα σε διαφορικές κλίνες άμμου με πηγή άνθρακα την γλυκόζη έτσι ώστε να αναπτυχθεί η κατάλληλη πειραματική διάταξη και διαδικασία για την περαιτέρω μελέτη της κινητικής ανάπτυξης του μικροοργανισμού Pseudomonas fluorescens. Στην συνέχεια μελετήθηκε η κινητική ανάπτυξης του μικροοργανισμού χρησιμοποιώντας ως πηγή άνθρακα την φαινόλη σε κλίνες άμμου. Παράλληλα έγιναν και πειράματα διαλείποντος έργου για την μελέτη της κινητικής ανάπτυξης του συγκεκριμένου μικροοργανισμού σε υγρές καλλιέργειες με θρεπτικό υπόστρωμα τόσο την γλυκόζη όσο και την φαινόλη. Σκοπός των πειραμάτων αυτών ήταν ο προσδιορισμός των κινητικών παραμέτρων. Τέλος αναπτύχθηκε κατάλληλο θεωρητικό μοντέλο για την προσομοίωση της κινητικής ανάπτυξης ενός βακτηριακού πληθυσμού στην μικροσκοπική κλίμακα. Απώτερος στόχος του θεωρητικού μοντέλου σε συνδυασμό με τα πειραματικά αποτελέσματα είναι να γίνει αποσαφήνιση των μηχανισμών αποδόμησης τοξικών ρύπων στην μικροσκοπική κλίμακα απο γηγενή βακτήρια και να αναπτυχθούν απλά κριτήρια για την πρόβλεψη και τον σχεδιασμό αποτελεσματικών μεθόδων αντιμετώπισης περιπτώσεων ρύπανσης του υπεδάφους και του υδροφόρου ορίζοντα. / The problem of soil and groundwater contamination has been increasing in the last few decades. Industrial growth is usually accompanied by pollution of groundwater with hazardous organic compounds. Irresponsible disposal of organic compounds into the soil has serious adverse consequences for the ecosystem and public health. Among methods that have been proposed for remediation of contaminated soils, biological methods using microorganisms which are indigenous in soil, are preferable because of their low cost, effectiveness and the low production of byproducts. Growth kinetics of microorganisms in soil differs significantly from growth kinetics of microorganisms suspended in a well-mixed stirred tank reactor. The aim of the present work was the experimental study of growth kinetics of a soilindigenous strain of the bacterium Pseudomonas fluorescens in sand packs (model soil) during the biodegradation of phenol. Phenol is an aromatic organic compound, which is widely used in industry, e.g. in paints, plastics, pharmaceuticals and many other products. Due to its extensive use, phenol is a common pollutant, especially in soil and groundwater. Experiments were initially conducted in sand packs, using glucose as a carbon source. The purpose of these experiments was the setup and test of the experimental procedure. Further experiments of growth kinetics in sand packs were conducted using phenol as a carbon source. In order to determine the growth kinetic parameters of Pseudomonas fluorescens for glucose and phenol biodegradation, batch experiments in liquid cultures were conducted. Finally, a hybrid simulator was developed for the theoretical investigation of growth kinetics of a bacterial population consisted a biofilm in microscale. The further aim of the theoretical simulator combined with the experimental results, was the elucidation of biodegradation mechanisms of toxic compounds by soil-indigenous bacteria in microscale, in order simple criteria for the prediction and remediation of polluted soils and groundwater to be developed.