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.

Submitted by Maicon Juliano Schmidt (maicons) on 2015-07-06T13:37:21Z No. of bitstreams: 1 Joice Brochier Schneider.pdf: 4213539 bytes, checksum: 49fa8f402cb598050e77b581c7d7d449 (MD5) / Made available in DSpace on 2015-07-06T13:37:21Z (GMT). No. of bitstreams: 1 Joice Brochier Schneider.pdf: 4213539 bytes, checksum: 49fa8f402cb598050e77b581c7d7d449 (MD5) Previous issue date: 2012-08-21 / FAPERGS - Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul / Projeconsult Engenharia Ltda. / A ideia de se transformar resíduos em matéria prima tem produzido esforços no sentido de estudá-los e qualificá-los, já que o aproveitamento integral de resíduos é uma necessidade cada vez maior na indústria moderna, principalmente pela crescente escassez de recursos naturais não renováveis e a necessidade de preservação e recuperação do meio ambiente. O resíduo cinza de casca de arroz (CCA), resultante da queima da casca de arroz para geração de energia, vem sendo utilizado em diversos ramos industriais. Destaca-se sua aplicação na construção civil e também como material adsorvente. A CCA utilizada neste trabalho está misturada com carvão ativado (CA). Esta mistura é proveniente de filtros de adsorção de sistemas de remediação de áreas degradadas com hidrocarbonetos de petróleo. Com isto, o objetivo deste trabalho foi avaliar a solidificação/estabilização de hidrocarbonetos de petróleo, em especial, benzeno, tolueno, etilbenzeno e xileno (BTEX), contidos no adsorvente composto por CCA e CA, em matriz de cimento Portland. Para tal, foram confeccionadas argamassas com substituição do agregado natural, em volume, pelos seguintes materiais: resíduo, nos teores de 10% e 30%, adsorvente CCA/CA in natura no teor de 30% e adsorvente CA in natura, também no teor de 30%. Essas argamassas foram caracterizadas ambientalmente, através dos ensaios descritos nas Normas Brasileiras. Analisou-se também a influência dessa substituição, através da determinação de propriedades no estado fresco (evolução da temperatura semi-adiabática de hidratação, penetração de cone e tempo de pega), de propriedades mecânicas (resistência à tração na flexão e à compressão) e caracterização dos produtos de hidratação através das técnicas de difração de Raio-X e espectroscopia de infravermelho. A argamassa RESÍDUO 10% atingiu a maior temperatura e menor tempo entre o início e fim da evolução da temperatura devido à hidratação. Já a argamassa RESÍDUO 30%, ao contrário, apresentou o maior tempo, fato justificado pela ação do óleo, presente no resíduo incorporado, que impediu, em parte, a passagem da água, retardando o processo de hidratação. Todas as argamassas, em relação a REFERÊNCIA, apresentaram menor consistência, na penetração de cone, e menor tempo de início e fim de pega. Resultados estes que corroboram, para as argamassas RESÍDUO 10%, CCA/CA 30% e CA 30% com a evolução da temperatura semi-adiabática da temperatura. A incorporação do resíduo não interferiu na formação dos compostos de hidratação do cimento, porém, a hidratação, conforme os resultados obtidos na evolução da temperatura semi-adiabática, ocorreu mais lentamente com a substituição de 30% da areia natural pelo resíduo. Os resultados da espectroscopia de infravermelho sugerem a presença BTEX nas argamassas RESÍDUO 30% e RESÍDUO 10%. Carbonatos e silicatos também foram identificados em todas as argamassas. Quanto aos resultados de resistência mecânica, observou-se, na resistência à tração na flexão, que a diferença entre o maior e menor desempenho, entre as argamassas REFERÊNCIA, RESÍDUO 10% e RESÍDUO 30%, foi de 8,9% e 5,6% para 7 e 21 dias, respectivamente. Já na resistência à compressão, aos 7 dias, os resultados obtidos das argamassas RESÍDUO 10% e RESÍDUO 30% foram superiores ao de REFERÊNCIA. Aos 21 dias, a REFERÊNCIA apresentou o melhor desempenho, 31,7% e 52,5% superior à argamassa RESÍDUO 30% e RESÍDUO 10%, respectivamente. Com os resultados de resistência mecânica obtidos, não foi possível avaliar a melhoria de desempenho com relação à idade. Porém, observou-se que a contaminação presente contribuiu para a resistência das argamassas, quando comparadas a CCA/CA 30%. Logo, sugere-se que a presença do contaminante possivelmente contribuiu quanto à aderência entre as partículas da mistura. Na caracterização ambiental, as argamassas confeccionadas foram classificadas como Classe II A, resíduo não perigoso, não inerte. A análise do extrato lixiviado e solubilizado das argamassas RESÍDUO 30% e RESÍDUO 10% não identificou a presença de hidrocarbonetos de petróleo. Estes resultados, associados à espectroscopia de infravermelho, às propriedades mecânicas bem como ao odor característico dos corpos de prova, confirmam a s/s do contaminante na matriz de cimento Portland. Este resultado positivo representa um avanço na busca da viabilidade de se empregar o resíduo CCA/CA contaminado com hidrocarbonetos de petróleo, direta ou indiretamente, para algum fim comercial. / The idea of turning waste into raw material has made efforts to study them and qualify them as the full utilization of waste is an increasing need in modern industry, mainly by increasing scarcity of non-renewable natural resources and need for preservation and restoration of the environment. The residue of rice husk ash (RHA), resulting from the burning of rice husk for power generation, has been used in various industries. We highlight its application in construction and as adsorbent material. The CCA used in this work is mixed with activated carbon (AC). This mixture is from adsorption filter remediation systems of degraded with petroleum hydrocarbons. With this, the objective of this study was to evaluate the solidification / stabilization of petroleum hydrocarbons, in particular benzene, toluene, ethylbenzene and xylene (BTEX), composed of adsorbent contained in CCA and CA, in Portland cement matrix. To this end, mortars were prepared with substitution of natural aggregate, by volume, of the following materials: residue, content of 10% and 30%, adsorbent CCA / CA in natura content of 30% and CA adsorbent in nature, also the content 30%. These environmentally mortars were characterized by the tests described in the Brazilian Standards. It was also analyzed the influence of substitution by determining the properties in the fresh state (temperature evolution semi-adiabatic hydration, penetration cone and setting time), mechanical properties (tensile strength in bending and compression), and characterization of the hydration products through the techniques of X-ray diffraction and infrared spectroscopy. The mortar RESIDUE 10% reached the highest temperature and shortest time between the beginning and end of the temperature due to hydration. Already 30% RESIDUE mortar, instead, showed the greatest time, which may be explained by the action of the oil present in the residue incorporated, which prevented partly the passage of water, slowing the hydration process. All mortars, for the reference, showed less consistency, cone penetration, and shorter start and end of the handle. These results corroborate that, for mortars RESIDUE 10% CCA/CA 30% CA and 30% with the temperature evolution of the semi-adiabatic temperature. The incorporation of the residue did not affect the formation of the compounds of the cement hydration, however, hydration, as the results in the evolution of semi-adiabatic temperature, was slower by replacing 30% of the natural sand residue. The results of infrared spectroscopy suggests the presence BTEX in mortars RESIDUE RESIDUE 30% and 10%. Silicates and carbonates have also been identified in all mortars. Regarding the results of mechanical strength was observed in tensile strength in bending, the difference between the highest and lowest performance among REFERENCE mortars, 10% Residue and Residue 30%, was 8.9% and 5 6% for 7 and 21 days, respectively. In the compressive strength after 7 days, the results of mortar RESIDUE RESIDUE 10% and 30% were higher than the reference. At 21 days, the REFERENCE showed the best performance, 31.7% and 52.5% higher than the mortar WASTE WASTE 30% and 10%, respectively. With the results obtained from mechanical strength, it was not possible to evaluate the performance improvement with respect to age. However, it was observed that this contributed to the contamination resistance of mortars, compared to CCA / CA 30%. Therefore, it is suggested that the presence of the contaminant as possibly contributing to adhesion between the particles of the mixture. In characterizing environmental mortars made were classified as Class II, non-hazardous waste, not inert. The analysis of the extract solubilized and leached mortar WASTE WASTE 30% and 10% failed 17 to identify the presence of petroleum hydrocarbons. These results, combined with the infrared spectroscopy, the mechanical properties and the odor of the specimens, confirm / s of the contaminant in the matrix of Portland cement. This result represents a breakthrough in the search for feasibility of employing the waste CCA/CA contaminated with petroleum hydrocarbons, directly or indirectly, for any commercial purpose.

Sulfate- and Fe(III)-reducing, and methanogenic prokaryotes (SRP, FRP, MGP) are key players in metabolic pathways involved in anaerobic biodegradation processes. Understanding the metabolic activity of these microbes in environments can enhance microbe-mediated processes such as oil spill bioremediation and methane biogas production. In this study, anaerobic microbial activities in Deepwater Horizon oil spill-impacted salt marsh sediments, and in methanogenic coal bed production water enrichment cultures amended with trace elements (TE), were elucidated by employing an approach combining methods in molecular biology and geochemistry. In situ metabolic activity of SRP, FRP and MGP were monitored seasonally and metabolically-active communities were identified in oil-impacted sediments using quantitative real time Reverse Transcription -PCR and clone library analysis of key functional genes: Dissimilatory (bi)sulfite reductase (dsrAB), Geobactereceae-specific citrate synthase (gltA), methyl coenzyme M reductase (mcrA), and benzyl succinate synthase (bssA). In situ application of montmorillonite clay was assessed for its potential at accelerating PHC degradation by stimulating microbial activities. Levels of dsrA, gltA and bssA transcripts suggested that PHC-oxidizing SRP are more active in summer while FRP are more active in winter, indicating their activities linked to the seasonal changes of redox potential and vegetation. BssA gene expression peaked in winter, and was highest at more highly oil-impacted sites. Expression of all genes was higher in clay-amended sites. bssA transcript level and Fe(II) production were highest in clay-amended microcosm. Total petroleum hydrocarbon (TPH) levels were lower in oil and clay-amended microcosm incubation than one with oil only amendment, suggesting enhanced TPH degradation by clay amendment. Pyrosequencing analysis 16S rRNA gene in clay-amended microcosms demonstrated the highest percentage abundance of groups closely related to known anaerobic aromatic degraders. Levels of mcrA transcripts correlated with methane production rates in TE-amended coal bed production water enrichments. The findings of the present study clearly support the advantage of gene expression analyses for estimating microbial activity. To the best of our knowledge, this is the first in situ study which employs key functional gene markers as molecular proxies for metabolic activity and diversity assessments in anaerobic oil-contaminated salt marsh sediment and also elucidates clay-enhanced in situ TPH degradation.

Ο Πατραϊκός Κόλπος βρίσκεται στη Δυτική Ελλάδα μεταξύ Στερεάς Ελλάδας και Πελοποννήσου. Είναι ένας σχετικά αβαθής θαλάσσιος κόλπος που συνδέει το βαθύ Κορινθιακό Κόλπο με το Ιόνιο Πέλαγος. Η περιοχή μελέτης εκτείνεται από την παραλία της Καλόγριας, Δ. Λαρισσού, μέχρι το Ακταίο του Δήμου Ρίου. Πραγματοποιηθήκαν 2 εποχικές δειγματοληψίες, για τη συλλογή θαλάσσιου νερού, μια χειμερινή το Μάρτιο του 2009 και μία θερινή το Σεπτέμβριο του ίδιου έτους. Εμβόλιμα έγινε δειγματοληψία λίγο μετά από ατύχημα πετρελαιοκηλίδας στο λιμάνι της Πάτρας. Στην εργασία αυτή με μία τροποποίηση της μεθόδου MARPOLMON-P, μετρήθηκε η εκπομπή φθορισμού των δειγμάτων μετά από την εκχύλιση τους με εξάνιο και διερευνήθηκε η παρουσία και η συγκέντρωση πετρελαϊκών ενώσεων καθώς και η διασπορά των πετρελαιοειδών στις παράκτιες περιοχές του Πατραϊκού Κόλπου. Σε κάθε δείγμα μετρήθηκαν φυσικές παράμετροι όπως η θερμοκρασία, το pH, η ηλεκτρική αγωγιμότητα και η θολερότητα του θαλάσσιου νερού. Η σύσταση των δειγμάτων της δεύτερης δειγματοληψίας διερευνήθηκε με τη χρήση GC-MS για τον εντοπισμό της πηγής των πετρελαϊκών ρύπων. Τα αποτελέσματα των δύο κύριων δειγματοληψιών παρουσίασαν μεγάλες διακυμάνσεις στη συγκέντρωση αλλά και στην κατανομή των πετρελαϊκών υδρογονανθράκων, με τα εύρη των τιμών των συγκεντρώσεων να κυμαίνονται για τη χειμερινή από 0 – 290 μg/L ισοδύναμων μονάδων χρυσενίου (Λιμάνι Προβλήτα Αγ. Νικολάου) και για τη θερινή δειγματοληψία από 0- 56 μg/L μονάδων χρυσενίου (Μαρίνα Τερψιθέας). Η κατανομή και η διασπορά των πετρελαιοειδών φαίνεται να επηρεάζεται άμεσα από τη διεύθυνση και ταχύτητα των κυμάτων και του επικρατούντος άνεμου στις περιοχές δειγματοληψίας, αλλά και από την ωκεανογραφική συμπεριφορά του Πατραϊκού Κόλπου. Στην ανάλυση GC/MS βρέθηκε μεγάλη αναλογία αλκάνιων σε όλα τα δείγματα, ενώ σε κάποια από αυτά βρέθηκαν πολυκυκλικοί αρωματικοί υδρογονάνθρακες και αλκένια, παράγωγα του πετρελαίου και των καυσίμων. Άλλες οργανικές ενώσεις όπως φθαλικοί εστέρες, σουλφίδια, αλκοόλες κ.α., ανιχνεύτηκαν σε χαμηλές συνήθως συγκεντρώσεις και πιθανόν προέρχονται από ρυπογόνες χερσαίες πηγές (επιφανειακή απορροή, αστικά και βιομηχανικά λύματα κ.α.). / The Gulf of Patras located between Continental Greece and Peloponnesus, in West Greece. The Gulf of Patras is relatively shallow and connects the deep Gulf of Corinth with Ionian Open Sea. The experimental area of our study extends from the beach of Kalogria, department of Municipality of Larissos, to Aktaion, department of Municipality of Rion. Two samplings, one in March of 2009 and one in September of the same year, were carried out in order to get sea water samples. After the occurrence of an oil slick accident in the port of Patras, an interstitial sampling was carried out. In this study, MARPOLMON-P method partially modified was used, in order to estimate the fluorescence emission of the hexane extracted sea water samples. The presence of Dissolved/Dispersed petroleum hydrocarbons (DDPH) was also investigated as well as their concentration and the distribution of those in the maritime areas of the Gulf of Patras. In every sample, physical parameters such as temperature, pH, electrical conductivity and turbidity of sea water were estimated. The identification of various substances within the samples of the second sampling (September of 2009) was conducted with GC-MS method, in order to find out the source of oil pollution. Considering our results of the two main samplings we found out that there were important ranges in concentration as well as in distribution of DDPH. At first sampling the range of values was between 0 to 290 μg/L of chrysene equivalents (Port of St. Nikolaos) and at second sampling was between 0 to 56 μg/L of chrysene equivalents (Port of Marina Terpsithea). The results showed that wave’s direction and speed, wind speed and oceanographical status of Gulf of Patras affected by the distribution and dispersion of petroleum hydrocarbons. During the GC/MS analysis high content of alkanes in all collected samples was identified, while some of them contained polycyclic aromatic hydrocarbons and alkenes, such as products of crude oil and mineral fuel. Other organic compounds such as pthallic esters, sulphides, alcoholes etc were found in low concentrations. These organic compounds were probably derived from pollutant ground sources (superficial rain flow or dilution drainage, urban and manufacturing wastesreams).

[pt] Esta dissertação apresenta os resultados de duas técnicas de investigação em alta resolução: investigação passiva de vapores do solo e investigação com o uso de Membrane Interface Probe (MIP), em uma área de interesse com contaminação por hidrocarbonetos, localizada no município de Duque de Caxias/RJ. O processo de gerenciamento ambiental iniciou-se em 2012 na área e contemplou as etapas do gerenciamento de áreas contaminadas preconizadas nas legislações vigentes. Os resultados obtidos a partir das investigações tradicionais foram insuficientes para a obtenção da compreensão dos aspectos físicos e geoquímicos necessária para o sucesso das fases de diagnóstico e, consequentemente, da remediação. Portanto, duas investigações em alta resolução foram conduzidas com o objetivo de refinar o modelo conceitual de forma a atender adequadamente a Resolução CONAMA número 420/09 e Resolução CONEMA número 44/12, permitindo ações futuras mais eficientes. A investigação passiva de vapores do solo utilizou amostradores compostos por materiais adsorventes granulares, encapsulados em uma membrana microporosa hidrofóbica e quimicamente inerte que permite a difusão dos vapores presentes no meio. Os resultados, fornecidos em massa, representam qualitativamente a presença de contaminação no subsolo. O MIP é uma ferramenta de direct push com medição em tempo real, que mapeia a presença da contaminação tanto em meios insaturados quanto saturados inconsolidados. A partir dos resultados integrados, foi possível constatar que a distribuição de VOCs em água subterrânea ocorre de forma descontínua ao longo da área, sendo possível identificar cinco hot-spots distintos e suas diferentes áreas fonte, incluindo uma região com presença de LNAPL. / [en] The sources of contaminated sites are related to several factors such as the lack of knowledge of safe procedures for handling hazardous and / or toxic substances, disrespect to these safe procedures and the occurrence of accidents or leaks during industrial processes, transportation or storage of unprocessed materials and products. In addition, contamination is usually associated with the exploration of natural resources and with the expansion of the industry and/or agrarian activities, which have happened, and are still happening, at the cost of high environmental and social risks. A contaminated site is considered a risk, since its existence can generate several problems such as damages to health, impairment of the quality of water resources, restrictions on land use and damage to public and private property, and damage to the environment. These situations, in general, involve complex risks with regard to the effects of exposure to contaminants on human health (CETESB, 2013), and may have short -, medium - or long-term effects.

Orientador: Rodrigo Sequinel / Coorientador: Danilo Luiz Flumignan / Banca: Edilene Cristina Ferreira / Banca: Erica Regina Filletti Nascimento / Banca: Mária Cristina Breitkreitz / Banca: Heron Dominguez Torres da Silva / Resumo: Segundo dados, de 2017, da Companhia Ambiental do Estado de São Paulo (CETESB), os postos de combustíveis são responsáveis pela contaminação ambiental de 72% das 5942 áreas contaminadas cadastradas no estado de São Paulo. A contaminação de solos e águas subterrâneas por combustíveis fósseis causam imensos danos ambientais devido à alta toxicidade dos constituintes destes combustíveis, além de apresentarem propriedades carcinogênicas e elevada permanência no solo. O monitoramento ambiental em áreas de risco potencial de contaminação, como postos de combustíveis, é realizado através da análise de hidrocarbonetos totais do petróleo (TPH), entre outros hidrocarbonetos individuais. Estas análises são realizadas através de métodos cromatográficos em fase gasosa que requerem etapas de extração com solventes halogenados, purificação e, muitas vezes, pré-concentração. O elevado custo e o tempo demandado para a quantificação de TPH em solo tornam-se barreiras para o crescimento do monitoramento e acompanhamento de processos de remediação das áreas contaminadas. Desta forma, este trabalho objetivou o desenvolvimento de métodos analíticos mais rápidos e de menor custo para a identificação e quantificação de TPH em solo através da espectroscopia na região do infravermelho próximo (NIR). Três métodos NIR foram desenvolvidos: (i) sem preparo de amostra; (ii) após extração por hexano; e (iii) após extração por etanol. Os modelos de classificação foram desenvolvidos pelo método de análise dis... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: According to the Environmental Company of the State of São Paulo (CETESB), the gas stations are responsible for the environmental contamination of 72% of the 5942 contaminated areas registered in the state of São Paulo. Contamination of soils and groundwater by fossil fuels causes immense environmental damages due to their high toxicity, carcinogenic properties and high permanence in the soil. Environmental monitoring in areas of potential contamination risk, such as gas stations, is carried out through the analysis of total petroleum hydrocarbons (TPH), among other individual compounds. These analyzes are performed by gas chromatographic methods which require some sample preparation steps, such as extraction with halogenated solvents, purification, and often preconcentration. The high cost and time demanded for the quantification of TPH in the soil become barriers for the growth of the monitoring program and remediation processes of the contaminated areas. Therefore, this work aimed at the development of faster and lower cost analytical methods for the identification and quantification of TPH in soil through near-infrared spectroscopy (NIR). Three NIR methods were developed: (i) without sample preparation; (ii) after hexane extraction; and (iii) after extraction with ethanol. The classification models were developed by partial least squares discriminant analysis (PLS-DA) method and the calibration models by partial least squares (PLS) method. In the development of the models... (Complete abstract click electronic access below) / Doutor

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O presente trabalho teve por objetivo apresentar e discutir um caso de identificação e remediação emergencial de compostos orgânicos voláteis, oclusos em camada arenosa do Terciário da Formação São Paulo, em decorrência do vazamento de tanques de combustíveis de um posto de serviços. A técnica de remediação adotada para o caso consistiu na extração in situ dos vapores do solo e no tratamento dos mesmos por adsorção em filtros de carvão ativado (SVE - soil vapor extraction). Os processos de seleção, projeto, implantação, operação e descomissionamento da tecnologia SVE seguiram as metodologias indicadas pela literatura, adaptadas às condições locais. O acompanhamento da eficiência da remediação foi baseado na quantificação inicial dos hidrocarbonetos totais de petróleo leves presentes no subsolo, através das técnicas de cromatografia gasosa e espectrometria de massa, e na medição em campo das concentrações de voláteis e dos respectivos teores de explosividade. O resultado da campanha laboratorial apresentou fortes indícios de que a contaminação local fosse proveniente do combustível gasolina e indicou a ocorrência do composto benzeno em concentrações superiores aos limites adotados como referência. As leituras realizadas em campo mostraram rápido declínio das concentrações de voláteis e dos teores de explosividade com a operação da tecnologia SVE, indicando baixa ocorrência de fatores limitantes do transporte de massa no local. Corroborou com tal hipótese, o fato das metas de remediação terem sido atingidas com poucas trocas de ar, parâmetro retro-analisado a partir de dados de ensaios geológico-geotécnicos. Assim, concluiu-se que, para áreas com características semelhantes à estudada, a tecnologia SVE pode ser eficiente como medida de remediação de voláteis e redução dos riscos de explosividade. / This work aims to present and to discuss a case study of identification and emergency remediation of volatile organic compounds, occluded in a sand layer of the São Paulo Tertiary Formation, as a result of the leakage of fuel tanks of a service station. The adopted remediation technique was in situ soil vapor extraction (SVE) and offgas treatment for adsorption in activated carbon filters. Selection, design, commissioning, operation and shutdown processes of SVE technology followed literature methodologies, which were adapted to local conditions. Remediation efficiency monitoring was based on the initial quantification of light total petroleum hydrocarbons in the subsoil, through gas chromatography and mass spectrometry techniques, and on measurement of the volatile concentrations and respective explosive contents in the field. The result of the laboratorial campaign presented strong indications that the local contamination proceeded from combustible gasoline and it indicated the occurrence of benzene in concentrations higher than the adopted reference. Field measurements showed fast decline of the volatile concentrations and explosive contents with the SVE technology operation, fact that indicated low occurrence of mass transfer limitations in the place. The fact that remediation goals were achieved with few air exchanges, parameter back-analyzed from geologicgeotechnical tests, contributed to reinforce such hypothesis. Thus, SVE technique can be considered efficient for volatile remediation and explosive risks reduction, for areas with characteristics similar to the studied one.

O presente trabalho teve por objetivo apresentar e discutir um caso de identificação e remediação emergencial de compostos orgânicos voláteis, oclusos em camada arenosa do Terciário da Formação São Paulo, em decorrência do vazamento de tanques de combustíveis de um posto de serviços. A técnica de remediação adotada para o caso consistiu na extração in situ dos vapores do solo e no tratamento dos mesmos por adsorção em filtros de carvão ativado (SVE - soil vapor extraction). Os processos de seleção, projeto, implantação, operação e descomissionamento da tecnologia SVE seguiram as metodologias indicadas pela literatura, adaptadas às condições locais. O acompanhamento da eficiência da remediação foi baseado na quantificação inicial dos hidrocarbonetos totais de petróleo leves presentes no subsolo, através das técnicas de cromatografia gasosa e espectrometria de massa, e na medição em campo das concentrações de voláteis e dos respectivos teores de explosividade. O resultado da campanha laboratorial apresentou fortes indícios de que a contaminação local fosse proveniente do combustível gasolina e indicou a ocorrência do composto benzeno em concentrações superiores aos limites adotados como referência. As leituras realizadas em campo mostraram rápido declínio das concentrações de voláteis e dos teores de explosividade com a operação da tecnologia SVE, indicando baixa ocorrência de fatores limitantes do transporte de massa no local. Corroborou com tal hipótese, o fato das metas de remediação terem sido atingidas com poucas trocas de ar, parâmetro retro-analisado a partir de dados de ensaios geológico-geotécnicos. Assim, concluiu-se que, para áreas com características semelhantes à estudada, a tecnologia SVE pode ser eficiente como medida de remediação de voláteis e redução dos riscos de explosividade. / This work aims to present and to discuss a case study of identification and emergency remediation of volatile organic compounds, occluded in a sand layer of the São Paulo Tertiary Formation, as a result of the leakage of fuel tanks of a service station. The adopted remediation technique was in situ soil vapor extraction (SVE) and offgas treatment for adsorption in activated carbon filters. Selection, design, commissioning, operation and shutdown processes of SVE technology followed literature methodologies, which were adapted to local conditions. Remediation efficiency monitoring was based on the initial quantification of light total petroleum hydrocarbons in the subsoil, through gas chromatography and mass spectrometry techniques, and on measurement of the volatile concentrations and respective explosive contents in the field. The result of the laboratorial campaign presented strong indications that the local contamination proceeded from combustible gasoline and it indicated the occurrence of benzene in concentrations higher than the adopted reference. Field measurements showed fast decline of the volatile concentrations and explosive contents with the SVE technology operation, fact that indicated low occurrence of mass transfer limitations in the place. The fact that remediation goals were achieved with few air exchanges, parameter back-analyzed from geologicgeotechnical tests, contributed to reinforce such hypothesis. Thus, SVE technique can be considered efficient for volatile remediation and explosive risks reduction, for areas with characteristics similar to the studied one.