The aim of this study was to understand the contribution of Linear Alkylbenzene Sulfonates (LAS) to the decline of Mediterranean coastal forest exposed to marine aerosols. LAS are a group of synthetic anionic surfactants widely used in the composition of household or industrial detergents and agrochemicals. This study was part of a large project (RISICO) aiming the assessment of the environmental impact of the LAS at multiple levels: biodegradation in the coastal waters, sorption – desorption processes in the sediments, toxicity to the aquatic life and toxicity to the coastal forest (by aerosolisation of the sea water). Previous studies pointed out this group of surfactants as the main cause of the coastal forest decline. However, the quantification of this surfactant in the environmental samples (mainly sea water and foliar deposition) was done using non-specific analytical methods as methylene blue active substances (MBAS), leading to overestimation of the environmental concentrations of LAS. The work hypothesis was that at actual environmental concentrations, the LAS does not play a key role in the foliar uptake of the sea salt deposited on the coastal vegetation by the marine aerosols, therefore the LAS may not be the main cause of the coastal forest decline. The research involved both greenhouse experiments and field measurements. The experimental work was conducted on young Mediterranean trees (Laurus nobilis L., Quercus ilex L. and Pinus halepensis P. Mill.) and investigated the synergistic toxic effects of exposure to simulated marine aerosol contaminated with surfactants. An array of endpoints was used including photosynthetic activity, relative water content, foliar deposition and uptake of salt and LAS, and pigments analysis. The results of those experiments revealed that LAS itself did not have phytotoxic effects. Nevertheless, the surfactant was shown to enhance the foliar uptake of the salt in the tested species, especially in Pinus halepensis, confirming the conclusions of previous studies regarding the sensitivity of this species to polluted marine aerosols. The field work was conducted in San Rossore National Park (Italy) and Porquerolles Island (France) and was focused on evaluating the health status of the Mediterranean forest (Quercus ilex L., Pinus halepensis Mill. and Pinus pinaster Aiton.) and also on quantification of LAS in coastal aerosols using highly specific analytical methods, like the mass spectrometry (MS). The frequencies and extent of injuries in the coastal trees were found to be correlated to the salt but not with the LAS content of the leaves. The concentrations of LAS in the Pinus and Quercus leaves were comparable in the two studied sites but the concentrations of salt were extremely high in San Rossore, suggesting that other factors may determine the excessive salt foliar uptake. The parallel MS and MBAS carried out in the same set of aerosol samples revealed that MBAS measurements were not relevant for LAS concentrations in the marine aerosols. Projecting the experimental results to the real LAS and salt exposure of the coastal forest, we concluded that LAS may play a marginal role in coastal vegetation decline.

No description available.

Made available in DSpace on 2016-06-02T19:31:40Z (GMT). No. of bitstreams: 1 1959.pdf: 1033941 bytes, checksum: 78e3218226ae4e1376a101c0d5d8d71f (MD5) Previous issue date: 2008-04-25 / Financiadora de Estudos e Projetos / The main anionic surfactants world widely used are the sodium dodecyl benzene sulfonate (LAS) and sodium dodecyl sulfate (DSS), which are mainly used in the manufacturing of domestic and personal hygiene products. As a consequence of the great and increasing consumption of LAS and DSS there is an increasing wareness regarding the adverse effects of these compounds to the organisms and environment. The present study aimed to evaluate the acute and chronic toxicity of the compounds LAS and DSS to the cladocerans Daphnia similis, Ceriodaphnia dubia and Ceriodaphnia silvestrii. It was also evaluated the toxicity of the water and sediments of four reservoirs and one stream of São Paulo State Analyses of LAS concentrations in the water of these reservoirs were also performed by Liquid chromatography. Acute toxicity tests indicated a value of CE(I)50;48h for LAS of 14.17 mg L-1 to D. similis, 11.84 mg L-1 to C. dubia and 13.51 mg L-1 to C. silvestrii. Significant changes in the viability of the cladoceran offsprings were observed for C. dubia and C. silvestrii exposed to the LAS, with values of CENO equal to 1.0 mg L-1 to C. dubia and 2.5 mg L-1 to C. silvestrii. It was concluded that the maximum permissible concentration of 0.5 mg L-1 surfactants as established by the resolution CONAMA nº. 357/2005 (Brazilian Ministry of Environment) in order to protect aquatic communities is adequate, considering the sensitivity of the native species C. silvestrii. The results of the acute toxicity tests with DSS indicated a CE(I)50;48h value of 12.82; 4.37 and 5.42 mg L-1, for D. similis, C. dubia and C. silvestrii, respectively. A CENO value of 2.0 mg L-1 was obtained in the chronic toxicity tests for C. silvestrii. The surfactant LAS was detected in all the water samples collected in the Lobo (Broa), Lagoa Dourada and Fazzari reservoirs, but at concentrations lower than 5 mg L-1 (the method limit of detection). The toxicity tests with environmental samples revealed that there is no toxicity in the water of the Lobo and Lagoa Dourada sampled, however the water of Monjolinho Reservoir was toxic to D. similis and Fazzari stream was toxic to D. similis and C. dubia. Only the sediment of Monjolinho Reservoir was not toxic to cladocerans. / Os principais surfactantes aniônicos disponíveis no mercado mundial são o dodecil benzeno sulfonato de sódio (LAS) e o dodecil sulfato de sódio (DSS), utilizados principalmente em produtos de limpeza doméstica e de higiene pessoal. Devido ao grande consumo mundial de LAS e de DSS há uma crescente preocupação sobre os efeitos adversos destes compostos no ambiente e aos organismos. Este trabalho teve por objetivo avaliar a toxicidade aguda e crônica do LAS e do DSS aos organismos-teste Daphnia similis, Ceriodaphnia dubia e Ceriodaphnia silvestrii. Foi também avaliada a toxicidade da água e dos sedimentos em quatro reservatórios e um riacho do estado de São Paulo por meio de testes de toxicidade aguda e da análise quantitativa do surfactante LAS. Os testes de toxicidade aguda indicaram uma CE(I)50;48h do LAS de 14,17 mg L-1 para D. similis, 11,84 mg L-1 para C. dubia e 13,51 mg L-1 para C. silvestrii. Nos testes crônicos realizados foi observada significativa alteração viabilidade da progênie de C. dubia e C. silvestrii exposta ao LAS, com valores de CENO igual a 1,0 mg L-1 para C. dubia e 2,5 mg L-1 para C. silvestrii. Pode-se concluir que o valor máximo permissível de surfactantes de 0,5 mg L-1, estabelecido pela Resolução CONAMA nº. 357/2005 em águas destinadas à proteção das comunidades aquáticas, é adequado para a espécie nativa C. silvestrii. Nos testes de toxicidade aguda de DSS foram obtidos valores de CE(I)50;48h de 12,82; 4,37 e 5,42 mg L-1, para D. similis, C. dubia e C. silvestrii, respectivamente. No ensaio de toxicidade crônica obteve-se valor de CENO igual a 2,0 mg L-1 para C. silvestrii. O surfactante LAS foi detectado nas amostras de água dos Reservatórios do Lobo (Broa), Lagoa Dourada e Represa do Monjolinho em concentração inferior a 5 mg L-1. Os testes revelaram que não há toxicidade aguda aos cladóceros da água da Lagoa Dourada e do Reservatório do Lobo, havendo, contudo, toxicidade da água da Represa do Monjolinho para D. similis e da água do Córrego do Fazzari para os cladóceros D. similis e C. dubia. Somente a amostra de sedimento da Represa do Monjolinho não causou toxicidade aos cladóceros.

Nesse trabalho avaliaram-se quatro hipóteses sobre a remoção do alquilbenzeno linear sulfonado (LAS) em reator EGSB (expanded granular sludge bed) alimentado ora com água residuária de lavanderia comercial, ora como meio sintético acrescido de LAS Padrão, com e sem suplementação de Fe(III) afluente. Para tanto, em todas as hipóteses utilizou-se reator EGSB (1,4 L) com tempo de detenção hidráulica (TDH) de 36h, condição mesofílica (30ºC) e carga de LAS específica aplicada (CLEA) variando de 1,0 - 2,7 mgLAS.gSTV-1.d-1. DGGE e sequenciamento massivo do gene rRNA 16S (Plataforma 454-Pirosequenciamento e Ion Torrent) foram utilizados para caracterização microbiana. Em relação à Hipótese A avaliou-se o efeito da adaptação prévia da biomassa na remoção do LAS em água residuária. Para tanto, o EGSB-BA (biomassa adaptada) teve uma etapa prévia com LAS padrão e meio sintético (Etapa I), seguida da Etapa II com água residuária; e o EGSB-BNA (biomassa não adaptada) teve etapa única e alimentação diretamente com água residuária. Para a Hipótese B avaliou-se o efeito da suplementação com meio sintético na remoção de LAS em água residuária. Para tanto, o EGSB-Ag.Lav foi alimentado apenas com água residuária e bicarbonato de sódio e duas CLE (Etapa II - 1,0 e Etapa III - 2,7 mg LAS.gSTV-1.d-1). Em relação às Hipóteses C e D, avaliou-se o efeito da suplementação de Fe(III) na remoção de LAS Padrão em meio sintético e LAS em água residuária, respectivamente. A Hipótese A foi refutada uma vez que as remoções de LAS em EGSB-BA-Etapa II (76%) e EGSB-BNA-Etapa I (78%) foram similares (ambas com água residuária). A remoção de LAS foi maior quando foi adicionada água residuária (EGSB-BA-Etapa II-76%) do que com LAS Padrão (EGSB-BA-Etapa I-63%). A Hipótese B foi aceita, uma vez que a alimentação do EGSB apenas com água residuária de lavanderia (CLE 1,0 mg LAS.gSTV-1.d-1) mais bicarbonato de sódio resultou em remoções do surfactante de 93%, ou seja, 15-17% maior que nos reatores suplementados com meio sintético (EGSB-BA Etapa II e EGSB-BNA Etapa I). Na Etapa III verificou-se diminuição da remoção em 30%. A Hipótese C foi aceita uma vez que se notou 20% de aumento na remoção de LAS quando comparado com reator não suplementado com Fe(III) (EGSB-Fe - 84,3% e EGSB-BA Etapa I - 63,5%). A Hipótese D foi refutada, uma vez que embora tenha sido obtida alta remoção de LAS (91,2%), esta não foi acompanhada pela redução férrica. Por meio do DGGE (domínio Bactéria) notou-se estratificação microbiana ao longo do reator na Etapa III (Hipótese B), provavelmente, em função do tamanho do grânulo que variou ao longo do reator. Por meio do sequenciamento massivo identificou-se bactérias semelhantes à Geobacter na amostra proveniente do reator EGSBFe da Hipótese C (17% da abundância relativa), portanto, as condições impostas favoreceram esse gênero. Fato este não observado para o reator EGSB-Fe-Ag.Lav. da Hipótese D. A comparação da análise filogenética das bactérias para os diferentes reatores permitiu identificar gêneros em comum relacionados com a degradação de LAS, a saber: Desulfobulbus, Geobacter, Syntrophorhabdus, Sporomusa, Comamonas, Holophaga, Mycobacterium, Pseudomonas, Stenotrophomonas e Synergistes. / This study evaluated four hypotheses about the removal of linear alkylbenzene sulfonate (LAS) in EGSB reactor (expanded granular sludge bed) fed sometimes with commercial laundry wastewater, sometimes with synthetic medium more Standard LAS, with and without Fe(III) influent supplementation. Therefore, in all hypotheses were used an EGSB reactor (1.4 L) with a hydraulic retention time (HRT) of 36 h, mesophilic condition (30°C) and load specific LAS (CLE) ranging from 1,0 to 2,7 mgLAS.gSTV-1.d-1. DGGE and massive sequencing of 16S rRNA gene (454-pyrosequencing and Ion Torrent platform) were used for microbial characterization. Regarding the Hypothesis A, it was evaluated the effect of biomass pre-adaptation for removal of LAS in wastewater. Then, the EGSBBA (adapted biomass) had a previous step with standard LAS and synthetic medium (Phase I), followed by Stage II with wastewater; and EGSB-BNA (not adapted biomass) had single step and feeding directly with wastewater. Regarding the Hypothesis B, it was evaluated the effect of synthetic medium supplementation in the removal of LAS in wastewater. Then, the EGSB-Ag.Lav was fed only with wastewater and sodium bicarbonate with two CLE (Stage II - 1,0 e Stage III - 2,7 mg LAS.gSTV-1.d-1). Regarding the Hypothesis C and D, it was evaluated the effect of Fe(III) supplementation in the removal of standard LAS and LAS in wastewater, respectively. The Hypothesis A was refuted since the LAS removal in EGSB-BA-Stage II (76%) and EGSB-BNA-Step I (78%) were similar (both with wastewater). The LAS removal was highest when wastewater was added (EGSB-BA-Stage-II 76%) than with standard LAS (EGSB-BAStage- I 63%). The Hypothesis B was accepted, since the feed of the EGSB only with wastewater from laundry (CLE 1,0 mg LAS.gSTV-1.d-1) more sodium bicarbonate resulted in removal of 93% of surfactant, in other words, 15-17% higher than in the reactors supplemented with synthetic medium (EGSB-BA Stage II e EGSB-BNA Stage I). In the Stage III, there was a decrease by 30% of LAS removal. The Hypothesis C was accepted, since there was an increase of 20% in the removal of LAS as compared to unsupplemented reactor with Fe (III) (EGSB-Fe - 84,3% e EGSB-BA Stage I - 63,5%). The Hypothesis D was refuted since although high LAS removal was obtained (91,2%), this was not accompanied by ferric reduction. By means of DGGE (Bacteria domain) was noted a microbial stratification along the reactor in the Stage III (Hypothesis B), probably in function of granule size along the reactor. By means of massive sequencing were identified bacteria similar to Geobacter in the sample from the reactor EGSB-Fe Hypothesis C (relative abundance 17%), therefore, the conditions favored this genre. This fact was not observed in the reactor EGSB-Fe-Ag.Lav. hypothesis D. A comparison of phylogenetic analysis of bacteria for different reactors allowed to identify common genera related to LAS degradation, namely: Desulfobulbus, Geobacter, Syntrophorhabdus, Sporomusa, Comamonas, Holophaga, Mycobacterium, Pseudomonas, Stenotrophomonas and Synergistes.

O objetivo desse trabalho foi avaliar a degradação de alquilbenzeno linear sulfonado (LAS) em condições anaeróbias. Os primeiros experimentos foram realizados em reatores em batelada alimentados com diferentes substratos e concentrações de LAS. Apesar do surfactante ficar adsorvido no lodo, não foram observadas interferências no metabolismo de microrganismos anaeróbios, pois dessa forma o LAS tornou-se indisponível para a degradação celular. Reatores anaeróbios horizontais de leito fixo (RAHLF) foram avaliados quanto à remoção de LAS e inoculados com lodos anaeróbios provenientes de reatores UASB usados respectivamente no tratamento de esgoto sanitário (R1) e tratamento de dejetos suinocultura (R2) imobilizados em espuma de poliuretano. A adição de LAS não influenciou na estabilidade do reator. O LAS começou a ser degradado após 108 dias da sua adição no afluente dos reatores. Porcentagens de remoção, considerando adsorção e degradação de LAS, com 313 dias de operação foram iguais a 50% e 91% para o R1 e R2, respectivamente, quando foram alimentados com esgoto sintético e 14 mg/L de LAS (reator - R1) e somente LAS a 14 mg/L (reator - R2). Em relação ao balanço de massa de LAS, os reatores apresentaram degradações muito semelhantes, sendo 35% para o reator R1 e 34% para o reator - R2. A diversidade microbiana referente aos domínios Bacteria e Archaea e ao grupo BRS foi avaliada utilizando a técnica de PCR/DGGE. Para o domínio Archaea, foram observadas diferenças significativas nas populações quando os reatores foram alimentados com LAS. Diferenças foram observadas no domínio Bactéria e grupo das BRS, para concentrações de LAS de 14 mg/L. A alteração na diversidade microbiana pode ter ocorrido devido à seleção dos microrganismos pela presença do surfactante. A biomassa presente no final da operação foi submetida à técnica de clonagem e seqüenciamento do fragmento do RNAr 16S para o domínio Bacteria. Observou-se que os reatores que apresentaram maior número de clones relacionados ao filo Firmicutes, classe Clostridia, ordem Clostridiales. Provavelmente os microrganismos pertencentes a esse grupo estejam envolvidos com a degradação do LAS / The objective of this work was to evaluate the degradation of linear alkylbenzene sulfonate (LAS) in anaerobic conditions. The first experiments were accomplished in reactors in batch fed with different substrates and concentration of LAS. In spite of the surfactant to be adsorbed in the sludge interferences was not observed in the metabolism of anaerobic microorganisms, because in that way LAS became unavailable for the cellular degradation. Horizontal anaerobic immobilized biomass (HAIB) reactors were appraised as for the removal of LAS and inoculated with coming anaerobic slugde of reactors UASB used respectively in the treatment of sanitary sewage (R1) and treatment of wastewater swine (R2) immobilized polyurethane foam. The addition of LAS didn’t influence in the stability of the reactor. LAS began to be degraded after 108 days of its addition in the tributary of the reactors. Removal percentages, considering adsorption and degradation of LAS, with 313 days of operation was same to 50% and 91% for R1 and R2, respectively, when they were fed with synthetic sewage and 14 mg/L of LAS (reactor – R1) and only LAS to 14 mg/L (reactor – R2). In relation to the balance of mass of LAS, the reactors presented very similar degradations, being 35% for the reactor R1 and 34% for the reactor R2. The microbial diversity regarding the Bacteria and Archaea domain and to the group BRS was evaluated using the technique of PCR/DGGE. The alteration in the microbial diversity might have happened due to the selection of the microorganisms for the presence of the surfactant. The biomass present in the end of the operation was submitted the cloning technique and sequencing of the fragment of 16S rRNA for the bacteria domain. It was observed that the reactors presented larger number of clones related to the phylum Firmicutes, Clostridia, Clostridiales. Probably the microorganisms belonging to that group are involved with the degradation of LAS

O objetivo desse trabalho foi avaliar a degradação de alquilbenzeno linear sulfonado (LAS) em condições anaeróbias. Os primeiros experimentos foram realizados em reatores em batelada alimentados com diferentes substratos e concentrações de LAS. Apesar do surfactante ficar adsorvido no lodo, não foram observadas interferências no metabolismo de microrganismos anaeróbios, pois dessa forma o LAS tornou-se indisponível para a degradação celular. Reatores anaeróbios horizontais de leito fixo (RAHLF) foram avaliados quanto à remoção de LAS e inoculados com lodos anaeróbios provenientes de reatores UASB usados respectivamente no tratamento de esgoto sanitário (R1) e tratamento de dejetos suinocultura (R2) imobilizados em espuma de poliuretano. A adição de LAS não influenciou na estabilidade do reator. O LAS começou a ser degradado após 108 dias da sua adição no afluente dos reatores. Porcentagens de remoção, considerando adsorção e degradação de LAS, com 313 dias de operação foram iguais a 50% e 91% para o R1 e R2, respectivamente, quando foram alimentados com esgoto sintético e 14 mg/L de LAS (reator - R1) e somente LAS a 14 mg/L (reator - R2). Em relação ao balanço de massa de LAS, os reatores apresentaram degradações muito semelhantes, sendo 35% para o reator R1 e 34% para o reator - R2. A diversidade microbiana referente aos domínios Bacteria e Archaea e ao grupo BRS foi avaliada utilizando a técnica de PCR/DGGE. Para o domínio Archaea, foram observadas diferenças significativas nas populações quando os reatores foram alimentados com LAS. Diferenças foram observadas no domínio Bactéria e grupo das BRS, para concentrações de LAS de 14 mg/L. A alteração na diversidade microbiana pode ter ocorrido devido à seleção dos microrganismos pela presença do surfactante. A biomassa presente no final da operação foi submetida à técnica de clonagem e seqüenciamento do fragmento do RNAr 16S para o domínio Bacteria. Observou-se que os reatores que apresentaram maior número de clones relacionados ao filo Firmicutes, classe Clostridia, ordem Clostridiales. Provavelmente os microrganismos pertencentes a esse grupo estejam envolvidos com a degradação do LAS / The objective of this work was to evaluate the degradation of linear alkylbenzene sulfonate (LAS) in anaerobic conditions. The first experiments were accomplished in reactors in batch fed with different substrates and concentration of LAS. In spite of the surfactant to be adsorbed in the sludge interferences was not observed in the metabolism of anaerobic microorganisms, because in that way LAS became unavailable for the cellular degradation. Horizontal anaerobic immobilized biomass (HAIB) reactors were appraised as for the removal of LAS and inoculated with coming anaerobic slugde of reactors UASB used respectively in the treatment of sanitary sewage (R1) and treatment of wastewater swine (R2) immobilized polyurethane foam. The addition of LAS didn’t influence in the stability of the reactor. LAS began to be degraded after 108 days of its addition in the tributary of the reactors. Removal percentages, considering adsorption and degradation of LAS, with 313 days of operation was same to 50% and 91% for R1 and R2, respectively, when they were fed with synthetic sewage and 14 mg/L of LAS (reactor – R1) and only LAS to 14 mg/L (reactor – R2). In relation to the balance of mass of LAS, the reactors presented very similar degradations, being 35% for the reactor R1 and 34% for the reactor R2. The microbial diversity regarding the Bacteria and Archaea domain and to the group BRS was evaluated using the technique of PCR/DGGE. The alteration in the microbial diversity might have happened due to the selection of the microorganisms for the presence of the surfactant. The biomass present in the end of the operation was submitted the cloning technique and sequencing of the fragment of 16S rRNA for the bacteria domain. It was observed that the reactors presented larger number of clones related to the phylum Firmicutes, Clostridia, Clostridiales. Probably the microorganisms belonging to that group are involved with the degradation of LAS

Nesse trabalho avaliaram-se quatro hipóteses sobre a remoção do alquilbenzeno linear sulfonado (LAS) em reator EGSB (expanded granular sludge bed) alimentado ora com água residuária de lavanderia comercial, ora como meio sintético acrescido de LAS Padrão, com e sem suplementação de Fe(III) afluente. Para tanto, em todas as hipóteses utilizou-se reator EGSB (1,4 L) com tempo de detenção hidráulica (TDH) de 36h, condição mesofílica (30ºC) e carga de LAS específica aplicada (CLEA) variando de 1,0 - 2,7 mgLAS.gSTV-1.d-1. DGGE e sequenciamento massivo do gene rRNA 16S (Plataforma 454-Pirosequenciamento e Ion Torrent) foram utilizados para caracterização microbiana. Em relação à Hipótese A avaliou-se o efeito da adaptação prévia da biomassa na remoção do LAS em água residuária. Para tanto, o EGSB-BA (biomassa adaptada) teve uma etapa prévia com LAS padrão e meio sintético (Etapa I), seguida da Etapa II com água residuária; e o EGSB-BNA (biomassa não adaptada) teve etapa única e alimentação diretamente com água residuária. Para a Hipótese B avaliou-se o efeito da suplementação com meio sintético na remoção de LAS em água residuária. Para tanto, o EGSB-Ag.Lav foi alimentado apenas com água residuária e bicarbonato de sódio e duas CLE (Etapa II - 1,0 e Etapa III - 2,7 mg LAS.gSTV-1.d-1). Em relação às Hipóteses C e D, avaliou-se o efeito da suplementação de Fe(III) na remoção de LAS Padrão em meio sintético e LAS em água residuária, respectivamente. A Hipótese A foi refutada uma vez que as remoções de LAS em EGSB-BA-Etapa II (76%) e EGSB-BNA-Etapa I (78%) foram similares (ambas com água residuária). A remoção de LAS foi maior quando foi adicionada água residuária (EGSB-BA-Etapa II-76%) do que com LAS Padrão (EGSB-BA-Etapa I-63%). A Hipótese B foi aceita, uma vez que a alimentação do EGSB apenas com água residuária de lavanderia (CLE 1,0 mg LAS.gSTV-1.d-1) mais bicarbonato de sódio resultou em remoções do surfactante de 93%, ou seja, 15-17% maior que nos reatores suplementados com meio sintético (EGSB-BA Etapa II e EGSB-BNA Etapa I). Na Etapa III verificou-se diminuição da remoção em 30%. A Hipótese C foi aceita uma vez que se notou 20% de aumento na remoção de LAS quando comparado com reator não suplementado com Fe(III) (EGSB-Fe - 84,3% e EGSB-BA Etapa I - 63,5%). A Hipótese D foi refutada, uma vez que embora tenha sido obtida alta remoção de LAS (91,2%), esta não foi acompanhada pela redução férrica. Por meio do DGGE (domínio Bactéria) notou-se estratificação microbiana ao longo do reator na Etapa III (Hipótese B), provavelmente, em função do tamanho do grânulo que variou ao longo do reator. Por meio do sequenciamento massivo identificou-se bactérias semelhantes à Geobacter na amostra proveniente do reator EGSBFe da Hipótese C (17% da abundância relativa), portanto, as condições impostas favoreceram esse gênero. Fato este não observado para o reator EGSB-Fe-Ag.Lav. da Hipótese D. A comparação da análise filogenética das bactérias para os diferentes reatores permitiu identificar gêneros em comum relacionados com a degradação de LAS, a saber: Desulfobulbus, Geobacter, Syntrophorhabdus, Sporomusa, Comamonas, Holophaga, Mycobacterium, Pseudomonas, Stenotrophomonas e Synergistes. / This study evaluated four hypotheses about the removal of linear alkylbenzene sulfonate (LAS) in EGSB reactor (expanded granular sludge bed) fed sometimes with commercial laundry wastewater, sometimes with synthetic medium more Standard LAS, with and without Fe(III) influent supplementation. Therefore, in all hypotheses were used an EGSB reactor (1.4 L) with a hydraulic retention time (HRT) of 36 h, mesophilic condition (30°C) and load specific LAS (CLE) ranging from 1,0 to 2,7 mgLAS.gSTV-1.d-1. DGGE and massive sequencing of 16S rRNA gene (454-pyrosequencing and Ion Torrent platform) were used for microbial characterization. Regarding the Hypothesis A, it was evaluated the effect of biomass pre-adaptation for removal of LAS in wastewater. Then, the EGSBBA (adapted biomass) had a previous step with standard LAS and synthetic medium (Phase I), followed by Stage II with wastewater; and EGSB-BNA (not adapted biomass) had single step and feeding directly with wastewater. Regarding the Hypothesis B, it was evaluated the effect of synthetic medium supplementation in the removal of LAS in wastewater. Then, the EGSB-Ag.Lav was fed only with wastewater and sodium bicarbonate with two CLE (Stage II - 1,0 e Stage III - 2,7 mg LAS.gSTV-1.d-1). Regarding the Hypothesis C and D, it was evaluated the effect of Fe(III) supplementation in the removal of standard LAS and LAS in wastewater, respectively. The Hypothesis A was refuted since the LAS removal in EGSB-BA-Stage II (76%) and EGSB-BNA-Step I (78%) were similar (both with wastewater). The LAS removal was highest when wastewater was added (EGSB-BA-Stage-II 76%) than with standard LAS (EGSB-BAStage- I 63%). The Hypothesis B was accepted, since the feed of the EGSB only with wastewater from laundry (CLE 1,0 mg LAS.gSTV-1.d-1) more sodium bicarbonate resulted in removal of 93% of surfactant, in other words, 15-17% higher than in the reactors supplemented with synthetic medium (EGSB-BA Stage II e EGSB-BNA Stage I). In the Stage III, there was a decrease by 30% of LAS removal. The Hypothesis C was accepted, since there was an increase of 20% in the removal of LAS as compared to unsupplemented reactor with Fe (III) (EGSB-Fe - 84,3% e EGSB-BA Stage I - 63,5%). The Hypothesis D was refuted since although high LAS removal was obtained (91,2%), this was not accompanied by ferric reduction. By means of DGGE (Bacteria domain) was noted a microbial stratification along the reactor in the Stage III (Hypothesis B), probably in function of granule size along the reactor. By means of massive sequencing were identified bacteria similar to Geobacter in the sample from the reactor EGSB-Fe Hypothesis C (relative abundance 17%), therefore, the conditions favored this genre. This fact was not observed in the reactor EGSB-Fe-Ag.Lav. hypothesis D. A comparison of phylogenetic analysis of bacteria for different reactors allowed to identify common genera related to LAS degradation, namely: Desulfobulbus, Geobacter, Syntrophorhabdus, Sporomusa, Comamonas, Holophaga, Mycobacterium, Pseudomonas, Stenotrophomonas and Synergistes.

The aim of this study was to understand the contribution of Linear Alkylbenzene Sulfonates (LAS) to the decline of Mediterranean coastal forest exposed to marine aerosols. LAS are a group of synthetic anionic surfactants widely used in the composition of household or industrial detergents and agrochemicals. This study was part of a large project (RISICO) aiming the assessment of the environmental impact of the LAS at multiple levels: biodegradation in the coastal waters, sorption – desorption processes in the sediments, toxicity to the aquatic life and toxicity to the coastal forest (by aerosolisation of the sea water). <p>Previous studies pointed out this group of surfactants as the main cause of the coastal forest decline. However, the quantification of this surfactant in the environmental samples (mainly sea water and foliar deposition) was done using non-specific analytical methods as methylene blue active substances (MBAS), leading to overestimation of the environmental concentrations of LAS. <p>The work hypothesis was that at actual environmental concentrations, the LAS does not play a key role in the foliar uptake of the sea salt deposited on the coastal vegetation by the marine aerosols, therefore the LAS may not be the main cause of the coastal forest decline. <p>The research involved both greenhouse experiments and field measurements. The experimental work was conducted on young Mediterranean trees (Laurus nobilis L. Quercus ilex L. and Pinus halepensis P. Mill.) and investigated the synergistic toxic effects of exposure to simulated marine aerosol contaminated with surfactants. An array of endpoints was used including photosynthetic activity, relative water content, foliar deposition and uptake of salt and LAS, and pigments analysis. The results of those experiments revealed that LAS itself did not have phytotoxic effects. Nevertheless, the surfactant was shown to enhance the foliar uptake of the salt in the tested species, especially in Pinus halepensis, confirming the conclusions of previous studies regarding the sensitivity of this species to polluted marine aerosols. <p>The field work was conducted in San Rossore National Park (Italy) and Porquerolles Island (France) and was focused on evaluating the health status of the Mediterranean forest (Quercus ilex L. Pinus halepensis Mill. and Pinus pinaster Aiton.) and also on quantification of LAS in coastal aerosols using highly specific analytical methods, like the mass spectrometry (MS). The frequencies and extent of injuries in the coastal trees were found to be correlated to the salt but not with the LAS content of the leaves. The concentrations of LAS in the Pinus and Quercus leaves were comparable in the two studied sites but the concentrations of salt were extremely high in San Rossore, suggesting that other factors may determine the excessive salt foliar uptake. The parallel MS and MBAS carried out in the same set of aerosol samples revealed that MBAS measurements were not relevant for LAS concentrations in the marine aerosols. Projecting the experimental results to the real LAS and salt exposure of the coastal forest, we concluded that LAS may play a marginal role in coastal vegetation decline. <p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Τις τελευταίες δεκαετίες η συνεχώς αυξανόμενη παγκόσμια δραστηριότητα, λόγω της έντονης αστικοποίησης και βιομηχανοποίησης, έχει σαν αποτέλεσμα την παραγωγή σημαντικών ποσοτήτων αποβλήτων. Μεταξύ αυτών είναι και η ιλύς, δηλαδή το ημιστερεό υπόλειμμα που παράγεται από τις μονάδες επεξεργασίας αστικών και βιομηχανικών αποβλήτων. Μολονότι η ιλύς αντιμετωπίζεται ως απόβλητο που πρέπει να διατεθεί, είναι στην πραγματικότητα ένας σοβαρά υποτιμημένος πόρος. Πιο συγκεκριμένα, η ιλύς διαθέτει πολύτιμα θρεπτικά συστατικά, ενώ παράλληλα έχει και υψηλή θερμική αξία, ιδιότητες που την καθιστούν κατάλληλη για ένα μεγάλο εύρος χρήσεων. Ωστόσο, η ιλύς είναι φορέας ρύπων, όπως οι παθογόνοι μικροοργανισμοί και οι ξενοβιοτικές ουσίες, η ύπαρξη των οποίων βρίσκεται στο επίκεντρο των ενδιαφερόντων των ερευνητών. Ανάμεσα στις διάφορες διεργασίες που έχουν εφαρμοσθεί μέχρι σήμερα τόσο για την επεξεργασία της ιλύος, όσο και για την απομάκρυνση των ξενοβιοτικών παραγόντων από το περιβάλλον, οι βιολογικές διεργασίες φαίνεται να υπερτερούν αισθητά έναντι των άλλων. Στόχος της παρούσας διατριβής ήταν η εφαρμογή μιας βιολογικής μεθόδου, της βιοσταθεροποίησης, για την επεξεργασία της ιλύος. Η ολοκλήρωση της μελέτης της βιοσταθεροποίησης έγινε με την ανάπτυξη ενός μαθηματικού μοντέλου ικανό να περιγράφει τη διεργασία. Παράλληλα, ερευνήθηκε η δυναμικότητα της διεργασίας αυτής στη βιοαποκατάσταση της ιλύος από το ξενοβιοτικό περιεχόμενό της. Επιπρόσθετα, μελετήθηκε η απομάκρυνση των ξενοβιοτικών ουσιών, μέσω της βιοαποδόμησής τους από αυτόχθονες μικροβιακούς πληθυσμούς της ιλύος, σε άλλα αερόβια περιβάλλοντα. Η εφαρμογή της διεργασίας της βιοσταθεροποίησης πραγματοποιήθηκε σε κατάλληλη πειραματική διάταξη που σχεδιάστηκε και υλοποιήθηκε για το σκοπό αυτό. Η διάταξη αυτή επέτρεπε τον πλήρη έλεγχο και τη σωστή ρύθμιση της διεργασίας. Η ολοκλήρωση των πειραμάτων της λιπασματοποίησης έδειξε ότι η διεργασία αυτή μπορεί να εφαρμοσθεί ως μέθοδος επεξεργασίας και σταθεροποίησης της ιλύος, αρκεί να ρυθμιστούν κατάλληλα καθοριστικές φυσικές και χημικές παράμετροι. Τα αποτελέσματα έδειξαν, επίσης, ότι η διεργασία δεν παρεμποδίζεται από την παρουσία υψηλών αρχικών συγκεντρώσεων ξενοβιοτικών ουσιών στην ιλύ, ενώ αντίθετα οδηγεί στην απομάκρυνσή τους. Τα ποσοστά απομάκρυνσης ήταν ιδιαίτερα υψηλά προκειμένου για τις επιφανειοδραστικές ενώσεις και αρκετά σημαντικά για το φθαλικό εστέρα και τους πολυκυκλικούς αρωματικούς υδρογονάνθρακες. Φαίνεται, λοιπόν, ο πολυποίκιλος μικροβιακός πληθυσμός της βιοσταθεροποίησης να συμβάλλει στην ουσιαστική, αν όχι πλήρη, απομάκρυνση των ξενοβιοτικών ουσιών κατά τη διάρκεια της διεργασίας και να οδηγεί στην παραγωγή σταθερού και ασφαλούς τελικού προϊόντος. Ωστόσο, υψηλά ποσοστά απομάκρυνσης των παραπάνω ξενοβιοτικών ουσιών κατέδειξαν και τα πειράματα που πραγματοποιήθηκαν σε αερόβιες υγρές μικτές καλλιέργειες. Ενδεχομένως, η μικροβιακή συνεργασία να παίζει τον καθοριστικό ρόλο στη βιοαποδόμηση αυτών των ουσιών. Η παρούσα μελέτη θα μπορούσε να συνεισφέρει αποτελεσματικά στην ανάπτυξη μιας αξιόπιστης μεθόδου για τη διαχείριση της ιλύος. Συνολικά, η λιπασματοποίηση μπορεί να αποδειχθεί ένα χρήσιμο εργαλείο για την επιθυμητή βιώσιμη ανάπτυξη της κοινωνίας μας, αφού αφ’ ενός μπορεί να συμβάλλει στη λύση του περιβαλλοντικού προβλήματος της διαχείρισης της ιλύος που παράγεται από τις εγκαταστάσεις επεξεργασίας λυμάτων, που την απασχολεί έντονα, και αφ’ ετέρου μπορεί να εξουδετερώσει το παθογόνο περιεχόμενο και να εξαλείψει τις τοξικές ξενοβιοτικές ουσίες. / The continuously increased human activity of the last few decades, because of the intense urbanization and industrialization, has resulted in the production of a serious amount of wastes. Among these is sewage sludge, which is the semi-solid residue produced by municipal and industrial waste treatment plants. Although sludge is considered as a waste product which must be disposed, it is actually an underestimated resource. Specifically, sludge contains valuable nutrients and high thermal value making sludge appropriate for a wide range of uses. Nevertheless, the existence of pathogens and xenobiotics in sludge has attracted the interest of scientific community. Among various methods that have been used for sludge treatment, as well as the removal of xenobiotics from environmental systems, biological methods are advantageous. The aim of the present work was to assess the sewage sludge treatment by a biological process, which is closed-vessel composting. This study involved also the development of a mathematical model capable of describing the composting process. The efficiency of bioremediation of xenobiotics content during sludge composting was also studied. Finally, the xenobiotics removal was investigated through biodegradation using sludge indigenous microbial populations in other aerobic environments. A suitable experimental configuration was designed and constructed in order to study the composting process. The composting system was designed for complete control and regulation of the process. Based on the results of the composting experiments, it can be concluded that composting is an efficient method allowing for treating and stabilization of sewage sludge, provided that critical physicochemical parameters are adjusted. Results revealed also that composting process is not inhibited by the presence of high initial concentration of xenobiotics. On the contrary, composting results in removal of xenobiotics. With reference to surfactants (LAS.NP and NPEO), the removal percentages were particularly high, while the relevant percentages for phthalate ester and polycyclic aromatics hydrocarbons were also significant. It seems, then, that the variable microbial population of the composting mixture contributes to the elimination of xenobiotic compounds and results in a safe and stable final product. The experiments which were conducted in aerobic mixed liquid cultures showed also high xenobiotic removal percentages. Probably, the microbial consortium could play a significant part in biodegradation of xenobiotic compounds. The present study contributes to the development of a reliable method of sewage sludge treatment. The composting process, totally complies with the desirable sustainable growth for our society by the treatment of sludge produced in waste water treatment plants and by the elimination of the xenobiotic compounds that limit its valorisation.