Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: kinetic modelling

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75–100 mg L−1. The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9–39.5, 18.6–32.0 and 32.3–50.4 mg g−1, respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.

Mercury, cadmium, lead and arsenic levels in three pelagic fish species from the Atlantic Ocean: intra- and inter-specific variability and human health risks for consumption

Three commonly consumed and commercially valuable fish species (sardine, chub and horse mackerel) were collected from the Northeast and Eastern Central Atlantic Ocean in Portuguese waters during one year. Mercury, cadmium, lead and arsenic amounts were determined in muscles using graphite furnace and cold vapour atomic absorption spectrometry. Maximum mean levels of mercury (0.1715 ± 0.0857 mg/kg, ww) and arsenic (1.139 ± 0.350 mg/kg, ww) were detected in horse mackerel. The higher mean amounts of cadmium (0.0084 ± 0.0036 mg/kg, ww) and lead (0.0379 ± 0.0303 mg/kg, ww) were determined in chub mackerel and in sardine, respectively. Intra- and inter-specific variability of metals bioaccumulation was statistically assessed and species and length revealed to be the major influencing biometric factors, in particular for mercury and arsenic. Muscles present metal concentrations below the tolerable limits considered by European Commission Regulation and Food and Agriculture Organization of the United Nations/World Health Organization (FAO/WHO). However, estimation of non-carcinogenic and carcinogenic health risks by the target hazard quotient and target carcinogenic risk, established by the US Environmental Protection Agency, suggests that these species must be eaten in moderation due to possible hazard and carcinogenic risks derived from arsenic (in all analyzed species) and mercury ingestion (in horse and chub mackerel species).

Caracterização química e ecotoxicológica de escórias e cinzas resultantes da co-combustão de lamas e carvão

Em 1999 a Fundação para a Ciência e a Tecnologia aprovou o financiamento do projecto “Behaviour of Heavy Metals on the Thermal Treatment of Residues” cujo acrónimo era Bimetal. Este projecto, cujos parceiros eram o Departamento de Engenharia Energética e Controlo Ambiental do Instituto Nacional de Engenharia e Tecnologia Industrial (INETI) e o Grupo de Disciplinas de Ecologia da Hidrosfera (GDEH) da Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa, tinha como objectivo a avaliação do comportamento de metais pesados durante a combustão de resíduos. Neste sentido, a equipa do INETI efectuou quatro ensaios de incineração: dois de mono-combustão de uma lama residual urbana, um de co-combustão de lama residual urbana e carvão e, finalmente, um de mono-combustão de carvão. Cada ensaio de incineração produziu uma cinza de fundo e duas cinzas volantes, provenientes de dois ciclones. A equipa do GDEH foi responsável pela caracterização físico-química e ecotoxicológica das cinzas provenientes dos ensaios realizados pela equipa do INETI. A avaliação incidiu em dois aspectos: 1) a determinação da composição das cinzas, relativamente a um dado conjunto de parâmetros físico-químicos considerados; e 2) produção de lixiviados a partir do contacto das cinzas com um agente lixiviante. Estes lixiviados foram submetidos à caracterização físico-química, relativamente a um dado conjunto de parâmetros físico-químicos e, ainda, à caracterização ecotoxicológica, recorrendo a dois indicadores biológicos. A determinação da composição das cinzas permitiu efectuar um balanço de massas dos ensaios de incineração realizados e, com isto, determinar as taxas de emissão, dos parâmetros analisados, para a atmosfera. Os ensaios de lixiviação permitiram classificar, de acordo com a metodologia de classificação de resíduos a que se recorreu, as doze cinzas produzidas pela equipa do INETI e os materiais que lhes deram origem, a areia do leito, o carvão e a lama residual urbana. De um modo geral, as duas cinzas volantes apresentaram uma concentração superior, dos parâmetros considerados, relativamente à cinza de fundo. Entre as duas cinzas volantes, a cinza do 2º ciclone apresentou um maior teor, relativamente aos parâmetros analisados, do que as cinzas do 1º ciclone.

Environmental data management in the Sado Estuary

Estuaries are perhaps the most threatened environments in the coastal fringe; the coincidence of high natural value and attractiveness for human use has led to conflicts between conservation and development. These conflicts occur in the Sado Estuary since its location is near the industrialised zone of Peninsula of Setúbal and at the same time, a great part of the Estuary is classified as a Natural Reserve due to its high biodiversity. These facts led us to the need of implementing a model of environmental management and quality assessment, based on methodologies that enable the assessment of the Sado Estuary quality and evaluation of the human pressures in the estuary. These methodologies are based on indicators that can better depict the state of the environment and not necessarily all that could be measured or analysed. Sediments have always been considered as an important temporary source of some compounds or a sink for other type of materials or an interface where a great diversity of biogeochemical transformations occur. For all this they are of great importance in the formulation of coastal management system. Many authors have been using sediments to monitor aquatic contamination, showing great advantages when compared to the sampling of the traditional water column. The main objective of this thesis was to develop an estuary environmental management framework applied to Sado Estuary using the DPSIR Model (EMMSado), including data collection, data processing and data analysis. The support infrastructure of EMMSado were a set of spatially contiguous and homogeneous regions of sediment structure (management units). The environmental quality of the estuary was assessed through the sediment quality assessment and integrated in a preliminary stage with the human pressure for development. Besides the earlier explained advantages, studying the quality of the estuary mainly based on the indicators and indexes of the sediment compartment also turns this methodology easier, faster and human and financial resource saving. These are essential factors to an efficient environmental management of coastal areas. Data management, visualization, processing and analysis was obtained through the combined use of indicators and indices, sampling optimization techniques, Geographical Information Systems, remote sensing, statistics for spatial data, Global Positioning Systems and best expert judgments. As a global conclusion, from the nineteen management units delineated and analyzed three showed no ecological risk (18.5 % of the study area). The areas of more concern (5.6 % of the study area) are located in the North Channel and are under strong human pressure mainly due to industrial activities. These areas have also low hydrodynamics and are, thus associated with high levels of deposition. In particular the areas near Lisnave and Eurominas industries can also accumulate the contamination coming from Águas de Moura Channel, since particles coming from that channel can settle down in that area due to residual flow. In these areas the contaminants of concern, from those analyzed, are the heavy metals and metalloids (Cd, Cu, Zn and As exceeded the PEL guidelines) and the pesticides BHC isomers, heptachlor, isodrin, DDT and metabolits, endosulfan and endrin. In the remain management units (76 % of the study area) there is a moderate impact potential of occurrence of adverse ecological effects and in some of these areas no stress agents could be identified. This emphasizes the need for further research, since unmeasured chemicals may be causing or contributing to these adverse effects. Special attention must be taken to the units with moderate impact potential of occurrence of adverse ecological effects, located inside the natural reserve. Non-point source pollution coming from agriculture and aquaculture activities also seem to contribute with important pollution load into the estuary entering from Águas de Moura Channel. This pressure is expressed in a moderate impact potential for ecological risk existent in the areas near the entrance of this Channel. Pressures may also came from Alcácer Channel although they were not quantified in this study. The management framework presented here, including all the methodological tools may be applied and tested in other estuarine ecosystems, which will also allow a comparison between estuarine ecosystems in other parts of the globe.

Microeukaryoticdiversity in the extreme environments of the Iberian PyriteBelt: a comparison between universal and fungi-specific primer sets, temperature gradient gel electrophoresis and cloning

FEMS Microbiology Ecology, Vol. 57, nº 1

Teor mineral e capacidade antioxidante em chás e infusões

Mestrado em Engenharia Química – Ramo Optimização Energética na Indústria Química

Freshwater arsenic detoxification through selenium-enriched food supplements. A proteomic approach

Dissertação apresentada para a obtenção do grau de doutor em Bioquímica pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Avaliação do papel da glutationa e do vacúolo como mecanismos de defesa contra a toxicidade induzida pelo chumbo na levedura Saccharomyces cerevisiae

A presença de metais pesados no meio ambiente deve-se, principalmente, a actividades antropogénicas. Ao contrário do Cu e do Zn, que em baixas concentrações são essenciais para o normal funcionamento celular, não se conhece para o chumbo nenhuma função biológica. O chumbo apresenta efeitos tóxicos, e considerado possível agente carcinogéneo, sendo classificado como poluente prioritário pela Agencia de Protecção Ambiental dos EUA (US-EPA). O presente trabalho teve como objetivo avaliar o papel da glutationa e do vacúolo, como mecanismos de defesa, contra os efeitos tóxicos induzidos pelo chumbo, usando como modelo a levedura Saccharomyces cerevisiae. A levedura S. cerevisiae quando exposta a varias concentrações de chumbo, durante 3h, perde a viabilidade e acumula espécies reativas de oxigénio (ROS). O estudo comparativo da perda de viabilidade e acumulação de ROS em células de uma estirpe selvagem (WT) e de estirpes mutantes, incapazes de produzir glutationa devido a uma deficiência no gene GSH1 (gsh1) ou GSH2 (gsh2) mostrou que as estirpes gsh1 ou(gsh2 não apresentavam um aumento da sensibilidade ao efeito toxico do chumbo. No entanto, o tratamento de células da estirpe WT com iodoacetamida (um agente alquilante que induz a depleção de glutationa) aumentou a sensibilidade das células a presença de chumbo. Pelo contrário, o enriquecimento em GSH, através da incubação de células WT com glucose e uma mistura de aminoácidos que constituem a GSH (acido L-glutâmico, L-cisteína e glicina), reduziu o stress oxidativo e a perda de viabilidade induzida por chumbo. A importância do vacúolo, como mecanismo de defesa, foi avaliada através da utilização de um mutante sem qualquer estrutura vacuolar (vps16) ou de mutantes deficientes na subunidade catalítica A (vma1) ou B (vma2) ou no proteolítico - subunidade C (vma3) da V-ATPase. As células da estirpe ƒ´vps16 apresentaram uma elevada suscetibilidade a presença de chumbo. As células das estirpes deficientes na subunidade A, B ou c da V-ATPase, apresentaram uma maior perda de viabilidade, quando expostas a chumbo, do que as células da estirpe WT, mas menor do que a da estirpe vps16 Em conclusão, os resultados obtidos, no seu conjunto, sugerem que a glutationa esta envolvida na defesa contra a toxicidade provocada por chumbo; todavia, a glutationa, por si só, parece não ser suficiente para suster o stress oxidativo e a perda de viabilidade induzida por chumbo. O vacúolo parece constituir um importante mecanismo de defesa contra a toxicidade provocada por chumbo. A V-ATPase parece estar envolvida na compartimentação de chumbo no vacúolo.

Produção de sideróforo pela bactéria Bacillus megaterium

Os agentes quelantes, como é o caso do EDTA, são utilizados numa ampla variedade de indústrias como a indústria têxtil, da pasta de papel, alimentar, de cosméticos ou de detergentes. Contudo, os agentes complexantes sintéticos, habitualmente usados, não são biodegradáveis, pelo que a sua acumulação no meio ambiente constitui motivo de preocupação. Deste modo, existe um interesse crescente na substituição destes compostos por compostos similares biodegradáveis sendo, deste modo, ambientalmente amigáveis. Alguns microrganismos são capazes de produzir moléculas com capacidade de captar metais. Um desses exemplos são os sideróforos: compostos produzidos por bactérias, fungos e plantas gramíneas, com capacidade de formar quelatos muito estáveis com o ferro. A presente dissertação teve como objetivo estudar o efeito de diferentes condições culturais e nutricionais na produção de sideróforo pela bactéria Bacillus megaterium. A avaliação da produção de sideróforo, utilizando o método colorimétrico Chrome Azurol S (CAS), durante o crescimento da bactéria, em meio de cultura deficiente em ferro, na presença de 5 ou de 20 g/L de glucose, mostrou que o início da sua produção ocorre, durante a fase exponencial de crescimento, não está relacionada com a esporulação e não é afetada pela concentração de glucose. Contudo, o crescimento da bactéria na presença de diferentes fontes de carbono (glicerol, frutose, galactose, glucose, manose, lactose, maltose ou sacarose) evidenciou que a produção de sideróforo é afetada pelo tipo de fonte de carbono. O crescimento na presença de glicerol promoveu a maior produção de sideróforo; efeito inverso foi observado na presença de manose. A bactéria B. megaterium, quando crescida na presença de frutose, galactose, glucose, lactose, maltose ou sacarose, produziu concentrações similares de sideróforo. O aumento da concentração de arginina, no meio de cultura, não aumentou a produção de sideróforo. A agitação apresentou um efeito positivo na produção de sideróforo; o crescimento em condições estáticas atrasou e diminuiu a produção de sideróforo. Em conclusão, o glicerol parece constituir uma fonte de carbono alternativa, aos monossacáridos e dissacáridos, para a produção de sideróforo. A agitação apresenta um efeito positivo na produção de sideróforo pela bactéria B. megaterium ATCC 19213.

Inoculation with Metal-Mobilizing Plant-GrowthPromoting Rhizobacterium Bacillus sp. SC2b and Its Role in Rhizoremediation

A plant growth-promoting bacterial (PGPB) strain SC2b was isolated from the rhizosphere of Sedum plumbizincicola grown in lead (Pb)/zinc (Zn) mine soils and characterized as Bacillus sp. based on (1) morphological and biochemical characteristics and (2) partial 16S ribosomal DNA sequencing analysis. Strain SC2b exhibited high levels of resistance to cadmium (Cd) (300 mg/L), Zn (730 mg/L), and Pb (1400 mg/L). This strain also showed various plant growth-promoting (PGP) features such as utilization of 1-aminocyclopropane-1-carboxylate, solubilization of phosphate, and production of indole-3-acetic acid and siderophore. The strain mobilized high concentration of heavy metals from soils and exhibited different biosorption capacity toward the tested metal ions. Strain SC2b was further assessed for PGP activity by phytagar assay with a model plant Brassica napus. Inoculation of SC2b increased the biomass and vigor index of B. napus. Considering such potential, a pot experiment was conducted to assess the effects of inoculating the metal-resistant PGPB SC2b on growth and uptake of Cd, Zn and Pb by S. plumbizincicola in metal-contaminated agricultural soils. Inoculation with SC2b elevated the shoot and root biomass and leaf chlorophyll content of S. plumbizincicola. Similarly, plants inoculated with SC2b demonstrated markedly higher Cd and Zn accumulation in the root and shoot system, indicating that SC2b enhanced Cd and Zn uptake by S. plumbizincicola through metal mobilization or plant-microbial mediated changes in chemical or biological soil properties. Data demonstrated that the PGPB Bacillus sp. SC2b might serve as a future biofertilizer and an effective metal mobilizing bioinoculant for rhizoremediation of metal polluted soils.

Serpentine bacteria influence metal translocation and bioconcentration of Brassica juncea and Ricinus communis grown in multi-metal polluted soils

The aim of this study was to assess the effects of inoculation of rhizosphere or endophytic bacteria (Psychrobacter sp. SRS8 and Pseudomonas sp. A3R3, respectively) isolated from a serpentine environment on the plant growth and the translocation and accumulation of Ni, Zn, and Fe by Brassica juncea and Ricinus communis on a multi-metal polluted serpentine soil (SS). Field collected SS was diluted to 0, 25, 50, and 75% with pristine soil in order to obtain a range of heavy metal concentrations and used in microcosm experiments. Regardless of inoculation with bacteria, the biomass of both plant species decreased with increase of the proportion of SS. Inoculation of plants with bacteria significantly increased the plant biomass and the heavy metal accumulation compared with non-inoculated control in the presence of different proportion of SS, which was attributed to the production of plant growth promoting and/or metal mobilizing metabolites by bacteria. However, SRS8 showed a maximum increase in the biomass of the test plants grown even in the treatment of 75% SS. In turn, A3R3 showed maximum effects on the accumulation of heavy metals in both plants. Regardless of inoculation of bacteria and proportion of SS, both plant species exhibited low values of bioconcentration factor (<1) for Ni and Fe. The inoculation of both bacterial strains significantly increased the translocation factor (TF) of Ni while decreasing the TF of Zn in both plant species. Besides this contrasting effect, the TFs of all metals were <1, indicating that all studied bacteria–plant combinations are suitable for phytostabilization. This study demonstrates that the bacterial isolates A3R3 and SRS8 improved the growth of B. juncea and R. communis in SS soils and have a great potential to be used as inoculants in phytostabilization scenarios of multi-metal contaminated soils.

The hyperaccumulator Sedum plumbizincicola harbors metal-resistant endophytic bacteria that improve its phytoextraction capacity in multi-metal contaminated soil

Endophyte-assisted phytoremediation has recently been suggested as a successful approach for ecological restoration of metal contaminated soils, however little information is available on the influence of endophytic bacteria on the phytoextraction capacity of metal hyperaccumulating plants in multi-metal polluted soils. The aims of our study were to isolate and characterize metal-resistant and 1-aminocyclopropane-1-carboxylate (ACC) utilizing endophytic bacteria from tissues of the newly discovered Zn/Cd hyperaccumulator Sedum plumbizincicola and to examine if these endophytic bacterial strains could improve the efficiency of phytoextraction of multi-metal contaminated soils. Among a collection of 42 metal resistant bacterial strains isolated from the tissues of S. plumbizincicola grown on Pb/Zn mine tailings, five plant growth promoting endophytic bacterial strains (PGPE) were selected due to their ability to promote plant growth and to utilize ACC as the sole nitrogen source. The five isolates were identified as Bacillus pumilus E2S2, Bacillus sp. E1S2, Bacillus sp. E4S1, Achromobacter sp. E4L5 and Stenotrophomonas sp. E1L and subsequent testing revealed that they all exhibited traits associated with plant growth promotion, such as production of indole-3-acetic acid and siderophores and solubilization of phosphorus. These five strains showed high resistance to heavy metals (Cd, Zn and Pb) and various antibiotics. Further, inoculation of these ACC utilizing strains significantly increased the concentrations of water extractable Cd and Zn in soil. Moreover, a pot experiment was conducted to elucidate the effects of inoculating metal-resistant ACC utilizing strains on the growth of S. plumbizincicola and its uptake of Cd, Zn and Pb in multi-metal contaminated soils. Out of the five strains, B. pumilus E2S2 significantly increased root (146%) and shoot (17%) length, fresh (37%) and dry biomass (32%) of S. plumbizincicola as well as plant Cd uptake (43%), whereas Bacillus sp. E1S2 significantly enhanced the accumulation of Zn (18%) in plants compared with non-inoculated controls. The inoculated strains also showed high levels of colonization in rhizosphere and plant tissues. Results demonstrate the potential to improve phytoextraction of soils contaminated with multiple heavy metals by inoculating metal hyperaccumulating plants with their own selected functional endophytic bacterial strains.

The use of nanoparticles in soil and water remediation processes

Environmental nanoremediation of various contaminants has been reported in several recent studies. In this paper, the state of the art on the use of nanoparticles in soil and groundwater remediation processes is presented. There is a substantive body of evidence on the growing and successful application of nanoremediation for a diversity of soil and groundwater contamination contexts, particularly, for heavy metals, other inorganic contaminants, organic contaminants and emerging contaminants, as pharmaceutical and personal care products. This review confirms the competence of the use of nanoparticles in the remediation of contaminated media and the prevalent use of iron based nanoparticles.

Fate Hazardous elements in soils surrounding a coal-fired power plant complex

Proceedings of the 13th International UFZ-Deltares Conference on Sustainable Use and Management of Soil, Sediment and Water Resources - 9–12 June 2015 • Copenhagen, Denmark

Responses of the alga Pseudokirchneriella subcapitata to long-term exposure to metal stress

The green alga Pseudokirchneriella subcapitata has been widely used in ecological risk assessment, usually based on the impact of the toxicants in the alga growth. However, the physiological causes that lead algal growth inhibition are not completely understood. This work aimed to evaluate the biochemical and structural modifications in P. subcapitata after exposure, for 72 h, to three nominal concentrations of Cd(II), Cr(VI), Cu(II) and Zn(II), corresponding approximately to 72 h-EC10 and 72 h-EC50 values and a high concentration (above 72 h-EC90 values). The incubation of algal cells with the highest concentration of Cd(II), Cr(VI) or Cu(II) resulted in a loss of membrane integrity of ~16, 38 and 55%, respectively. For all metals tested, an inhibition of esterase activity, in a dose-dependent manner, was observed. Reduction of chlorophyll a content, decrease of maximum quantum yield of photosystem II and modification of mitochondrial membrane potential was also verified. In conclusion, the exposure of P. subcapitata to metals resulted in a perturbation of the cell physiological status. Principal component analysis revealed that the impairment of esterase activity combined with the reduction of chlorophyll a content were related with the inhibition of growth caused by a prolonged exposure to the heavy metals.