Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

Dibenzothiophene oxidation by horseradish peroxidase in organic media: effect of the DBT:H2O2 molar ratio and H2O2 addition mode

Its is well known that in the biodesulfurization (BDS) process the low water solubility of sulfur compounds hinders its transference from the oil phase to the cells being the rate-limiting step in the metabolism of dibenzothiophenes (DBT). Thus sulfur compounds derivatives with high water solubility could be more easily transported increasing the BDS efficiency. The present work performed a stepwise evaluation of the enzymatic oxidation of DBT by horseradish peroxidase (HRP). Reactions were carried out in monophasic organic media containing 25% (v/v) acetonitrile. The following parameters were evaluated: DBT:H2O2 molar ratio (1:1-1:20); H2O2 addition mode (single or stepwise); pH (6.0-8.0) and temperature (37-50 degrees C). Best results were observed in a reaction medium at pH 8.0 presenting HRP 0.06IUml(-1), DBT 0.267mM, DBT:H2O2 molar ratio of 1:20 (stepwise hydrogen peroxide addition) and incubated at 45 degrees C for 60min. Under these conditions 60% of DBT was converted into dibenzothiophene sulfoxide (12%) and dibenzothiophene sulfone (46%). The DBT oxidation rate observed in this work, of 5mmolmin(-1)g(-1) of HRP, was 250-fold higher than the BDS rate, 20mumolmin(-1)g(-1) of catalyst. As such a combined enzyme-microbial desulfurization process could be envisaged. Products were determined by HPLC RP C-18.     

Influence of humic substances on the photolysis of aqueous pesticide residues

The present work investigated the direct and indirect photolysis of pesticide residues (atrazine, imazaquin, iprodione), in aqueous solutions and under UV-visible radiation (280-480nm). Different kinds of humic substances (HS) were added to samples in order to evaluate their behaviour as possible photocatalysts and their effect on the photolysis of pesticides. The fulvic acids were purchased from the International Humic Substances Society, and they were added to samples in concentrations ranging from 1 to 150 mgl(-1). Titanium dioxide was used as the photocatalyst, in concentration ranging from 10 to 150 mgl(-1). Pesticides photolysis were measured by UV-visible absorption spectroscopy and differential pulse polarography with all used pesticides, reaching total degradation after 2h of irradiation, thus indicating a fast direct photolysis. Photocatalysis by TiO(2) could increase the pesticides photolysis rate up to 40%. This effect, however, was not observed for imazaquin photolysis. Again, except for imazaquin, HS presence showed a positive effect in increasing pesticide degradation, but only within specific concentration ranges (below 10mg l(-1) for iprodione and about 30mgl(-1) for atrazine). Above these ranges HS induce a decrease in the pesticides photolysis rate. Spin-trapping measurements by electronic paramagnetic resonance spectroscopy, using the spin-trap DMPO, showed that HS are able to photogenerate hydroxyl radicals, increasing the pesticides molecule degradation. However, the HS also react with the photogenerated hydroxyl radical, influencing the pesticide photolysis, leading to a decrease in the photolysis rate and causing it to be strongly dependent on the nature and concentration of residues in the water to be treated.     

The environmental behaviour of polychlorinated phenols and its relevance to cork forest ecosystems: a review

Pentachlorophenol (PCP) has been used as a herbicide, biocide and preservative worldwide since the 1930s and as a result, extensive and prolonged contamination exists. The environmental impact increases when its many degradation products are taken into consideration. A number of chloroanisols and their related chlorophenols have been found in cork slabs collected from Portuguese oak tree forests before stopper manufacturing, and contamination by PCP and polychlorinated anisole (PCA) has been detected in Canadian forests. It is suggested that the use of polychlorinated phenols, in particular PCP, is thought to be a cause of the cork taint problem in wine, a major socio-economic impact not only for industry but on sensitive and highly biodiverse ecosystems. It also highlights particular issues relating to the regional regulation of potentially toxic chemicals and global economics world wide. To fully understand the impact of contamination sources, the mechanisms responsible for the fate and transport of PCP and its degradation products and assessment of their environmental behaviour is required. This review looks at the current state of knowledge of soil sorption, fate and bioavailability and identifies the challenges of degradation product identification and the contradictory evidence from field and laboratory observations. The need for a systematic evaluation of PCP contamination in relation to cork forest ecosystems and transfer of PCP between trophic levels is emphasised by discrepancies in bioaccumulation and toxicity. This is essential to enable long term management of not only transboundary contaminants, but also the sustainable management of socially and economically important forest ecosystems.     

Effects of the tsunami on fisheries and coastal livelihood: a case study of tsunami-ravaged southern Sri Lanka

Beyond the death toll, the tsunami of 26 December 2004 crippled many of the livelihood assets (human, social, physical, financial and natural) available to assist those directly affected. Drawing on surveys of three villages in three districts in the south of Sri Lanka, this paper describes the livelihood asset building capacity of the fishing communities. Assessments are also made of the impact of the tsunami on coastal communities and the impact of government policy on rebuilding. A livelihood asset score was calculated for each village by comparing their strengths in capacity building. In all aspects of capital building, including human, social, financial, physical and natural capital, the fishing community in Tangalle was significantly ahead of the fishing communities in Hikkaduwa and Weligama. Experienced fishermen with better educational backgrounds had a significant influence on the capacity building of livelihood assets. Relocation and resettlement plans brought persistent uncertainty to fishermen in Hikkaduwa and Weligama and threatened to disrupt their community bonds and social networks.     

Evaluation of genotoxicity and toxicity of water and sediment samples from a Brazilian stream influenced by tannery industries

This paper reports results of genotoxicity and toxicity studies of water and sediment samples collected from the Estancia Velha stream of southern Brazil, a stream transporting both domestic sewage and effluents from regional factories working in the leather industry. Three sites were selected: in the stream headwaters (Site 1), located downstream of an urban area (Site 2), and near the basin outfall (Site 3). Results obtained with Allium cepa showed no evidence of chromosomal mutation, either in water or in sediment, during winter or summer seasons, but samples collected below Site 1 showed high toxicity. Physical and chemical analyses showed high concentrations of pollutants at these sites. Ecotoxicity tests with Daphnia magna and Ceriodaphnia dubia measured toxicity in water from Sites 2 and 3 in summer 2004. A toxic effect on Hyalella azteca was only found in sediment from Site 3 during winter 2003 and summer 2004. The results suggest that the synergy among different compounds in domestic and industrial sewage discharges can make it difficult to maintain system stability.     

Cephalopods and cetaceans as indicators of offshore bioavailability of cadmium off Central South Brazil Bight

Regarding Brazilian coast, industrial and urban developments are concentrated along Central South Brazil Bight. Samples from inshore and offshore species from the concerned area were analyzed, comprising 24 cetaceans (9 species) and 32 squids (2 species). Cadmium was determined by GFAAS and our results were in agreement with certified values (DOLT-2, NRCC). Mean cadmium concentration (in microg/g, wet weight) observed in the digestive gland of sexually mature Argentine short-finned squids (Illex argentinus) was 1002.9. To our knowledge this is the highest cadmium level ever reported for a cephalopod. Concerning cetaceans, our results include one of the highest renal cadmium concentrations described for striped dolphins (71.29 microg/g, wet weight). Anthropogenic action, upwelling and cannibalism of Argentine short-finned squid on the studied area are possible reasons for such remarkable cadmium concentrations.