Study on fractions of adsorbed Pb and Cd onto natural surface coatings

The speciation and extent of migration of adsorbed Pb and Cd in natural surface coatings (NSCs) were investigated using sequential extraction procedure to provide an understanding of distribution of the adsorbed Pb and Cd. Extractions were conducted on NSCs before and after Pb and Cd adsorption treatment under controlled laboratory conditions with initial Pb and Cd concentrations ranging from 0.2-2.5 mol/l. The Langmuir adsorption isotherms were applied to estimate equilibrium coefficients of Pb and Cd adsorption to NSCs components. The results showed that 58.50% of adsorbed Pb in average existed in tightly adsorbed form, and the remaining Pb was mostly present as solid oxides/hydroxides (34.00%) and exchangeable and soluble form (7.50%) in NSCs, respectively. Large amount of adsorbed Cd (70.51% in average) was present in exchangeable and soluble form, following a decreasing order in tightly adsorbed form (18.61%), solid oxides/hydroxides (9.87%), and easily oxidizable solids/compounds (1.01%), respectively. No Cd was found in strongly held oxides and precipitates. Compared to the distribution of adsorbed Pb in NSCs, Cd distribution showed that less migration of Cd from exchangeable and soluble form to solid oxides/hydroxides after adsorbed to NSCs, indicating fewer sites for Cd to adsorb to NSCs and less affinity of Cd to the NSCs. These percent distributions of metals provided an additional interpretation to that Pb adsorption to the NSCs greater than that of Cd, less retention of Cd than that of Pb and less roles attributed for Pb/Cd adsorption by organic materials in NSCs, which were observed based on the selective extraction techniques in the independent investigations.     

New evidences for old biomarkers: effects of several xenobiotics on EROD and AChE activities in Zebra mussel (Dreissena polymorpha)

The biomarker approach is widely used both in vertebrates and invertebrates for environmental biomonitoring, because it can supply an integrated response for multi-xenobiotics contamination. However, the use of biomarkers requires the identification of every possible variation that can influence the biochemical response, because ecosystems are generally subject to a mixture of pollutants, which can create additive, opposite or competitive effects. In recent years, there has been considerable interest in the use of biomarkers within marine bivalves, while very few data are available for freshwater molluscs. The aim of this research was to investigate changes on EROD and AChE activities in the freshwater bivalve Zebra mussel (Dreissena polymorpha) exposed to different pollutants (Arochlor 1260, CB 153 and 126, pp'DDT, chlorpyrifos, carbaryl) at laboratory conditions, in order to standardize the analytical procedures and to highlight eventual interferences on enzyme activities. Chemical concentrations in the mussel soft tissues were analyzed by GC/MS-MS. Main results showed a significant induction of EROD activity when mussels were exposed to 100 ng/l of PCB mixture of Arochlor 1260 and dioxin-like CB 126, but this congener showed also a clear competitive inhibition after 48 h of exposure. Surprisingly, pp'DDT determined a significant decrease of basal EROD activity after only 24 h of exposure, even if it was not possible to discriminate between the effect of the parent compound and that of its metabolites (DDD, DDE). We also found an interaction between the organophosphate insecticide chlorpyrifos, which does not directly decrease the AChE activity, and terbutilazine. This herbicide increased the biotransformation of the organophosphate compound to its oxidized metabolite (oxon), a much stronger AChE inhibitor. The possible use of the oxime Pyridine-2-Aldoxime Methochloride (2-PAM) to bring back the catalytic activity to basal levels was also demonstrated.     

Impacts of COD and DCP loading rates on biological treatment of 2,4-dichlorophenol (DCP) containing wastewater in a perforated tubes biofilm reactor

Biofilm processes offer considerable advantages for biological treatment of chlorophenol containing wastewaters since such industrial effluents are difficult to treat by conventional activated sludge processes. A rotating perforated tubes biofilm reactor (RTBR) was developed and used for treatment of 2,4-dichlorophenol (DCP) containing synthetic wastewater. Effects of COD and DCP loading rates on COD, DCP and toxicity removals were investigated. Percent COD removal decreased and effluent COD increased with increasing COD and DCP loading rates due to toxic effects of high DCP content in the feed. DCP and toxicity removals showed similar trends. As the DCP loading rate increased the effluent DCP content increased yielding high toxicity levels in the effluent. COD and DCP loading rates should be below 90gCODm(-2)d(-1) and 2.8gDCPm(-2)d(-1) in order to obtain more than 90% DCP and toxicity removals. However, DCP loading rates lower than 1gDCPm(-2)d(-1) are required to obtain more than 90% COD removal. Empirical equations were developed to estimate percent COD, DCP and toxicity removals as functions of COD and DCP loading rates. The coefficients of the empirical equations were determined by using the experimental data. Empirical model predictions for percent COD, DCP and toxicity removals were in good agreement with the experimental data.     

Degradation of lansoprazole and omeprazole in the aquatic environment

Lansoprazole and omeprazole degrade in water leading to sulfides, benzimidazolones and a red complex material. Degradation is accelerated in acid medium and by solar simulator irradiation. Benzimidazoles, dianilines and pyridines have also been identified.     

Dye-sensitized photodegradation of the fungicide carbendazim and related benzimidazoles

The present work studies the visible-light-promoted photodegradation of the colorless fungicide carbendazim (methyl 2-benzimidazolecarbamate) and several 2-substituted benzimidazoles (SBZ's), in water or water-methanol solution, in the presence of air and, as a photosensitizer, the synthetic xanthene dye Rose Bengal (RB) or the natural pigment riboflavin (Rf). The results indicate that the degradation of each particular SBZ depends on its chemical structure and on the sensitizer employed. In the presence of RB, the degradation always operates via a singlet molecular oxygen (O(2)((1)Delta(g)))-mediated mechanism, through a highly efficient process, as deduced from the comparison of the rate constants for physical and chemical quenching of O(2)((1)Delta(g)). In the presence of Rf, the visible-light irradiation of any of the studied SBZ's produces a series of competitive processes that depend on the relative concentrations of Rf and SBZ. These processes include the quenching of excited singlet and triplet Rf states by the SBZ and the generation of both O(2)((1)Delta(g)) and superoxide radical anion (O(2)(-)), the latter generated by electron transfer from excited Rf species to the dissolved oxygen. The overall result is the photodegradation of the SBZ and the photoprotection of the sensitizer.     

Influence of cadmium on antioxidant capacity and four microelement concentrations in tomato seedlings (Lycopersicon esculentum)

Tomato (Lycopersicon esculentum) seedlings were grown in four cadmium (Cd) levels of 0-10 microM in a hydroponic system to analyze the antioxidative enzymes, Cd concentration in the plants, and the interaction between Cd and four microelements. The results showed that there was a significant increase in malondialdehyde (MDA) concentration, and superoxide dismutase (SOD) and peroxidase (POD) activities in the plants subjected to 1-10 microM Cd. This indicates that Cd stress induces an oxidative stress response in tomato plants, characterized by an accumulation of MDA and increase in activities of SOD and POD. Root, stem and leaf Cd concentrations increased with its exposure Cd level, and the highest Cd concentration occurred in roots, followed by leaves and stems. A concentration- and tissue-dependent response was found in the four microelement concentrations to Cd stress in the tomato leaves, stems and roots. Regression analysis showed that there was a significantly negative correlation between Cd and Mn, implying the antagonistic effect of Cd on Mn absorption and translocation. The correlation between Cd and Zn, Cu and Fe were inconsistent among leaves, stems and roots.     

Trace metals in arcid clam Scapharca inaequivalvis: effects of molluscan extracts on bioluminescent bacteria

The relationship between a supposed effect of molluscan extracts on bioluminescent bacteria and metal concentrations in the extracts was investigated. For this purpose a biotoxicological assay based on bioluminescent bacteria (BLB) and extracts from metal exposed molluscs, Scapharca inaequivalvis, was optimized to monitor Cd and Cu marine pollution. Cu and Cd concentrations increased in tissues of experimentally exposed molluscs. Molluscan extracts inhibited the bacterial luminescence, the inhibition decreasing as the time of mollusc exposure to metals increased, suggesting a reduction of the "bioactive" metals. In regard to the use of BLB test in environmental monitoring, the analysis of Cu, Cd, and metallothionein (MT) was first performed in tissues from molluscs collected in three different areas of Northern Adriatic Sea. Metal concentrations reached maximum values in the gills, while Cd was mostly bound to MT in the kidney. Significant differences in metals and MT concentrations were found depending on the sampling sites. The biotoxicological assay resulted slightly correlated with the biochemical parameters.     

Removal of SO2 from O2-containing flue gas by activated carbon fiber (ACF) impregnated with NH3

Adsorption of SO(2) from the O(2)-containing flue gas by granular activated carbons (GACs) and activated carbon fibers (ACFs) impregnated with NH(3) was studied in this technical note. Experimental results showed that the ACFs were high-quality adsorbents due to their unique textural properties. In the presence of moisture, the desulphurization efficiency for the ACFs was improved significantly due to the formation of sulfuric acid. After NH(3) impregnation of ACF samples, nitrogen-containing functional groups (pyridyl C(5)H(4)N- and pyrrolyl C(4)H(4)N-) were detected on the sample surface by using an X-ray photoelectron spectrometer. These functional groups accounted for the enhanced SO(2) adsorption via chemisorption and/or catalytic oxidization.     

Heavy metal ion influence on the photosynthetic growth of Rhodobacter sphaeroides

The potential of purple non-sulphur bacteria for bioremediation was assessed by investigating the ability of Rhodobacter sphaeroides strain R26.1 to grow photosynthetically in heavy metal contaminated environments. Bacterial cultures were carried out in artificially polluted media, enriched with the transition metal ions Hg2+, Cu2+, Fe2+, Ni2+, Co2+, MoO4(2-), and CrO4(2-) in millimolar concentration range. For each investigated ion the effect on growth parameters was evaluated. The analysis of concentration-effect curves revealed a differentiated response, indicating that diverse mechanisms of tolerance and/or resistance are involved. Adaptation or selection procedures were not applied, leading to assess intrinsic abilities of coping with these contaminants. The microorganism proved to be highly tolerant to heavy metal exposure, especially towards Co2+, Fe2+ and MoO4(2-). In addition Ni2+ and Co2+ were found to decrease the cellular content of light harvesting complexes. A characteristic behavior was observed with mercuric ions, which produced a significant increase of the lag-phase.     

Toxicity of copper excess on the lichen Dermatocarpon luridum: antioxidant enzyme activities

The aim of this study was to investigate the toxicity of copper on the aquatic lichen Dermatocarpon luridum focusing on the activities of some antioxidant enzymes. Investigations were conducted using increasing copper concentrations (0.00, 0.25, 0.50, 0.75 and 1.00 mM CuSO(4) x 5H(2)O) in synthetic freshwater that emulated the major ion compositions of its natural water biota; time course measurement was 0, 3, 6, 12, 24 and 48 h. The copper concentration in thalli increased with its increase in the medium and the duration of treatment. Copper induced lipid peroxidation, measured using the hydroperoxi-conjugated dienes (HPCD) concentration. The decrease in the protein concentrations was similar in thalli exposed to copper concentrations above 0.50 mM and the decrease was twice lower in thalli exposed to 0.25 mM copper. The activities of antioxidant enzymes measured were differently affected by copper excess. For 0.25 mM copper, the activities of SOD (superoxide dismutase) and APX (ascorbate peroxidase) were unchanged when compared with unstressed thalli whereas the CAT (catalase) activity increased and the GR (glutathione reductase) activity decreased. The activities of SOD and APX increased in thalli exposed to concentrations above 0.50mM copper. The CAT activity increased after the first 3h of experiments at these concentrations and then decreased with the duration of treatment at an activity lower than in the unstressed plant. Whereas the APX activity increased, the GR activity similarly decreased for the copper concentration tested whatever the duration of the experiment.