Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Mercury sorption to sediments: dependence on grain size, dissolved organic carbon, and suspended bacteria

A combination of laboratory scale derived correlations and measurements of grain size distribution, DOC (dissolved organic carbon) concentration, and density of suspended bacteria promises to be useful in estimating Hg(II) sorption in heterogeneous streambeds and groundwater environments. This was found by shaking intact sediment and fractions thereof (<63-2000mum) with solutions of HgCl(2) (1.0-10.0ngml(-1)). The intact sediment was also shaken with the Hg(II) solutions separately in presence of DOC (6.5-90.2mugml(-1)) or brought in contact with suspensions of a strain of groundwater bacteria (2x10(4)-2x10(6)cellsml(-1)). Hg(II) sorption was rather weak and positively correlated with the grain size, and the sorption coefficient (K(d)) varied between about 300 and 600mlg(-1). By using the relative surface areas of the fractions, K(d) for the intact sediment was back calculated with 2% deviation. K(d) was negatively correlated with the concentration of DOC and positively correlated with the number of bacteria. A multiple regression showed that K(d) was significantly more influenced by the number of bacteria than by the grain size. The findings imply that common DOC concentrations in groundwater and streambeds, 5-20mugml(-1), will halve the K(d) obtained from standard sorption assays of Hg(II), and that K(d) will almost double when the cell numbers are doubled at densities that are common in aquifers. The findings suggest that simultaneous measurements of surface areas of sediment particles, DOC concentrations, and bacterial numbers are useful to predict spatial variation of Hg(II) sorption in aquifers and sandy sediments.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

Chloramphenicol influence on antioxidant enzymes with preliminary approach on microsomal CYP1A immunopositive-protein in Chamelea gallina

Chloramphenicol (CA) is a largely used antibiotic and it is an inhibitor of protein synthesis that also induces ROS production. In this work there were investigated activities and expressions in the Adriatic bivalve Chamelea gallina of some antioxidant and detoxification proteins like superoxide dismutase (Mn-SOD, Cu/Zn-SOD), catalase (CAT) and Cytochrome P450 (CYP1A). Clams exposed to 5mgl(-1) of chloramphenicol were sampled 2, 4 and 8 days after treatment (CA2, CA4 and CA8). SODs, CAT, and CYP1A activity and/or expression were detected in pooled digestive glands by Western blotting and by spectrophotometrical analysis. Enzymes activities increase during the entire antibiotic exposure. With respect to the control Cu/Zn-SOD expression increases, while Mn-SOD expression decreases significantly after 4 days. Two CYP1A immunopositive-proteins (57.7 and 59.8kDa) were detected. The lower band significantly decreases in CA8, the upper one also in CA4 condition. High levels of Mn-SOD, CAT activity and Cu/Zn-SOD expression, indicate intense ROS production while Mn-SOD expression inhibition might be ascribable to mitochondrial alterations due to CA and indirectly to ROS. CYP1A1 action determines H(2)O(2) production that would contribute to a CYP1A1 gene promoter down regulation, a response to oxidative stress with the antioxidant enzymes activation as a final result. This study highlights the close association, in C. gallina, in presence of chloramphenicol, between SOD/CAT and CYP system, and it appear particularly interesting to the lack of similar researches on mollusc species.     

Haematological and biochemical effects of polyphenolics in animal models

Polyphenols of natural and synthetic origin are exploited in tanning sector to convert putrescible skin/hide to non-putrescible leather. However, only 30-40% of the inputs have been taken up for processing, the remaining is released as unspent. The existing conventional wastewater treatment systems are inefficient in removing or degrading these unspent polyphenols and thus detrimental to ecosystem. The present study demonstrates the evaluation of impact of both synthetic and natural polyphenols on biochemical and haematological properties of blood and serum in animal models. The results reveal that concentrations of polyphenols play a major role. At higher concentrations, irrespective of their nature, there was a marked change in the lipid profile (81% reduction), followed by insignificant change in glucose levels, RBC and WBC counts and other haematological parameters. At lower concentrations, no significant changes in the above said properties were observed.     

Antioxidant enzyme activities as affected by trivalent and hexavalent chromium species in Fontinalis antipyretica Hedw

The detoxification mechanisms of the aquatic moss, Fontinalis antipyretica Hedw., exposed to Cr was analyzed. In addition, the influence of Cr salts (as Cr nitrate, chloride and potassium bichromate) on these mechanisms has also been studied. The activity of antioxidant enzymes superoxide dismutase (SOD, EC 1.15.1.1.), catalase (EC 1.11.1.6.), ascorbate peroxidase (APX, EC 1.11.1.11.), guaiacol peroxidase (GPX, EC 1.11.1.7.) and glutathione reductase (GR, EC 1.6.4.2.) increased in plants treated with Cr concentrations ranging from 6.25x10(-5) to 6.25mM when given as Cr(NO(3))(3). Antioxidant enzymes responded to the other two salts CrCl(3) and K(2)Cr(2)O(7) only with Cr concentrations higher than 6.25x10(-2)mM. Glutathione level and GSSG/GSH ratio also responded to Cr exposure but no dose-effect relationship could be observed. Moreover, two unknown thiol compounds were observed in mosses exposed to the highest Cr concentrations. Effects on chlorophyll contents and chlorophyll a/b ratios were also shown even at low Cr concentrations. Our results indicated that environmentally realistic concentrations of Cr could lead to impairment of the cellular activity towards F. antipyretica and that Cr(III), when present as a nitrate salt, was as harmful as Cr(VI).     

Polymer biodegradation: mechanisms and estimation techniques

Within the frame of the sustainable development, new materials are being conceived in order to increase their biodegradability properties. Biodegradation is considered to take place throughout three stages: biodeterioration, biofragmentation and assimilation, without neglect the participation of abiotic factors. However, most of the techniques used by researchers in this area are inadequate to provide evidence of the final stage: assimilation. In this review, we describe the different stages of biodegradation and we state several techniques used by some authors working in this domain. Validate assimilation (including mineralisation) is an important aspect to guarantee the real biodegradability of items of consumption (in particular friendly environmental new materials). The aim of this review is to emphasise the importance of measure as well as possible, the last stage of the biodegradation, in order to certify the integration of new materials into the biogeochemical cycles. Finally, we give a perspective to use the natural labelling of stable isotopes in the environment, by means of a new methodology based on the isotopic fractionation to validate assimilation by microorganisms.     

Assessment of heavy metals phytotoxicity using seed germination and root elongation tests: a comparison of two growth substrates

Seed germination and root elongation test is used to evaluate hazardous waste sites and to assess toxicity of organic and inorganic compounds. Paper substrate, especially circular filter paper placed inside a Petri dish has long been used for this test. Same reports indicate that filter paper might interfere with the toxicity of inorganic substances, especially metal cations. This study evaluate toxicity of Cd, Pb, Ni, Cu on lettuce, broccoli, tomato and radish seed using two bed material: agar and filter paper. The results show that percent germination is not affected by substrates; vice versa, as for root elongation, the test in agar showed to be more sensible than that the one on filter paper. The radical growth inhibition depends on the metal, on the tested concentration and on the species; among the tested metals, cadmium was the one determining the highest toxic effects on different species and lettuce was the plant that suffered more. From the comparison, it is clearly evident the greater sensibility of the test in agar; on the other hand, the lower sensibility of the test on the filter paper might be caused by the partial and not homogeneous exposition of the root to metal cations.     

Seasonal variation of extracellular enzymatic activity (EEA) and its influence on metal speciation in a polluted salt marsh

The influence of salt marsh sediment extracellular enzymatic activity (EEA) on metal fractions and organic matter cycling was evaluated on a seasonal basis, in order to study the relation between organic matter cycles and the associated metal species. Metals in the rhizosediment of Halimione portulacoides were fractioned according to the Tessier's scheme and showed a similar pattern regarding the organic-bound fraction, being always high in Autumn, matching the season when organic matter presented higher values. Both organic-bound and residual fractions were always dominant, being the seasonal variations due to interchanges between these two fractions. Phenol oxidase and beta-N-acetylglucosaminidase had higher activities during the Spring and Summer, contrarily to peroxidase which had higher activity during Winter. Protease showed high activities in both Spring and Winter. These different periods of high organic matter hydrolysis caused two periods of organic metal bound decrease. Sulphatase peaks (Spring and Winter) matched the depletion of exchangeable metal forms, probably due to sulphides formation and consequent mobilization. This showed an interaction between several microbial activities affecting metal speciation.