The chronic toxicity of zinc oxide nanoparticles (ZnO-NP) to Folsomia candida was determined in natural soil. To unravel the contribution of particle size and free zinc to NP toxicity, non-nano ZnO and ZnCl₂ were also tested. Zinc concentrations in pore water increased with increasing soil concentrations, with Freundlich sorption constants Kf of 61.7, 106 and 96.4 l/kg (n = 1.50, 1.34 and 0.42) for ZnO-NP, non-nano ZnO and ZnCl₂ respectively. Survival of F. candida was not affected by ZnO-NP and non-nano ZnO at concentrations up to 6400 mg Zn/kg d.w. Reproduction was dose-dependently reduced with 28-d EC50s of 1964, 1591 and 298 mg Zn/kg d.w. for ZnO-NP, non-nano ZnO and ZnCl₂, respectively. The difference in EC50s based on measured pore water concentrations was small (7.94–16.8 mg Zn/l). We conclude that zinc ions released from NP determine the observed toxic effects rather than ZnO particle size.

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.

Nanoscale zero valent iron (NZVI) was immobilized on the organobentonite (CTMA-bent), so as to enhance the reactivity of NZVI and prevent its aggregation. This novel composite (NZVI/CTMA-Bent) was characterized by transmission electron microscope and X-ray diffraction. Good dispersion of NZVI particles on the bentonite was observed. Its performance on removing pentachlorophenol (PCP) was investigated by batch experiments. Results showed NZVI/CTMA-Bent could rapidly and completely dechlorinate PCP to phenol with an efficiency of 96.2%. It was higher than the sum (54.5%) of reduction by NZVI (31.5%) and adsorption by CTMA-Bent (23.0%) separately. The kinetic studies indicated the removal rate of PCP was positively related to the adsorption. We proposed that the adsorption of PCP by CTMA-Bent enhanced the mass transfer of PCP from aqueous to iron surface. Besides, NZVI/CTMA-Bent exhibited good stability and reusability, and CTMA-Bent could also reduce the amount of iron ions released into the solution.

CuO nanoparticles (CuO-NP) were synthesized in a hydrogen diffusion flame. Particle size and morphology were characterized using scanning mobility particle sizing, Brunauer–Emmett–Teller analysis, dynamic light scattering, and transmission electron microscopy. The solubility of CuO-NP varied with both pH and presence of other ions. CuO-NP and comparable doses of soluble Cu were applied to duckweeds, Landoltia punctata. Growth was inhibited 50% by either 0.6mgL⁻¹ soluble copper or by 1.0mgL⁻¹ CuO-NP that released only 0.16mgL⁻¹ soluble Cu into growth medium. A significant decrease of chlorophyll was observed in plants stressed by 1.0mgL⁻¹ CuO-NP, but not in the comparable 0.2mgL⁻¹ soluble Cu treatment. The Cu content of fronds exposed to CuO-NP is four times higher than in fronds exposed to an equivalent dose of soluble copper, and this is enough to explain the inhibitory effects on growth and chlorophyll content.

Eight marine-derived fungi that were previously selected for their abilities to decolorize RBBR dye were subjected to pyrene and benzo[a]pyrene degradation. The fungus Aspergillus sclerotiorum CBMAI 849 showed the best performance with regard to pyrene (99.7%) and benzo[a]pyrene (76.6%) depletion after 8 and 16days, respectively. Substantial amounts of benzo[a]pyrene (>50.0%) depletion were also achieved by Mucor racemosus CBMAI 847. Therefore, these two fungal strains were subjected to metabolism evaluation using the HPLC-DAD-MS technique. The results showed that A. sclerotiorum CBMAI 849 and M. racemosus CBMAI 847 were able to metabolize pyrene to the corresponding pyrenylsulfate and were able to metabolize benzo[a]pyrene to benzo[a]pyrenylsulfate, suggesting that the mechanism of hydroxylation is mediated by a cytochrome P-450 monooxygenase, followed by conjugation with sulfate ions. Because these fungi were adapted to the marine environment, the strains that were used in the present study are considered to be attractive targets for the bioremediation of saline environments, such as ocean and marine sediments that are contaminated by PAHs.

Soil dispersion is a prerequisite process for the separation of metal oxides from bulk soil when magnetic separation is employed to enhance the efficiency for soil treatment. This study examined the stability of goethite, hematite, birnessite, and manganite in common dispersion solutions. The stability of pH in the oxide suspension decreased in the order carbonate (50 mM Na2CO3) > pyrophosphate (50 mM Na4P2O7) > simple alkaline (1 mM NaOH) solutions regardless of the oxides. Dissolution of the four oxides was negligible in the carbonate and the simple alkaline solutions. In the pyrophosphate solutions, however, the oxides were subject to ligand-promoted dissolution by pyrophosphate ion. The extent of dissolution was highest for goethite followed by manganite, hematite, and birnessite. Dissolved Fe and Mn concentrations reached 68.3 and 4.1 μM for goethite and manganite suspensions, respectively, in 21 days with 5 mM pyrophosphate. Higher pyrophosphate concentrations (up to 150 mM) did not substantially affect the extent of ligand-promoted dissolution due to the limited surface sites of the oxides. The results of this study suggest that the carbonate solution would be more desirable than the simple alkaline or the pyrophosphate solution for soil dispersion in the presence of common Fe or Mn oxides.

The use of multiwall carbon nanotubes (MWCNT) as an efficient solid extractor in preconcentration/cleanup studies for tin determination in water samples by electrothermal atomic absorption spectrometry (ETAAS) is proposed. In the proposed method, tin adsorption onto MWCNT was carried out by percolating the solution previously buffered (pH 4.79 with 0.24 mol L−1 acetic acid/acetate buffer) at 4.0-mL min−1 flow rate, followed by elution with 1.0 mL of 2.7 mol L−1 HNO3. Factors such as sample pH, preconcentration/cleanup flow rate, type and concentration of eluent, and buffer concentration were appraised and optimized from chemometric tools based on fractional factorial design and Doehlert design. A limit of detection of 0.73 μg L−1 and precision (n = 8) assessed as relative standard deviation of 8.6% and 7.0% for tin concentration of 8.0 and 43.0 μg L−1, respectively, were achieved. Foreign metallic ions (Ni2+, Pb2+, Co2+, Zn2+, Cd2+, Mn2+, and Fe3+) were checked as potential interferents, and no interference was observed up to an analyte/interference ratio of 1:10 (m/v). Direct tin determination by ETAAS in water samples containing high salt amount is drastically affected by background signal. However, previous cleanup of sample by MWCNT has promoted a significant improvement and makes the method useful for tin monitoring in water samples (mineral, lake, mine, and natural waters) by ETAAS. Quantitative recovery values ranging from 91.5% to 103.0% attested the applicability of the proposed preconcentration/cleanup for tin determination in water samples.

This study evaluated the copper ion adsorption capacity of sugarcane bagasse in natura and chemically modified with citric acid and sodium hydroxide. Adsorption analyses in batch system were carried out in function of contact time with the adsorbent and adsorbate concentration. Flame atomic absorption spectrometry was used to determine the copper concentrations. Adsorption experimental data were fitted to Langmuir and Freundlich linear models, and the maximum adsorption capacity was estimated for copper ions in function of modifications. The chemical modifications were confirmed at 1,730 cm−1 peak in infrared spectra, referring to the carboxylate groups. The required time for the adsorption to reach equilibrium was 24 h and the kinetics follows the behavior described by the pseudo-second order equation. Besides, a significant improvement of the copper adsorption has been observed after the bagasse treatment, where the maximum adsorption capacity was 31.53 mg g−1 for copper using modified bagasse with nitric acid according to Langmuir isotherm linear model. The high uptake of copper ions from aqueous medium verified by chemically modified sugarcane bagasse makes this material an attractive alternative for effluent treatment and avoids environmental contamination.

The influence of a change from daily to weekly sampling of bulk precipitation on the obtained deposition values was studied with parallel sampling for 8 months at the station of Virolahti in 2004. Due to dry deposition, the deposition values of the whole period were found to be 5–70% higher from weekly sampling than from daily sampling, the biggest difference being for K+, Ca2+, Mg+ and Na+. The collection efficiencies of the summer sampler and the winter sampler compared to the standard rain gauge were studied from daily sampling in 1991–2003 and weekly sampling in 2004–2008. The performance was best in summer and in winter with rain samples (median value 85–88%), while the median value for daily snow samples was 72%. In winter, the total sum of precipitation collected in the daily sampler and the weekly sampler was 78% and 69%, respectively. The deficit in the weekly sampler in winter was concluded to be due to evaporation, while from the summer sampler no evaporation seemed to occur. Use of the precipitation amount measured by the standard rain gauge when calculating annual precipitation-weighted mean values gave higher mean concentrations than the use of the precipitation measured by the deposition sampler itself, the biggest difference of 8–11% being in the sea-salt ions Cl−, Mg+ and Na+. It was concluded that the concentration and deposition values measured by daily and weekly bulk sampling are incompatible, and should not be combined into the same time series.

Mechanism of zinc iron removal by zero-valent iron was discussed through zinc removal responses to several operational conditions of a packed column reactor with zero-valent iron powder. The adsorption isotherm observed implied that a kind of chemisorption was responsible for zinc removal. Zinc removal by zero-valent iron was enhanced by dissolved oxygen and ferric ion addition. However, it was deteriorated under acidic pH. In addition, zinc adsorbed on zero-valent iron was eluted by a reducing agent such as citric acid, whereas the zinc was not eluted by diluted sulfuric acid. Consequently, the zinc removal mechanism by zero-valent iron was inferred to be as follows: Zero-valent iron was firstly corroded and oxidized into ferric ion by dissolved oxygen. The ferric ion was precipitated as iron hydroxide onto the surface of the zero-valent iron powder. Zinc ion was adsorbed on and/or coprecipitated with the iron hydroxide. The iron hydroxide was finally oxidized and transformed into iron oxides.