The role of charged polymer coatings of nanoparticles on the speciation and fate of metal ions in the environment.

Determining the environmental risk of metals requires an in-depth understanding of the environmental matrices composition, which currently also includes the presence of manufactured metallic nanoparticles (NPs) usually, stabilized by a polymer surface coating. As a consequence, is necessary to take into account effects of the NP core, the polymer surface coating and their mutual interaction as well as with other environmental components. The release of metal ions from metallic NPs is a well-known outcome, however, the effect of the presence of the NP polymer coating in the NPs solubilization mechanism is not well understood. In this study the dynamic speciation of Cd and Pb in presence of a polyacrylic acid (PAA)-stabilized CdTe/CdS NP was quantified by scanned stripping chronopotentiometry (SSCP). It was found that although the NP solubility was 5.8× larger at pH 8.5 than at pH 6.0, the amount of free Cd ions was much smaller (2.4 % at pH 8.5 vs. 57 % at pH 6.0). The concentration of free Cd and Pb ions in solution was larger in presence of the PAA-shells than when in presence of the same amount of polymer but when this is at the surface of the NP. This effect is attributed to the metal ions interaction with the particle itself. The effect is notably larger for Pb ions and might results from the exchange of Cd by Pb ions at the particle surface since PbS is less soluble than CdS.

The suitability of EBC-Pb as a new biomarker to assess occupational exposure to lead.

Occupational exposure to lead (Pb) requires continuous surveillance to assure, as much as possible, safe and healthful working conditions. This study addresses the suitability of assessing Pb exposure in relevant workers using their exhaled breath condensate (EBC). This study enrolled workers of two different Pb processing industries characterized by moderate and high Pb exposure levels in the work environment, and a group of non-exposed individuals working in offices who served as baseline for Pb exposure. The EBC-Pb of workers reflected the Pb levels in the work environment of all three settings, although the relationship with B-Pb was not clear. The lack of correlation between EBC-Pb and B-Pb most probably indicates the time lag for Pb to enter in the two body pools. The EBC-Pb seems to reflect immediate exposure, providing a prompt signature of Pb in the environmental that may interact directly with the organ. By delivering short-term evaluation of exposure, EBC-Pb represents a clear advantage in biomonitoring and may become an interesting tool for estimating organ burden.

Bioavailability of cadmium and biochemical responses on the freshwater bivalve Corbicula fluminea--the role of TiO2 nanoparticles.

The increasing and widespread applications of TiO2 engineered nanoparticles (nTiO2) led to the release of these materials into aquatic environments and consequently a change on the assessment of the environmental risk of trace metals. In this work, the role of two commercial nTiO2 with distinct crystalline phases and sizes (nTiO2-P25: 80% anatase+20% rutile, d=20nm; nTiO2-NA: 100% anatase, d=5 nm; 0.1 and 1.0 mg L(-1)) on Cd (112 µg L(-1)) speciation, biouptake and toxicity for the freshwater bivalve Corbicula fluminea was evaluated. The electroanalytical technique 'absence of gradients and Nernstian equilibrium stripping (AGNES)' was used to quantify the free Cd concentrations in the exposure medium in presence of both particles. Despite ca. 30-40% decrease of free Cd in the medium in presence of nTiO2, Cd uptake by C. fluminea was similar in the absence and presence of either of the particles. Superoxide dismutase and glutathione-S-transferase activities remained unchanged for Cd in absence and presence of nTiO2, whereas a significant increase of the catalase activity was obtained at the third day for Cd in presence of both nTiO2. Despite lipid peroxidation data shows that the presence of both nTiO2 seems to exert cells damage, a more quantitative description is not possible with the obtained data. The lack of clear-cut responses by the studied biomarkers, even when only in presence of Cd, do not allow insights into the effect of the presence of nTiO2 on the Cd toxicity to the bivalves. Notwithstanding, morphological changes in the digestive gland were clearly obtained in the presence of Cd, nTiO2 and Cd+nTiO2 indicating an inflammatory response.

Stability of core/shell quantum dots--role of pH and small organic ligands.

The improvement of knowledge about the toxicity and even processability, and stability of quantum dots (QD) requires the understanding of the relationship between the QD binding head group, surface structure, and interligand interaction. The scanned stripping chronopotentiometry and absence of gradients and Nernstian equilibrium stripping techniques were used to determine the concentration of Cd dissolved from a polyacrylate-stabilized CdTe/CdS QD. The effects of various concentrations of small organic ligands such as citric acid, glycine, and histidine and the roles of pH (4.5-8.5) and exposure time (0-48 h) were evaluated. The highest QD dissolution was obtained at the more acidic pH in absence of the ligands (52%) a result of the CdS shell solubility. At pH 8.5 the largest PAA ability to complex the dissolved Cd leads to a further QD solubility until the equilibrium is reached (24% of dissolved Cd vs. 4% at pH 6.0). The citric acid presence resulted in greater QD dissolution, whereas glycine, an amino acid, acts against QD dissolution. Surprisingly, the presence of histidine, an amino acid with an imidazole functional group, leads to the formation of much strong Cd complexes over time, which may be non-labile, inducing variations in the local environment of the QD surface.