Environmental implications of one-century COPRs evolution in a single industrial site: From leaching impact to sustainable remediation of CrVI polluted groundwater.

The Stoppani factory manufactured chromium for more than one century, dumping millions of tons of Chromite Ore Processing Residues (COPRs) over decades. The massive presence of COPRs resulted in an intense CrVI leaching and consequent contamination of percolating groundwater. The site offers a unique opportunity to follow COPRs evolution from the primary roasting process to the aged Cr-bearing mineral phases. Herein, new insights on COPRs mineralogy evolution and their role in CrVI release are provided by a dry sample preparation protocol, coupled with in-depth multi-technique characterization. Besides typical COPRs mineral assemblages, highly soluble Na2CrO4 and the first evidence of crocoite (PbCrO4) in a COPR contaminated site are revealed. Selective extraction experiments confirmed a strong reactivity for Cr-bearing minerals as confirmed by concentrations as high as 375 mg L-1 of leached CrVI. The mineralogical approach was combined with a nanotechnological solution for CrVI wastewater remediation. The application of naked colloidal maghemite (γ-Fe2O3) nanoparticles (SAMNs) on the complex industrial wastewater, led to > 90% CrVI removal, either under acidic or in-situ conditions. The present case study of a highly polluted site, ranging from mineral characterization to wastewater remediation, highlights the use of multidisciplinary approaches to cope with complex environmental issues.

Environmental implications of metal mobility in marine sediments receiving input from a torrent affected by mine discharge.

Acid Mine Drainage (AMD) is one of the most important sources of pollution in fluvial systems and can enrich rivers in dissolved and suspended metals of environmental concern. Colloidal particles may favour the transport of metals to the sea, where metals can be accumulated in bottom sediments. The aim of this paper was to evaluate the mobility of metals in the "Baia delle Favole" bottom sediments (Sestri Levante, Italy), which receive the input of the AMD impacted Gromolo Torrent, using chemical speciation (BCR sequential extraction). Basing on the Risk Assessment Code (RAC), our results showed a systematic and widespread high risk classification for Mn, whereas a medium risk is associated to Co, Cu, and Zn in the sediments collected near the mouth of the Gromolo Torrent. Moreover, in these sediments the occurrence of Fe oxyhydroxides has been observed, reflecting an increase of metals in the reducible fraction obtained with BCR.

Functional and molecular effects of mercury compounds on the human OCTN1 cation transporter: C50 and C136 are the targets for potent inhibition.

The effect of mercury compounds has been tested on the organic cation transporter, hOCTN1. MeHg(+), Hg(2+), or Cd(2+) caused strong inhibition of transport. 1,4-Dithioerythritol (DTE), cysteine (Cys), and N-acetyl-l-cysteine reversed (NAC) the inhibition at different extents. 2-Aminoethyl methanethiosulfonate hydrobromide (MTSEA), a prototype SH reagent, exerted inhibition of transport similar to that observed for the mercurial agents. To investigate the mechanism of action of mercurials, mutants of hOCTN1 in which each of the Cys residues was substituted by Ala have been constructed, over-expressed in Escherichia coli, and purified. Tetraethylammonium chloride (TEA) uptake mediated by each mutant in proteoliposomes was comparable to that of wild type (WT). IC50 values of the WT and mutants for the mercury compounds were derived from dose-response analyses. The mutants C50A and C136A showed significant increase of IC50 indicating that the 2 Cys residues were involved in the interaction with the mercury compounds and inhibition of the transporter. The double mutant C50A/C136A was constructed; the lack of inhibition confirmed that the 2 Cys residues are the targets of mercury compounds. MTSEA showed similar behavior with respect to the mercurial reagents with the difference that increased IC50 was observed also in the C81A mutant. Similar results were obtained when transport was measured as acetylcholine uptake. Ethyl mercury (Thimerosal) inhibited hOCTN1 as well. C50A, C50A/C136A and, at very lower extent, C136A showed increased IC50 indicating that C50 was the major target of this mercury compound. The homology model of hOCTN1 was built using as template PiPT and validated by the experimental data on mutant proteins.