Geochemical modeling of chromium oxidation and treatment of polluted waters by RO/NF membrane processes

<p>Geogenic Cr(VI) contamination is a worldwide environmental issue which mainly occurs in areas where ophiolitic rocks crop out. In these areas Cr (VI) can reach high concentrations into groundwaters becoming highly dangerous for human health. Indeed Cr(VI) is recognized as highly toxic element with high mobility and bioavailability [1]. Due to these features, starting from July 2017, Italian government has lowered the Cr(VI) limit value for drinking water to 10 µg/L. To improve the living standards in contaminated areas, it is needed (i) to understand the release and fate of contaminant during the water-rock interaction and (ii) to develop efficient remediation systems for natural polluted waters. In this regard, a complementary study on genesis and treatment of a Cr-rich groundwater coming from Italian ophiolitic aquifers was conducted. Reaction path modelling is a proven geochemical tool to understand the release of Cr and its oxidation from Cr(III) to Cr(VI) during the water-rock interaction. The generally accepted hypothesis of scientific community is that geogenic Cr(III) oxidation  is driven by the reduction of trivalent and tetravalent manganese (Mn(III); Mn (IV)) [2] whereas in this work the role of trivalent Fe hosted in serpentine minerals was re-evaluated. Unlike Mn, Fe is the main oxidant present in suitable amount in these rocks. Literature data confirmed the presence of Fe(III) into serpentine minerals hence reaction path modelling was performed varying the Fe (III)/Fe(tot) ratio ranging  from 0.60 to 1.00. The theoretical paths, reproduce the analytical concentrations of relevant solutes, including Cr(VI), in the Mg-HCO<sub>3</sub> water type hosted in the ophiolitic aquifers of Italy [3]. With increasing of Fe(III)/Fe(tot) ratio in serpentine minerals, high Cr(VI) concentration hold into solution until high alkalinity values. In addition, the spring with the highest Cr(VI) content (75 µg/L) was treated to lower its concentration below the threshold values.  In this work membrane technologies were used as  innovative method considering their many benefits, like the improvement of product quality without using chemicals [4]. A laboratory-scale set-up was used to carry out both Nanofiltration (NF) and Reverse Osmosis (RO) experiments. The experiments were conducted on different commercial membranes: one NF membrane module named DK (polyamide) and two RO membrane modules named AD (polyamide) and CD (cellulose).Tests were performed varying the operating pressures, and high Cr(VI) rejections (around 95%) were reached for all tested membranes, leading to a water containing Cr(VI) in concentrations below the threshold limits. The high flux, obtained already at lower operating pressures (27 L/m<sup>2</sup>h-10bar), combined with high selectivity towards Cr(VI) makes NF a favorable remediation option. The results obtained in this work are in line with the few data available in the literature for natural contaminated waters and there are quite promising for future scientific developments and application.</p><p> </p><p> </p><p>References</p><p>[1]Marinho B. A. et al., 2019. Environ Sci Pollut Res, 26(3), 2203-2227</p><p>[2]Oze C. et al., 2007. Proc. Natl. Acad. Sci. 104, 6544–6549</p><p>[3]Apollaro C. et al., 2019. Sci. Total Environ. 660, 1459-1471</p><p>[4]Figoli  A. & Criscuoli  A., 2017. Springer (Singapore); ISBN:9789811056215</p>

Clay mineral precipitation and low silica in glacier meltwaters explored through reaction-path modelling

The subglacial chemical weathering environment is largely controlled by low temperatures and the presence of freshly comminuted minerals with a high surface area. These characteristics are believed to promote dissolution processes that give rise to low silica and high Ca2+fluxes emanating from glacierized basins. We test an alternative hypothesis, that mineral precipitation reactions in the subglacial environment play an equally important role in controlling the water chemistry in glacierized basins. We analyze borehole and proglacial water chemistry from a subarctic polythermal glacier, complemented by mineral XRD analysis of suspended sediment, till and bedrock samples. In conjunction with a thermodynamic analysis of the water and mineral chemistry, we use reaction-path modelling to study the chemical enrichment of water through the glacier system. We find that the high pH of the subglacial environment is conducive to secondary mineral precipitation, and that it is not possible to balance the water chemistry using dissolution reactions alone. We show that low silica can be explained by standard weathering reactions without having to invoke mineral-leaching reactions. Our results suggest that subglacial weathering intensity may be significantly underestimated if the production of secondary minerals is not considered.

Reaction of aniline with ammonium persulphate and concentrated hydrochloric acid: Experimental and DFT studies

In this paper, the reaction of aniline with ammonium persulphate and concentrated HCl was studied. As a result of our experimental studies, 2,4,6-trichlorophenylamine was identified as the main product. This shows that a high concentration of HCl does not favour oxidative polymerisation of phenylamine, even though the ammonium persulphate/HCl system is widely used in polyaniline synthesis. On the basis of the experimental data and density functional theory for reaction path modelling, we proposed a mechanism for oxidative chlorination of aniline. We assumed that this reaction proceeded in three cyclically repeated steps; protonation of aniline, formation of singlet ground state phenylnitrenium cation, and nucleophilic substitution. In order to confirm this mechanism, kinetic, thermochemical, and natural bond orbital population analyses were performed.