Conformational changes of dissolved humic and fulvic superstructures with progressive iron complexation

Conformational changes of a humic acid (HA) and a fulvic acid (FA) induced by iron complexation were followed by high-performance size exclusion chromatography (HPSEC) with both UV–vis and refractive index (RI) detectors. Molecular size distribution was reduced for HA and increased for FA with progressive iron complexation. Since interactions of Fe with humic components are electrostatic, it is likely that the triple-charged Fe ions formed stronger complexes with the more acidic hydrophilic and hydrated FA than with the less acidic and more hydrophobic HA. The large content of ionized carboxyl groups in FA, thus favored the formation of intra- or intermolecular bridges between the negatively charged fulvic acid molecules, and led to more compact and larger size network than for HA. Conversely, iron complexation with HA disrupted the humic conformational arrangements stabilized by only weak hydrophobic bonds into smaller-size aggregates of greater conformational stability due to formation of strong metal complexes. These results confirmed that humic molecules in solution were organized in supramolecular associations of relatively small molecules loosely bound together by dispersive interactions and hydrogen bonds, and they specifically responded to chemical changes brought about by metal additions. The present study revealed the molecular changes occurring in superstructures of natural organic matter when in metal complexes and contributed to understand and predict the environmental behavior in waters and soil of metal complexes with natural organic matter.

Brackish groundwater desalination by reverse osmosis in southeastern Spain. Presence of emerging contaminants and potential impacts on soil-aquifer media

Desalinated brackish groundwater is becoming a new source of water supply to comply with growing water demands, especially in (semi-) arid countries. Recent publications show that some chemical compounds may persist in an unaltered form after the desalination processes and that there is an associated risk of mixing waters with different salinity for irrigation. At the university of Alicante campus (Spain), a mix of desalinated brackish groundwater and water from the existing aquifer is currently applied for landscape irrigation. The presence of 209 emerging compounds, surfactants, priority substances according to the 2008/105/EC Directive, 11 heavy metals and microbiological organisms in blended water and aquifer samples was investigated. Thirty-five compounds were detected (pesticides, pharmaceuticals and surfactants) among them two priority substances α-endosulfan and Ni were found above the permitted maximum concentration. Blended water used for landscape irrigation during the summer period is supersaturated with respect to carbonates, which may ultimately lead to mineral precipitation in the soil-aquifer media and changes in hydraulic parameters.

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.