The complete removal of biorecalcitrant xenobiotics, including most notably the pharmaceutical pollutants, by advanced oxidation processes is often difficult to be reached in urban or industrial wastewater because of the high concentration of organic and inorganic scavengers that compete with the xenobiotics for the oxidizing species. This work investigates a coupled treatment train in which wastewater effluents are pretreated with a negatively charged loose nanofiltration (NF) membrane (HydraCoRe70, made up of sulfonated polyethersulfone) to enhance the removal of xenobiotics with the thermal Fenton process. Carbamazepine (CBZ), a drug prescribed mainly for epilepsy treatment, is used here as a model xenobiotic. After optimizing the conditions for separation and degradation, the NF–Fenton approach was applied to both synthetic wastewater and real samples to assess the overall efficiency of CBZ removal. The Fenton degradation of CBZ was drastically enhanced in nanofiltered samples, thanks to the removal by the membrane of nearly all organic matter that would otherwise consume the reactive oxidizing species (e.g., the hydroxyl radical). On the basis of a preliminary treatment cost analysis, it can be concluded that the combined process is potentially applicable to the treatment of several kinds of wastewaters (e.g., industrial ones) to favor the removal of biorecalcitrant contaminants. Key cost savings of NF–Fenton concern the lower amounts of Fenton reagents needed to degrade CBZ and (even more importantly) the decreased levels of acids and bases for pH adjustment before and after the oxidative process because of the lower buffer capacity of the NF permeate compared to feed wastewater, after the removal by the NF of many inorganic ions and most organic carbon.
In this work, an evaluation of the air of two Italian industrial cities, Turin and Biella, has been performed to identify the main sources affecting its quality and to evaluate its evolution along 15 years. These two cities are placed at the border of the Po valley, one of the most polluted areas of Europe, and the automotive and textile industries have been their main economic sectors. The elemental analysis of the PM10 collected there in 2007 has been performed by ICP-MS and ICP-AES. The results identify the urban activities and the soil/road dust resuspension as the main sources of metals. Biella was overall less polluted in PM10 than Turin, probably because of its smaller size, its smaller traffic volume, and the lower number of industries. However, the limit value imposed by the European legislation for daily average PM10 mass concentration (50 μg m−3) was frequently exceeded in the collected samples: 22% and 50%, respectively for Biella and Turin. The concentration of specific toxic metals regulated by Italian legislation was never higher than the limit value for Cd (4 ng m−3) and Pb (0.5 μg m−3), whereas it was exceeded for Ni (20 ng m−3) in 22% of the samples from Turin and only in the 5% of those from Biella. In the same way, the risk analysis, performed using the target hazard quotient (THQ), calculated for children and adult populations, did not reveal warning values. Only for Cd in children were concerning values found (median THQ = 4.9). Element concentrations showed a seasonal trend, with higher values in November and December due to a combination of stable atmospheric conditions and strengthening of anthropic sources (e.g., combustion for heat generation). Finally, data concerning the amount of Cd, Ni, and Pb in the atmosphere provided by the regional agency for environmental protection (ARPA Piedmont) have been used to follow the evolution of these elements from 2007 to 2021 in the two cities. The data reveal a significant reduction of the concentrations of all considered metals in all the sites (higher than 50%), however maintaining the seasonal variability observed in PM10 samples of 2007, with higher concentrations during the cold months and lower concentrations during the summer.
The determination of the authenticity of extra virgin olive oils (EVOOs) has become more interesting in recent years. Italy is the first country in Europe in terms of number of Protected Designation of Origin (PDO) oils, which connects consumers to a feeling of tradition and thus to higher quality standards. This work focused on the consideration of the inorganic content as a possible marker of EVOOs. Ten vegetable oils (VOs), eight Italian EVOOs and seven not Italian EVOOs were analyzed. After pretreatment by acid mineralization, Al, Ba, Ca, Cu, Fe, K, Li, Mg, Mn, Na, P, Sb, Se and Zn were determined by ICP-OES. The electrochemical properties of a selected group of EVOOs and other vegetal oils of different botanical origin were investigated by voltammetry. Carbon paste electrodes (CPEs) were prepared. The features observed in the voltammograms reflect the reactions of electroactive compounds, which are present in the oils. A chemometric treatment of the results was performed to assess the possibility to distinguish (i) the region of provenience considering the inorganic profile; and (ii) the plant species from which each oil was obtained on the basis of the current profile registered during voltammetric analysis. Inorganic composition seems to be a useful marker for the assessment of the geographical origin of an EVOO. The EVOO-CPEs voltammetry seems to have a good ability to distinguish the plant species of origin. This method could be useful to monitor the conservation status of the oils, as the redox profile is linked to the oxidative degradation state.
Lead content, enrichment factors, and isotopic composition (208Pb/206Pb and 207Pb/206Pb) measured in atmospheric particulate matter (PM10) samples collected for nine years at Ny-Ålesund (Svalbard islands, Norwegian Arctic) during spring and summer are presented and discussed. The possible source areas (PSA) for particulate inferred from Pb isotope ratio values were compared to cluster analysis of back-trajectories. Results show that anthropogenic Pb dominates over natural crustal Pb, with a recurring higher influence in spring, compared to summer. Crustal Pb accounted for 5–16% of the measured Pb concentration. Anthropogenic Pb was affected by (i) a Central Asian PSA with Pb isotope signature compatible with ores smelted in the Rudny Altai region, at the Russian and Kazakhstan border, which accounted for 85% of the anthropogenic Pb concentration, and (ii) a weaker North American PSA, contributing for the remaining 15%. Central Asian PSA exerted an influence on 71–86% of spring samples, without any significant interannual variation. On the contrary, 59–87% of summer samples were influenced by the North American PSA, with higher contributions during 2015 and 2018. Back-trajectory analysis agreed on the seasonal difference in PSA and highlighted a possible increased influence for North American air masses during summer 2010 and 2018, but not for summer 2015.