The last 50 years of organic contamination of a highly anthropized tributary of the Po River (Italy).

We examined the temporal profiles of many organic micropollutants analysed in a sediment core sampled from a highly anthropized tributary of the Po River, the Lambro River. Analysed for extractable organic halogens (EOX), total petroleum hydrocarbons (C10-C40TPH), polycyclic aromatic hydrocarbons (PAHs), common legacy pollutants (DDTs, PCBs), halogenated flame retardants (PBDEs, DBDPE, TBBPA-bis, TCBPA, TBBPA, HBCDs), organotins (TBT, TPhT), antimicrobials (TCS, TCC), fragrances (AHTN, HHCB) and phthalates (DMP, DEP, DnBP, BBP, DEHP, DnOP), the dated sediment core revealed the historical record of 50 years of chemical contamination discharged into the Lambro and thereby the Po River. In this regard, the peak levels of PCBs and DDTs found in Lambro sediments were also identified in other sediment cores collected from the Po River prodelta in the Adriatic Sea, thus hundreds of kilometres downstream (Combi et al., 2020). The highest risk to aquatic organisms was associated with decades of high levels of C10-C40 TPH, PBDEs, PCBs, PAHs, DDTs, EOX, TCC, AHTN and DEHP, which in different periods of the contamination history, showed exceedances of guideline/threshold values. C10-C40 TPH and TCC, for example, were very high in the 1960s, whereas PCBs, DDTs, and PBDEs, peaked from the 1980s onward. The corresponding sums of PEC quotients ranged between 0.48 and 28.63, with a mean value (±SD) for the entire recording period of 10.62 ± 9.83. Environmental legislations and improved wastewater treatments were the main drivers of the recent downward trends observed for most of the chemicals investigated. Floods in turn resulted in macroscopic yet temporary improvements in the chemical quality of the tributary, conveying contaminated sediments into the Po River.

Effectiveness of UV-based advanced oxidation processes for the remediation of hydrocarbon pollution in the groundwater: a laboratory investigation.

The effectiveness of advanced oxidation processes in a batch and a flow reactor was investigated for the remediation of hydrocarbon pollution in the groundwater underlying a petrochemical industrial site. The main organic contaminants present in the groundwater were MTBE, benzene, alkyl-benzenes and alkyl-naphthalenes. Experimental results with a batch reactor showed that for all the organic contaminants the removal efficiency order is UV/TiO2 approximately UV/H2O2>UV (medium-pressure) in a synthetic aqueous solution, compared to UV/H2O2>UV (medium-pressure)>UV/TiO2 for the real polluted groundwater. The much lower performance of UV/TiO2 with respect to UV/H2O2 was inferred to the matrix of the groundwater, i.e. the salt content, as well as the organic and particulate matter. In fact, it is likely that the salts and dissolved organic matter quench the superoxide anion O2(-) and hydroxyl radicals just formed at the surface of the TiO2 catalyst. MTBE was the hardest compound to remove with each of the investigated treatments. UV and UV/TiO2 treatments were not able to reach a residual concentration of 10 microg/L (set by Italian legislation) even after 180 min. As for the UV/H2O2 process, only the MTBE degradation rate resulted affected by the initial H2O2 concentration, while for other compounds a complete removal was obtained within 20 min even with the lowest H2O2 concentration used (0.13 g/L). Only after 120 min of treatment, with an initial H2O2 concentration of 0.13 g/L, did the residual MTBE concentration fall below the above reported maximum admissible concentration. Instead, by using an initial concentration of 2g/L a residual concentration lower than 5 microg/L was obtained after just 30 min of reaction. The UV/H2O2 process was also investigated with a flow reactor. Results showed that it was more efficient than the batch reactor for removing MTBE, in terms of reaction time and initial H2O2 concentration required. This is consistent with the higher power of the UV lamp and with the different geometry of the flow reactor, which has a much shorter optical path than the batch reactor. By-product characterisation was also performed showing that t-butyl-formate and low molecular weight organic acids are formed as intermediate and final by-products, respectively. Finally, a preliminary evaluation of the operational cost of the UV/H2O2 process showed a value of 1.7 euro/m3 under the optimised condition.

Quality assessment of bed sediments of the Po River (Italy).

Comprehensive and contemporary evaluations of physical, chemical and toxicological endpoints have been performed on bed sediments of the Po River, the major Italian watercourse. Two extensive sampling campaigns were conducted in summer and winter low-flow conditions. Composite sediment samples were collected from ten reaches of the main river: the first was located in the upper region (ambient control), and the others downstream of the confluences of nine principal tributaries. The two sampling programs were paralleled by contemporary investigations on the macroinvertebrate community. The particle-size composition along the Po River showed a relatively uniform distribution of fine sand, a progressive downstream decrease of coarse sands and a corresponding increase of fine materials. The levels of polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), extractable organo halides (EOX), Cd, Cr, Cu, Hg, Ni, Pb and Zn were determined in sediment fine particles (< 63 microm), and showed marked changes across the ten river reaches. Their longitudinal trends, as those of organic carbon and total nitrogen, were very similar and largely independent of the survey season. Sediment quality benchmarks were used to evaluate sediment chemistry, and, although the overall level of contamination was from moderate to low, the reaches located downstream of the tributaries Dora Riparia, Dora Baltea, Lambro and Oglio were considered to be at risk. Sediments were tested for toxicity on Oncorhynchus mykiss, Ceriodaphnia dubia, Raphidocelis subcapitata and Vibrio fischeri. The toxicity tests were conducted both with sediment extracts and whole samples. Sediment extracts showed toxic potentials that were consistent with the spatial distribution of contaminants. Whole-sediment toxicity showed moderate/low effects which also included false positives and negatives. Alterations of the macroinvertebrate community were found for many kilometers downstream of Dora Riparia, and with a seasonal dependence, also in other reaches of the Italian river. Principal component analysis (PCA) was used to describe the longitudinal and temporal changes of the Po River, and allowed the selection of the most useful and discriminating indicators.