Geostatistical assessment of groundwater arsenic contamination in the Padana Plain.

Arsenic (As) in groundwater from natural and anthropogenic sources is one of the most common pollutants worldwide affecting people and ecosystems. A large dataset from >3600 wells is employed to spatially simulate the depth-averaged As concentration in phreatic and confined aquifers of the Padana Plain (Northern Italy). Results of in-depth geostatistical analysis via PCA and simulations within a Monte Carlo framework allow the understanding of the variability of As concentrations within the aquifers. The most probable As contaminated zones are located along the piedmont areas in the confined aquifers and in the lowland territories in the phreatic aquifers. The distribution of the As contaminated zones has been coupled with hydrogeological, geological, and geochemical information to unravel the sources and mechanisms of As release in groundwater. The reductive dissolution of Fe oxyhydroxides and organic matter mineralization under anoxic conditions resulted to be the major drivers of As release in groundwater. This phenomenon is less evident in phreatic aquifers, due to mixed oxic and reducing conditions. This large-scale study provides a probabilistic perspective on As contamination, e.g. quantifying the spatial probability of exceeding national regulatory limits, and to outline As major sources and drivers.

Nanocrystalline and Amorphous Calcium Carbonate from Waste Seashells by Ball Milling Mechanochemistry Processes.

Nanocrystalline calcium carbonate (CaCO3) and amorphous CaCO3 (ACC) are materials of increasing technological interest. Nowadays, they are mainly synthetically produced by wet reactions using CaCO3 reagents in the presence of stabilizers. However, it has recently been discovered that ACC can be produced by ball milling calcite. Calcite and/or aragonite are the mineral phases of mollusk shells, which are formed from ACC precursors. Here, we investigated the possibility to convert, on a potentially industrial scale, the biogenic CaCO3 (bCC) from waste mollusk seashells into nanocrystalline CaCO3 and ACC. Waste seashells from the aquaculture species, namely oysters (Crassostrea gigas, low-Mg calcite), scallops (Pecten jacobaeus, medium-Mg calcite), and clams (Chamelea gallina, aragonite) were used. The ball milling process was carried out by using different dispersing solvents and potential ACC stabilizers. Structural, morphological, and spectroscopic characterization techniques were used. The results showed that the mechanochemical process produced a reduction of the crystalline domain sizes and formation of ACC domains, which coexisted in microsized aggregates. Interestingly, bCC behaved differently from the geogenic CaCO3 (gCC), and upon long milling times (24 h), the ACC reconverted into crystalline phases. The aging in diverse environments of mechanochemically treated bCC produced a mixture of calcite and aragonite in a species-specific mass ratio, while the ACC from gCC converted only into calcite. In conclusion, this research showed that bCC can produce nanocrystalline CaCO3 and ACC composites or mixtures having species-specific features. These materials can enlarge the already wide fields of applications of CaCO3, which span from medical to material science.

Benchmarking biochar with activated carbon for immobilizing leachable PAH and heterocyclic PAH in contaminated soils.

Remediation of residually contaminated soils remains a widespread problem. Biochar can immobilize polycyclic aromatic hydrocarbons (PAH). However, studies on its ability to immobilize PAH and N, S, and O substituted PAH (hetero-PAH) in real soils, and benchmarking with commercial activated carbon are missing. Here, we compared the ability of pristine biochar (BC), steam-activated biochar (SABC), and commercial activated carbon (AC) to immobilize PAH and hetero-PAH. The three carbons were tested on soils from four different contaminated sites in Austria. Different amendment rates (w/w) of the carbons were investigated (BC: 1.0, 2.5, and 5%; SABC: 0.5, 1.0, and 2.0%; AC: 1%) in batch experiments to cover meaningful ranges in relation to their performance. SABC performed better than AC, removing at least 80% PAH with the lowest application rate of 0.5%, and achieving a complete removal at an application rate of 1.0%. BC performed slightly worse but still acceptable in residually contaminated soils (40 and 100% removal at 1 and 5% amendment, respectively). The ability of BC and SABC to immobilize PAH decreased as the PAH-molar volume increased. PAH with three or more rings were preferentially removed by AC compared to SABC or BC. This can be explained by the difference in pore size distribution of the carbons which could limit the accessibility of PAH and hetero-PAH to reach sorption sites for π- π electron donor-acceptor interactions, which drive PAH and hetero-PAH sorption to carbons. Column percolation tests confirmed the results obtained in batch tests, indicating, that decisions for soil remediation can be derived from simpler batch experiments. In soil samples with 1% BC, a reduction of over 90% in the total concentration of PAH in the leached water was observed. Overall, BC and SABC were demonstrated to be valid substitutes for AC for stabilizing residually contaminated soils.

Quantification and mapping of fish waste in retail trade and restaurant sector: Experience in Emilia-Romagna, Italy.

The circular economy approach imposes the complete recovery of components, materials and energy from waste. Many active compounds with biomedical and nutraceutical applications can be extracted by Fish Waste (FW), but few are the operating industrial plants. Quantification and mapping of the potential FW availability along the entire fish value-chain is crucial in fostering its actual valorisation. Apart at industrial processing, in the distribution segment the estimation of FW availability is absent. This paper aimed to quantify and locate FW generated by point sources such as supermarkets, fishmongers and restaurants as well as to establish the diffuse domestic FW production in a 4,5M inhabitants region. The study provides an exportable method and indications for comparable worldwide areas. A simplified valorisation scenario for equivalent biomethane production is also presented. Direct interviews and indirect approach based on fish consumption have been adopted and compared. Large supermarkets and medium-large restaurants are the main FW producers (239 and 125 kg/week, respectively) followed medium-large fishmongers and medium supermarkets (63 and 86 kg/week, respectively). In the investigated region the larger FW point sources are supermarkets (average 3000 Mg/y), while fishmongers are the smaller (average 750 Mg/y). Restaurants (average 1400 Mg/y) show the wider range of variability between 460 and 8000 Mg/y. The indirect methodology reveals that domestic FW production ranges from 2376 to 3961 Mg/y. Per capita estimations of FW ranged from 0.5 - 3 kg/y. The economic value of FW (biomethanation route) is 68 EUR/Mg. A qualification as "highly potential waste" would promote FW valorization.

Integration of physical, geochemical and biological analyses as a strategy for coastal lagoon biomonitoring.

Coastal lagoons are complex environments threatened by natural and anthropogenic stressors. Here, we tested the effectiveness of combining physical, geochemical and chemical measurements with biomarker data obtained in field-exposed marine mussels (Mytilus galloprovincialis) as a biomonitoring strategy for a highly pressured lagoon (Pialassa Baiona, Ravenna, Italy). Data showed a spatial trend of sediment contamination by Hg, Pt, Au, Ag, Mo, Re, Cd, Pd and Zn. Local conditions of high water temperature/low conductivity were detected among selected sites. After a 30-day in situ exposure, Ag and Hg were the most bioaccumulated elements (10 and 5 folds, respectively) in mussels followed by Sb, Al, Ti and Fe. Decreased survival, lysosomal dysfunctions, increased metallothionein content and peroxisome proliferation were observed in mussels in relation to metal spatial distribution and physico-chemical fluctuations. Overall, this study provides a further confirmation of the role of biomonitoring to reliably assess the environmental quality of highly pressured lagoons.

Comparative life cycle assessment of microalgae cultivation for non-energy purposes using different carbon dioxide sources.

The ability of microalgae to sequester carbon and at the same time synthesise valuable compounds with potential applications in nutraceutical, pharmaceutical and cosmetic industries makes them attractive for commercial deployment, especially in view of a blue bioeconomy. Among microalgae, the diatom Phaeodactylum tricornutum is considered as an important potential source of omega-3 polyunsaturated fatty acids, such as eicosapentanoic acid, an essential polyunsaturated fatty acid with anti-inflammatory and antimicrobial properties. The aim of this study was to perform the Life Cycle Assessment of the cultivation of P. tricornutum - at semi-industrial scale in photobioreactor - for the production of high-quality bioactive compounds comparing synthetic carbon dioxide supply to a supply with waste carbon dioxide from a biogas upgrading process hypothesizing industrial symbiosis network. The effect of renewable energy use instead of the European electricity mix was also examined. Primary data on the production process, including the stages of cleaning and sterilisation, cultivation, harvesting and freeze-drying, were used. The midpoint impact categories recommended in the ILCD Handbook were used for performing the impact assessment. A sensitivity analysis was also performed on algal productivity, culture medium recirculation factor and amount of solvents per cleaning cycle. Firstly, results indicate in general cultivation and freeze-drying as the most contributing stages to the impacts. Secondly, they demonstrate in the comparative assessment that the use of carbon dioxide from the biogas upgrading is a feasible and attractive alternative to the synthetic one, as it allows for the improvement of the environmental performance of the production process in all the analysed impact categories. Finally, sensitivity analysis suggests that the environmental performance could be further improved by acting on other key factors, such as electricity source, nutrients culture medium and cleaning solutions.

Exploitable fish waste and stranded beach debris in the Emilia-Romagna Region (Italy).

Within Circular Economy principles, this paper analyses and estimates exploitable marine residues, such as fish waste and stranded debris in beaches and their potential valorisation scenarios. The Emilia-Romagna Region (Italy) has been chosen as a case study. Based on the sold fish, about 200 Mg/year of fish waste are produced at the five major fish markets of the Region. Including all regional fish processing plants and retail trade, the estimated availability of fish waste increases up to 30,000 Mg/year. Stranded beach debris collected by mechanical cleaning operations are currently deposited in landfill. About 63,000 Mg/year of sieved debris are collected each year, out of which the recoverable fractions consist of 19,000 Mg/year of organic material, 8,000 Mg/year of shells and 5,200 Mg/year of stones. Classification and valorisation routes for these residual biomasses are proposed and their applicability to other regions discussed. In order to investigate the possible use in anaerobic digestion plants and the effects on biogas production, Biochemical Methane Potential (BMP) assays have been carried out with fish waste samples and with organic material found in marine debris. Salt content in driftwood has been quantified to assess its potential use in Combined Heat and Power (CHP) plants. Proposed valorisation routes for shells and stones include the production of calcium carbonate (cement industry, wastewater treatment and mulching) and the application in building industry, respectively.