Approccio SEM-AVS (Simultaneously Extracted Metals-Acid Volatile Sulfides) per la valutazione del rischio ambientale dei metalli nei sedimenti della Pialassa Baiona

La Pialassa Baiona è una laguna sottoposta a diversi vincoli normativi, visto il suo inquadramento tra le aree SIC e ZPS, e soggetta a diverse sorgenti di disturbo antropico, più intense negli anni ‘50-‘70. Questa tesi si propone lo scopo di valutare il rischio associato ai metalli bivalenti presenti nei sedimenti della Pialassa Baiona attraverso tre approcci: il primo riguarda la determinazione della frazione biodisponibile dei metalli presenti nei sedimenti attraverso la determinazione dei solfuri acidi volatili (AVS) e dei metalli simultaneamente estraibili (SEM), nonché la valutazione della potenziale tossicità dei sedimenti attraverso la valutazione del rapporto molare SEM/AVS, il secondo approccio considera invece il contenuto pseudo totale dei metalli bivalenti (Cd, Cu, Ni, Pb e Zn) e il loro confronto sia con i valori tipici di fondo naturale del Mar Adriatico che con i valori guida di riferimento internazionale (Threshold Effect Level, TEL e Probable Effect Level, PEL) al fine di valutare lo stato di qualità dei sedimenti della zona d’indagine. Il terzo approccio considera l’influenza del gradiente naturale terra-mare tipico delle zone di transizione e del gradiente antropico legato alla vicinanza dell’area industriale alla Pialassa Baiona, sulla distribuzione spaziale dei metalli oggetto di questo studio. I risultati ottenuti evidenziano che l’area più prossima alla zona industriale e al contempo più lontana dall’effetto del ricambio delle acque e di dilavamento ad opera del mare, è risultata quella con livelli significativamente più elevati per la maggior parte dei metalli analizzati. Questo permette di ipotizzare un’influenza diretta delle sorgenti di inquinanti, ma anche un effetto dispersivo della circolazione. Gli AVS hanno invece evidenziato un gradiente terra-mare; ciò comporta che nelle zone più prossime all’influenza del mare si sono riscontrate concentrazioni minori di AVS. La valutazione della potenziale tossicità dei metalli in termini di rapporto SEM/AVS non ha evidenziato la presenza di siti a rischio per il biota acquatico, se non per un unico sito prossimo all’area industriale.

Distribution of metals in several vineyards of North Italy: from soil to wine

Nowadays we live in densely populated regions and this leads to many environmental issues. Among all pollutants that human activities originate, metals are relevant because they can be potentially toxic for most of living beings. We studied the fate of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in a vineyard environment analysing samples of plant, wine and soil. Sites were chosen considering the type of wine produced, the type of cultivation (both organic and conventional agriculture) and the geographic location. We took vineyards that cultivate the same grape variety, the Trebbiano). We investigated 5 vineyards located in the Ravenna district (Italy): two on the Lamone Valley slopes, one in the area of river-bank deposits near Ravenna city, then a farm near Lugo and one near Bagnacavallo in interfluve regions. We carried out a very detailed characterization of soils in the sites, including the analysis of: pH, electric conductivity, texture, total carbonate and extimated content of dolomite, active carbonate, iron from ammonium oxalate, Iron Deficiency Chlorosis Index (IDCI), total nitrogen and organic carbon, available phosphorous, available potassium and Cation Exchange Capacity (CEC). Then we made the analysis of the bulk chemical composition and a DTPA extraction to determine the available fraction of elements in soils. All the sites have proper ground to cultivate, with already a good amount of nutrients, such as not needing strong fertilisations, but a vineyard on hills suffers from iron deficiency chlorosis due to the high level of active carbonate. We found some soils with much silica and little calcium oxide that confirm the marly sandstone substratum, while other soils have more calcium oxide and more aluminium oxide that confirm the argillaceous marlstone substratum. We found some critical situations, such as high concentrations of Chromium, especially in the farm near Lugo, and we noticed differences between organic vineyards and conventional ones: the conventional ones have a higher enrichment in soils of some metals (Copper and Zinc). Each metal accumulates differently in every single part of grapevines. We found differences between hill plants and lowland ones: behaviors of plants in metal accumulations seems to have patterns. Metals are more abundant in barks, then in leaves or sometimes in roots. Plants seem trying to remove excesses of metal storing them in bark. Two wines have excess of acetic acid and one conventional farm produces wine with content of Zinc over the Italian law limit. We already found evidence of high values relating them with uncontaminated environments, but more investigations are suggested to link those values to their anthropogenic supplies.

Heavy Metals distribution in drainage canals sediments of the Ravenna province

This work, in collaboration with the Romagna Reclamation Consortium, has the aim of studying the heavy metals concentration distribution in the drainage canals of the Ravenna coastal basins, Italy. Particular attention was given to the area of the V Fosso Ghiaia and VI Bevanella basins, where water and sediment samples were collected in the field and integrated with existing databases. The hydrological regime is controlled and managed by the Consortium, which has divided the territory into several mechanical drainage basins. XRF was performed on 21 sediment samples and pH, EC, T°, Fe2+ and Fetot were measured on 15 water samples by probes and spectrophotometer, respectively. Heavy metals concentrations exceeding legal limits of the D.LGS n ° 152/2006 were found for As, Co, Cr, Pb and Zn. These results were then integrated with canal sediment analyses provided by the Consortium to perform a Principal Component Analysis. PCA results show that the main variable affecting heavy metals distribution is the use of fertilizers, followed by distance from sea, and altimetry, which are directly linked to salinity. Heavy metals concentrations increase with increasing use of fertilizers, which are mainly due to the widespread agricultural practices and industrial land use in the area. High heavy metals concentrations are also found in the canals interested by higher salinity (especially Pinetale Ramazzotti). In fact, the area is affected by salinization caused by a water table below sea level and upward seepage of salty oxygen-poor saline water from the bottom of the aquifer. According to the literature, iron and manganese oxides were found to be an important factor in controlling the heavy metals distribution.