Soil organic carbon data comparison after 85 years and new 13 C/12 C compositions: The case study of the Ferrara province (Northeastern Italy).

The main causes of soil organic matter (SOM) loss are land use (e.g., conventional agriculture) and land-use change (e.g., conversion of wetlands into croplands). Before World War II and until 1960s, the Ferrara province in the Emilia-Romagna region (Northeast Italy) enlarged its agricultural production area through drainage of wetlands. After that, the newly drained area was put into intensive agricultural production with practices that proved to be unsustainable, and whose negative effects (depletion of soil organic carbon [SOC] and emissions of greenhouse gases [GHGs], e.g., CO2 ) have never been quantified. In this work, we estimated the changes in SOC 85 years after the drainage of the palustrine environment, by comparing 1937 SOC measurements with those made in 2022. Comparison of SOC maps from 1937 and 2022 indicates that most of the area suffered a significant SOC loss (∆OC85 years from 0.05 to 18.57 wt%), except for northern areas in which the peat nature of the soil has been preserved. We also measured the 13 C/12 C on the 2022 soil samples and generated a present-day map of the SOC isotopic ratios, which could be used in future as a benchmark to evaluate changes in soil carbon stocks and fluxes.

The trace element distribution in peat soils affected by natural burning events: A proxy of the original composition and metals mobility assessment.

This work evaluates for the first time the effects on the trace element composition of peat soils affected by natural burning events, a recurrent phenomenon in the reclaimed wetland of the Mezzano Lowland (Padanian plain, NE Italy). The trace element distribution of two neighboring soil profiles, one pristine and one deeply affected by burning events, were compared to identify the original geochemical fingerprint of saltmarsh peat environment. The pre-combustion composition of the fired profile was reconstructed to infer the physico-chemical changes occurred as a consequence of the burning event, with a special attention to the mobility of elements of environmental concern, such as potentially toxic trace metals. The increase in concentration of potentially toxic elements (PTE) was particularly evident in two layers of the fired profile. V, Cr, Cu, Zn, Pb, and As contents progressively increase toward intermediate depths (30-75 cm) together with Th, Sr, Ba, U. On the contrary, Tl, Bi and Cd show a concentration peak in a thin, shallower (14-17 cm depth) horizon. The trace element composition of the unfired profile allowed the identification of specific ratios between immobile elements that can be used as geochemical fingerprint of the soils horizons with different soil organic matter (SOM) content. On the basis of Sr/Rb, Th/U and Ba/Sr it was possible to classify three types of sedimentary deposits characterizing both the unfired and fired profile, as well as to delineate the fire severity trends occurred in the different soil horizons of the fired profile. The distribution of immobile trace element, representative of the organic (U) and mineral (silicate, Th, Ba, REE and non-silicate, Sr) soil fractions with organic matter and bulk density in the non-fired profile, allowed the reconstruction of the original physico-chemical composition of the fired/burned profile and the accurate determination of the relative CO2 lost during the burning event. Moreover, the distribution of PTE with respect to immobile trace elements, used to estimate the element redistribution and mobility after burning in the fired profile, suggested that elements such as Cr, Ni, Zn, V were mainly immobile, whereas Pb, Mo and in particular Tl and Bi suffered a significant redistribution along the burned profile. Nonetheless, results of the gain/loss calculation for the whole soil profile suggested that no significant entry or leak of these elements occurred, limiting their redistribution inside the investigated soil system.

High temperature behaviour of Ag-exchanged Y zeolites used for PFAS sequestration from water.

Per- and polyfluorinated alkyl substances (PFAS) are anthropogenic compounds which have recently drawn great attention due to their high biological, chemical and physical stability and lipid/water repelling properties. The present work aims to provide for the first time insights on the thermal behaviour of Ag-exchanged Y zeolite loaded with perfluorooctanoic acid (PFOA, C8HF15O2) and perfluorooctane sulfonate (PFOS, C8HF17O3S) emphasizing the close link between crystal structure and desorption/dehydration processes. Elemental and isotopic abundance of carbon analysis, thermal analysis, and in situ high-temperature synchrotron X-ray powder diffraction were used to evaluate critically if the thermal regeneration affects the initial zeolites structural features. Rietveld refinements revealed that PFAS sites are emptied in the 550-650 °C temperature range, when the thermal degradation of PFOA and PFOS are reached. The crystallinity of the samples is not affected by the adsorption/desorption processes. Upon heating, the removal of both PFAS and coadsorbed water molecules induced a cation migration of the silver ions and changes of initial geometry of the framework. The dimensions of the channels remain comparable to those of the pristine materials thus suggesting the potential re-use of the samples in other adsorption PFAS cycles. Additionally, once regenerated and reloaded Ag-exchanged Y can re-adsorb PFAS in amounts comparable to that adsorbed in the first cycle with clear benefits on the costs of the whole water treatment process.

Peat Soil Burning in the Mezzano Lowland (Po Plain, Italy): Triggering Mechanisms and Environmental Consequences.

The effects of peat burning on organic-rich agricultural soils of the Mezzano Lowland (NE Italy) were evaluated on soil profiles variously affected by smoldering. Profiles were investigated for pH, electrical conductivity, bulk density, elemental and isotopic composition of distinct carbon (and nitrogen) fractions. The results suggest that the horizons affected by carbon loss lie at depths 10-70 cm, where the highest temperatures are developed. We suggest that the exothermal oxidation of methane (mediated by biological activity) plays a significant role in the triggering mechanism. In the interested soils we estimated a potential loss of Soil Organic Carbon of approximately 110 kg m -2 within the first meter, corresponding to 580 kg CO2 m -3. The released greenhouse gas is coupled with a loss of soil structure and nutrients. Moreover, the process plausibly triggers mobility of metals bound in organometallic complexes. All these consequences negatively affect the environment, the agricultural activities and possibly also health of the local people.

Traceability and Authentication of Manila Clams from North-Western Adriatic Lagoons Using C and N Stable Isotope Analysis.

In the Adriatic lagoons of northern Italy, manila clam (Ruditapes philippinarum) farming provides important socio-economic returns and local clams should be registered with the Protected Designations of Origin scheme. Therefore, there is a need for the development of rapid, cost-effective tests to guarantee the origin of the product and to prevent potential fraud. In this work, an elemental analysis (EA) coupled with isotope ratio mass spectrometry (IRMS) was employed to identify the isotopic fingerprints of clams directly collected onsite in three Adriatic lagoons and bought at a local supermarket, where they exhibited certification. In particular, a multivariate analysis of C/N, δ13C and δ15N in manila clam tissues as well as δ13C in shells and Δ13C (calculated as δ13Cshell-δ13Ctissues) seems a promising approach for tracking the geographical origin of manila clams at the regional scale.