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Instruments / Technical Area	Publication Details	Published
B18-Core EXAFS	Evaluation of cadmium and arsenic effects on wild and cultivated cardoon genotypes selected for metal phytoremediation and bioenergy purposes Chiara Leonardi , Valeria Toscano , Claudia Genovese , Julian Frederick Willem Mosselmans , Bryne Tendolo Ngwenya , Salvatore Antonino Raccuia Environmental Science And Pollution Research 15 DOI: 10.1007/s11356-021-14705-9 Diamond Proposal Number(s): [15231] Open Access Show Abstract ▼ Abstract: Cynara cardunculus L. is a multipurpose crop, characterized by high production of biomass suitable for energy purposes and green chemistry. Taking advantage of its already demonstrated ability to grow in polluted environments that characterize many world marginal lands, the aim of this work was to investigate the response of different cardoon genotypes to exposure to cadmium (Cd) and arsenic (As) pollution, in order to use this crop for rehabilitation of contaminated sites and its biomass for energy production. In this study, seeds of two wild cardoon accessions harvested in rural and industrial Sicilian areas and of a selected line of domestic cardoon were used, and the grown plants were spiked with As and Cd, alone or in combination, at two different concentrations (500 and 2000 μM) and monitored for 45 days. The growth parameters showed that all the plants survived until the end of experiment, with growth stimulation in the presence of low concentrations of As and Cd, relative to metal-free controls. Biomass production was mostly allocated in the roots in As treatment and in the shoots in Cd treatment. Cd EXAFS analysis showed that tolerance to high concentrations of both metals was likely linked to complexation of Cd with oxygen-containing ligands, possibly organic acids, in both root and leaf biomass with differences in behaviour among genotypes. Under As+Cd contamination, the ability of the plants to translocate As to aboveground system increased also showing that, for both metal(loid)s, there were significant differences between genotypes studied. Moreover, the results showed that Cynara cardunculus var. sylvestris collected in an industrial area is the genotype that, among those studied, had the best phytoextraction capability for each metal(loid).	Jun 2021
B18-Core EXAFS I18-Microfocus Spectroscopy	Abiotic reduction of Cr(VI) by humic acids derived from peat and lignite: kinetics and removal mechanism Suha T. Aldmour , Ian T. Burke , Andrew W. Bray , Daniel L. Baker , Andrew B. Ross , Fiona L. Gill , Giannantonio Cibin , Michael E. Ries , Douglas I. Stewart Environmental Science And Pollution Research 29 DOI: 10.1007/s11356-018-3902-1 Diamond Proposal Number(s): [12696, 15711] Open Access Show Abstract ▼ Abstract: Hexavalent chromium contamination of groundwater is a worldwide problem caused by anthropogenic and natural processes. We report the rate of Cr(VI) removal by two humic acids (extracted from Miocene age lignite and younger peat soil) in aqueous suspensions across a pH range likely to be encountered in terrestrial environments. Cr(VI) was reduced to Cr(III) in a first-order reaction with respect Cr(VI) concentration, but exhibited a partial order (~ 0.5) with respect to [H+]. This reaction was more rapid with the peat humic acid, where Cr(VI) reduction was observed at all pH values investigated (3.7 ≤ pH ≤ 10.5). 13C NMR and pyrolysis GC-MS spectroscopy indicate that the reaction results in loss of substituted phenolic moieties and hydroxyl groups from the humic acids. X-ray absorption spectroscopy indicated that at all pH values the resulting Cr(III) was associated with the partially degraded humic acid in an inner-sphere adsorption complex. The reaction mechanism is likely to be controlled by ester formation between Cr(VI) and phenolic/hydroxyl moieties, as this initial step is rapid in acidic systems but far less favourable in alkaline conditions. Our findings highlight the potential of humic acid to reduce and remove Cr(VI) from solution in a range of environmental conditions.	Dec 2018
I08-Scanning X-ray Microscopy beamline (SXM)	Zinc incorporation in marine bivalve shells grown in mine-polluted seabed sediments: a case study in the Malfidano mining area (SW Sardinia, Italy) Daniela Medas , Ilaria Carlomagno , Carlo Meneghini , Giuliana Aquilanti , Tohru Araki , Diana Bedolla , Carla Buosi , Maria Antonietta Casu , Alessandra Gianoncelli , Andrei C. Kuncser , V. Adrian Maraloiu , Giovanni De Giudici Environmental Science And Pollution Research 209 DOI: 10.1007/s11356-018-3504-y Diamond Proposal Number(s): [16496] Show Abstract ▼ Abstract: Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0–80 mg/kg of Zn, 5.4–60 mg/kg of Fe and 0.5–4.5 mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.	Oct 2018

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