Thallium speciation in water and sediments from an abandoned mine site: the case of Valdicastello Carducci (Tuscany, Italy)

The analysis of chemical speciation has an important role in environmental protection since availability, fate and toxicity of a number of potentially toxic elements depend on their chemical form. In particular, thallium has been identified as an environmental significant element, being more toxic to humans than many heavy metals including Hg, Pb and Cd. Thallium can occur in the aqueous phase and sediments in the state of oxidation Tl(I) and Tl(III). Tl(I) is the more thermodynamically stable species under the typical conditions for natural waters. Italian Regulations pose a concentration limit of 2 µg/l for total Tl in groundwater, and do not distinguish among the different Tl species, although some studies highlight a higher toxicity for Tl(III). Thallium concentrations limits are 1 mg/kg and 10 mg/kg (on a dry basis) in soils for residential and industrial use, respectively. This Thesis is focused on the study of occurrence and oxidation state of thallium in waters and sediments sampled in a watershed impacted by past mining, characterized by high thallium concentrations in orebodies. Thallium concentration and speciation were determined at the Hydro Sciences Laboratory of CNRS of Montpellier (France) by High Pressure Liquid Chromatography coupled with Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS). In addition, major ion and trace elements analysis on waters samples were obtained by Ion Chromatography (IC) and ICP-MS at the Department of Earth Sciences of the University of Pisa. Thallium speciation analysis and some trace element abundance were also done at the Institute for Chemistry of OrganoMetallic Compounds (CNR) of Pisa, for a comparison. The results indicate a Tl concentration in the range between 375 and 923 μg/l in acid mine drainages, 9.11-157 μg/l in spring and surface waters, and 58.6-570 μg/g in sediments at the drainages outflow and stream. It was found that in waters thallium occurs mainly in the monovalent form Tl(I), even if in some cases a significant amount of Tl(III) was detected. In particular, Tl(I) characterizes acid mine drainages, while Tl(III) with a maximum concentration of 91.7 μg/l (up to the 40% of the total amount) has been measured in surface waters in two different stations along the stream course. This observation poses the question of the possible mechanisms for Tl(I) oxidation processes in these settings. This point requires additional investigations. Satisfactory results for Tl speciation in sediments were not obtained, since only a small fraction of the total Tl was actually extracted by both DTPA and H3PO4 for speciation analysis. However, despite not quantitative, speciation results seem to indicate the occurrence of Tl(I) and Tl(III) in different amounts in sediments. Possible oxidation reactions involve the role of manganese oxides. Finally, the role of changing the oxygenation state of waters on thallium speciation was preliminary investigated by microcosm experiments on samples consisting of sediment and water. The results indicate that, in both oxic and anoxic conditions, Tl(I) and Tl(III) concentrations increased as a function of incubation time, although Tl(III) presents a slight increase. The observed increase of Tl(I) and Tl(III) concentrations probably indicates the migration of species from sediment to the aqueous phase

Desempenho do pomeleiro "marsh seedles" enxertado em trifoliata inoculado com viróides no Brasil

Alguns viróides reduzem o crescimento dos citros e podem ser usados para o controle do tamanho das plantas objetivando a instalação de pomares adensados que podem ter maior produtividade que os pomares com espaçamentos convencionais. Para estudar o efeito da inoculação de viróides no desenvolvimento vegetativo, produção e qualidade dos frutos de pomeleiro 'Marsh Seedless' (Citrus paradisi Macf.) enxertado em trifoliata [Poncirus trifoliata (L.) Raf.], foi instalado um experimento em Janeiro de 1991, em Bebedouro, Estado de São Paulo, Brasil. O delineamento experimental foi em blocos casualizados com quatro tratamentos e duas plantas por parcela: viróides dos citros (CEVd + CVd-II + CVd-III) e (CVd-II + CVd-III) e testemunhas: enxertia de duas borbulhas sadias (testemunha) e sem enxertia (testemunha absoluta). A inoculação foi feita no campo, seis meses após o plantio, por enxertia de borbulhas. Ambos isolados reduziram o crescimento das árvores (diâmetro do tronco, altura da planta diâmetro e volume da copa). As árvores não inoculadas produziram mais que as inoculadas nas onze colheitas realizadas, mas as produtividades foram similares. A qualidade dos frutos foi afetada pela inoculação de viróides, mas não de maneira restritiva. O uso de isolados ananicantes severos não deve ser recomendado para plantios de alta densidade de pomelo enxertado em trifoliata.Some viroids reduce citrus tree growth and may be used for tree size control aiming the establishment of orchards with close tree spacing that may provide higher productivity than conventional ones. To study the effects of citrus viroids inoculation on vegetative growth, yield and fruit quality of 'Marsh Seedless' grapefruit (Citrus paradisi Macf.) grafted on trifoliate orange [Poncirus trifoliata (L.) Raf.], an experiment was set up in January 1991, in Bebedouro, São Paulo State, Brazil. The experimental design was randomized blocks with four treatments with two plants per plot: viroid isolates Citrus Exocortis Viroid (CEVd) + Hop stunt viroid (HSVd - CVd-II, a non cachexia variant) + Citrus III viroid (CVd-III) and Hop stunt viroid (HSVd - CVd-II, a non cachexia variant) + Citrus III viroid (CVd-III) and controls: two healthy buds (control), and no grafting (absolute control). Inoculation was done in the field, six months after planting by bud grafting. Both isolates reduced tree growth (trunk diameter, plant height, canopy diameter and volume). Trees not inoculated yielded better (average of eleven harvests) than inoculated ones but the productivity was the same after 150 months. Fruit quality was affected by viroids inoculation but not in a restrictive way. The use of such severe dwarfing isolates for high density plantings of grapefruit on trifoliate orange rootstock is not recommended

Caveolin-1 protects B6129 mice against Helicobacter pylori gastritis.

Caveolin-1 (Cav1) is a scaffold protein and pathogen receptor in the mucosa of the gastrointestinal tract. Chronic infection of gastric epithelial cells by Helicobacter pylori (H. pylori) is a major risk factor for human gastric cancer (GC) where Cav1 is frequently down-regulated. However, the function of Cav1 in H. pylori infection and pathogenesis of GC remained unknown. We show here that Cav1-deficient mice, infected for 11 months with the CagA-delivery deficient H. pylori strain SS1, developed more severe gastritis and tissue damage, including loss of parietal cells and foveolar hyperplasia, and displayed lower colonisation of the gastric mucosa than wild-type B6129 littermates. Cav1-null mice showed enhanced infiltration of macrophages and B-cells and secretion of chemokines (RANTES) but had reduced levels of CD25+ regulatory T-cells. Cav1-deficient human GC cells (AGS), infected with the CagA-delivery proficient H. pylori strain G27, were more sensitive to CagA-related cytoskeletal stress morphologies ("humming bird") compared to AGS cells stably transfected with Cav1 (AGS/Cav1). Infection of AGS/Cav1 cells triggered the recruitment of p120 RhoGTPase-activating protein/deleted in liver cancer-1 (p120RhoGAP/DLC1) to Cav1 and counteracted CagA-induced cytoskeletal rearrangements. In human GC cell lines (MKN45, N87) and mouse stomach tissue, H. pylori down-regulated endogenous expression of Cav1 independently of CagA. Mechanistically, H. pylori activated sterol-responsive element-binding protein-1 (SREBP1) to repress transcription of the human Cav1 gene from sterol-responsive elements (SREs) in the proximal Cav1 promoter. These data suggested a protective role of Cav1 against H. pylori-induced inflammation and tissue damage. We propose that H. pylori exploits down-regulation of Cav1 to subvert the host's immune response and to promote signalling of its virulence factors in host cells

Water and sediments geochemistry and elemental fluxes on a Large Dam: case study of Ridracoli reservoir.

Since the study of Large Dam Reservoirs is of worldwide interest, in this PhD project we investigated the Ridracoli reservoir, one of the main water supply in Emilia-Romagna (north-eastern Italy). This work aims to characterize waters and sediments to better understand their composition, interactions and any process that occurs, for a better geochemical and environmental knowledge of the area. Physical and chemical analyses on the water column have shown an alternation of stratification and mixing of water in the reservoir’s water body due to seasonal variations in temperature and density. In particular, it was observed the establishment, in late summer, of anoxic conditions at the bottom, which in turn affects the concentration and mobility of some elements of concern (e.g. Fe and Mn) for the water quality. Sediments within the reservoir and from surrounding areas were analysed for organic matter, total inorganic composition and grain size, assessing the inter-element relationship, grain size, geological background and damming influences on their chemistry, through descriptive statistics, Principal Component Analysis and Cluster Analysis. The reservoir’s area was also investigated by pseudo total composition (Aqua Regia digestion), degree of elements extractability, and enrichment factors, then analysed and compared to limits by law and literature. Sediment cores, interstitial waters, and benthic chamber data from the bottom were of great interest due to organic matter degradation, early diagenesis, mineral formation at water-sediment interface and observed flows. Finally, leaching test and extraction procedures, of environmental interest, showed peculiar partitioning, both regarding spatial and in-depth distribution, and the absence of pollution. Collectively, our results are useful for the comprehension of processes that occur in water and sediments of Ridracoli reservoir, providing important knowledges on the site that could be relevant for the management of the resource and the planning of future interventions

Sediment quality of the Ridracoli fresh water reservoir in Italy: Insights from aqua regia digestion and sequential extractions

The inter-element relationships and the forms in which metals exist strongly influence their mobility and, in turn, have a signature on the environment and human health. Located in the northern Apennines within the Emilia-Romagna re-gion, the Ridracoli artificial lake is one of Italy's most important reservoirs that provides drinking water for about one million people. This work characterized the reservoir sediments by ICP-MS after aqua regia digestion (ARD), compar-ing the limits by law to assess environmental compliance and XRF data from the same sample-set taken as total con-centrations. The Degree of Extraction (DE) from pseudo-total concentrations of ARD analysis allows assessing elements mobility and the associated environmental risk. Principal Component Analysis (PCA) on the obtained data helped to investigate inter-element relationships better; for example, we observed carbonate-sourced sediments, many trace elements (e.g., Ni, Zn) linked to FeMn oxyhydroxides, the importance of the grain size in elements distri-bution, and the central role of the organic matter in element partitioning. In addition, a Sequential Extraction Proce-dure (SEP) was applied to the sediment samples to understand the partitioning of many analytes, including Potentially Harmful Elements (PHE) such as Fe, Mn, Cu, Cr, Ni, Pb, and Zn. The results indicated that the most easily mobilized forms were predominant in the area near the dam, in correspondence to sediments affected by the formation of a seasonal anoxic layer

Urban mining of municipal solid waste incineration (MSWI) residues with emphasis on bioleaching technologies: a critical review

Metals are essential in our daily lives and have a finite supply, being simultaneously contaminants of concern. The current carbon emissions and environmental impact of mining are untenable. We need to reclaim metals sustainably from secondary resources, like waste. Biotechnology can be applied in metal recovery from waste streams like fly ashes and bottom ashes of municipal solid waste incineration (MSWI). They represent substantial substance flows, with roughly 46 million tons of MSWI ashes produced annually globally, equivalent in elemental richness to low-grade ores for metal recovery. Next-generation methods for resource recovery, as in particular bioleaching, give the opportunity to recover critical materials and metals, appropriately purified for noble applications, in waste treatment chains inspired by circular economy thinking. In this critical review, we can identify three main lines of discussion: (1) MSWI material characterization and related environmental issues; (2) currently available processes for recycling and metal recovery; and (3) microbially assisted processes for potential recycling and metal recovery. Research trends are chiefly oriented to the potential exploitation of bioprocesses in the industry. Biotechnology for resource recovery shows increasing effectiveness especially downstream the production chains, i.e., in the waste management sector. Therefore, this critical discussion will help assessing the industrial potential of biotechnology for urban mining of municipal, post-combustion waste