Potential of Castanea sativa for biomonitoring As, Hg, Pb, and Tl: A focus on their distribution in plant tissues from a former mining district.

Bioavailability of potentially toxic elements (PTEs) from the Earth's crust in the soil, e.g., As, Hg, Tl, and Pb, can pose a potential environmental and health risk because of human activities, especially related to mining extraction. The biomonitoring allows to detect PTE contamination through their measurement in living organisms as trees. However, the choice of which plant species and tissue to analyse is a key point to be evaluated in relation to PTE absorption and translocation. The aim of this work was to assess the As, Hg, Tl, and Pb distribution in Castanea sativa Mill. plant tissues, given its importance for both biomass and food production. The study identified two sites in the Alpi Apuane (Italy), with similar environmental conditions (e.g., elevation, exposure, forest type, and tree species) but different soil PTE levels. The topsoil was characterized, and the PTE fractions with different bioavailability were measured. The PTE concentrations were also analysed in chestnut plant tissues (leaves, bark, wood, nuts, and shells) in parallel with and evaluation of plant health status through the determination of micro and macronutrient concentrations and the leaf C and N isotope composition (δ13C or δ15N). Chestnut trees showed a good health status highlighting its suitability for Tl, As, Hg, and Pb biomonitoring, displaying a tissue-specific PTE allocation. Thallium and Hg were detected in all plant tissues at similar concentrations, As was found in leaves, wood, and nuts while Pb only in the bark. The δ15N negatively correlated with leaf Mn and Tl concentrations, suggesting possible changes in N source and/or plant metabolism due to the high contamination level and acid soil pH. Thallium in La Culla site trees was associated with its presence in the carbonate rocks but not in the topsoil, highlighting the potentiality of chestnut in providing valuable information for geochemical surveying.

Timescale of a magmatic-hydrothermal system revealed by 40Ar-39Ar geochronology: the Mio-Pliocene Campiglia Marittima system (Tuscany, Italy).

Petrology and timing of magmatic-hydrothermal systems and the linkage between plutonic and volcanic domains are central topics in geosciences, because of broad implications for natural hazards and exploitation of natural resources. We investigated by the 40Ar-39Ar method the timescale of a well-characterized natural example, the Mio-Pliocene Campiglia Marittima magmatic-hydrothermal system (Tuscany, Italy). 40Ar-39Ar data from pristine and homogeneous trioctahedral micas and sanidine from the plutonic-hydrothermal-subvolcanic-volcanic sequence (from the Botro ai Marmi Granite to the San Vincenzo Rhyolite) record crystallization ages and define a temporal sequence lasting 973 ± 43 ka, starting from 5.409 ± 0.043 Ma. K-feldspar from mafic and felsic porphyries, unlike micas, are affected by submillimetre, micropore laden, alteration domains consisting of secondary K-feldspar and albite, and yielded staircase-shaped age spectra, compatible with a ternary mixing. Results document that the San Vincenzo Rhyolite consists of two diachronous batches, the first emplaced at 5.0024 ± 0.0062 Ma, closely following emplacement of mafic porphyries, the second at 4.4359 ± 0.0045 Ma. Bulk of hydrothermal deposits, consisting of skarns and associated Zn-Pb(-Ag) mineralization predating Fe-Cu ore, formed within the first ~ 400-ka lifetime of the whole sequence and was closely followed by the first eruption which should have run out most of the ore-forming potential of the system.

Thallium-rich rust scales in drinkable water distribution systems: A case study from northern Tuscany, Italy.

Following the detection of a severe thallium contamination of the drinkable water from the public distribution system of Valdicastello Carducci-Pietrasanta (northern Tuscany, Italy), and the identification of the source of contamination in the Molini di Sant'Anna spring (average Tl content≈15µgL-1), the replacement of the contaminated water with a virtually Tl-free one (Tl<0.10µgL-1) caused an increase in Tl concentration in the drinkable water. This suggested that the pipeline interior had become a secondary source of Tl contamination, promoting its mineralogical and geochemical study. Rust scales samples taken from several pipeline segments, as well as leaching products obtained from these samples, were investigated through scanning electron microscopy, X-ray fluorescence chemical analyses, inductively coupled plasma - mass spectrometry, X-ray diffraction, and X-ray absorption spectroscopy. Thallium-rich rust scales (up to 5.3wt% Tl) have been found only in pipeline samples taken downstream the water treatment plant, whereas the sample taken upstream contains much less Tl (~90µgg-1). The Tl-rich nature of such scales is related to the occurrence of nano- and micro-spherules of Tl2O3 and less abundant nanocrystalline µm-sized encrustations of TlCl. Leaching experiments on Tl-rich rust scales indicate that a fraction of the available Tl is easily dissolved in tap water; X-ray absorption spectroscopy suggests that monovalent thallium occurs in water equilibrated with the rust scales, probably related to the dissolution of TlCl encrustations. Therefore, Tl dissolved as Tl+ only in the water from the Molini di Sant'Anna spring was partially removed through oxidative precipitation of Tl2O3 and precipitation of TlCl. This highlights the critical role played by the addition of chlorine-based oxidants in water treatment plants that could favour the deposition of Tl-rich coatings within the pipelines, giving rise to unexpected secondary sources of contamination.