Influence of environmental and anthropogenic parameters on thallium oxidation state in natural waters

The abandoned mining area of Valdicastello Carducci (Tuscany, Italy) is characterized by the massive presence of thallium in the acid mine drainages and in the valley stream crossing the region. We previously found that Tl(III), generally considered the less stable oxidation state of thallium, is present both in the stream and in tap water distributed in the area, whereas acid mine drainages only contain Tl(I). These findings posed some concern related to the reactivity and dispersion of this toxic element in the environment. Since the valence state of thallium determines its toxicity, distribution and mobility, the study of thallium redox speciation appears crucial to understand its environmental behaviour. In this work, water samples collected from the mine drainages and the contaminated stream were adopted as model to study the distribution of aqueous Tl(I)/Tl(III) as a function of light exposure and solution properties and composition. The influence of three light sources and organic acids was evaluated. Thallium speciation was also assessed in tap water after treatment with common oxidizing agents, and in the rust crust collected from the public waterworks

Human exposure to thallium through tap water: A study from Valdicastello Carducci and Pietrasanta (northern Tuscany, Italy)

A geological study evidenced the presence of thallium (Tl) at concentrations of concern in groundwaters near Valdicastello Carducci (Tuscany, Italy). The source of contamination has been identified in the Tl-bearing pyrite ores occurring in the abandoned mining sites of the area. The strongly acidic internal waters flowing in the min- ing tunnels can reach exceptional Tl concentrations, up to 9000 μg/L. In September 2014 Tl contamination was also found in the tap water distributed in the same area (from 2 to 10 μg/L). On October 3, 2014 the local authorities imposed a Do Not Drink order to the population. Here we report the results of the exposure study carried out from October 2014 to October 2015, and aimed at quantifying Tl levels in 150 urine and 318 hair samples from the population of Valdicastello Carducci and Pietrasanta. Thallium was quantified by inductively coupled plasma — mass spectrometry (ICP-MS). Urine and hair were chosen as model matrices indicative of different time periods of exposure (short-term and long- term, respectively). Thallium values found in biological samples were correlated with Tl concentrations found in tap water in the living area of each citizen, and with his/her habits. Thallium concentration range found in hair and urine was 1–498 ng/g (values in unexposed subjects 0.1–6 ng/g) and 0.046–5.44 μg/L (reference value for the European population 0.006 μg/L), respectively. Results show that Tl levels in biological samples were significantly associat- ed with residency in zones containing elevated water Tl levels. The kinetics of decay of Tl concentration in urine samples was also investigated. At the best of our knowledge, this is the first study on human contamination by Tl through water involving such a high number of samples

Loading of halloysite nanotubes with BSA, α-Lac and β-Lg: A Fourier transform infrared spectroscopic and thermogravimetric study

Halloysite nanotubes (HNTs) are considered as ideal materials for biotechnological and medical applications. An important feature of halloysite is that it has a different surface chemistry on the inner and outer sides of the tubes. This property means that negatively-charged molecules can be selectively loaded inside the halloysite nanoscale its lumen. Loaded HNTs can be used for the controlled or sustained release of proteins, drugs, bioactive molecules and other agents. We studied the interaction between HNTs and bovine serum albumin, α lactalbumin and β -lactoglobulin loaded into HTNs using Fourier transform infrared spectroscopy and thermogravimetry. These techniques enabled us to study the protein conformation and thermal stability, respectively, and to estimate the amount of protein loaded into the HNTs. TEM images confirmed the loading of proteins into HTNs

Coupling of electron and vibrational spectroscopy with false colour imaging for the investigation of natural dyes in historical fabrics (15th-18th centuries)

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Evaluation of potsherds features using hyperspectral maps generated by μ-LIBS scanner

The micro-laser induced breakdown spectroscopy (µ-LIBS) technique allows performing fast elemental analyses, without sample preparation and thus making it specifically useful in the analysis of the composition of ancient potsherd. The µ-LIBS instrument is equipped with a microscope and a scanning system allowing to realize small craters (about Ø = 25 µm) in order to obtain detailed hyperspectral surfaces maps (up to a maximum size of one square centimeter). The data are processed by Self-Organizing Maps (SOMs) method to visualize in 2D representations allowing significant information on the technological features of ceramic samples.The micro-laser induced breakdown spectroscopy (µ-LIBS) technique allows performing fast elemental analyses, without sample preparation and thus making it specifically useful in the analysis of the composition of ancient potsherd. The µ-LIBS instrument is equipped with a microscope and a scanning system allowing to realize small craters (about Ø = 25 µm) in order to obtain detailed hyperspectral surfaces maps (up to a maximum size of one square centimeter). The data are processed by Self-Organizing Maps (SOMs) method to visualize in 2D representations allowing significant information on the technological features of ceramic samples

Micro-chemical evaluation of ancient potsherds by μ-LIBS scanning on thin section negatives

In the study of ancient pottery, thin section analysis represents the basic approach to study mineralogical and petrografic features in order to obtain preliminary information about the production technology and origin of archaeological ceramics. However, even if thin section analysis allows investigating the textural and structural characteristics of potteries, peculiar features related to clay paste and temper composition, as well as provenance issues, can be detailed addressed only by quantitative mineralogical and chemical studies. In the realization of thin sections, a negative face is always produced, similar to the thin section itself; these remains can be used for additional analyses, such as high spatial resolution micro-chemical studies using, for example, a micro-laser induced breakdown spectroscopy (LIBS) scanner. LIBS is a spectroscopic technique that, exploiting the laser radiation, is able to bring into the plasma state micrometric portions of the sample, and to analyse its content through the study of the optical emission of the plasma itself. Unlike other techniques, LIBS can detect and quantify also light elements such as aluminium and magnesium. Images produced by the micro-LIBS instrument show the spatial distribution of the chemical elements within a portion of the sample, which may have dimensions from a few hundred microns up to several centimeters. The combination of these images with algorithms derived from image processing techniques may return interesting information and supporting data to in-depth investigate pottery components detected by optical microscopy observations. In this work, we present the results of an experimental study performed on thin-section negatives with different grain size, surface treatments and aggregates, coming from some Neolithic Italian sites, exploring the potential of the LIBS method in micro-chemical studies of ancient potsherds

Multivariate calibration in Laser-Induced Breakdown Spectroscopy quantitative analysis: The dangers of a ‘black box’ approach and how to avoid them

The introduction of multivariate calibration curve approach in Laser-Induced Breakdown Spectroscopy (LIBS) quantitative analysis has led to a general improvement of the LIBS analytical performances, since a multivariate approach allows to exploit the redundancy of elemental information that are typically present in a LIBS spectrum. Software packages implementing multivariate methods are available in the most diffused commercial and open source analytical programs; in most of the cases, the multivariate algorithms are robust against noise and operate in unsupervised mode. The reverse of the coin of the availability and ease of use of such packages is the (perceived) difficulty in assessing the reliability of the results obtained which often leads to the consideration of the multivariate algorithms as ‘black boxes’ whose inner mechanism is supposed to remain hidden to the user. In this paper, we will discuss the dangers of a ‘black box’ approach in LIBS multivariate analysis, and will discuss how to overcome them using the chemical-physical knowledge that is at the base of any LIBS quantitative analysis

The choice of μ-vinyliminium ligand substituents is key to optimize the antiproliferative activity of related diiron complexes

Diiron vinyliminium complexes constitute a large family of organometallics displaying a promising anticancer potential. The complexes [Fe2Cp2(CO)(mu-CO){mu-eta(1):eta(3)-C(R-3)C(R-4)CN(R-1)(R-2)}]CF3SO3 (2a-c, 4a-d) were synthesized, assessed for their behavior in aqueous solutions (D2O solubility, Log P-ow, stability in D2O/Me2SO-d(6) mixture at 37 degrees C over 48 h) and investigated for their antiproliferative activity against A2780 and A2780cisR ovarian cancer cell lines and the nontumoral one Balb/3T3 clone A31. Cytotoxicity data collected for 50 vinyliminium complexes were correlated with the structural properties (i.e. the different R-1-R-4 substituents) using the partial least squares methodology. A clear positive correlation emerged between the octanol-water partition coefficient and the relative antiproliferative activity on ovarian cancer cell lines, both of which appear as uncorrelated to the cancer cell selectivity. However, the different effects played by the R-1-R-4 substituents allow tracing guidelines for the development of novel, more effective compounds. Based on these results, three additional complexes (4p-r) were designed, synthesized and biologically investigated, revealing their ability to hamper thioredoxin reductase enzyme and to induce cancer cell production of reactive oxygen species

Portrait of an artist at work: exploring Max Ernst's surrealist techniques

AbstractMax Ernst was one of the most influential artists associated with both the Dada and Surrealist movements. However, until now, only few scientific studies have been devoted to his works. This paper presents the results of a multi-analytical investigation on six oil paintings, made between 1927 and 1942, belonging to the Peggy Guggenheim Collection in Venice (Solomon R. Guggenheim Foundation, New York). Through a combined art historical and scientific approach, this study aims at understanding Ernst's painting techniques, including frottage, grattage, dripping, and decalcomania, the used materials, and the state of conservation of the artworks. Non-invasive in situ investigations were performed by means of Vis–NIR multi-spectral imaging, X-ray fluorescence, external reflection FTIR and Raman spectroscopy. Imaging analysis revealed important information about Ernst's painting methods while the other techniques provided useful information about the ground layer, the painting materials and the presence of alteration products. Ernst's palette discloses great freedom in his use of materials and evolution during the time. This investigation demonstrates that an integrated, non-invasive, diagnostic approach provides a thorough analysis of materials and execution techniques of Ernst' masterworks allowing an in-depth knowledge of his highly skilled work

Multi-technique characterization of madder lakes: A comparison between non- and micro-destructive methods

The chemical characterization of paint material is paramount for the understanding of painting techniques, provenance studies and for assessing conservation strategies. In particular, the chemical characterization of both the organic and inorganic fraction of lakes is fundamental to assess the technologies used in their production. In this short note, we present a pilot study by comparing several micro-destructive and non-destructive methods for the comprehensive characterization of the organic and inorganic fraction of reference madder lakes. In the final procedure, the chromophores-containing molecules were separated using a sample preparation procedure based on acid hydrolysis and solvent extraction, and analysed by high-pressure liquid chromatography with UV-Vis detector (HPLC-UV/Vis). Laser induced breakdown spectroscopy (LIBS) and X-Ray Fluorescence (XRF) were used for the study of the elemental composition. Multispectral Imaging was also applied in order to evaluate its potentialities to distinguish amongst different red lakes. The final multi-technique method allowed for the characterization of both organic and inorganic fraction from the same lake micro sample