Mineralogical and Geochemical Characterization of Asbestiform Todorokite, Birnessite, and Ranciéite, and Their host Mn-Rich Deposits from Serra D'Aiello (Southern Italy)

Manganese ores, especially the oxyhydroxides in their different forms, are the dominant Mn-bearing minerals that occur in marine and terrestrial environments, where they are typically found as poorly crystalline and intermixed phases. Mn oxyhydroxides have a huge range of industrial applications and are able to exert a strong control on the mobility of trace metals. This paper reports the results of a detailed study on the Mn oxyhydroxides occurring in the manganiferous deposit outcropping in the Messinian sediments from Serra D'Aiello (Southern Italy). Nine Mn samples were characterized in detail using X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), thermogravimetry (TG), transmission electron microscopy combined with energy dispersive spectrometry (TEM/EDS), and X-ray fluorescence (XRF). The results indicated that the Mn deposit included the oxyhydroxide mineral species birnessite, todorokite, and rancièite. The size, morphology, and chemical composition of Mn oxyhydroxide samples were investigated in order to define their impact on the environment and human health. Todorokite displayed asbestiform shapes and could disperse fibers of breathable size in the air. Furthermore, since in-depth characterization of minerals within Mn deposits may be the first step toward understanding the genetic processes of manganese deposits, hypotheses about the genesis of the Mn oxyhydroxide deposits were discussed

Plastic breeze: Volatile organic compounds (VOCs) emitted by degrading macro- and microplastics analyzed by selected ion flow-tube mass spectrometry

Pollution from microplastics (MPs) has become one of the most relevant topics in environmental chemistry. The risks related to MPs include their capability to adsorb toxic and harmful molecular species, and to release additives and degradation products into ecosystems. Their role as a primary source of a broad range of harmful volatile organic compounds (VOCs) has also been recently reported.In this work, we applied a non-destructive approach based on selected-ion flow tube mass spectrometry (SIFT-MS) for the characterization of VOCs released from a set of plastic debris collected from a sandy beach in northern Tuscany.The interpretation of the individual SIFT-MS spectra, aided by principal component data analysis, allowed us to relate the aged polymeric materials that make up the plastic debris (polyethylene, polypropylene, and polyethylene terephthalate) to their VOC emission profile, degradation level, and sampling site. The study proves the potential of SIFT-MS application in the field, as a major advance to obtain fast and reliable information on the VOCs emitted from microplastics. The possibility to obtain qualitative and quantitative data on plastic debris in less than 2 min also makes SIFT-MS a useful and innovative tool for future monitoring campaigns involving statistically significant sets of environmental samples

Analisi morfologica e meccanica di strutture gerarchiche elettrofilate per la rigenerazione del tessuto tendineo e legamentoso

I tendini e i legamenti sono fondamentali per lo svolgimento dei movimenti e spesso sono soggetti a rotture o lesioni che rappresentano circa il 50% di tutto il sistema muscoloscheletrico. Il tessuto è poco cellularizzato per questo ad oggi non esistono dispositivi impiantabili, come protesi o innesti biologici in grado di riprodurre in maniera soddisfacente la struttura gerarchica e le proprietà meccaniche. Le tecniche attuali ossia quelle conservative e chirurgiche hanno significative limitazioni per questo i ricercatori stanno sviluppando strutture innovative, detti scaffold, per guidare le cellule nella rigenerazione del tessuto di interesse. Tra le varie tecnologie per produrre scaffold per i tendini e i legamenti, l’elettrofilatura è una delle più promettenti. Questa consente di produrre nanofibre dalle caratteristiche morfologiche e meccaniche simili alle fibrille di collagene di tendini e legamenti. Questo lavoro di tesi presenta la descrizione di procedure e metodi di produzione e caratterizzazione di strutture gerarchiche elettrofilate in acido poli-L-lattico e in acido poli-L-lattico e collagene. I bundles elettrofilati, in entrambi i materiali, sono in grado di replicare i fascicoli di collagene mentre gli scaffold gerarchici sono stati prodotti assemblando i bundles con una membrana elettrofilata, in grado di riprodurre fedelmente l’ epitenon/epiligament e l’endotenon/endoligament, riproducendo l’intera struttura gerarchica di tendini e legamenti. Gli scaffolds gerarchici sono stati prodotti assemblando i bundles con una membrana elettrofilata, in grado di riprodurre fedelmente l’epitenon/ epiligament e l’endotenon/endoligament. Tutte le strutture realizzate sono state analizzate e testate sia morfologicamente che meccanicamente per valutare la similitudine con i rispettivi tessuti biologici

Fluoride Polluted Groundwaters in Calabria Region (Southern Italy): Natural Source and Remediation

Excessive ingestion of fluoride through the consumption of F−-rich drinking water could cause adverse effects to human health. For this reason, the WHO has fixed 1.5 mg/L as the maximum F- concentration for drinking water. In this work, a detailed geochemical characterization was performed to define the source of natural pollution of two groundwaters (samples Pc and Bg) coming from deep crystalline aquifers located in the Calabria region (southern Italy) and to define and optimize the most appropriate water treatment strategy. The samples were classified as a F− enriched NaHCO3 type of water. In particular, the F− concentrations observed were 30 mg/L and 8.9 mg/L for the Pc and Bg samples, respectively. Based on the acquired geochemical characterization knowledge, the groundwaters were treated by two thin-film composite NF membranes, namely SPR 10113 and SPR 10114 which have so far not been used for water defluoridation. It was found that the SPR 10114 membrane was able to guarantee water permeates with F− contents lower than the threshold value of 1.5 mg/L for both treated waters, whereas the fluoride content remained above the threshold value when the Pc sample was treated using the SPR 10113 membrane. The obtained permeates were characterized by a low ionic load and were not suitable for long-term consumption as drinking water. However, all of the produced waters did not need any further re-mineralizing processes for agricultural irrigation or other purposes

Mineralogical and Geochemical Characterization of Asbestiform Todorokite, Birnessite, and Ranciéite, and Their host Mn-Rich Deposits from Serra D’Aiello (Southern Italy)

Manganese ores, especially the oxyhydroxides in their different forms, are the dominant Mn-bearing minerals that occur in marine and terrestrial environments, where they are typically found as poorly crystalline and intermixed phases. Mn oxyhydroxides have a huge range of industrial applications and are able to exert a strong control on the mobility of trace metals. This paper reports the results of a detailed study on the Mn oxyhydroxides occurring in the manganiferous deposit outcropping in the Messinian sediments from Serra D’Aiello (Southern Italy). Nine Mn samples were characterized in detail using X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), thermogravimetry (TG), transmission electron microscopy combined with energy dispersive spectrometry (TEM/EDS), and X-ray fluorescence (XRF). The results indicated that the Mn deposit included the oxyhydroxide mineral species birnessite, todorokite, and rancièite. The size, morphology, and chemical composition of Mn oxyhydroxide samples were investigated in order to define their impact on the environment and human health. Todorokite displayed asbestiform shapes and could disperse fibers of breathable size in the air. Furthermore, since in-depth characterization of minerals within Mn deposits may be the first step toward understanding the genetic processes of manganese deposits, hypotheses about the genesis of the Mn oxyhydroxide deposits were discussed

Assessment of Naturally Occurring Asbestos in the Area of Episcopia (Lucania, Southern Italy)

Over the last few years, the risk to human health related to asbestos fiber exposure has been widely demonstrated by many studies. Serpentinites are the main rocks associated with naturally occurring asbestos (NOA). In order to investigate the presence of NOA, a mineralogical study was conducted on eleven serpentinite samples collected nearby the village of Episcopia (Lucania, Southern Italy). Various analytical techniques such as X-ray powder diffraction (XRPD), scanning electron microscopy combined with energy dispersive spectrometry (SEM-EDS) and derivative thermogravimetry (DTG) were used to determine the occurrence of asbestos minerals and to make morphological observations. Results pointed out that all of the samples contain asbestos minerals (e.g., tremolite, actinolite and chrysotile). Moreover, it was observed that both natural processes and human activity may disturb NOA-bearing outcrops and provoke the formation of potentially inhalable airborne dust causing the release of asbestos fibers into the environment, thereby increasing the risk to human health. For this reason, our study aims to highlight the requirement of a natural asbestos survey and periodic update in the area

Analytical Procedure for Mapping the Distribution of 10B and 99Tc Markers in Cryo-sections of Animal Tissue Samples by Secondary Ion Mass Spectrometry

The development of a complete, standard analytical procedure for a quantitative use of secondary ion mass spectrometry to map the distribution in animal tissues of exogenous isotopes presents difficulties inherently related to sample preparation and preservation, as well as to the specific application being considered. We have tested in two very different cases a procedure based on the cryo-preparation of samples and calibration standards. The applications under investigation were the mapping of 10B in mouse brain tissue, with relevance to the boron neutron capture therapy, and of the perfusion tracer 99Tc in mouse heart tissue, with relevance to the study of microcirculation and cardiovascular pathologies. Scanning electron microscopy and inductively coupled mass spectrometry analysis were used as reference techniques for secondary ion mass spectrometry images and analyte measurements, respectively. Cryo-preparation of tissue sections for ion microscopy proved to be simple and efficient (in terms of structural and chemical integrity) for both brain and heart samples derived from fresh organs. This technique, however, turned out to be reliable only on the brain tissue when applied to the preparation of standards, which required chemical fixation of portions of organs. Brain and heart tissues showed a totally different response to chemical fixation, from both a structural and an analytical point of view. On the one hand, we were able to estimate a relative sensitivity factor for 10B in the cryo-sectioned brain matrix; on the other hand, even without the possibility of an absolute quantification of the 99Tc signal and notwithstanding the presence of an isobaric interference, secondary ion mass spectrometry mapping however proved to be capable to resolve the specific response of the cardiac tissue to the perfusion mechanism.JRC.E.5-Nuclear chemistr

Determination of salivary alpha-amylase and cortisol in psoriatic subjects undergoing the Trier Social Stress Test

The study was aimed to investigate the response in psoriatic patients of the two primary neuroendocrine systems, namely the Autonomic Nervous System and the Hypothalamic-Pituitary-Adrenal (HPA) axis, whose main biomarkers of activation are salivary alpha-amylase and cortisol, respectively. Reliable analytical procedures for the determination of salivary alpha-amylase enzymatic activity and cortisol concentration in oral fluid were developed. The non-invasive sampling that does not require trained personnel represents one of the main advantages of oral fluid analysis compared to the analysis of blood and its derivatives (e.g. plasma). Since oral fluid offers the advantage of a simple and stress free sample collection, it is particularly useful to quantify stress related molecules. Alpha-amylase activity was measured by a spectrometric method, whereas salivary cortisol by Reversed-Phase High-Performance Liquid Chromatography coupled to Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry. The effect of salivary pH and flow rate on salivary alpha-amylase activity and cortisol were also investigated. Finally, both methods were preliminary tested on oral fluid samples of psoriatic volunteers underwent to a psychosocial stress task (the Trier Social Stress Test), as a first step of a more comprehensive study on the responsiveness of psoriatic subjects to stressors