Development and machine learning-based calibration of low-cost multiparametric stations for the measurement of CO2 and CH4 in air.

The pressing issue of atmospheric pollution has prompted the exploration of affordable methods for measuring and monitoring air contaminants as complementary techniques to standard methods, able to produce high-density data in time and space. The main challenge of this low-cost approach regards the in-field accuracy and reliability of the sensors. This study presents the development of low-cost stations for high-time resolution measurements of CO2 and CH4 concentrations calibrated via an in-field machine learning-based method. The calibration models were built based on measurements parallelly performed with the low-cost sensors and a CRDS analyzer for CO2 and CH4 as reference instrument, accounting for air temperature and relative humidity as external variables. To ensure versatility across locations, diversified datasets were collected, consisting of measurements performed in various environments and seasons. The calibration models, trained with 70 % for modeling, 15 % for validation, and 15 % for testing, demonstrated robustness with CO2 and CH4 predictions achieving R2 values from 0.8781 to 0.9827 and 0.7312 to 0.9410, and mean absolute errors ranging from 3.76 to 1.95 ppm and 0.03 to 0.01 ppm, for CO2 and CH4, respectively. These promising results pave the way for extending these stations to monitor additional air contaminants, like PM, NOx, and CO through the same calibration process, integrating them with remote data transmission modules to facilitate real-time access, control, and processing for end-users.

Closing the knowledge gap on the composition of the asbestos bodies.

Asbestos bodies (AB) form in the lungs as a result of a biomineralization process initiated by the alveolar macrophages in the attempt to remove asbestos. During this process, organic and inorganic material deposit on the foreign fibers forming a Fe-rich coating. The AB start to form in months, thus quickly becoming the actual interface between asbestos and the lung tissue. Therefore, revealing their composition, and, in particular, the chemical form of Fe, which is the major component of the AB, is essential to assess their possible role in the pathogenesis of asbestos-related diseases. In this work we report the result of the first x-ray diffraction measurements performed on single AB embedded in the lung tissue samples of former asbestos plant workers. The combination with x-ray absorption spectroscopy data allowed to unambiguously reveal that Fe is present in the AB in the form of two Fe-oxy(hydroxides): ferrihydrite and goethite. The presence of goethite, which can be explained in terms of the transformation of ferrihydrite (a metastable phase) due to the acidic conditions induced by the alveolar macrophages in their attempt to phagocytose the fibers, has toxicological implications that are discussed in the paper.

A multifrequency EPR approach to travertine characterisation.

The understanding of processes that give rise to travertine deposits is important. This is so because of its widespread use as decorative material, but more so in environmental studies due to the significance, by proxy, of travertine in climatology. In this paper, a multifrequency EPR spectroscopy study of the behaviour of an ubiquitary vicariant of Ca in calcite, Mn(II), is presented. EPR spectra were obtained from a natural sample at 9.5 (X-band), 95, 190, and 285GHz, and interpreted through numerical simulation. An analysis of the distribution of the zero-field splitting interaction revealed the source of some unexpected spectral features in the width of the lines in the X-band. By contrast, the homogeneous broadening plays only a minor role. Moreover, field-dependent anisotropies of the Zeeman and hyperfine tensors were observed at higher frequency. On the basis of results garnered in this study, the ZFS interaction of Mn(II) has been ascribed to the microstructural anomalies of the Mn(II) distribution in calcite. This may be considered as the fingerprint of the physical-chemical conditions at the time of travertine deposition. As a consequence, X-band EPR spectroscopy represents a specific tool to investigate the genesis, and to check the homogeneity of Mn(II) distribution in travertines as well as in other calcite-based materials.

Sulfur species in volcanic gases.

A new analytical method for the determination of the sulfur species (SO2, H2S, S8(0)) in volcanic gases is proposed by revising, updating, and improving previous methods. The most significant advantages of the proposed procedure can briefly be summarized, as follows: (i) the reaction among sulfur species stops during the gas sampling by using preevacuated thorion-tapped vials with purified 0.15M Cd(OH)2 in 4 M NaOH to favor the precipitation of H2S as CdS; (ii) all the sulfur species (SO2, H2S, S8(0)) are analyzed by ion chromatography, after conversion to SO4, which allows the detection limit to be lowered significantly with respect to the previous studies; (iii) appropriate aliquots from intermediate steps may be used to determine other species commonly present in volcanic gases such as CO2, HCI, HF, HBr, HI, and so forth; (iv) determination of all the other gas species is not jeopardized by the proposed method, i.e., one single vial can be used for analyzing the full chemical composition of a volcanic gas with the exception of NH3. Statistical parameters calculated from gas sampling data at the F5 crater fumarole in Vulcano Island (Aeolian Islands, southern Italy), suggest that the standard error of mean (s/ root n) is higher for S (0.10), followed by SO2, H2S, and CO2 (0.04, 0.038, and 0.028, respectively). SO2 shows the higher variation coefficient (12.1%) followed by H2S, S, and CO2 (5.7, 1.5, and 0.8%, respectively). Furthermore, if the time dependence of sampling is taken into account, the measured values, instead of fluctuating in a random manner, tend to follow systematic patterns, out of statistical control, possibly suggesting a sort of natural fluctuation of the volcanic system. Other crater fumaroles from volcanic systems located in different geodynamical areas (Hawaii, USA, El Chichon, Mexico, Poas, Costa Rica) have been analyzed as well.