Potentially harmful elements released by volcanic ash of the 2021 Tajogaite eruption (Cumbre Vieja, La Palma Island, Spain): Implications for human health.

This study assesses the potential impacts on human health of volcanic ash emitted during the 2021 Tajogaite eruption (La Palma Island, Spain). Ash samples were physically and chemically characterized and leaching tests (with deionized water and acidic solution) were performed according to the IVHHN protocols to elucidate i) the leachable elements that may affect water quality and represent a potential threat for livestock and humans through drinking water supply; and ii) the bioaccessible fraction of toxicants able to be solubilized from ash surfaces if ashes are incidentally ingested by children. The most abundant readily water-soluble compounds were SO4, F, Cl, Na, Ca, Ba, Mg, and Zn. Fluoride and chloride (up to 1085 and 1347 mg/kg) showed higher values in distal ash samples than closer ones. The potential F availability assessed from water leachates may suggest important environmental and health implications. In addition, long-term health hazard due to a long-term weathering of tephra deposits should be possible as confirmed by the greater amount of F extracted by acidic solution. Concentration of other trace elements (e.g., As, V, Mn, Mo, Cr, Fe, Se, Ti, Pb) were low compared to global medians and within the range globally assessed. Indicative calculation of hazard for water supply showed that F concentration may exceed both the recommended value (1 mg/L) for irrigation purpose and the health-based drinking water limits of 1.5 mg/L (for humans) and 2 mg/L (for livestock). If the predicted concentrations in water were compared with the toxicologically dose, F showed a potential health-risk for children through drinking water. The indicative health-risk characterization via accidental ash ingestion showed that the direct exposure does not represent a primary source of F daily intake for children. This important outcome confirmed F as element with the greatest health threat during Tajogaite 2021 eruption.

Ammonium N-(pyridin-2-ylmethyl)oxamate (AmPicOxam): A Novel Precursor of Calcium Oxalate Coating for Carbonate Stone Substrates.

Ammonium N-(pyridin-2-ylmethyl)oxamate (AmPicOxam), synthesized from O-methyl-N-(pyridin-2-ylmethyl)oxamate, was spectroscopically and structurally characterized and assayed as a novel precursor for the protection and consolidation of carbonate stone substrates. An in-depth characterization of treated and untreated biomicritic limestone and white Carrara marble samples was carried out by means of SEM microscopy, X-ray powder diffraction, helium pycnometry, determination of water transport properties, and pull-off tests. The improved solubility (1.00 M, 16.5% w/w) of the title compound with respect to ammonium oxalate (0.4 M, 5% w/w) results in the formation of a thicker protective coating of calcium oxalate (CaOx) dihydrate (weddellite) on marble and biomicrite samples after the treatment with 5% and 12% w/w water solutions, producing a reduction in the stone porosity and increased cohesion. Theoretical calculations were carried out at the DFT level to investigate both the electronic structure of the N-(pyridin-2-ylmethyl)oxamate anion and the hydrolysis reaction leading from AmPicOxam to CaOx.

On the suitability of phillipsite-chabazite zeolitite rock for ammonia uptake in water: a case study from the Pescara River (Italy).

Ionic exchange tests have been performed on superficial wastewaters to remove ammonia using a volcanic zeolitized rock from Lazio Region (Central Italy). The zeolitite (natural zeolite) is characterized by chabazite, phillipsite and minor amounts of sanidine, leucite and analcime. After preliminary column experiments in laboratory focused to determine the saturation time of the zeolitite, a pilot plant was built up on a little water course near the area of San Giustino channel (Abruzzo Region, Central Italy). Wastewaters, characterized by starting ammonia value ranging between 5 and 120 mg/l, were filtered with a zeolitic bed. The first experimental results indicate a positive ammonia reduction of about 80-90% and, in all cases, NH4+ concentration values under the EU law limits. A main purpose of this paper is to evidence that most of studies published on uptake of ammonia by means of zeolitite lead with clinoptilolite-dominant zeolitite despite the large and best performance of phillipsite-chabazite zeolites (up to 61-79% improvement of ammonia uptake). Last but not least, a large number of published studies are of difficult comparison because of poor characterization of the zeolitite used.

Synthesis and characterization of analcime (ANA) zeolite using a kaolinitic rock.

Analcime is nowadays an important component in dental porcelain systems, in heterogeneous catalysis, in the nanoelectronic field, in selective adsorption and in stomatology (dental filling and prosthesis). Analcime synthesis from an impure, silica-rich kaolinite rock coming from Romana (Sassari, Italy) is here presented. A synthesis protocol is proposed that aims to make an improvement of synthesis conditions compared to the past. The hydrothermal treatment is in fact here achieved without aging times and without the use of sodium silicate or other additional silica source reported in the literature. Lower calcination temperature, synthesis temperature and crystallization time are verified in this work. The kaolin is subjected to calcination at the temperature of 650 °C and then mixed with NaOH. The experiment is performed at ambient pressure and 170 ± 0.1 °C. The degree of purity of analcime is calculated in 97.57% at 10 h. Analcime is characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, inductively coupled plasma optical emission spectrometry and thermal analysis. Density is also calculated. Cell parameters and the amount of amorphous phase in the synthesis powders is estimated with quantitative phase analysis using the combined Rietveld and reference intensity ratio methods. The experimental conditions make the synthesis protocol particularly attractive from an economic point of view. Also this work does not use a commercial kaolin but silica-rich impure kaolinitic rock from a disused quarry. This further reduces the costs of the experimental protocol. It also gives the protocol an added value, as the synthesis of a useful mineral is obtained through the valorization of an otherwise unused georesource. Both chemical and physical characterization of analcime is satisfactory making the experimental protocol very promising for an industrial transfer.

Synthesis and characterization of Na-P1 (GIS) zeolite using a kaolinitic rock.

This work focuses on the hydrothermal synthesis of Na-P1 zeolite by using a kaolinite rock coming from Romana (Sassari, Italy). The kaolin is calcined at a temperature of 650 °C and then mixed with calculated quantities of NaOH. The synthesis runs are carried out at ambient pressure and at variable temperatures of 65 and 100 °C. For the first time compared to the past, the Na-P1 zeolite is synthesized without the use of additives and through a protocol that reduces both temperatures and synthesis times. The synthesis products are analysed by X-ray diffraction, high temperature X-ray diffraction, infrared spectroscopy, scanning electron microscopy and inductively coupled plasma optical emission spectrometry. The cell parameters are calculated using the Rietveld method. Density and specific surface area are also calculated. The absence of amorphous phases and impurities in synthetic powders is verified through quantitative phase analysis using the combined Rietveld and reference intensity ratio methods. The results make the experimental protocol very promising for an industrial transfer.

Surface reactivity of Etna volcanic ash and evaluation of health risks.

This work is a part of a research project conducted in order to characterize the volcanic ash from Mount Etna, focusing in particular on the surface reactivity of ashes and possible consequence for human health. In this framework, a sampling campaign began on 16 March 2013, taking advantage of the intense volcanic activity on Etna. The interaction between volcanic ash and human organism was simulated treating two classes of representative Etnean particles with ultrapure water (grainsize of 850 um) and Gamble's solution mimic lug fluids (grainsize <38 µm) with the aim to evaluate the risk due to gastric and respiratory exposure to volcanic particles. The leachates were analysed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Ionic Chromatography (CI) in order to highlight possible dangerous elements released in water solutions according to USGS protocol. Analyses of Gamble's solution highlighted a release of elements smaller than in watery solutions and always below the thresholds established by the Italian law. On the contrary, analyses of watery solutions evidenced, for some elements (B, Cd, Ni and As), levels higher than permitted by Italian law. Considering the effects of these elements on human health, further investigations are necessary and currently carried out in order to better constrain the release process and the specific effects on human organism.

Improvement in the Synthesis Conditions and Studying the Physicochemical Properties of the Zeolite Li-A(BW) Obtained from a Kaolinitic Rock.

Crystallization of zeolite Li-A(BW) from kaolinite (Standard Porcelain by the IMERYS Minerals Ltd) through a conventional hydrothermal treatment is here achieved for the first time with no additives as reported in the literature. Moreover lower kaolin calcination temperatures and lower synthesis temperatures are tested and verified in this work. The synthesis process is rather simple as the reaction of kaolinite with alkali occurs very readily after calcination of at 650 °C. Metakaolin is mixed with calculated amount of aluminum hydroxide and lithium hydroxide and the experiment is performed at ambient pressure and 180 ± 0.1 °C. Li-A(BW) is characterized by powder X-ray diffraction, high temperature X-ray diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry, thermal analysis and infrared spectroscopy. Calculation of cell parameters (through Rietveld Refinement) and density, specific surface and pore size are also achieved. The amount of amorphous phase in the synthesis powders is estimated with quantitative phase analysis using the combined Rietveld and reference intensity ratio methods. The results become notably attractive in view of a possible industrial transfer of the synthesis protocol.

Synthesis and Characterization of Leucite Using a Diatomite Precursor.

Leucite is nowadays an important component in ceramic restoration systems with particular suitability to dental porcelains. The leucite synthesis from a hydrothermally-derived precursor is here presented. A silicate solution was prepared by mixing a naturally derived amorphous silica (diatomitic rock from Crotone, southern Italy) with potassium hydroxide and an aluminate solution was obtained by mixing aluminium hydroxide and potassium hydroxide. Three mixtures of varying ratios of aluminate and silicate solutions were prepared and submitted to hydrothermal treatment at 150 °C for one hour. Subsequently these hydrothermal precursors were subjected to calcination at the temperature of 1000 °C for variable time intervals, thus resulting in 3 series of syntheses. The synthesis run 3 turned out to be the best from the point of view of temporal yield showing the crystallization of the leucite after only 15 hours of heat treatment. The products of synthesis run 3 were fully characterised by Powder X-Ray Diffraction, Inductively Coupled Plasma Optical Emission Spectrometry, Infrared Spectroscopy and Thermal Analysis. The amorphous phase in the synthesis powders was estimated by quantitative phase analysis using the combined Rietveld and reference intensity ratio methods. Density of leucite was also achieved by He-pycnometry. The use of a cost effective starting material such as a diatomite in the experimental route makes the process highly attractive for expansion to an industrial scale especially considering that both the chemical and physical characterizations of our leucite product are highly satisfactory. Last but not least we explain some inferences that can be obtained from this process of synthesis in order to a better understanding of some natural occurrences of leucite in geologic systems related to basaltic magmas.

Multivariate factorial analysis to design a robust batch leaching test to assess the volcanic ash geochemical hazard.

A method to obtain robust information on short term leaching behaviour of volcanic ashes has been developed independently on the sample age. A mixed factorial design (MFD) was employed as a multivariate strategy for the evaluation of the effects of selected control factors and their interactions (amount of sample (A), contact time (B), and liquid to solid ratio or L/S (C)) on the leaching process of selected metals (Na, K, Mg, Ca, Si, Al, V, Mn, Fe, and Co) and anions (Cl(-) and SO(4)(2-)). Box plots of the data acquired were used to evaluate the reproducibility achieved at different experimental conditions. Both the amount of sample (A) and leaching time (B) had a significant effect on the element stripping whereas the L/S ratio influenced only few elements. The lowest dispersion values have been observed when 1.0 g was leached with an L/S ratio equal to 10, shaking during 4 h. The entire method is completed within few hours, and it is simple, feasible and reliable in laboratory conditions.

Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain).

BACKGROUND, AIM, AND SCOPE: The first step in the restoration of a medieval stained glass window is the evaluation of its degree of degradation. This implies the study of the chemical composition of the stained glass as well as the new mineral phases developed on its surface (patinas). Patinas are clearly related to glass composition, time, environmental conditions, microenvironments developed in local zones, bioactivity, physical and chemical factors, etc. This study was carried out on patinas developed in selected Na-rich stained glass of the Santa Maria de Pedralbes Monastery (Barcelona, Spain). The location of this monument in the city (about 5 km from the shoreline and close to the Collserola hill flank) helped to determine the environmental conditions in which patinas developed. The aim of our study was to characterize the patinas formed on the surface of the selected glass of this monastery in order to understand the role of the chemical composition of the original glass (Na-rich) as well as the environmental conditions in which they developed. MATERIALS AND METHODS: Powdered samples of two different color-type patinas (ochre-orange and brownish) were collected in the external and internal parts of the stained glass windows of the Prebystery and Chapter House of the Pedralbes Monastery by using a precision (odontological) drill. These patinas were subsequently analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). RESULTS: XRD analyses evidenced the presence of sulfates (gypsum and thenardite), calcite, Ca-oxalates (whewellite and weddellite), and quartz forming part of the patinas. Although these mineral phases can be found in both color-type patinas, whewellite and thenardite are more common in the ochre-orange patinas. The results obtained were validated by the FTIR measurements. It has been observed, when thenardite is present, that gypsum occurs as traces. Thenardite is in most of the cases associated with whewellite and mainly occurs in the internal parts of the glass. In contrast, weddellite is limited to the absence of thenardite and whewellite and to the external parts of the stained glass. Quartz is present in all the patinas independent of their location and color. Calcite also occurs in many samples. It appears in both color-type patinas and, in some cases, is associated to the presence of weddellite but not to whewellite and/or thenardite. DISCUSSION: Glass composition together with environmental conditions and location of the patinas (internal or external parts of the stained glass window), as well as the provenance of the glass within the monastery, are the main factors that define the development of the new mineral phases. Moreover, the action of microorganisms, when present, can also strongly influence the development of some mineral phases. For example, the formation of calcite in the external parts of the stained glass (associated with the presence of oxalates) is related to the action of microorganisms. When calcite is formed in the internal parts of the glass and it is not associated with the presence of Ca-oxalates, an inorganic origin can be invoked. The presence of weddellite requires a very humid microenvironment with very little exposure to sunlight. In fact, this mineral phase has only been observed in the external parts of some glass located in the humid and shady side of the monastery. Whewellite (which only appears in the internal parts) needs a low degree of relative humidity. It has been observed that sulfur precipitating in basically one mineral phase (thenardite or gypsum) depends on the microenvironmental conditions of the moment and the glass composition. When thenardite occurs, it can be maintained that the original glass is of Na composition. The occurrence of quartz in all samples is interpreted as being due to the deposition of atmospheric particulate matter. The color of the patinas can be originated by different processes (presence of carotenes, organic pigmentation, atmospheric contamination, etc.). CONCLUSIONS: In the case of moderately weathered stained glass windows, the combination of XRD and FTIR techniques is very useful to obtain a fast preliminary evaluation of the degree of weathering of a stained glass window. The presence of specific mineral phases in the patina (e.g., thenardite) confirms the Na composition of the original stained glass. This is important since Na-rich glass underwent a lesser degree of weathering than K- or K-Ca-rich glass. However, their absence cannot preclude other possibilities. It has been extensively evidenced through time that environmental conditions play an important role on the formation of the different mineral phases which form part of the patinas. RECOMMENDATIONS AND PERSPECTIVES: The first step in the restoration of a stained glass window is the evaluation of the degree of deterioration of the glass. This evaluation includes a chemical analysis of the glass as well as a characterization of the patinas developed on their surfaces. The obtained results will be essential in order to define the best restoration practices to be followed.