Abstract This study aimed at investigating the surface modifications occurring on amphibole asbestos (crocidolite and tremolite) during leaching in a mimicked Gamble’s solution at pH of 4.5 and T = ...37 °C, from 1 h up to 720 h. Results showed that the fibre dissolution starts with the release of cations prevalently allocated at the various M - and (eventually) A -sites of the amphibole structure (incongruent dissolution). The amount of released silicon, normalized to fibre surface area, highlighted a leaching faster for the crocidolite sample, about twenty times higher than that of tremolite. Besides, the fast alteration of crocidolite promotes the occurrence of Fe centres in proximity of the fibre surface, or possibly even exposed, particularly in the form of Fe(II), of which the bulk is enriched with respect to the oxidized surface. Conversely, for tremolite fibres the very slow fibre dissolution prevents the underlying cations of the bulk to be exposed on the mineral surface, and the iron oxidation, faster than the leaching process, significantly depletes the surface Fe(II) centres initially present. Results of this work may contribute to unravel possible correlations between surface properties of amphibole asbestos and its long-term toxicity.
Fibrous erionite-Na from Rome (Oregon, USA) was K-exchanged and characterized from the structural point of view. In addition, the modifications experienced after contact with a Fe(II) source were ...investigated for evaluating if the large potassium ions, blocking off nearly all the erionite cavity openings, might prevent the Fe(II) binding process, which is currently assumed to be one of the reasons of the toxicity of erionite. The K-exchanged sample had a 95% reduction of the BET surface area indicating that it behaves as a mesoporous material. Exchanged K is segregated at K2 and at OW sites commonly occupied by H
O. The latter K cations provide a relevant contribution to the reduction of the surface area. Surprisingly, despite the collapse of its surface area the sample preserves the tendency to bind Fe(II). Therefore, yet in the case of a peculiar and potentially hostile structural environment the Fe(II) ion-exchange process has essentially the same kinetics observed in a typical erionite sample. This is a clear evidence of the very limited effect of the chemical composition of erionite on the Fe(II) binding process and reasonably it does not play a significant role in its toxicity.
This study aimed at investigating both the surface and bulk modifications occurring on fibrous erionite during leaching in a mimicked Gamble’s solution (MGS) at pH of 4.5 and T = 37 °C, up to one ...month of incubation. Samples were characterized by a multi-analytical approach: field-emission scanning electron microscopy (FE-SEM) was employed to investigate the morphological changes of both pristine and reacted fibres, inductively coupled plasma optical emission spectrometry (ICP-OES) was used to measure the concentration of the released cations; X-ray photoelectron spectroscopy (XPS) was exploited for highlighting possible modifications of surface chemistry; X-ray powder diffraction (XRPD) and high-resolution transmission electron microscopy (HR-TEM) were applied aiming to get information on the structural state of the fibres following the incubation. ICP results integrated with those obtained by both bulk- and surface-chemical characterization highlighted that erionite binds Na especially in the first 24 h of sample incubation in the MGS, following ion exchange with the extra framework cations, in particular Ca. Moreover, our new results show that the Na binding process caused structural modifications with the migration of Na toward the Ca2 site and redistribution of the cations within the erionite cage. TEM investigation pointed out that the interaction between erionite and MGS results in the formation of a new surface amorphous layer with an irregular lobate pattern on an earlier surface weathered layer. However, the silicate framework is not weakened by incubation in the MGS at acidic pH. In addition, on the basis of the Si release normalized to the mineral surface area, fibrous erionite resulted significantly more biodurable than amphibole asbestos. Notably, considering the primary role played by biodurability in inducing pathogenicity, this result certainly supports in vivo observations showing that erionite is much more tumorigenic than asbestos. Moreover, the ions released by erionite when immersed in MGS may trigger biological effects, such as those on lipid packing and membrane permeability. On this basis, we expect a regulatory definition that would provide protection from this carcinogenic fibre.
This study focuses on the dissolution process and surface characterization of amosite fibres following interaction with a mimicked Gamble’s solution at a pH of 4.5 and T = 37 °C, up to 720 h. To ...achieve this, a multi-analytical approach was adopted, and the results were compared to those previously obtained on a sample of asbestos tremolite and UICC crocidolite, which were investigated under the same experimental conditions. Combining surface chemical data obtained by XPS with cation release quantified by ICP-OES, an incongruent behaviour of the fibre dissolution was highlighted for amosite fibres, similarly to asbestos tremolite and UICC crocidolite. In particular, a preferential release of Mg and Ca from the amphibole structure was observed, in agreement with their Madelung site energies. Notably, no Fe release from amosite fibres was detected in our experimental conditions (pH of 4.5 and atmospheric pO2), despite the occurrence of Fe(II) at the M(4) site of the amphibole structure, where cations are expected to be rapidly leached out during mineral dissolution. Moreover, the oxidation of both the Fe centres initially present on the fibre surface and those promoted from the bulk, because of the erosion of the outmost layers, was observed. Since biodurability (i.e., the resistance to dissolution) is one of the most important toxicity parameters, the knowledge of the surface alteration of asbestos possibly occurring in vivo may help to understand the mechanisms at the basis of its long-term toxicity.
In this investigation, the crystal chemical characterization of one sample of woolly erionite-K (Lander County, NV, USA) was examined after suspension in a FeCl2 solution, in anaerobic conditions. ...The aim of this study was to determine the effect of the chemical composition of erionite on its efficiency to bind iron. Inductively coupled plasma (ICP) results showed that the sample bound Fe(II) through an ion-exchange mechanism mainly involving Ca. In addition, chemical and structural data indicated that Fe(II) is fixed at the Ca3 site, six-fold coordinated to water molecules. According to Brunauer-Emmett-Teller (BET) sample surface area the amount of Fe(II) bound by the fibers was comparable with that retrieved for fibrous erionite-Na sample from Rome (OR, USA) for which the ion-exchange process mainly affected Na. This finding provides clear evidence of a strong tendency of Fe(II) to bind to the erionite structure. Furthermore, considering that the woolly erionite-K from Langer County differs markedly from erionite-Na from Rome in the extra-framework cation content, our observations indicate that the Fe binding efficiency is not significantly modulated by the chemical composition. Notably, Fe ion-exchanged and/or accumulated on the fiber surface can generate hydroxyl radicals via the Fenton reaction, thus influencing the potential carcinogenicity of the different erionite species.
This study concerns the occurrence of arsenic in the groundwater system of the Cimino-Vico volcanic area (central Italy), different parts of which are currently widely used for local drinking water ...supply and for irrigation. The system shows a complex groundwater circulation, including a continuous basal aquifer, discontinuous perched aquifers, groundwater flows at high altitude, and local interactions with rising thermal fluids. Data on arsenic contents in 250 water samples from springs and wells and in 68 samples from rock outcrops were measured and combined with already existing information. Results highlight that arsenic concentrations of groundwater are influenced by type of aquifer, groundwater flow path, arsenic content of the aquifer rocks, and interaction with fluids rising from depth. Waters circulating in the Vico volcanics, one of the prominent rock units of the area, have high concentrations of arsenic, both for the basal and the perched aquifers. A large fraction of the waters associated with this rock unit have arsenic contents higher than 10 μg/L (82 percent for basal, 40 percent for perched). In contrast, waters circulating in the Cimino volcanics have lower arsenic contents: 30 percent of the basal and 10 percent of the perched aquifers have arsenic concentrations greater than 10 μg/L. Through an integrated approach, including leaching tests to investigate the arsenic behavior concerning the water-rock interaction and a geostatistical modeling of data, it has been possible to identify and tentatively quantify suitable water resources that have arsenic content not exceeding the quality standards for human consumption.
Purpose
The assessment of risk related to the presence of potentially toxic elements in soils is strictly related to the knowledge of their form and mobility. These relevant properties depend on the ...complex interactions of the elements of concern with the soil particles that generally cannot be addressed by a single technique. This study presents an integrated approach implementing geochemical and mineralogical investigation techniques on samples from a former mining area (Tolfa Mountains district, northern Latium, Italy), where exploiting activities occurred until the recent past. In particular, the As total concentration and the As distribution in solid phases is studied with the aim to evaluate the possibility of environmental pollution and consequent risks for the health of people living in the area and possibly affected in case of significant mobilization of this toxic element.
Materials and methods
Chemical (ICP-MS, ICP-OES) and mineralogical (X-ray diffraction (XRD), scanning electron microscopy–energy dispersive X-ray (SEM-EDX), X-ray absorption near-edge structure (XANES)) analyses and the evaluation of the heavy metal mobility (by means of a sequential extraction procedure) were performed.
Results and discussion
Chemical analyses show a high As content in the soils collected immediately downstream the marcasite mine waste deposit, that is the starting point of As pollution over the whole area. XANES analyses show that As occurs in two oxidation states (As
III
and As
V
) simultaneously in the tailing samples and nearby, while it has been mainly or totally transformed into As
V
at increasing distance from the mine. XRD data show that sheet silicates don’t affect As behavior, whereas sequential extractions and SEM-EDX analyses reveal the evident association of As and Fe oxyhydroxides content.
Conclusions
The use of an integrated geochemical-mineralogical approach allows to single out the contaminant forms and the relative potential threat. Arsenic in the surface level of such soils could be mobilized in the case of extreme meteorological or of a not well planned human event, even though there is no evidence yet of any serious contamination of either underground or flowing waters.
Fine airborne particulate matter (PM2.5) has been repeatedly associated with adverse health effects in humans. The PM2.5 soluble fraction, and soluble metals in particular, are thought to cause lung ...damage. Literature data, however, are not consistent and the role of leachable metals is still under debate. In this study, Winter and Summer urban PM2.5 aqueous extracts, obtained by using a bio-compatible solution and different contact times at 37 °C, were used to investigate cytotoxic effects of PM2.5 in cultured lung epithelial cells (A549) and the role played by the leachable metals Cu, Fe, Zn, Ni, Pb and Cd. Cell viability and migration, as well as intracellular glutathione, extracellular cysteine, cysteinylglycine and homocysteine concentrations, were evaluated in cells challenged with both PM2.5 extracts before and after ultrafiltration and artificial metal ion solutions mimicking the metal composition of the genuine extracts. The thiol oxidative potential was also evaluated by an abiotic test. Results demonstrate that PM2.5 bioactive components were released within minutes of PM2.5 interaction with the leaching solution. Among these are i) low MW (<3 kDa) solutes inducing oxidative stress and ii) high MW and/or water-insoluble compounds largely contributing to thiol oxidation and to increased homocysteine levels in the cell medium. Cu and/or Ni ions likely contributed to the effects of Summer PM2.5 extracts. Nonetheless, the strong bio-reactivity of Winter PM2.5 extracts could not be explained by the presence of the studied metals. A possible role for PM2.5 water-extractable organic components is discussed.
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•PM2.5 low and high MW components are leached fast in a physiological solution.•Fast leached compounds affect human lung alveolar cells redox status and migration.•Low MW soluble compounds, including some metal ions, induce cell oxidative stress.•High MW and/or insoluble compounds promote extracellular homocysteine accrual.•Pb, Cd, Fe, Zn, Cu and Ni ions do not explain Winter PM2.5 soluble fraction effects.
Two samples of fibrous erionite from different localities of Oregon, USA were suspended in FeCl2 solutions at different concentrations, at pH ca. 5, in anaerobic conditions. Comparison between ...released and acquired charges under the form of Fe confirms that erionite binds Fe (II) by ion exchange with the extra framework (EF) cations, mainly Na. The Fe (II) binding process exhibited by both studied samples here investigated indicates a direct correlation between the extent of the ion-exchange process and the Fe (II) concentration of the solution used for fibres incubation. In the sample from Rome no further Fe (II) acquisition was observed for concentrations exceeding 500 μM FeCl2. XPS investigation revealed that, when comparing surface and bulk composition of the samples, no Fe enrichment of the fibre surface was observed. Moreover, the location of Fe (II) within the erionite cage has been devised by combining chemical and structural data. Results highlight that, for both samples, Fe (II) is fixed at the Ca3 site being six-fold coordinated to water molecules. The occurrence of Fe (II) within the erionite cage causes a gradual migration of the other EF cations and in addition, induces a small rearrangement of the water molecules positions. It is worth mentioning that, in Fe-loaded zeolites at rather low Fe content, the Fe sites with very low nuclearity, located in well-defined crystallographic positions, represent the active sites for the formation of reactive oxygen species. Therefore, identification of segregation of Fe (II) at Ca3, which is coupled with the high surface area of erionite, provides very important information for the understanding of the molecular mechanism/s inducing its strong carcinogenicity.
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•Fibrous erionite was suspended in FeCl2 at pH ca. 5 in anaerobic conditions.•Erionite binds Fe (II) by ion exchange with the extra framework (EF) cations.•Fe (II) is fixed at the Ca3 site being six-fold coordinated to water molecules.•Fe sites with low nuclearity form ROS in Fe-loaded zeolites.•Those results are crucial to understand the mechanism/s inducing carcinogenicity.
Coastal lagoons are important but sensitive environments, being transitional zones between land and sea. The Khnifiss lagoon is the most important desert wetland in Morocco, but little data have been ...produced concerning heavy metal geochemistry and enrichments in the sediments. Therefore, 26 surface sediments (15 intertidal and 11 subtidal) and 2 sediment cores were collected in 2016 and analyzed for a selection of heavy metals. The data were processed to assess the degree of contamination and the corresponding potential ecological risk, using several accumulation/enrichment indices, and the singular and multi-metal risk indices. Mean concentrations in the bottom layers of the two cores, dating from a pre-industrial age according to geochronological analysis, were used as the local geochemical background. The resulting values were on the whole lower than those reported for other areas of the northeastern coast of Morocco. Multivariate statistics were also applied to better understand relationships among variables (metals and other geochemical parameters) and to reveal similarities among sample groups. The results showed that, although the lagoon is not yet affected by significant anthropogenic influences, small enrichments can be recognized, especially for Ni and Cd. The cause may be related to the proximity to the main national highway, the vehicles and machinery used in the saltworks located in the area, and the small harbors used principally for fishing. In addition, industrial emissions from the Atlantic coast of Morocco and adjacent countries can be reasonably attributed as additional contributors to the enrichments. In terms of potential ecological risk, Cd shows the greatest impact compared to the other metals investigated.
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