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The Fe content and the morphometry of asbestos are two major factors linked to its toxicity. This study explored the use of microbe-mineral interactions between asbestos (and asbestos-like) minerals and thermophilic chemolithoautotrophic microorganisms as possible mineral dissolution treatments targeting their toxic properties. The removal of Fe from crocidolite was tested through chemolithoautotrophic Fe(III) reduction activities at 60°C. Chrysotile and tremolite-actinolite were tested for dissolution and potential release of elements like Si and Mg through biosilicification processes at 75°C. Our results show that chemolithoautotrophic Fe(III) reduction activities by Deferrisoma palaeochoriense were supported with crocidolite as the sole source of Fe(III) used as a terminal electron acceptor during respiration. Microbial Fe(III) reduction activities resulted in higher Fe release rates from crocidolite in comparison to previous studies on Fe leaching from crocidolite through Fe assimilation activities by soil fungi. Evidence of biosilicification in Thermovibrio ammonificans did not correspond with increased Si and Mg release from chrysotile or tremolite-actinolite dissolution. However, overall Si and Mg release from chrysotile into our experimental medium outmatched previously reported capabilities for Si and Mg release from chrysotile by fungi. Differences in the profiles of elements released from chrysotile and tremolite-actinolite during microbe-mineral experiments with T. ammonificans underscored the relevance of underlying crystallochemical differences in driving mineral dissolution and elemental bioavailability. Experimental studies targeting the interactions between chemolithoautotrophs and asbestos (or asbestos-like) minerals offer new access to the mechanisms behind crystallochemical mineral alterations and their role in the development of tailored asbestos treatments. IMPORTANCE We explored the potential of chemosynthetic microorganisms growing at high temperatures to induce the release of key elements (mainly iron, silicon, and magnesium) involved in the known toxic properties (iron content and fibrous mineral shapes) of asbestos minerals. We show for the first time that the microbial respiration of iron from amphibole asbestos releases some of the iron contained in the mineral while supporting microbial growth. Another microorganism imposed on the two main types of asbestos minerals (serpentines and amphiboles) resulted in distinct elemental release profiles for each type of asbestos during mineral dissolution. Despite evidence of microbially mediated dissolution in all minerals, none of the microorganisms tested disrupted the structure of the asbestos mineral fibers. Further constraints on the relationships between elemental release rates, amount of starting asbestos, reaction volumes, and incubation times will be required to better compare asbestos dissolution treatments studied to date.
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Asbestos Serpentinas , Amianto , Asbestos Serpentinas/química , Asbesto Crocidolita , Compuestos Férricos , Amianto/química , Minerales , Hierro/química , Bacterias AnaerobiasRESUMEN
There are six elongate mineral particles (EMPs) corresponding to specific dimensional and morphological criteria, known as asbestos. Responsible for health issues including asbestosis, and malignant mesothelioma, asbestos has been well researched. Despite this, significant exposure continues to occur throughout the world, potentially affecting 125 million people in the workplace and causing thousands of deaths annually from exposure in homes. However, there are other EMPS, such as fibrous/asbestiform erionite, that are classified as carcinogens and have been linked to cancers in areas where it has been incorporated into local building materials or released into the environment through earthmoving activities. Erionite is a more potent carcinogen than asbestos but as it is seldom used for commercial purposes, exposure pathways have been less well studied. Despite the apparent similarities between asbestos and fibrous erionite, their health risks and exposure pathways are quite different. This article examines the hazards presented by EMPs with a particular focus on fibrous erionite. It includes a discussion of the global locations of erionite and similar hazardous minerals, a comparison of the multiple exposure pathways for asbestos and fibrous erionite, a brief discussion of the confusing nomenclature associated with EMPs, and considerations of increasing global mesothelioma cases.
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Amianto , Asbestosis , Mesotelioma Maligno , Mesotelioma , Zeolitas , Amianto/toxicidad , Asbestosis/epidemiología , Carcinógenos/toxicidad , Humanos , Mesotelioma/inducido químicamente , Mesotelioma/epidemiologíaRESUMEN
Road sediment is a pervasive environmental medium that acts as both source and sink for a variety of natural and anthropogenic particles and often is enriched in heavy metals. Road sediment is generally understudied in the United States (U.S.) relative to other environmental media and compared to countries such as China and the United Kingdom (U.K.). However, the U.S. is an ideal target for these studies due to the diverse climates and wealth of geochemical, socioeconomic, demographic, and health data. This review outlines the existing U.S. road sediment literature while also providing key international perspectives and context. Furthermore, the most comprehensive table of U.S. road sediment studies to date is presented, which includes elemental concentrations, sample size, size fraction, collection and analytical methods, as well as digestion procedure. Overall, there were observed differences in studies by sampling time period for elemental concentrations, but not necessarily by climate in the U.S. Other key concepts addressed in this road sediment review include the processes controlling its distribution, the variety of nomenclature used, anthropogenic enrichment of heavy metals, electron microscopy, health risk assessments, remediation, and future directions of road sediment investigations. Going forward, it is recommended that studies with a higher geographic diversity are performed that consider smaller cities and rural areas. Furthermore, environmental justice must be a focus as community science studies of road sediment can elucidate pollution issues impacting areas of high need. Finally, this review calls for consistency in sampling, data reporting, and nomenclature to effectively expand work on understudied elements, particles, and background sediments.
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Ciencia Ambiental , Metales Pesados , China , Ciudades , Polvo/análisis , Monitoreo del Ambiente/métodos , Contaminación Ambiental , Sedimentos Geológicos , Metales Pesados/análisis , Medición de Riesgo , Estados UnidosRESUMEN
Amphibole asbestos is related to lung fibrosis and several types of lung tumors. The disease-triggering mechanisms still challenge our diagnostic capabilities and are still far from being fully understood. The literature focuses primarily on the role and formation of asbestos bodies in lung tissues, but there is a distinct lack of studies on amphibole particles that have been internalized by alveolar epithelial cells (AECs). These internalized particles may directly interact with the cell nucleus and the organelles, exerting a synergistic action with asbestos bodies (AB) from a different location. Here we document the near-atomic- to nano-scale transformations induced by, and taking place within, AECs of three distinct amphiboles (anthophyllite, grunerite, "amosite") with different Fe-content and morphologic features. We show that: (i) an Fe-rich layer is formed on the internalized particles, (ii) particle grain boundaries are transformed abiotically by the internal chemical environment of AECs and/or by a biologically induced mineralization mechanism, (iii) the Fe-rich material produced on the particle surface does not contain large amounts of P, in stark contrast to extracellular ABs, and (iv) the iron in the Fe-rich layer is derived from the particle itself. Internalized particles and ABs follow two distinct formation mechanisms reaching different physicochemical end-states.
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Células Epiteliales Alveolares/metabolismo , Asbestos Anfíboles/análisis , Asbestos Anfíboles/metabolismo , Hierro/metabolismo , Pulmón/metabolismo , Nanopartículas/química , Células Epiteliales Alveolares/patología , Humanos , Pulmón/patologíaRESUMEN
Lead (Pb) soil contamination in urban environments represents a considerable health risk for exposed populations, which often include environmental justice communities. In Philadelphia, Pennsylvania (PA), Pb pollution is a major concern primarily due to extensive historical Pb-smelting/processing activity and legacy use of Pb-based paints and leaded gasoline. The U.S. Environmental Protection Agency (USEPA) organized and/or compiled community-driven soil sampling campaigns to investigate Pb content in surface soils across Philadelphia. Using these data (n = 1277), combined with our own dataset (n = 1388), we explored the spatial distribution of Pb content in soils across the city using ArcGIS. While assessing Zone Improvement Plan (ZIP)-code level data, we found strong correlations between factors, such as the percentage of children with elevated blood lead levels (% EBLL) and % minority population as well as between % EBLL and % children in poverty. We developed a "Lead Index" that took demographics, median measured Pb-in-soil content, and % EBLLs into account to identify ZIP codes in need of further assessment. Our results will be used to help lower the Pb-exposure risk for vulnerable children living in disproportionately burdened communities.
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Plomo , Contaminantes del Suelo , Niño , Demografía , Salud Ambiental , Humanos , Plomo/análisis , Philadelphia , Contaminantes del Suelo/análisisRESUMEN
A multi-analytical geochemical investigation of Pb-contaminated collocated road dust and soils, at two size fractions, was performed in Fishtown, Philadelphia, PA, USA. The combinations of methods employed in this case study were chosen to better characterize the contamination, enhance identification of pollution sources, improve understanding of the impact of former Pb smelters, and to study the relationships between two media and between two size fractions. High concentrations of Cu and Sn were observed in both bulk and finer road dust, whereas large concentrations of Zn and Pb were found in both bulk and finer soil samples, implying pollution. There were no obvious associations between Pb soil concentrations and former smelter locations. Therefore, the primary source of the high mean Pb content in bulk (595 ppm) and fine soils (687 ppm) was likely legacy lead paint and/or leaded-gasoline products. Using electron microscopy, we found that Pb particles were mainly 0.1-10 µm in diameter and were ubiquitous in both soil and dust samples. Two-way analysis of variance tests revealed that, for most chemical elements explored here, there were statistically significant differences in concentrations based on media and size fractions, with finer sizes being more polluted than the bulk. The mineralogical composition and the sources of several pollutant elements (Cr, Cu, Zn, Pb), however, were similar for both soil and dust, pointing to material exchange between the two media. We suggest that future investigations of collocated road dust and soils in urban environments use the methodologies applied in this study to obtain detailed insights into sources of roadside pollution and the relationships between neighboring media.
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Metales Pesados , Contaminantes del Suelo , Polvo/análisis , Monitoreo del Ambiente , Plomo , Metales Pesados/análisis , Philadelphia , Suelo , Contaminantes del Suelo/análisisRESUMEN
In this paper, we present the results of a multi-analytical characterization of a glaucophane sample collected in the Piedmont region of northwestern Italy. Investigation methods included optical microscopy, powder X-ray diffraction, Fourier-transform infrared spectroscopy, µ-Raman spectroscopy, Mössbauer spectroscopy, electron probe microanalysis, environmental scanning electron microscopy and energy-dispersive X-ray spectroscopy, and scanning/transmission electron microscopy combined with energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy. In addition to the crystal-chemical characterization of the sample from the mesoscale to the near-atomic scale, we have also conducted an extended study on the morphology and dimensions of the mineral particles. The main finding is that studying the same particle population at different magnifications yields different results for mineral habit, dimensions, and dimensional distributions. As glaucophane may occur as an elongate mineral particle (e.g., asbestiform glaucophane occurrences in California and Nevada), the observed discrepancies therefore need to be considered when assessing potential breathability of such particles, with implications for future regulations on elongate mineral particles. While the sample preparation and particle counting methods are not directly investigated in this work, our findings suggest that different magnifications should be used when characterizing an elongate mineral particle population, irrespective of whether or not it contains asbestiform material. These results further reveal the need for developing improved regulation for elongate mineral particles. We thus propose a simple methodology to merge the datasets collected at different magnifications to provide a more complete description and a better risk evaluation of the studied particle population.
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Pollution from heavy metals in urban environments is a topic of growing concern because many metals, including Pb and Cr, are a human health hazard. Exposure to Pb and Cr has been linked to the inhibition of neurological development as well as toxic effects on many organs. Yellow traffic paint (YTP) is a mixture that contains organic polymers, binders, and pigments, which in some cases consist of crocoite (PbCrO4) that may be coated by silica. The primary aim of this study was to investigate the behavior of the crocoite pigment grains within YTP and their silica coatings in simulated environmental and human body conditions. To do this, both YTP and asphalt were collected in Philadelphia, PA, USA. These samples as well as a standard PbCrO4 were investigated with powder X-ray diffraction, X-ray fluorescence, environmental scanning electron microscopy (ESEM), transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Using this multi-analytical approach, mineral phases were determined in the YTP, their shape, dimensional distributions, crystallinity, and chemical composition, as well as elemental distributions before and after experimental interactions. Three batch dissolution experiments with YTP, asphalt, and standard PbCrO4 were performed to simulate ingestion, inhalation, and environmental interaction with rainwater. Elemental releases were determined with inductively coupled plasma-optical emission spectrometry, and results indicated that little (ingestion) to no (environmental and inhalation) Pb and Cr were leached from the YTP during the three experimental procedures. This is likely due to the silica coating that encapsulates the crocoite particles, which persisted during all interactions. The ESEM results for YTP showed dimensional reductions after interactions with all three fluids. The silica coating must be further explored to determine how it breaks down in real environmental conditions.
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Metales Pesados , Pintura , Monitoreo del Ambiente , Contaminación Ambiental/análisis , Humanos , Metales Pesados/análisis , Dióxido de Silicio , Espectrometría por Rayos XRESUMEN
BACKGROUND: Chronic beryllium disease (CBD), a granulomatous disease with similarities to sarcoidosis, arises only in individuals exposed to beryllium. Inhaled beryllium can elicit a T-cell-dominated alveolitis leading nonnecrotizing granulomata. CBD can be distinguished from sarcoidosis by demonstrating beryllium sensitization in a lymphocyte proliferation test. RESEARCH QUESTION: Beryllium exposure usually occurs in an occupational setting. Because of the diagnosis of CBD in a patient without evident beryllium exposure, we performed a beryllium-lymphocyte proliferation test (BeLPT) among his work colleagues. STUDY DESIGN AND METHODS: This field study investigated a cohort of work colleagues without obvious beryllium exposure. Twenty-one of 30 individuals were assessed in our outpatient clinic for beryllium sensitization. Therefore, BeLPT was performed with freshly collected peripheral blood mononuclear cells. Data were extracted from clinical charts, including geographical data. Beryllium content in dust samples collected at the workplace was measured by graphite-furnace atomic absorption spectroscopy and was compared with samples from different areas of Germany. RESULTS: For the initial patient, the diagnosis of sarcoidosis was reclassified as CBD based on two positive BeLPT results. Assessment of his workplace did not identify a source of beryllium. However, BeLPTs performed on his workmates demonstrated beryllium sensitization in 5 of 21 individuals, suggesting a local beryllium source. Concrete dust obtained from the building yard, the workplace of the index patient, contained high amounts of beryllium (1138 ± 162 µg/kg), whereas dust from other localities (control samples) showed much lower beryllium content (range, 147 ± 18-452 ± 206 µg/kg). Notably, the control dust collected from different places all over Germany exhibit different beryllium concentrations. INTERPRETATION: We describe a cluster of beryllium-sensitized workers from an industry not related to beryllium caused by environmental exposure to beryllium-containing concrete dust, which exhibited markedly elevated beryllium content. Importantly, analyses of dust samples collected from different localities showed that they contain markedly different amounts of beryllium. Thus, besides workplace-related exposure, environmental factors also are capable of eliciting a beryllium sensitization.
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Beriliosis , Berilio , Polvo/análisis , Exposición a Riesgos Ambientales , Granuloma del Sistema Respiratorio , Activación de Linfocitos/inmunología , Sarcoidosis Pulmonar/diagnóstico , Adulto , Beriliosis/diagnóstico , Beriliosis/etiología , Beriliosis/inmunología , Beriliosis/prevención & control , Berilio/análisis , Berilio/toxicidad , Industria de la Construcción , Diagnóstico Diferencial , Exposición a Riesgos Ambientales/efectos adversos , Exposición a Riesgos Ambientales/análisis , Femenino , Alemania/epidemiología , Granuloma del Sistema Respiratorio/inducido químicamente , Granuloma del Sistema Respiratorio/diagnóstico , Humanos , Pruebas Inmunológicas/métodos , Leucocitos Mononucleares , Masculino , Agrupamiento Espacio-Temporal , Lugar de Trabajo/normasRESUMEN
The aim of the present method is to reduce the dimensional variability of asbestos, elongate mineral particles, and other asbestiform minerals for use in biological assays. Here, the pristine mineral sample is filtered through two nylon meshes of different sizes to obtain a narrower dimensional distribution following a power law. Furthermore, we show that anoxic preparation, autoclaving and storage of the mineral prior to addition into biological cultures did not affect the mineral's chemical properties. This approach avoids the use of highly reactive chemicals modifying mineralogical characteristics and surface properties, which can affect to a major extent mineral toxicity as well as interactions between minerals and biological matter or biofluids. The method can be combined with additional selective approaches to further refine the dimensional range of the minerals. The advantages of this protocol over previous methods are: â¢Exclusive use of distilled water and 2-propanol, thus eliminating chemicals that can modify bulk or surface properties of the studied minerals.â¢Successful sterilization of the resulting mineral particles for use in biological assays without compromising mineralogical characteristics.â¢Applicability of this method across various types of asbestos, elongate mineral particles and, potentially, other hazardous minerals.
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Neutrophilic, microaerobic Fe(II)-oxidizing bacteria (FeOB) from marine and freshwater environments are known to generate twisted ribbon-like organo-mineral stalks. These structures, which are extracellularly precipitated, are susceptible to chemical influences in the environment once synthesized. In this paper, we characterize the minerals associated with freshwater FeOB stalks in order to evaluate key organo-mineral mechanisms involved in biomineral formation. Micro-Raman spectroscopy and Field Emission Scanning Electron Microscopy revealed that FeOB isolated from drinking water wells in Sweden produced stalks with ferrihydrite, lepidocrocite and goethite as main mineral components. Based on our observations made by micro-Raman Spectroscopy, field emission scanning electron microscopy and scanning transmission electron microscope combined with electron energy-loss spectroscopy, we propose a model that describes the crystal-growth mechanism, the Fe-oxidation state, and the mineralogical state of the stalks, as well as the biogenic contribution to these features. Our study suggests that the main crystal-growth mechanism in stalks includes nanoparticle aggregation and dissolution/re-precipitation reactions, which are dominant near the organic exopolymeric material produced by the microorganism and in the peripheral region of the stalk, respectively.
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Bacterias , Compuestos Férricos , Compuestos Ferrosos , Hierro , Minerales , Nanoestructuras , Oxidación-Reducción , SueciaRESUMEN
The correct presentation of the 4th sentence in the 2nd paragraph of section Remediation method is shown in this paper.
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Road dust was investigated within Philadelphia, a major United States city with a long history of industrial activities, in order to determine pollution levels. Almost all of the investigated minor elements were enriched relative to the continental crust. Furthermore, mean concentrations of Cr, Co, Cu, and Pb were high compared with those reported in cities in other countries. Lead pollution should be investigated further in Philadelphia, where 8 of the 30 sample sites, including those heavily trafficked by civilians, were at or above the EPA's child safety threshold for Pb in bare soil. High Spearman correlations between Zn and Cu, Zn and Cr, Cu and Cr, and Sn and V, as well as factor analysis of minor elements suggests that the primary sources of these elements were anthropogenic. Potential sources included the breakdown of alloys, non-exhaust traffic emissions, paint, smelting, and industry. We found that higher organic content in road dust may be related to higher traffic densities, which could be due to tire-wear particles. Additionally, higher mean concentrations of Fe, Cr, Cu, and Zn were found at sites with elevated traffic densities. Land use impacted some of the elements not influenced by traffic density, including Co, Sn, and Pb. Bulk mineral content was similar across different land uses and traffic densities and, thus, did not appear to be influenced by these factors. Our research emphasized the complexity of road dust and utilized a more comprehensive approach than many previous studies. This study established fundamental groundwork for future risk assessment in Philadelphia, as it identified several key pollutants in the city. Overall, this assessment serves as an informative reference point for other formerly heavily industrialized cities in the USA and abroad.
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Polvo/análisis , Metales Pesados/análisis , Niño , Ciudades , Monitoreo del Ambiente , Contaminación Ambiental/análisis , Humanos , Philadelphia , Embarazo , Medición de Riesgo , Estados UnidosRESUMEN
This study presents the latest results of the groundwater monitoring of a research project, which tested an innovative pump and treat method in combination with an in-situ remediation. This technique was assessed on an abandoned site in Austria, where two hot spots of hexavalent chromium (Cr(VI)) were located. For the in-situ remediation, a strong reducing agent (sodium dithionite) was injected into the underground to reduce Cr(VI) to Cr(III) by using different injection strategies. Throughout this treatment, part of the Cr(VI) is mobilized and not instantly reduced. To prevent a further spreading of the mobilized Cr(VI), the pump and treat method, which uses zero-valent iron to clean the groundwater, was installed downgradient of the hot spots. Based on the groundwater sample analyses, it was possible to distinguish different remediation phases, characterized by excess chromate and excess sulfite. During the excess sulfite conditions, Cr(VI) was successfully removed from the system, but after terminating the sodium dithionite injection, the Cr(VI) rebounded.
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Restauración y Remediación Ambiental , Agua Subterránea , Contaminantes Químicos del Agua/análisis , Austria , CromoRESUMEN
Substitution of cement clinker with suitable excess materials from other processes is an effective way to reduce CO2 emissions of cement production. Moreover, specific properties of the resulting mortar or concrete can be designed with different clinker replacement materials and their mixing ratios. In this study, bottom and fly ashes from six biomass power plants with different power scales and various flue-gas treatment strategies were admixed to mortars, whose properties (influence of water requirement and final compressive strength) were then assessed in the laboratory by following industrial standard procedures. Results reveal that fly ash from a cyclone of a medium-scale combustor burning Miscanthus straw amended with 2 wt % Ca(OH)2 (to prevent slagging during combustion) turned out to be well suited as a clinker replacement material, even boosting final compressive strength of the mortar. Wood-chip bottom ashes and fly ash from a cyclone exhibited acceptable results, whereas fly ash from electrostatic precipitators (ESPs) and baghouse filters lowered final compressive strength of the mortar when admixed. The scale of the power plant is positively correlated with final compressive strength in the case of ESPs. Cenospheres, typical fly ash particles present in cyclone ash, seem to have a positive effect on water-to-binder ratio and final compressive strength. In contrast, potassium salts, which are most abundant in ash from ESPs and baghouse filters, appear to have a negative influence on these properties. Grinding of the biomass ashes to a typical Portland cement fineness had a positive effect on mortar quality. All fly ashes had high contents of Cd, and baghouse filter ash contained As in amounts about four times the Swiss limit value for cement of 30 ppm; only bottom ash and cyclone ash from Miscanthus exhibited concentrations below respective limit values for all critical trace elements. To assess the immobilization potential of contaminating elements during the cement hardening process, blended mortars were crushed and subjected to multistep leaching, followed by subsequent analysis of the leachates by atomic absorption spectroscopy. Immobilization of Cd by the mortar was particularly effective. Our results indicate that fly ash from wood-chip combustion is most suitable as an amendment to cement when it was trapped by a cyclone rather than by the ESPs or baghouse filters.
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The ferrierite crystal structure has often been subject to discussion because of the possible lowering of symmetry from the space group Immm. It mainly occurs in nature with a fibrous crystal habit, and because of the existence of line/planar defects in the framework, texture and preferred orientation effects it has been difficult to obtain an exact crystallographic model based only on the results from powder diffraction data. Therefore, nano-single-crystal diffraction and tomography data have been combined in order to improve the refinement with a meaningful model. High-quality single-crystal data, providing reliable structural information, and tomography images have been used as input for a Rietveld refinement which took into account a phenomenological description of stacking disorder and the analytical description of the preferred orientation, by means of spherical harmonics for strong texture effects. This is one of the first examples of application of synchrotron nano-diffraction for the structure solution of fibrous minerals of micrometre to nanometre size. The high quality of the crystals allowed collection of single-crystal X-ray diffraction data of up to 0.6â Å resolution, leading to an unambiguous solution and precise anisotropic refinement. Nano-single-crystal diffraction and phase contrast tomography data were collected at ID11 and the high-resolution powder diffraction patterns at ID22 of the European Synchrotron Radiation Facility. This detailed crystallographic characterization provides a basis for understanding the potential of ferrierite for toxicity and carcinogenicity.
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Bottom and fly ash samples from six biomass power plants with different power scales and various flue gas treatment strategies were collected and analyzed in regard to their mineralogical composition, and their bulk major and trace element contents, all of which are of concern for regulations on biomass ash for further utilization. Furthermore, individual ash particles were investigated by scanning electron microscopy to characterize their physicochemical microstructures. Thermal behavior of wood-pellet ash, i.e. decomposition processes and mineral transformations during combustion, was indicated by thermogravimetric analysis and X-ray diffraction. Results reveal extensive variation of physicochemical features across the different ash types: wood-chip fly ash from electrostatic precipitators mainly consisted of water-soluble salts, whereas wood-chip fly ash from cyclones contained predominantly cenospheres (hollow spherical fly ash particles) and higher heavy metal concentrations. In addition, the fuel type and admixture had influences on ash compositions; some fuels like Miscanthus straw require a liming agent such as calcium hydroxide to be admixed to prevent fouling, which is then predominantly found in the ash. Furthermore, boiler size had an influence on fly ash composition. Cadmium concentrations were elevated in some fly ash samples at levels of concern for further utilization, whereas concentrations of troublesome Cr(VI) were below the detection limit for all investigated ash samples. Other contaminating elements such as Ni, Pb and Zn were variable but below limit values. Results clearly show that the nature of biomass ash calls for careful analyses prior to further application as, e.g., cement clinker replacement material.
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Vibrational spectroscopies (Fourier Transform Infra Red, FTIR, and Raman) are exceptionally valuable tools for the identification and crystal-chemical study of fibrous minerals, and asbestos amphiboles in particular. Raman spectroscopy has been widely applied in toxicological studies and thus a large corpus of reference data on regulated species is found in the literature. However, FTIR spectroscopy has been mostly used in crystal-chemical studies and very few data are found on asbestos amphiboles. This paper is intended to fill this gap. We report new FTIR data collected on a suite of well-characterized samples of the five regulated amphibole species: anthophyllite, amosite, and crocidolite, provided by the Union for International Cancer Control (UICC) Organization, and tremolite and actinolite, from two well-known occurrences. The data from these reference samples have been augmented by results from additional specimens to clarify some aspects of their spectroscopic features. We show that the FTIR spectra in both the OH-stretching region and in the lattice modes region can be effective for rapid identification of the asbestos type.
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In this paper, we report the results of the first study focused on the thermal stability and dehydration dynamics of the natural zeolite mineral ferrierite. A sample from Monastir, Sardinia [(Na0.56K1.19Mg2.02Ca0.52Sr0.14) (Al6.89Si29.04)O72·17.86H2O; a = 19.2241(3) Å; b = 14.1563(2) Å; c = 7.5106(1) Å, V = 2043.95(7) Å3] was investigated by thermogravimetric analysis and in-situ synchrotron X-ray powder diffraction. Thermogravimetric data show that H2O release begins already in the range 50-100 °C and is complete at ~600 °C. The results of the structure refinements performed in Immm space group by Rietveld analysis with data collected up to 670 °C show that ferrierite belongs to the group of zeolites that do not undergo phase transitions. Upon heating to 670 °C, ferrierite behaves as a non-collapsible structure displaying only a slight contraction of the unit-cell volume (ΔV = -3%). The unit-cell parameter reductions are anisotropic, more pronounced for a than for b and c (Δa = -1.6%; Δb = -0.76%; Δc = -0.70%). This anisotropic response to a temperature increase is interpreted as due to the presence in the ferrierite framework of five-membered ring chains of SiO4 tetrahedra, which impart a higher structural rigidity along b and c. Upon dehydration we observe: (1) the gradual H2O loss, beginning with the molecules hosted in the 10MR channel, is almost complete at 670 °C, in good agreement with the TG data; (2) as a consequence of the decreased H2O content, Mg and K migrate from their original positions, moving from the center of the 10MR channel toward the walls to coordinate the framework oxygen atoms. The observation of transmission electron microscopy selected-area electron diffraction patterns revealed defective crystals with an occasional and moderate structural disorder. Beyond providing information on the thermal stability and behavior of natural ferrierite, the results of this work have significant implications for possible technological applications. These data allow for comparison with the dehydration kinetics/mechanisms of the corresponding synthetic phases, clarifying the role played by framework and extra-framework species on the high-temperature behavior of porous materials with ferrierite topology. Moreover, the information on the thermal behavior of natural ferrierite can be used to predict the energetic performances of analogous synthetic Si-pure counterparts, namely "zeosil-electrolyte" systems, under non-ambient conditions. Specifically, the very high thermal stability of ferrierite determined in this study, coupled with the baric behavior determined in other investigations, suggests that the "Si-FER-electrolyte" system may be an excellent candidate for use as an energy reservoir. Indeed, ferrierite exhibits the so-called "spring behavior," i.e., upon compression in water or in an electrolyte solution, it converts the mechanical energy into interfacial energy, and-when pressure is released-it can completely restore the supplied mechanical energy accumulated during the compression step.