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Potential for respirable quartz exposure from North Carolina farm soils.

Sandy-loam soils from six active farms in the coastal plains of North Carolina (USA) were analyzed for aerodynamic equivalent diameter and quartz content and compared with results to similar analyses of clay soils of the Piedmont and sandy soils from the sand hills of North Carolina to see whether respirable quartz content varies with soil type. The respirable fraction of sandy loam-soils averaged 0.04 (SD 0.02) versus 0.13 (SD 0.03) for clay soils and 0.04 (SD 0.03) for sandy soils. Quartz content in the 4.25 mu m fraction of sandy-loam soils averaged 15.2 (SD 4.1) % versus 2.2 (SD 0.8) % in clay soils and 29.0 (SD 11.1) % in sandy soils. The mass of respirable quartz in sandy-loam soils averaged 0.7 (SD 0.4)% versus 0.3 (SD 0.1)% in clay soils and 1.0 (SD 0.4) % in sandy soils. These results suggest that, during dusty farm activities, there is a potential for greater respirable quartz exposures associated with work with sandy or sandy-loam soils than from work with clay soils.

Agriculture↗

[The concentration levels of airborne quartz at an urban site].

The IARC has recently included crystalline silica among substances considered carcinogenic for man. This new evaluation immediately posed the need to measure the exposure levels of the general population. The paper reports the results of measurements of the concentrations of quartz (i.e., the most common form of crystalline silica) in a location in the urban area of Rome. First we studied the respirable fractions of the airborne particles (PM10) sampled in the Spring of 1996 with a cascade impactor, which were characterized using a scanning electron microscope equipped with an X-ray microprobe. Ten components were identified including total silica (crystalline and amorphous), which was present in a percentage of 3.7% on average. On the basis of these data a methodological study was undertaken of the concentration of quartz in the historic series of PM10 sampled daily at the same site by means of an AMP instrument (Airborne Particles Monitor). The filters of mixed cellulose esters on which the PM10 was collected were incinerated at low temperature in oxygen plasma to eliminate the organic component. The residue was deposited on silver filters which were read with a conventional X-ray diffractometer in order to determine the quantity of quartz. We analyzed 28 filters from four representative weeks of the four seasons of 1994, the year in which systematic sampling was initiated. The results showed a mean weekly concentration of airborne quartz of between 0.6 and 1.5 micrograms/Nmc, which gives a percentage over PM10 of 1.7 and 3.4 respectively. These data substantially agree with previous results obtained with electron microscopy and show that the levels of quartz in the urban atmosphere under study were about one hundred times lower than the TLV currently recommended by the ACGIH for working environments (100 micrograms/Nmc) and which are also in force in Italy.

Aerosols↗

Evidence for the Formation of Trioctahedral Clay upon Sorption of Co(2+) on Quartz.

The sorption mechanism of Co on quartz at room temperature has been investigated by an in-depth analysis of published extended X-ray absorption fine structure (EXAFS) spectroscopy and solution chemistry data. In particular, the 3.5-5 Å mid-range atomic environment of Co has been determined with unprecedented precision by combining ad initio FEFF7.02 calculations and results obtained by polarized EXAFS on the mid-distance structure of sheet silicate minerals. The local atomic environment around sorbed Co atoms is identical to that of Co in trioctahedral clays and substantially different from that in the cobalt hydroxide Co(OH)(2(s)). Neoformation of a trioctahedral clay is consistent with calculated thermodynamic solubilities, which indicate that 2:1 and 1:1 Co-rich hydrous silicates, similar to kerolite and chrysotile, are less soluble than Co(OH)(2(s)). Consequently, precipitation of Co-rich clay is favored over that of Co(OH)(2(s)) at pH values below 9 and for a dissolved Si concentration equal to quartz solubility. New experimental data show that dissolved Si concentrations can approach, and even exceed, that of quartz solubility during the short times of sorption experiments. Based on the available data, it is not possible to conclude unequivocally if the Co layer silicate grew epitaxially on the quartz surface, topotactically in a surface amorphous layer, or independently of the quartz framework structure. The structural and chemical interpretation is supported by recent published studies in which sorption of a hydrolyzable cation leads to the neoformation of a mixed layer phase formed from the sorbate species and the sorbent metal. This surface-induced precipitation mechanism is a general phenomenon that may account for the formation of secondary clays as coatings on silicates. Copyright 1999 Academic Press.

Journal Article↗

The therapeutic action of aluminium compounds on the development of experimental lesions produced by pure quartz or mixed dust.

The prophylactic and curative effect of aluminium salts administered as aerosols on the development of lung lesions caused by the dust inhalation of quartz, two coal-quartz mixtures with 17% and 8% silica, respectively, and pure coal, was studied experimentally on rats. It appears that the preventive treatment is very efficient either in the case of pure quartz or coal-quartz mixtures. The curation treatment with regard to pure quartz leads to constant lung weight and reduced rate of collagen formation; the effect is the more evident as the silica content of the dust is higher and becomes nil with pure coal. The effectiveness is slightly increased when aerosols at higher concentrations are used, but the difference is not proportional to the dose. Under these experimental conditions, the aerosols used showed no toxicity.

Aerosols↗

Neoplastic transformation by quartz in the BALB/3T3/A31-1-1 cell line and the effects of associated minerals.

Quartz, the most common form of crystalline silica, was tested quantitatively for neoplastic transformation in the mouse embryo cell line, BALB/3T3/A31-1-1. Five quartz dust samples of respirable size [Min-U-Sil 5 (MQZ); hydrofluoric-acid-etched MQZ (HFMQZ); Chinese standard quartz (CSQZ); DQ12; and F600] all induced significant levels of neoplastic transformation, showing dose-dependent increases in the frequency of morphologically transformed foci at lower tested doses and a plateau level of response at higher doses. The plateau levels reached by the five tested samples did not differ substantially (maximum transformation frequencies per 10(5) cells ranging from 53.2 for MQZ to 28.3 for HFMQZ). F600 had minimal cytotoxicity but transforming activity comparable to the other samples. Cells from all tested transformed foci, when injected s.c. in nude mice, grew as sarcomas. Cytogenetic analysis showed that all tested silica-transformed cell lines had acquired one to five additional marker chromosomes, of types not seen in untreated control lines, indicative of induced chromosomal translocations and amplification. Increased expression of one or more of five genes (p53, myc, H-ras, K-ras, and abl) was observed in several quartz-transformed cell lines. No transforming activity was found for hematite and anatase (both nontoxic), and for rutile (more toxic than MQZ). Combined exposure (1:1 w/w per unit culture area) of each of these dusts with MQZ showed that hematite and anatase inhibited MQZ toxicity as well as transformation, whereas rutile markedly enhanced MQZ toxicity but not MQZ-induced transformation.

3T3 Cells↗

Electroosmosis injection of blood serum into biocompatible microcapillary chip fabricated on quartz plate.

A chip which allows the detection of various human health markers from a trace amount of blood has been studied. As a goal, a microcapillary with a 30 x 30 microm cross-section was fabricated using all-dry etching technologies on a 2 x 2 cm SiO2 chip. The coating of the biocompatible 2-methacryloyloxyethylphosphorylcholine (MPC) polymer on the inner quartz wall of the microcapillary demonstrated a sufficiently long adsorption suppression of proteins in the serum on the quartz surface, while rapid stopping occurred for serum injected into the microcapillary with a bare quartz surface. The latter rapid stopping corresponded well to fast electroosmosis flow due to the negatively increasing zeta-potential by the adsorption of proteins on the quartz surface. The electroosmosis pump arranged a downstream of the microcapillary was also developed to inject serum into it. As a preliminary application, a given concentration-standard solution was injected into the ion-sensitive field-effect transistor (ISFET) embedded in the chip, employing the electroosmosis pump arranged downstream of the sensor position. Hence, the pH and Na+ and K+ cation concentrations were measured.

Blood Chemical Analysis↗

Reaction of macrophages activated by agents in vivo to quartz dust in vitro.

A comparative study was made of the cytotoxic action of quartz dust in vitro on macrophages activated in vivo by intraperitoneal inoculation of physiological saline, thioglycolate and starch. The liberation of lactate dehydrogenase (LDH) into the supernatant culture medium, adherence to a plastic surface, extent of acid dye exclusion and ultrastructural alteration in the surface morphology of macrophages were taken as parameters of the cytotoxic action of the dusts. Thioglycolate and starch stimulated cells when exposed in vitro to quartz dust released more LDH into the supernatant culture medium and resulted in a greater decrease in macrophage adherence than similarly exposed cells derived from saline stimulated animals. No difference was observed between cells obtained from differently stimulated animals in increased acid dye uptake, loss of surface filopodia and rounding of cells which phagocytosed quartz particles. The results show that quartz is cytotoxic for macrophages, irrespective of their degree of activation and the extent of damage induced is related to the chemical agent used for activation of macrophages in vivo.

Animals↗

Molecular and supramolecular structure of adsorbed fibrinogen and adsorption isotherms of fibrinogen at quartz surfaces.

The adsorption of fibrinogen to quartz surfaces was measured by ellipsometry, ELISA, and electron microscopy. The initial adsorption at low concentrations was diffusion rate limited as determined by the ELISA and by counting the number of adsorbed molecules at electron micrographs. From ellipsometry, ELISA, and electron microscopy measurements it was found that the surface concentration of adsorbed fibrinogen increased continuously over four decades in bulk concentration of fibrinogen. At a hydrophilic quartz surface a plateau level of the adsorption isotherm was found at a surface concentration of 0.1 pmol/cm2 where the adsorbed molecules had a mean intermolecular distance of 10 +/- 5 nm between neighbors. At higher surface concentrations the molecules were densely packed and formed a layer where single molecules could not be identified. Adsorbed fibrinogen showed different structure at hydrophobic and hydrophilic quartz surfaces. At a hydrophilic surface, the fibrinogen molecules appeared as a 46 nm nodose rod consisting of 6-7 nodes with a diameter of 4 nm. At a hydrophobic surface, the molecule appeared as a binodular or trinodular rod with a node diameter of 5-9 nm, connected with a thin filament to form a 40-nm rod. Adsorption from higher concentrations of fibrinogen in solution resulted in adsorbed spheric structures with a diameter of 18-24 nm at the hydrophobic surface and in end-to-end polymers at the hydrophilic quartz membrane.

Adsorption↗

Adsorption of N-tallow 1,3-propanediamine-dioleate collector on albite and quartz minerals, and selective flotation of albite from greek stefania feldspar ore.

The adsorption behavior of tallow 1,3-propanediamine-dioleate (Duomeen TDO) collector on albite and quartz minerals is assessed through Hallimond flotation, zeta potential, and diffuse reflectance FTIR investigations, together with the species distribution of the collector. The collector performance on albite separation from a natural feldspar material is evaluated in bench scale flotation tests. The Hallimond flotation responses of the minerals as a function of pH and collector concentration indicate that albite can be selectively floated from quartz at pH 2 where the doubly positively charged collector species adsorb on albite but not on quartz. However, the zeta potential and infrared spectra reveal that the adsorption behavior of the collector is similar on both minerals. The discrepancy in the flotation and adsorption results is attributed to the coarse and fine particle size fractions, and the shorter and longer equilibration periods employed in these studies respectively. The comparable adsorption on fine particles of albite and quartz at pH 2 is explained by the interaction of ammonium ions on silanol groups by hydrogen bonding as well as electrostatic interactions. The changes in zeta potentials are in good agreement with the formation of ionic species and free molecular forms of the collector. The IR spectra show the coexistence of neutral oleic acid together with charged amine species at low pH values in accordance with the species distribution diagram. Selective flotation of albite is accomplished from a natural feldspar material with tallow diamine-dioleate collector at pH 2 using sulfuric acid, only when the feed is deslimed prior to the bench scale flotation tests. An albite recovery exceeding 85% is achieved from a feed material containing about 50% albite.

Adsorption↗

Asymmetric adsorption by quartz: a model for the prebiotic origin of optical activity.

One mechanism previously proposed for the abiotic accumulation of molecules of one chirality in nature is asymmetric adsorption on the chiral surfaces of optically active quartz crystals. Earlier literature in this field is reviewed, with the conclusion that previous investigations of this phenomenon, using optical rotation criteria, have afforded ambiguous results. We now have studied the adsorption of radioactive D- and L-alanine on powdered d- and l-quartz, using change in radioactivity level as a criterion for both gross and differential adsorption. d-Quartz preferentially adsorbed D-alanine from anhydrous dimethyl-formamide solution, and l-quartz L-alanine. The differential adsorption varied between 1.0 and 1.8%. The implications of these observations are discussed from the viewpoint of early chemical evolution and the origin of optically active organic compounds in nature.

Alanine↗

Pulmonary alveolar proteinosis in rats after administration of quartz: its possible role in morphogenesis of lung cancer.

In rats, primary peripheral lung tumors composed predominantly of alveolar type II cells have been induced by inhalation of alpha quartz. In our retrospective study on proliferation markers we evaluated lung specimens of 140 Wistar rats from larger experiments, which had been exposed to Dörentrup quartz (DQ12) by inhalation (10 mg/m3, 56 Weeks, 5 days/week, 7 h/day: n = 27) or intratracheal instillations (5 mg: n = 38; 20 mg: n = 10; 50 mg: n = 28; 15 x 3 mg: n = 12). In the last group 8/12 animals developed lung tumors. Animals were sacrificed 1-32 months after administration. For identification of an increased proliferation of alveolar type II cells the DNA content was monitored by microscopic (static) cytophotometry in histological slides. The argyrophil (AgNOR) method for the demonstration of nucleolar organizer regions (NOR) was used as second marker of type II cell proliferation. Measurements made 24 months after inhalation of DQ12 showed a slight increase of pneumocytic proliferation with 1.64 +/- 0.14 AgNOR/nucleus compared to the controls (1.23 +/- 0.04 mean AgNOR/nucleus). After intratracheal instillation of DQ12 a significant increase of AgNOR was found, e.g. 5 mg: 1.93 +/- 0.23 AgNOR/nucleus (6 months) and 1.96 +/- 0.19 (12 months); 50 mg: 1.77 +/- 15 (6 months) and 2.18 +/- 0.05 (12 months); 15 x 3 mg (+2 ml 2% polyvinylpyridine N-oxide s.c.): 1.81 +/- 0.13 AgNOR/nucleus (27-32 months). With the aid of the 2 c deviation index, i.e. the mean square deviation from the diploid DNA value, it was possible also to identify the pathologically increased proliferation of type II cells after intratracheal instillation of quartz: 0.02 +/- 0.01-0.06 +/- 0.04 c2 (controls); 0.07 +/- 0.04 c2 (5 mg/12 months); 0.12 +/- 0.08 c2 (15 x 3 mg/>27 months) and 0.68 +/- 0.48 c2 (50 mg/12 months). Only in the last group were nearly triploid values detected. Summarizing our results, intratracheal instillation and inhalation of quartz in rats regularly induces alveolar proteinosis and interstitial fibrosis in combination with a dose- and time-dependent increase of the type II cell proliferation rate. As mitogenesis increases carcinogenesis, alveolar proteinosis with increased pneumocytic proliferative activity might be a prerequisite for enhanced tumor development.

Animals↗

Up-regulation of antigens on alveolar macrophages in quartz exposed rats.

We have analysed the expression of the OX-6 and OX-42 antigens on alveolar macrophages in rats after intratracheal exposure to quartz. Eight female Sprague Dawley rats were included in the study. Four were exposed to physiological saline and four to quartz dust. The rats were sacrificed after 58 +/- 2 weeks and alveolar macrophages were harvested and analysed by flow cytometry. We found a significant higher amount of both antigens on alveolar macrophages harvested from quartz exposed rats. However, we did not find any significant difference in the percentage positive labeled cells between the two groups. We conclude that quartz dust induces up-regulation of functional receptors on alveolar macrophages in rats and that quantitative analysis of these receptors may serve as inflammatory markers in the bronchoalveolar space.

Animals↗

Cellular uptake and cytotoxic potential of respirable bentonite particles with different quartz contents and chemical modifications in human lung fibroblasts.

Considering the biological reactivity of pure quartz in lung cells, there is a strong interest to clarify the cellular effects of respirable siliceous dusts, like bentonites. In the present study, we investigated the cellular uptake and the cytotoxic potential of bentonite particles (Ø< 10 microm) with an alpha-quartz content of up to 6% and different chemical modifications (activation: alkaline, acidic, organic) in human lung fibroblasts (IMR90). Additionally, the ability of the particles to induce apoptosis in IMR90-cells and the hemolytic activity was tested. All bentonite samples were tested for endotoxins with the in vitro-Pyrogen test and were found to be negative. Cellular uptake of particles by IMR90-cells was studied by transmission electron microscopy (TEM). Cytotoxicity was analyzed in IMR90-cells by determination of viable cells using flow cytometry and by measuring of the cell respiratory activity. Induced apoptotic cells were detected by AnnexinV/Propidiumiodide-staining and gel electrophoresis. Our results demonstrate that activated bentonite particles are better taken up by IMR90-cells than untreated (native) bentonite particles. Also, activated bentonite particles with a quartz content of 5-6% were more cytotoxic than untreated bentonites or bentonites with a quartz content lower than 4%. The bentonite samples induced necrotic as well as apoptotic cell death. In general, bentonites showed a high membrane-damaging potential shown as hemolytic activity in human erythrocytes. We conclude that cellular effects of bentonite particles in human lung cells are enhanced after chemical treatment of the particles. The cytotoxic potential of the different bentonites is primarily characterized by a strong lysis of the cell membrane.

Air Pollutants↗

Application of a novel apparatus, the quartz chemical analyzer, to the determination of endotoxin in blood.

A novel apparatus called a quartz chemical analyzer (QCA) has been developed using a quartz crystal resonator. This apparatus measures sample viscosity changes based on resonant frequency changes of the quartz crystal. The apparatus was used to determine bacterial endotoxin concentrations by monitoring the gelation reaction of Limulus amebocyte lysate. The QCA determined endotoxin concentrations with good accuracy and reproducibility in the range of 0.001-3 EU/ml for endotoxin standard (JP XII). For endotoxin determination in human whole blood and plasma samples, the inhibitory reaction was eliminated by pretreatment of a fourfold dilution at 60 degrees C and incubation for 30 min. There are many advantages of the QCA method compared with the turbidimetric and chromogenic methods. For example, QCA can measure sample viscosity changes with high sensitivity and accuracy because QCA detects minor resonant frequency changes and the frequency data give a numerical value for easy quantitation. QCA can examine turbid samples, and the required quantities of samples and reagents are small, since the quartz crystal detects sample viscosity changes directly. The endotoxin determination time may be shortened by raising the reaction temperature, and QCA can detect other types of coagulation reactions.

Antithrombin III↗

Cytotoxic action of quartz dust on stimulated and nonstimulated peritoneal macrophages in vitro.

Quartz dust cytotoxicity was studied in starch-stimulated and nonstimulated mouse peritoneal macrophage cultures in vitro. Morphological changes, release of lactate dehydrogenase (LDH) into the culture medium, and lactate production were used as parameters of cell damage. Phagocytosis of quartz dust by macrophages increased cell detachment of both the stimulated and nonstimulated cells. Both cell types released significant amounts of LDH into the supernatant culture medium. The increased LDH release was more from stimulated dust-free and corundum- and quartz-exposed macrophages than from nonstimulated macrophages. There was no statistically significant difference in lactate production between stimulated and nonstimulated macrophage cultures in the presence or absence of quartz or corundum dust.

Aluminum Oxide↗

Monitoring of integrin-mediated adhesion of human ovarian cancer cells to model protein surfaces by quartz crystal resonators: evaluation in the impedance analysis mode.

The quartz crystal microbalance (QCM) was used to monitor specific, integrin-mediated adhesion of human ovarian cancer cells to distinct extracellular matrix (ECM) proteins immobilized on gold-coated quartz crystal resonators. The QCM was operated in the impedance analysis mode, where frequency shift as well as bandwidth are accessible on a broad range of overtones. The increase in bandwidth caused by covering the quartz resonator with cells was reproducible and largely independent of overtone order, whereas the frequency shift displayed some variability. Thus the bandwidth proved to be the more robust parameter for sensing cell adhesive events. The bandwidth increased in proportion to the number of seeded cells to the quartz crystal as long as the number was below 150,000 cells/ml. Comparing the resonance parameters on different harmonics, one finds that viscoelastic modeling with homogeneous layer systems cannot reproduce the results: lateral heterogeneity has to be taken into account. The differences in adhesive strength of human ovarian cancer cells towards selected ECM proteins monitored by QCM was in good agreement with data obtained by conventional cell adhesion assays. Strong cell adhesion was observed to the ECM proteins vitronectin (VN) and fibronectin (FN), while only weak attachment occurred on laminin. In order to prove specific, integrin alphavbeta3-mediated cell adhesion to its ligands FN and VN, the cyclic integrin alphavbeta3-directed peptide c(RGDfV) was used as competitor and significantly reversed cell adhesion. Since integrin interaction with ECM proteins is dependent on the presence of bivalent cations, cell detachment was also seen after treatment of cell monolayers with the chelator ethylene-dinitro-tetra-acetic acid (EDTA). The QCM technique is a reliable method to monitor cell adsorption to ECM-pretreated surfaces in real time. It may be an alternative tool for screening specific and selective antagonists of integrin/ECM interaction.

Biosensing Techniques↗

Comparative histopathological and biochemical analysis of early stages of exposure to non-silicogenic aluminium silicate- and strongly silicogenic quartz-dust in rats.

One group of male CFY rats was given bentonite with high aluminium silicate content, the other group was given quartz dust, intratracheally. It has been stated that between 12-72 hours after the dust-exposure, the histological reactions developing upon the effect of non-silicogenic bentonite and silicogenic quartz are identical. Similarly in both groups lipid and phospholipid content of the lung shows a slight increase; the composition of phospholipids does not alter due to the effect of the two dusts. Between 12-72 hours after the exposure to both dusts the inflammatory response characterizing the histological reaction consists mainly of leukocytes; while between 48-72 hours macrophages appear in large numbers. The dust particles are swallowed both by leukocytes and macrophages. The confluating bronchopneumonia developed at the end of the 72nd hour is characterized by necrosis. Ninety days after exposure, bentonite causes storage-focal tissue reaction and quartz produces progressive pulmonary fibrosis; due to the effect of quartz, the lipid and phospholipid content of the lung significantly increases, the ratio of phospholipid fractions alters; bentonite does not increase the amount of pulmonary lipid and phospholipid. On the basis of the strong aldehyde bisulphite-toluidine blue (ABT) positivity of the macrophages containing bentonite, it may be assumed that the bentonite particle surface has an oriented polysaccharide and/or protein coat released from necrotized leukocytes, which protects the macrophage from the strong cytotoxic (necrotizing) effect of bentonite.

Animals↗

Characteristics of acoustic plate modes on rotated Y-cuts of quartz utilized for biosensing applications.

Acoustic plate modes (APM) on various quartz substrates have been investigated in order to determine their usefulness for liquid-sensing applications. The modes have been characterized in terms of their mass sensitivity, mode separation, temperature sensitivity, and reproducibility of the experimental results. Promising characteristics are found for rotated Y-cuts of quartz with the direction of acoustic mode propagation being perpendicular to the X-axis of the quartz crystal. Experiments on the detection of immunochemical reactions are performed using different quartz APM sensors, and the results are compared to similar experiments utilizing APM devices on ZX-LiNbO3.

Animals↗