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Nitrate-cancrinite precipitation on quartz sand in simulated Hanford tank solutions.

Caustic NaNO3 solutions containing dissolved Al were reacted with quartz sand at 89 degrees C to simulate possible reactions between leaked nuclear waste and primary subsurface minerals at the U.S. Department of Energy's Hanford site in Washington. Nitrate-cancrinite began to precipitate onto the quartz after 2-10 days, cementing the grains together. Estimates of the equilibrium constant for the precipitation reaction differ for solutions with 0.1 or 1.0 m OH- (log Keq = 30.4 +/- 0.8 and 36.2 +/- 0.6, respectively). The difference in solubility may be attributable to more perfect crystallinity (i.e., fewer stacking faults) in the higher-pH cancrinite structure. This is supported by electron micrographs of crystal morphology and measured rates of Na volatilization under an electron beam. Precipitate crystallinity may affect radionuclide mobility, because stacking faults in the cancrinite structure can diminish its zeolitic cation exchange properties. The precipitation rate near the onset of nucleation depends on the total Al and Si concentrations in solution. The evolution of experimental Si concentrations was modeled by considering the dependence of quartz dissolution rate on AI(OH)4- activity, cancrinite precipitation, and the reduction of reactive surface area of quartz due to coverage by cancrinite.

Aluminum↗

Spatial variation in deposition rate coefficients of an adhesion-deficient bacterial strain in quartz sand.

The transport of bacterial strain DA001 was examined in packed quartz sand under a variety of environmentally relevant ionic strength and flow conditions. Under all conditions, the retained bacterial concentrations decreased with distance from the column inlet at a rate that was faster than loglinear, indicating that the deposition rate coefficient decreased with increasing transport distance. The hyperexponential retained profile contrasted againstthe nonmonotonic retained profiles that had been previously observed for this same bacterial strain in glass bead porous media, demonstrating that the form of deviation from log-linear behavior is highly sensitive to system conditions. The deposition rate constants in quartz sand were orders of magnitude below those expected from filtration theory, even in the absence of electrostatic energy barriers. The degree of hyperexponential deviation of the retained profiles from loglinear behavior did not decrease with increasing ionic strength in quartz sand. These observations demonstrate thatthe observed low adhesion and deviation from log-linear behavior was not driven by electrostatic repulsion. Measurements of the interaction forces between DA001 cells and the silicon nitride tip of an atomic force microscope (AFM) showed that the bacterium possesses surface polymers with an average equilibrium length of 59.8 nm. AFM adhesion force measurements revealed low adhesion affinities between silicon nitride and DA001 polymers with approximately 95% of adhesion forces having magnitudes < 0.8 nN. Steric repulsion due to surface polymers was apparently responsible for the low adhesion to silicon nitride, indicating that steric interactions from extracellular polymers controlled DA001 adhesion deficiency and deviation from log-linear behavior on quartz sand.

Bacterial Adhesion↗

The role of quartz in the origin of optical activity on earth.

A thorough analysis of literature data on distribution of right and left quartz in many locations on the surface of Earth indicates that quartz enantiomorph crystals are distributed in equal amounts in all locations. Therefore optically active quartz crystals of one or the other enantiomorph could not serve as the source of homochirality in the evolution of biosphere. Hence the calculation of a PVED based on published 'small excess of left quartz crystals' on Earth lacks a sound physical basis.

Crystallization↗

Effect of two particle surface-modifying agents, polyvinylpyridine-N-oxide and carboxymethylcellulose, on the quartz and asbestos mineral fiber-induced production of reactive oxygen metabolites by human polymorphonuclear leukocytes.

We studied the capacity of quartz and asbestos fibers to induce the generation of reactive oxygen metabolites in human polymorphonuclear leukocytes (PMNs) with a chemiluminescence (CL) assay. On an equal weight basis, the particulates induced CL in the following order of magnitude: chrysotile, quartz greater than amosite, crocidolite, greater than anthophyllite, wollastonite. The intensity of CL correlated positively with the Alcian blue (a cationic dye) binding capacity of the particles. Polyvinylpyridine-N-oxide (0.5 microgram/ml) inhibited completely the CL induced by quartz but had little effect on the CL induced by asbestos fibers. Carboxymethylcellulose (1.0 microgram/ml), however, reduced the CL caused by chrysotile asbestos but had no effect on the CL induced by the other particulates. Our results suggest that in addition to length and diameter, the effect of quartz and asbestos fibers on inflammatory cells will depend on surface characteristics, including the charge of the particles.

Adult↗

Effects of simulated pulmonary surfactant on the cytotoxicity and DNA-damaging activity of respirable quartz and kaolin.

Respirable-sized quartz and kaolin dusts were pretreated with simulated pulmonary surfactant dispersions of dipalmitoyl phosphatidylcholine (DPPC) in saline to model the conditioning of particles depositing in alveolar regions of the lung. DPPC-treated and untreated dusts were used to challenge lavaged rat pulmonary alveolar macrophages in vitro. Cytotoxicity was determined over a 5-d period using both total and viable cell counts from a fluorescence-based viability assay. DNA damage, as an indication of genotoxicity, was determined over a 7-d period by the single-cell gel electrophoresis assay. Untreated quartz and kaolin both expressed a significant and potent cytotoxicity, which increased with concentration and time. DPPC-surfactant pretreatment delayed significant expression of this cytotoxicity until 3 to 5 d after challenge. Untreated quartz also caused DNA damage, which increased with concentration and time. DPPC-surfactant treatment of quartz delayed most DNA damage expression to 5 and 7 d. Untreated kaolin expressed weaker activity for DNA damage, significant at the highest concentration through 5 d, and at the higher concentrations on d 7. Surfactant treatment delayed most kaolin activity for DNA damage to 7 d after challenge.

1,2-Dipalmitoylphosphatidylcholine↗

Clara-cell hyperplasia after quartz and coal-dust instillation in rat lung.

Bronchiolo-alveolar hyperplasia of type II cells in rat lungs after particle exposure is a well-known preneoplastic lesion. The Clara cell, stem cell of the bronchiolar epithelium and the main carrier of cytochrome P-450 isoenzyme system in the lung, has barely been evaluated with regard to this effect. The aim of this study was to examine Clara-cell hyperplasia after particle exposure and to characterize cell proliferation and its normal function. Female Wistar rats were intratracheally instilled with coal dust samples of variable quartz content, quartz (DQ12), titanium dioxide, or saline solution containing 0.5% Tween 80. After 126-129 wk, all coal mine dust- and quartz-exposed animals developed Clara-cell hyperplasia: up to 0.48% of the total lung area, which was significantly increased compared to titanium dioxide (p <.05) and control (p <.03) animals. Proliferation and hyperplasia of bronchiolar Clara cells by coal dusts was independent of their quartz content. The lack of proliferating cell nuclear antigen staining in most of the hyperplastic Clara cells suggests that following damage of alveolar epithelial cells, Clara cells migrate in and remodulate the alveolar epithelium. After the migration they keep their function in the xenobiotic metabolism, as shown by expansion of CYP2E1 active Clara cells. The minor development of Clara-cell hyperplasia in titanium dioxide-treated rats indicates that this is not a general particle effect, and is possibly due to its lower toxicity to epithelial cells.

Animals↗

Cytotoxic effects of quartz and chrysotile asbestos: in vitro interspecies comparison with alveolar macrophages.

Cytotoxic effects of DQ12 quartz and chrysotile asbestos on alveolar macrophages of different animal species were compared in vitro. The type of cell reaction toward the cytotoxic dusts was always the same: a loss of cell viability (trypan blue dye exclusion test) was accompanied by the release of cytoplasmic and lysosomal enzymes. The extent of cellular destruction depended upon the amount of dust applied. In the range of 50-100 micrograms/ml quartz or chrysotile asbestos, species-specific variations were observed in the sensitivity of the cells. At this concentration alveolar macrophages of dogs, monkeys, and human patients were damaged to a greater extent than the cells from rats and cattle. Simultaneous incubation of the cells with quartz and L-alpha-dipalmitoyl lecithin resulted in a reduction of the cytotoxic quartz effect. The extent of the protective effect varied according to the species. In the case of chrysotile asbestos no reduction of the fibers cytotoxicity was observed in the presence of L-alpha-dipalmitoyl lecithin.

Acetylglucosaminidase↗

Variability in quartz exposure in the construction industry: implications for assessing exposure-response relations.

The aims of this study were to determine implications of inter- and intraindividual variation in exposure to respirable (quartz) dust and of heterogeneity in dust characteristics for epidemiologic research in construction workers. Full-shift personal measurements (n = 67) from 34 construction workers were collected. The between-worker and day-to-day variances of quartz and respirable dust exposure were estimated using mixed models. Heterogeneity in dust characteristics was evaluated by electron microscopic analysis and electron spin resonance. A grouping strategy based on job title resulted in a 2- and 3.5-fold reduction in expected attenuation of a hypothetical exposure-response relation for respirable dust and quartz exposure, respectively, compared to an individual based approach. Material worked on explained most of the between-worker variance in respirable dust and quartz exposure. However, for risk assessment in epidemiology, grouping workers based on the materials they work on is not practical. Microscopic characterization of dust samples showed large quantities of aluminum silicates and large quantities of smaller particles, resulting in a D(50) between 1 and 2 microm. For risk analysis, job title can be used to create exposure groups, although error is introduced by the heterogeneity of dust produced by different construction workers activities and by the nonuniformity of exposure groups. A grouping scheme based on materials worked on would be superior, for both exposure and risk assessment, but is not practical when assessing past exposure. In dust from construction sites, factors are present that are capable of influencing the toxicological potency.

Construction Materials↗

Assessment of exposure to quartz, cristobalite and silicon carbide fibres (whiskers) in a silicon carbide plant.

The main objective of the present paper is to report on the concentration of silicon carbide (SiC) fibres, crystalline silica and respirable dust in a Canadian SiC production plant and to compare the results with earlier investigations. The second objective is to tentatively explain the differences in concentration of the fibrogenic substances between different countries. The assessment of SiC fibres, dusts, respirable quartz and cristobalite was performed according to standard procedures. The highest 8 h time-weighted average concentrations of fibres were found among the crusher and backhoe attendants and the carboselectors with an arithmetic mean of 0.63 fibres ml(-1) for the former group and 0.51 fibres ml(-1) for the latter group. The results of respirable SiC fibres in the Canadian plant were lower than in the Norwegian and Italian industries. Most of the 8 h time-weighted average concentrations for quartz were less than or around the limit of detection of 0.01 mg m(-3). The maximum 8 h time-weighted average concentration for quartz was found among the carboselectors (0.157 mg m(-3)), followed by the labourers (0.032 mg m(-3)). Similarly, most of the 8 h time-weighted average cristobalite measurements were less than the limit of detection of 0.01 mg m(-3) except for the carboselectors where it was found to be 0.044 mg m(-3). The assessment of the Italian occupational settings exposure demonstrated elevated quartz concentrations, while cristobalite was absent. The authors have concluded that the investigations that were performed in the last two decades in this field by researchers from different countries seem to support that SiC fibres (whiskers) constitute a major airborne health hazard.

Air Pollutants, Occupational↗

Retrospective dosimetry: dose evaluation using unheated and heated quartz from a radioactive waste storage building.

In the assessment of dose received from a nuclear accident, considerable attention has been paid to retrospective dosimetry using heated materials such as household ceramics and bricks. However, unheated materials such as mortar and concrete are more commonly found in industrial sites and particularly in nuclear installations. These materials contain natural dosemeters such as quartz, which usually is less sensitive than its heated counterpart. The potential of quartz extracted from mortar in a wall of a low-level radioactive-waste storage facility containing distributed sources of 60Co and 137Cs has been investigated. Dose-depth proliles based on small aliquots and single grains from the quartz extracted from the mortar samples are reported here. These are compared with results from heated quartz and polymineral fine grains extracted from an adjacent brick, and the integrated dose recorded by environmental TLDs.

Construction Materials↗

Simulation of the experimental pre-dose technique for retrospective dosimetry in quartz.

The pre-dose technique of thermoluminescence for quartz has been used extensively for retrospective dosimetry of quartz and other natural materials. A recently published model that is a modification of the well-known Zimmerman theory is used here to simulate the complete sequence of experimental steps taken during the additive dose version of the pre-dose technique. The results of simulation show how the method can reproduce accurately the accumulated dose or paleodose received by the sample. The solution of the kinetic differential equations elucidates the various electron and hole processes taking place during the experimental pre-dose procedure and shows clearly the mechanism of hole transfer from the reservoir to the luminescence centre caused by heating to the activation temperature. The numerical results show that the pre-dose technique can reproduce the paleodose with an accuracy of +/- 1-5%, even when the paleodose is varied over more than an order of magnitude. New quantitative results are presented for the effect of the test dose and of the calibration beta dose, beta, on the accuracy of the pre-dose technique. The conclusions drawn from the simple model for quartz can be used to make improvements to more general quartz models.

Calibration↗

On the defensive action of glutamate against the cytotoxicity and fibrogenicity of quartz dust.

The cytotoxic action of quartz (DQ12) particles on cultures of rat peritoneal macrophages, as estimated by the inhibition of the TTC-reductase activity, is considerably reduced by preincubation with glutamic acid and by adding sodium glutamate (15 mg/ml) to the drinking water of the rats donating the macrophages. This increase in macrophage resistance under the influence of glutamate is the most probable cause of the delay in the development of silicotic fibrosis shown in several experiments on rats intratracheally injected with quartz and then treated by prolonged administration of glutamate. This effect is probably connected with the influence of glutamate on the stability of the macrophage membranes, which can in its turn be explained by different mechanisms, including the influence on the synthesis and phosphorylation of adenosine nucleotides. Such an influence was shown in rats receiving glutamate by the change of the ATP/ADP ratio in macrophages, but not in erythrocytes. The resistance of rat erythrocytes to the haemolytic action of quartz is also not influenced by the action of glutamate neither in vitro nor in vivo. Such differences in the influences of glutamate on two types of cells, equally susceptible to quartz cytotoxicity but considerably differing in the character of energy metabolism, is an indirect proof of the role of the latter in the realisation of the anticytotoxic, and thereby antifibrogenic, effect of glutamate.

Animals↗

Rat alveolar and interstitial macrophages in the fibrosing stage following quartz exposure.

Exposure to quartz induces pulmonary inflammation and development of fibrosis. In order to study the fibrosing process, we investigated morphology, function and phenotype of alveolar (AMs) and interstitial (IMs) macrophages at an early stage of fibrosis in rats. Rats were exposed by intratracheal instillations of 10 mg quartz (n=8) or saline (n=8) and studied 3 months later. AMs were obtained by bronchoalveolar lavage and IMs by mechanical fragmentation, followed by enzymatic digestion of lung tissue. Histology revealed subacute silicosis, with early focal fibrosis and alveolar lipoproteinosis. AM quartz exposure increased phagocytic activity and expression of major histocompatibility complex (MHC) Ia antigens, the latter being associated with cellular antigen presenting capacity. IM had an even more pronounced expression of MHC than AM after quartz exposure. Both macrophage fractions had a higher expression of OX-42 (complement receptor 3, CR3) than controls, but the increase in the IM fraction might be explained by the remaining AM in the IM fraction. Exposed AM adhered less to extracellular matrix components (vitronectin and fibronectin) than controls. In contrast, the adhesion of IM to vitronectin increased after exposure. Besides increased adhesion, the effects on IM were scarce. Our results therefore do not support the hypothesis that IM has a key role in the process of inflammation, including fibrosis.

Animals↗

Measurement of fluid viscosity at microliter volumes using quartz impedance analysis.

The purpose of this work was to measure viscosity of fluids at low microliter volumes by means of quartz crystal impedance analysis. To achieve this, a novel setup was designed that allowed for measurement of viscosity at volumes of 8 to 10 microL. The technique was based on the principle of electromechanical coupling of piezoelectric quartz crystals. The arrangement was simple with measurement times ranging from 2 to 3 minutes. The crystal setup assembly did not impose any unwanted initial stress on the unloaded quartz crystal. Quartz crystals of 5- and 10-MHz fundamental frequency were calibrated with glycerol-water mixtures of known density and viscosity prior to viscosity measurements. True frequency shifts, for the purpose of this work, were determined followed by viscosity measurement of aqueous solutions of sucrose, urea, PEG-400, glucose, and ethylene glycol at 25 degrees C +/- 0.5 degrees C. The measured viscosities were found to be reproducible and consistent with the values reported in the literature. Minor inconsistencies in the measured resistance and frequency shifts did not affect the results significantly, and were found to be experimental in origin rather than due to electrode surface roughness. Besides, as expected for a viscoelastic fluid, PEG 8000 solutions, the calculated viscosities were found to be less than the reported values due to frequency dependence of storage and loss modulus components of complex viscosity. From the results, it can be concluded that the present setup can provide accurate assessment of viscosity of Newtonian fluids and also shows potential for analyzing non-Newtonian fluids at low microliter volumes.

Electric Impedance↗

Aluminum lactate treatment alters the lung biological activity of quartz.

Previous studies of surface modification of quartz particles have suggested that the biological activity of silica is at least in part related to its surface properties. In the present study, we exposed the tracheal lobe of 8 sheep to either 100 ml saline (saline group), 100 mg of quartz (Minusil-5) in 100 ml saline (SI group) or 100 mg of Al lactate treated quartz in 100 ml saline (SI-Al group). The 24 sheep were studied by bronchoalveolar lavage at days 0, 12, 24, 40, 60 and by autopsy at day 60. In the saline group, BAL analyses were as previously reported [1]. In the SI group, we found significant and sustained increases in total BAL cells (x 2, P less than 0.05), macrophages and lymphocytes (x 2, P less than 0.05), neutrophils (x 5-10, P less than 0.01), IgG (x 1.2-1.8, P less than 0.05), fibronectin (x 2-3, P less than 0.05), lactate dehydrogenase (x 3, P less than 0.01) and alkaline phosphatase (x 2, P less than 0.05). Histologically, a macrophagic and lymphocytic alveolitis was observed at day 60. In the SI-Al group, these changes were significantly attenuated and in the above parameters, SI-Al group did not differ from saline group after day 24. These data of BAL and histology of the sheep tracheal lobe model document clearly that aluminum lactate treatment alters the biological activity of quartz.

Animals↗

Quartz exposure, retention, and early silicosis in sheep.

The purposes of this study were (1) to investigate the chronology of events in cellular and biochemical changes thought to be important in the development of silicosis, (2) to relate these to changes in lung function and radiograph, and (3) to evaluate the relation of quartz exposure and retention to individual response leading to early silicosis. Thirty-six sheep were exposed by repeated intratracheal infusion at 10-day intervals to 100 mg Minusil-5 in 100 ml saline (Si group), and 10 sheep were exposed at the same intervals to 100 ml saline (control). All sheep were investigated at 3-month intervals by chest radiograph, lung function, and lung lavage. At month 9, chest radiograph score of parenchymal opacities was significantly increased at 2.8 +/- 0.6 versus 0.4 +/- 0.4 in the Si group (p less than .05), establishing early radiologic silicosis. Lung function was significantly altered with reduction in lung compliance, vital capacity, and diffusion capacity (p less than .05). Lung lavage cellularity revealed significant increase in total cells (X 2.5), macrophages (X3), and neutrophils (X3). Albumin in BAL remained at the control level. Fibronectin production was significantly increased, as was the fibroblast growth activity, without significant change in procollagen 3 at this early stage of disease. Total phospholipids were significantly elevated in the Si-exposed sheep, and the profile demonstrated an increase in all the phospholipid components. Spontaneous release of hydrogen peroxide by alveolar cells was not increased, but in the presence of phorbol myristate acetate (PMA) higher levels of peroxide were found in the quartz-exposed sheep (p less than .05). The cellular and biochemical alterations of lung lavage preceded other changes. At month 12, there were good correlations (r greater than .49, p less than .001) between parameters evaluating related phenomena but poor correlations between measurements evaluating different aspects of the disorder. To investigate the heterogeneity in the individual response of sheep to the same exposure (susceptibility), individual quartz retention levels at month 12 were measured and found to correlate well with individual parameters of disease activity. We concluded that in early silicosis of sheep, cellular and biochemical changes in lung lavage preceded derangements of pulmonary function and radiographic abnormalities. Thereafter, parameters of lung lavage, lung function, and radiograph were significantly interrelated, but for a given exposure the degree of quartz retention appeared to determine the intensity of the silicotic process.

Animals↗

Determination of quartz on membrane filters by X-ray diffraction.

An X-ray diffraction method is described for the quantitative determination of quartz in dust samples. The analysis was done directly on a collecting cellulose ester membrane filter of the type used in an air sampler. Quantitation was achieved by the measurement of the quartz line intensities with a digital integrator and by the comparison of these values with those measured from calibration standards prepared on similar filters with water suspensions. The overall precision of the procedure was 8%. When the method was applied to foundry dusts, the accuracy of the quartz analysis was fou,d to be within 10% at the 1- to 10-mg level of total loading. The detection limit for quartz was below 0.1 mg.

Air Pollutants↗

In vitro and in vivo tests for determination of the pathogenicity of quartz, diatomaceous earth, mordenite and clinoptilolite.

The effects of samples of crystalline quartz, diatomaceous earth, mordenite and clinoptilolite were investigated in vitro (as concerns erythrocyte haemolysis and lactate dehydrogenase (LDH) release from peritoneal macrophages) and in vivo (on LDH, protein and phospholipids in rat bronchoalveolar lavage (BAL), and phospholipids in rat lung tissue). The respirable mineral samples were instilled intratracheally. Determinations in the BAL were carried out after 15, 60 and 180 days, and in the lung tissue after 90, 180 and 360 days. Quartz DQ and quartz FQ induced acute, subacute and chronic inflammation and progressive fibrosis. However, due to the Al2O3 contamination on the surface of the particles quartz FQ caused a delayed response in vivo. Diatomaceous earth produced acute/subacute inflammation that gradually became more moderate after 60 days. Clinoptilolite was inert, whereas the other zeolite sample, mordenite, was cytotoxic in vivo. The reason for this was presumably the needle and rod-shaped particles in the mordenite samples. The investigation revealed that different in vitro and in vivo methods canprovide valuable data concerning the pulmonary toxicity of minerals.

Aluminum Silicates↗