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Determination of the oxide layer thickness on beryllium metal particles.

The hypothesis was tested that beryllium metal particles have a uniformly thick surface coating of beryllium oxide and that smaller particles should have a higher oxide fraction by mass because they have a higher surface to volume ratio. The mass fraction of oxygen, physical density, and specific surface area were determined for size-fractionated samples of respirable beryllium metal particles. The largest particles analyzed (count median diameter 4.6 microns with geometric standard deviation 1.6) contained 7% +/- 1% beryllium oxide by mass; had a physical density of 1.90 +/- 0.02 g/cm3; and had a specific surface area of 4.0 +/- 0.3 m2/g. The smallest particles analyzed (count median diameter 0.4 micron with geometric standard deviation 1.8) contained 31% +/- 3% beryllium oxide by mass; had a physical density of 2.00 +/- 0.17 g/cm3; and had a specific surface area of 20.8 +/- 2.1 m2/g. These shifts in density and oxide content with size and surface area are consistent with a beryllium metal core of density 1.84 +/- 0.02 g/cm3 (1.848 g/cm3 is theoretical); a beryllium oxide layer of density of 2.53 +/- 0.16 g/cm3 (3.025 g/cm3 is the perfect crystalline density); and an oxide layer thickness of 49 +/- 4 A for all particle sizes. These results indicate that the inhalation toxicity of beryllium metal particles may be similar to that of beryllium oxide formed at low temperatures.

Berylliosis↗

Surface area of respirable beryllium metal, oxide, and copper alloy aerosols and implications for assessment of exposure risk of chronic beryllium disease.

The continued occurrence of chronic beryllium disease (CBD) suggests the current occupational exposure limit of 2 microg beryllium per cubic meter of air does not adequately protect workers. This study examined the morphology and measured the particle surface area of aerodynamically size-separated powders and process-sampled particles of beryllium metal, beryllium oxide, and copper-beryllium alloy. The beryllium metal powder consisted of compact particles, whereas the beryllium oxide powder and particles were clusters of smaller primary particles. Specific surface area (SSA) results for all samples (N=30) varied by a factor of 37, from 0.56 +/- 0.07 m(2)/g (for the 0.4-0.7 microm size fraction of the process-sampled reduction furnace particles) to 20.8 +/- 0.4 m(2)/g (for the </=0.4 microm size fraction of the metal powder). Large relative differences in SSA were observed as a function of particle size for the powder of beryllium metal, from 4.0 +/- 0.01 m(2)/g (for the particle size fraction >6 microm) to 20.8 +/- 0.44 m(2)/g (for the particle size fraction </=0.4 microm). In contrast, little relative difference in SSA (<25%) was observed as a function of particle size for the beryllium oxide powder and particles collected from the screening operation. The SSA of beryllium metal powder decreases with increasing particle size, as expected for compact particles, and the SSA of the beryllium oxide powders and particles remains constant as a function of particle size, which might be expected for clustered particles. These associations illustrate how process-related factors can influence the morphology and SSA of beryllium materials. To avoid errors in predicting bioavailability of beryllium and the associated risks for CBD, the mechanisms of particle formation should be understood and the SSA of beryllium particles should be measured directly.

Aerosols↗

Characterization of physicochemical properties of beryllium aerosols associated with prevalence of chronic beryllium disease.

Little is known about the physicochemical properties of beryllium aerosols associated with increased risk of beryllium sensitization and chronic beryllium disease (CBD). Such information is needed to evaluate whether airborne mass of beryllium is the appropriate metric of exposure or alternatively to provide a scientific basis for using information on particle size, surface area, and chemistry to support an improved exposure limit based on bioavailability through the inhalation and dermal routes of exposure. Thus, we used a suite of analytical techniques to characterize aerodynamically size-fractionated beryllium particles and powders that have been associated in epidemiological studies with higher prevalence of CBD. Aerosol particles were sampled from the ventilation systems of production lines for powders of beryllium metal and beryllium oxide and for ingots of copper-beryllium alloy. End product powders from the metal and oxide production lines were also collected. Particles released during production of beryllium metal were found to be complex, having heterogeneous composition, including reactive species such as fluorine. Powders from beryllium metal production were of high purity with only a minor component of beryllium oxide. Both particles and powders from oxide production were high-purity oxide. Particles released during production of copper-beryllium alloy were heterogeneous, being predominantly copper oxides. Thus, all particles and powders contain at least some beryllium in the form of beryllium oxide. These data justify efforts to thoroughly characterize beryllium aerosol properties when performing exposure assessments. The data also suggest that differences in particle chemical composition, size, number, and surface area may influence bioavailability of beryllium and contribute to risk of CBD. However, a scientific basis does not yet exist to replace mass as the current metric of exposure.

Aerosols↗

Effects of asbestos and beryllium on release of alveolar macrophage enzymes.

Rabbit alveolar macrophages were exposed in culture medium to asbestos, beryllium sulfate, and beryllium oxide. The specific activities of the lysosomal hydrolases, acid phosphatase beta-N-acetylglucosaminidase and beta-glucuronidase plus the glycolytic enzyme, phosphohexose isomerase were determined in the medium, whole-cell homogenates, mitochondrial fractions, and supernatant. These hydrolases increased significantly in the medium but not in the mitochondrial fraction of cells exposed to dusts. Asbestos and beryllium sulfate were highly cytotoxic for alveolar macrophages in vitro and the data suggested that these agents were not associated with an increase in enzyme synthesis but rather a direct cytotoxic effect at the macrophage membrane level. For induction of enzyme release in vitro, a higher concentration of beryllium oxide was needed when compared with asbestos and beryllium sulfate. The cytotoxicity and enzyme release induced by these agents may represent an important nonspecific mechanism by which they induce inflammation and perhaps local proliferation of fibroblasts.

Acetylglucosaminidase↗

A theoretical framework for evaluating analytical digestion methods for poorly soluble particulate beryllium.

Complete digestion of all chemical forms and sizes of particulate analytes in environmental samples is usually necessary to obtain accurate results with atomic spectroscopy. In the current study, we investigate the physicochemical properties of beryllium particles likely to be encountered in samples collected from different occupational environments and present a hypothesis that a dissolution theory can be used as a conceptual framework to guide development of strategies for digestion procedures. For monodisperse single-chemical constituent primary particles, such as those encountered when handling some types of beryllium oxide (BeO) powder, theory predicts that a digestion procedure is sufficient when it completely dissolves all primary particles, independent of cluster size. For polydisperse single-chemical constituent particles, such as those encountered during the handling of some types of beryllium metal powder, theory predicts that a digestion procedure is sufficient only when it completely dissolves the largest particle in the sample. For samples with unknown or multi-chemical constituent particles and with particles having undefined sizes, e.g., fume emissions from a copper-beryllium alloy furnace operation or dust from a beryl ore crushing operation, a surface area-limited and single-constituent-dependent dissolution theory may not predict complete dissolution, thereby requiring non-routine robust treatment procedures with post-digestion filtration, followed by examination of residual particulate material. Additionally, for beryllium, and likely other poorly soluble materials, particulate reference materials of various chemical forms and size distributions are needed to better evaluate and harmonize analytical digestion procedures. Figure Generation of aerosol particles during machining of beryllium oxide.

Aerosols↗

The effect of beryllium compound solubility on in vitro canine alveolar macrophage cytotoxicity.

Pulmonary alveolar macrophage cells (PAM), obtained by bronchopulmonary lavage of Beagle dogs, were exposed in vitro to beryllium oxide (BeO) particles calcined at either 500 or 1000 degrees C or to beryllium sulfate (BeSO4). Cell viability was determined by trypan blue dye exclusion after 20 h in culture. The most toxic material tested was BeSO4, followed by BeO calcined at 500 degrees C, then BeO calcined at 1000 degrees C. An in vitro dissolution technique was used to measure the relative solubility of the BeO particles. The BeO prepared at 500 degrees C exhibited greater solubility compared with BeO prepared at 1000 degrees C. This study extends previous work by examining the effects of beryllium compounds on canine PAM, and by relating PAM cytotoxicity with measured values of beryllium compound solubility.

Animals↗

Differences in dissolution behavior in a phagolysosomal simulant fluid for single-constituent and multi-constituent materials associated with beryllium sensitization and chronic beryllium disease.

Particle dissolution within macrophage phagolysosomes is hypothesized to be an important source of dissolved beryllium for input to the cell-mediated immune reaction associated with development of beryllium sensitization and chronic beryllium disease (CBD). To better understand the dissolution of beryllium materials associated with elevated prevalence of sensitization and CBD, single-constituent (beryllium oxide (BeO) particles sampled from a screener operation, finished product BeO powder, finish product beryllium metal powder) and multi-constituent (particles sampled from an arc furnace during processing of copper-beryllium alloy) aerosol materials were studied. Dissolution rates were measured using phagolysosomal simulant fluid (PSF) in a static dissolution technique and then normalized to measured values of specific surface area to calculate a chemical dissolution rate constant (k) for each material. Values of k, in g/(cm2 day), for screener BeO particles (1.3 +/- 1.9 x 10(-8)) and for BeO powder (1.1 +/- 0.5 x 10(-8)) were similar (p = 0.45). The value of k observed for beryllium metal powder (1.1 +/- 1.4 x 10(-7)) was significantly greater than observed for the BeO materials (p < 0.0003). For arc furnace particles, k (1.6 +/- 0.6 x 10(-7)) was significantly greater than observed for the BeO materials (p < 0.00001), despite the fact that the chemical form of beryllium in the aerosol was BeO. These results suggest that dissolution of beryllium differs among physicochemical forms of beryllium and direct measurement of dissolution is needed for multi-constituent aerosol. Additional studies of the dissolution behavior of beryllium materials in a variety of mixture configurations will aid in developing exposure-response models to improve understanding of the risk of beryllium sensitization and CBD.

Aerosols↗

Beryllium sensitization, chronic beryllium disease, and exposures at a beryllium mining and extraction facility.

In this study, we examine beryllium sensitization, chronic beryllium disease (CBD), and workplace exposures at a beryllium mining (mine) and extraction facility (mill) in Delta, Utah. Historical airborne beryllium data collected between 1970-1999 included general area (GA), breathing zone (BZ), and personal lapel (LP) measurements and calculations of job-specific quarterly daily-weighted averages (DWVAs). We compared GA, BZ, and DWA data to airborne beryllium data from a mixed beryllium products facility and a beryllium ceramics facility located in Elmore, Ohio and Tucson, Arizona, respectively. At the Delta facility, jobs involving beryllium hydrolysis and wet-grinding activities had the highest air concentrations; annual median GA concentrations were less than 0.3 microg/m3 or both areas. Annual median GA sample concentrations ranged from 0.1-0.4 microg/m(-3) at Delta. These levels were generally lower than Elmore (0.1-1.0 microg/m3) and were comparable to the Tucson facility (0.1-0.4 microg/m3). Median BZ concentrations were higher, whereas DWAs were lower at the Delta facility than at the other two facilities. Among the 87 employees at the Delta facility, 75 participated in the medical survey; there were three persons sensitized, one with CBD. The individual with CBD previously worked at the Elmore facility for 10 years. Cumulative CBD incidence rates were significantly lower at the Delta facility: 0.3 percent compared to 2.0 percent for Elmore and 2.5 percent for the Tucson facility. Sensitization and CBD prevalence rates determined from cross-sectional surveys for the Delta facility were lower than but not significantly different from rates at the other two facilities. There was no sensitization or CBD among those who worked only at the mine where the only exposure to beryllium results from working with bertrandite ore. Although these results are derived from a small sample, this study suggests that the form of beryllium may affect the likelihood of developing CBD. Specifically, exposure to beryl and bertrandite ore dusts or to beryllium salts, in the absence of exposure to beryllium oxide particulates appears to pose a lower risk for developing CBD.

Adult↗

Experimental beryllium-induced lung disease. I. Differences in immunologic responses to beryllium compounds in strains 2 and 13 guinea pigs.

Granulomatous lung disease was produced in strain 2 but not strain 13 guinea pigs by endotracheal injection of beryllium oxide (BeO), although isolated multinucleated giant cells containing crystalline material were found in lungs of both strains. Disease was also produced in (2 x 13) F1 hybrids, but of a milder form than in strain 2. In BeO-treated strain 2 and F1 animals, challenge with beryllium salts produced delayed hypersensitivity skin reactivity, and in vitro, enhanced tritiated thymidine uptake and lymphokine production by lymph node cells. No evidence was found for involvement of humoral immunity in the disease. Responses were not seen in BeO-treated strain 13 guinea pigs, and immunization of animals with BeO in complete Freund's adjuvant produced similar immunologic findings. These data emphasize the involvement of genetically determined cellular immune mechanisms in beryllium lung disease.

Animals↗

Validation of a standardized portable fluorescence method for determining trace beryllium in workplace air and wipe samples.

Beryllium is widely used in industry for its unique properties; however, occupational exposure to beryllium particles can cause potentially fatal disease. Consequently, exposure limits for beryllium particles in air and action levels on surfaces have been established to reduce exposure risks for workers. Field-portable monitoring methods for beryllium are desired in order to facilitate on-site measurement of beryllium in the workplace, so that immediate action can be taken to protect human health. In this work, a standardized, portable fluorescence method for the determination of trace beryllium in workplace samples, i.e., air filters and dust wipes, was validated through intra- and inter-laboratory testing. The procedure entails extraction of beryllium in 1% ammonium bifluoride (NH(4)HF(2), aqueous), followed by fluorescence measurement of the complex formed between beryllium ion and hydroxybenzoquinoline sulfonate (HBQS). The method detection limit was estimated to be less than 0.02 microg Be per air filter or wipe sample, with a dynamic range up to greater than 10 microg. The overall method accuracy was shown to satisfy the accuracy criterion (A< or = +/-25%) for analytical methods promulgated by the US National Institute for Occupational Safety and Health (NIOSH). Interferences from numerous metals tested (in >400-fold excess concentration compared to that of beryllium) were negligible or minimal. The procedure was shown to be effective for the dissolution and quantitative detection of beryllium extracted from refractory beryllium oxide particles. An American Society for Testing and Materials (ASTM) International voluntary consensus standard based on the methodology has recently been published.

Air Pollutants↗

[EPR and TL measurements of BeO "Termalox 995" irradiated with photons].

Beryllium oxide dosimeters (Termalox 995) have been irradiated (at 60-Co facility) with graduated doses from 3 X 10(-1) to 1 X 10(2) Gy (30 to 10.000 rad). EPR measurements show a very good linear correlation between the amplitude of signal and the absorbed dose. This method has the advantage that the stored information into dosimeter doesn't regress "after reading procedure".

Beryllium↗

Measurement of radiation from photochemotherapy equipment using thermoluminescence detector elements (BeO TLD).

The results of experimental dosimetry carried out with beryllium oxide thermoluminiscent material (BeO TLD) are presented. In particular, this material shows a good linearity of response to UV radiation at 365 nm, up to 200 mJ/cm2, and a spectral sensitivity with a peak at 340 nm. The advantages and disadvantages of BeO TLD in comparison with solid state detectors are discussed and suggested for personal and environmental dosimetry of UVA radiation in photochemotherapy.

Beryllium↗