Beryllium Industry Research Articles

Solvent extraction and recovery of beryllium from hydrochloric acid solution with naphthenic acid

Beryllium is an essential metal for strategic purposes but remains an under-explored element. The separation of beryllium and aluminium and the purification of beryllium hydroxide from a multi-component solution has always been a challenging task in the beryllium industry and offers great research potential in academic fields. In this research, a solvent extraction method was used to purify and recover beryllium from trace impurities. A systematic investigation of the extraction process revealed that under optimal conditions, 98.66% of the beryllium was extracted in a three-stage countercurrent extraction using naphthenic acid (NA) as the extractant. The aluminium, iron and other trace impurities in the organic phase can be scrubbed with 1 mol/L HCl, then 99.27% of the beryllium was stripped with 5 mol/L NaOH by two-stage stripping. Be(OH)2 with a purity of 99.67% was recovered from the stripped beryllium solution by hydrolysis precipitation method. Furthermore, FT-IR analysis and slope analysis demonstrate the mechanism of beryllium extraction with naphthenic acid accompanied by cation exchange. The influence of temperature on the beryllium extraction was investigated and the thermodynamic parameters and the equilibrium constant of the extraction reaction were calculated. Accordingly, a process flowsheet for the separation of beryllium from multiple impurities using naphthenic acid was developed. This process is believed to offer the advantages of high efficiency, recyclability, and a favorable beryllium-aluminium separation effect; presenting a promising new approach to beryllium recovery.

Management of occupational health for adverse health effects of beryllium and its compounds in workplaces - Recent trends and issues in Japan

Beryllium is primarily used in its metallic form, in alloys, or in beryllium oxide ceramics. Its physical and mechanical properties make it useful for many applications across a range of industries. Because beryllium is recognized as a sensitizing and carcinogenic agent, the management of occupational health for workers who may be occupationally exposed to beryllium has long been an important issue in the world. Under these circumstances, the U.S. Occupational Safety and Health Administration (OSHA) had published a rule in January 2017, to prevent the development of chronic beryllium disease and lung cancer. This rule strengthens the regulations governing the use of beryllium and its compounds. With the announcement of the OSHA rule in January 2017, the purpose of this study is to gain insight into the health problems and industrial hygiene associated with the use of beryllium and share the issues related to the management of occupational health for persons working with beryllium in Japan. We collected information regarding the beryllium industry, beryllium exposure, beryllium-induced health disorders, OSHA rule of January 2017, and regulations for beryllium use in Japan. After reviewing them, we discussed the issues concerning occupational health management of workers exposed to beryllium in Japan. It has been reconfirmed that in recent years, the most serious health problem due to beryllium exposure is chronic beryllium disease caused by beryllium sensitization. Management of occupational health that emphasizes reduction of beryllium sensitization and early detection of beryllium-sensitized workers is important. It was suggested that the following should be considered as the issues of management of occupational health of workers exposed to beryllium in Japan: (1) Collect epidemiologic data on health hazards from beryllium exposure in Japan. (2) Review the diagnostic items of special medical check-ups. (3) Review the definition of beryllium and its compounds in the Ordinance on Prevention of Hazards due to Specified Chemical Substances.

A Novel Alternative to Environmental Monitoring to Detect Workers at Risk for Beryllium Exposure-Related Health Effects

The purpose of this study was to describe a methodology for surveillance and monitoring of beryllium exposure using biological monitoring to complement environmental monitoring. Eighty-three Israeli dental technicians (mean age 41.6 ± 1.36 years) and 80 American nuclear machining workers (54.9 ± 1.21 years) were enrolled. Biological monitoring was carried out by analyzing particle size (laser technique) and shape (image analysis) in 131/163 (80.3%) induced sputum samples (Dipa Analyser, Donner Tech, Or Aquiva, Israel). Environmental monitoring was carried out only in the United States (Sioutas impactor, SKC, Inc., Eighty Four, Pa.). Pulmonary function testing performance and induced sputum retrieval were done by conventional methods. Sixty-three Israeli workers and 37 American workers were followed up for at least 2 years.Biological monitoring by induced sputum indicated that a >92% accumulation of <5 μm particles correlated significantly to a positive beryllium lymphocyte proliferation test result (OR 3.8, 95% CI 1.2–11.4, p = 0.015) among all participants. Environmental monitoring showed that beryllium particles were <1 μm, and this small fraction (0.1–1 μ) was significantly more highly accumulated in nuclear machining workers compared to dental technicians. The small fractions positively correlated with induced sputum macrophages (r = 0.21 p = 0.01) and negatively correlated with diffusion lung carbon monoxide single breath (DLCO-SB r = 0.180 p = 0.04) in all subjects. Years of exposure were positively correlated to the number of accumulated particles 2–3 μ in diameter (r = 0.2, p = 0.02) and negatively correlated to forced expiratory volume in one second/forced vital capacity findings (r = −0.18, p = 0.02). DLCO was decreased in both groups after two years of monitoring.Biological monitoring is more informative than environmental monitoring in the surveillance and monitoring of workers in beryllium industries. Induced sputum is a feasible and promising biomonitoring method that should be included in the surveillance of exposed workers.

Chronic Beryllium Disease, HLA-DPB1, and the DP Peptide Binding Groove

Multiple epidemiologic studies demonstrate associations between chronic beryllium disease (CBD), beryllium sensitization (BeS), and HLA-DPB1 alleles with a glutamic acid residue at position 69 (E69). Results suggest that the less-frequent E69 variants (non-*0201/*0202 alleles) might be associated with greater risk of CBD. In this study, we sought to define specific E69-carrying alleles and their amino acid sequences in the DP peptide binding groove, as well as their relationship to CBD and BeS risk, using the largest case control study to date. We enrolled 502 BeS/CBD subjects and 653 beryllium-exposed controls from three beryllium industries who gave informed consent for participation. Non-Hispanic white cases and controls were frequency-matched by industry. HLA-DPB1 genotypes were determined using sequence-specific primer PCR. The E69 alleles were tested for association with disease individually and grouped by amino acid structure using logistic regression. The results show that CBD cases were more likely than controls to carry a non-*02 E69 allele than an *02 E69, with odds ratios (95% confidence interval) ranging from 3.1 (2.1-4.5) to 3.9 (2.6-5.9) (p < 0.0001). Polymorphic amino acids at positions 84 and 11 were associated with CBD: DD versus GG, 2.8 (1.8-4.6), p < 0.0001; GD versus GG, 2.1 (1.5-2.8), p < 0.0001; LL versus GG, 3.2 (1.8-5.6), p < 0.0001; GL versus GG, 2.8 (2.1-3.8), p < 0.0001. Similar results were found within the BeS group and CBD/BeS combined group. We conclude that the less frequent E69 alleles confer more risk for CBD than does *0201. Recent studies examining how the composition and structure of the binding pockets influence peptide binding in MHC genes, as well of studies showing the topology of the TCR to likely bind DPB1 preferentially, give plausible biological rationale for these findings.

Beryllium's Public Relations Problem: Protecting Workers When There is No Safe Exposure Level

news magazine in April 2000, Bill Richardson, Secretary of the U.S. Department of Energy (DOE), acknowl edged that his agency collaborated with the beryllium industry to defeat a 1975 attempt by the Occupational Safety and Health Administration (OSHA) to reduce workers' exposure to beryllium, a collaboration that was brought to public attention in a 1999 investiga tion by Toledo Blade reporter Sam Roe.1 Priority one was production of our nuclear weapons, Richardson stated. [The] last priority was the safety and health of the workers that build these weapons.2 The Secretary's declaration was remarkable; rarely do the most senior officials in government admit deception that resulted in death and disability of its own citizens. Yet, for those in the public health community, the Secretary's candid announcement was long overdue. Scores of workers employed in the production of nuclear weapons had been diagnosed with chronic beryllium disease (CBD), a progressive and irreversible inflammatory lung disease, and there was increasingly powerful evidence that CBD was associated with expo sure at levels below the permissible exposure limit in place at the time. In response to this evidence, the beryllium industry waged a concerted campaign to delay a more protective workplace exposure standard. Eventually, when the scientific evidence became so great that it was no longer credible to deny that work ers developed CBD at levels permitted by an outdated exposure limit, the beryllium industry responded with a new rationale to delay promulgation of a more pro tective standard.

The Beryllium Occupational Exposure Limit: Historical Origin and Current Inadequacy

The Beryllium Occupational Exposure Limit: Historical Origin and Current Inadequacy

Sensitization and Chronic Beryllium Disease Among Workers in Copper???Beryllium Distribution Centers

Little is known about the risk of sensitization and chronic beryllium disease (CBD) among workers performing limited processing of copper-beryllium alloys downstream of the primary beryllium industry. In this study, we performed a cross-sectional survey of employees at three copper-beryllium alloy distribution centers. One hundred workers were invited to be tested for beryllium sensitization using the beryllium blood lymphocyte proliferation test (BeLPT); a sensitized worker was further evaluated for CBD. Available beryllium mass concentration air sampling data were obtained for characterization of airborne exposure. One participant, who had exposure to other forms of beryllium, was found to be sensitized and to have CBD, resulting in a prevalence of sensitization/CBD of 1% for all tested. The overall prevalence of beryllium sensitization and CBD for workers in these three copper-beryllium alloy distribution centers is lower than for workers in primary beryllium production facilities.

Industries in the United States with Airborne Beryllium Exposure and Estimates of the Number of Current Workers Potentially Exposed

Estimates of the number of workers in the United States occupationally exposed to beryllium were published in the 1970s and 1980s and ranged from 21,200 to 800,000. We obtained information from several sources to identify specific industries with beryllium exposure and to estimate the number of current workers potentially exposed to beryllium. We spoke with representatives from the primary beryllium industry and government agencies about the number of exposed workers in their facilities. To identify industries in the private sector but outside the primary industry, we used data from the Integrated Management Information System (IMIS), which is managed by the Occupational Safety and Health Administration, and the Health Hazard Evaluation program of the National Institute for Occupational Safety and Health. We used IMIS data from OSHA inspections with a previously developed algorithm to estimate the number of potentially exposed workers in nonprimary industries. Workers potentially exposed to beryllium included 1500 current employees in the primary beryllium industry and 26,500 individuals currently working for the Department of Energy or the Department of Defense. We identified 108 four-digit Standard Industrial Classification (SIC) categories in which at least one measurement of airborne beryllium was ≥ 0.1 μ g/m3. Based on the subset of 94 SIC categories with beryllium ≥ 0.1 μ g/m3, we estimated 26,400 to 106,000 workers may be exposed in the private sector (outside the primary industry). In total, there are as many as 134,000 current workers in government and private industry potentially exposed to beryllium in the United States. We recommend that the results of this study be used to target at-risk audiences for hazard communications intended to prevent beryllium sensitization and chronic beryllium disease.

Development of a Filter Assembly to Match the Deposition of Ultrafine Aerosol in the Lung: A Pilot Study with Beryllium

A new criterion has previously been proposed for assessing inhalation risk from ultrafine aerosols. This deposited submicrometer particulate (DSP) criterion matches the lung deposition curve for aerosols with a size of <1 µm. A method for matching the DSP criterion using racketched polycarbonate filters has been described in the literature, but the sampling results must be adjusted by a correction factor to match the DSP curve. A new design that matches the criterion without the need for any correction factors and has been used with a real-time particle counter to measure processes in the beryllium industry where data suggest that the ultrafine (<0.1 µm) fraction of beryllium might be an important metric for predicting disease.

Racial differences in prevalence of a supratypic HLA‐genetic marker immaterial to pre‐employment testing for susceptibility to chronic beryllium disease

A beryllium materials manufacturer is conducting a limited pilot program that offers testing for HLA-DP beta 1E69 with genetic counseling through a third party to applicants for employment. An important consideration in this regard is the prevalence of this marker in the general population, and its consequent positive predictive value of disease susceptibility. Polymerase chain reaction and restriction fragment length polymorphism analyses were used to determine HLA-DP beta 1E69 population frequencies. Estimation of positive predictive values assumed a disease frequency among beryllium workers of either 5 or 15% and used an odds ratio for disease risk of 35 for the HLA-DP beta 1E69 marker. Allelic/carrier frequencies were found to be 0.21/0.33, 0.24/0.40, 0.27/0.47, and 0.38/0.59 for Caucasians, African-Americans, Hispanics, and Chinese, respectively. Ranges of positive predictive values for a genetic test based on HLA-DP beta 1E69 in these populations were calculated to be 8.3-14.3% for carriers with an assumed disease frequency of 5%. For high risk subgroups with disease frequencies of 15%, the range of positive predictive values was found to span between 24.9-43.0%. These estimates suggest that using HLA-DP beta 1E69 genotyping for general pre-employment screening in the beryllium industry has a low positive predictive value, which varies little among racial groups where carrier frequencies differ significantly.

Introduction to Beryllium: Uses, Regulatory History, and Disease

Beryllium is an ubiquitous element in the environment, and it has many commercial applications. Because of its strength, electrical and thermal conductivity, corrosion resistance, and nuclear properties, beryllium products are used in the aerospace, automotive, energy, medical, and electronics industries. What eventually came to be known as chronic beryllium disease (CBD) was first identified in the 1940s, when a cluster of cases was observed in workers from the fluorescent light industry. The U.S. Atomic Energy Commission recommended the first 8-hour occupational exposure limit (OEL) for beryllium of 2.0 microg/m3 in 1949, which was later reviewed and accepted by the American Conference of Governmental Industrial Hygienists (ACGIH), the American Industrial Hygiene Association (AIHA), the American National Standards Institute (ANSI), the Occupational Safety and Health Administration (OSHA), and the vast majority of countries and standard-setting bodies worldwide. The 2.0 microg/m3 standard has been in use by the beryllium industry for more than 50 years and has been considered adequate to protect workers against clinical CBD. Recently, improved diagnostic techniques, including immunological testing and safer bronchoscopy, have enhanced our ability to identify subclinical CBD cases that would have formerly remained unidentified. Some recent epidemiological studies have suggested that some workers may develop CBD at exposures less than 2.0 microg/m3. ACGIH is currently reevaluating the adequacy of the current 2.0 microg/m3 guideline, and a plethora of research initiatives are under way to provide a better understanding of the cause of CBD. The research is focusing on the risk factors and exposure metrics that could be associated with CBD, as well as on efforts to better characterize the natural history of CBD. There is growing evidence that particle size and chemical form may be important factors that influence the risk of developing CBD. These research efforts are expected to provide data that will help identify a scientifically based OEL that will protect workers against CBD.

A Comparison and Critique of Historical and Current Exposure Assessment Methods for Beryllium: Implications for Evaluating Risk of Chronic Beryllium Disease

The primary beryllium industry has generated a large amount of data on airborne beryllium concentrations that has been used to characterize exposure by task-specific activities, job category, individual worker, and processing area using a variety of methods. These methods have included high-volume breathing zone sampling, high-volume process sampling, high- and low-volume respirable and area sampling, real-time monitoring, and personal sampling. Many of the beryllium studies have used these air sampling methods to assess inhalation exposure and chronic beryllium disease (CBD) risk to beryllium; however, available data do not show a consistent dose-response relationship between airborne concentrations of beryllium and the incidence of CBD. In this article, we describe the air sampling and exposure assessment methods that have been used, review the studies that have estimated worker exposures, discuss the uncertainties associated with the level of beryllium for which these studies have reported an increased risk of CBD, and identify future investigative exposure assessment strategies. Our evaluation indicated that studies of beryllium workers are often not directly comparable because they (1) used a variety of exposure assessment methods that are not necessarily representative of individual worker exposures, (2) rarely considered respirator use, and (3) have not evaluated changes in work practices. It appears that the current exposure metric for beryllium, total beryllium mass, may not be an appropriate measurement to predict the risk of CBD. Other exposure metrics such as mass of respirable particles, chemical form, and particle surface chemistry may be more related to the prevalence of CBD than total mass of airborne beryllium mass. In addition, assessing beryllium exposure by all routes of exposure (e.g., inhalation, dermal uptake, and ingestion) rather than only inhalation exposure in future studies may prove useful.

Risks of beryllium disease related to work processes at a metal, alloy, and oxide production plant.

OBJECTIVES: To describe relative hazards in sectors of the beryllium industry, risk factors of beryllium disease and sensitisation related to work process were sought in a beryllium manufacturing plant producing...

A Study of Beryllium Exposure Measurements, Part 2: Evaluation of the Components of Exposure in the Beryllium Processing Industry

Abstract The characterization of exposure in the beryllium processing industry included collection of samples in the breathing zone during work near emission sources and the general area when employees performed other tasks. The amount of time an average employee spent at each task or area was determined. The arithmetic average exposure at each task was calculated and weighted by multiplying by the time spent performing the activity. These time-weighted results were added, and then divided by the total work time to estimate the daily weighted average (DWA). Each breathing zone and general area exposure measurement is identified by “BZ” or “GA” on the DWA calculation form. 643 individual DWA exposure values for workers with 38 job titles employed in the beryllium industry from 1972 to 1975 have been analyzed. Sixty-seven percent of mean breathing zone values exceeded 2 μg/m3, and 73 percent of the maximum exposures exceeded 2 μg/m3. In contrast, only 18 percent of the general area mean exposures exceeded 2 μg/m3. In general, breathing zone tasks were associated with shorter exposure times than general area sample tasks; for example, 83 percent of the breathing zone tasks and 42 percent of the general area tasks were of 30 minutes or less in duration. When task-specific data are available, cumulative exposure is only one of several exposure metrics which may be constructed (e.g., highest intensity, peak cumulative). This analysis of beryllium exposure data illustrates identification of several exposure excursions within the overall time-weighted exposure. These may be useful for construction of exposure metrics for occupational epidemiology studies and for targeting efforts to control exposure.

A Study of Beryllium Exposure Measurements, Part 1: Estimation and Categorization of Average Exposures from Daily Weighted Average Data in the Beryllium Industry

Abstract Time-weighted exposure measurements are frequently available for use in occupational epidemiology studies of exposure–response relationships. Generally, these measurements must be combined and extrapolated over time to develop job-specific exposure estimates. A stepwise strategy for the development of exposure estimates from time-weighted data is described. Elements include describing the distribution of the data, exploring trends over time, calculating estimates, and methods of categorizing the estimates. The process is applied to more than 2200 time-weighted exposures from the beryllium processing industry collected from 1950 through 1978. The data were approximately lognormally distributed, requiring the calculation of the mean of the log-transformed data, and subsequent estimation of the arithmetic mean exposure for each job title at the five facilities. Few trends in exposure estimates over time were detected in the data, which may be a result of the small number of data points for each job....

Half a Century of History of Beryllium Industry in Japan

(1994). Half a Century of History of Beryllium Industry in Japan. Mineral Processing and Extractive Metallurgy Review: Vol. 13, No. 1, pp. 13-18.

The first years of the Atomic Energy Commission New York Operations Office Health and Safety Laboratory

The Health and Safety Laboratory (HASL) of the Atomic Energy Commission has provided much of the data on exposure assessment in uranium contractor facilities and on fallout radionuclides in the environment. The research performed in the beryllium industry 1947–1949 led to establishment of the protection standards that exist to this day. This laboratory was formed in 1947, as part of the Medical Division of the New York Operations Office, directed by B.S. Wolf. HASL was directed initially by Merril Eisenbud and subsequently by S. Allen Lough and John Harley. The history of the Laboratory is traced from its beginning, and the projects described that led to HASL's reputation as a trouble-shooting arm of the Atomic Energy Commission.

Properties of beryllium consolidated by several near-net shape processes

A study was performed to characterize mechanical and physical properties of two beryllium grades consolidated by four potential near-net shape (NNS) methods. Powder metallurgy is used extensively in the beryllium industry to yield fine grain sizes necessary for good mechanical properties. The powder is typically consolidated into machining stock by vacuum hot pressing into right circular cylinders. The impetus for this study was to evaluate the properties of beryllium consolidated by cost effective NNS methods. Consolidation of two powders, a structural grade (S-200F) and an instrument grade (I-220B), was studied. The consolidation methods evaluated were direct hot isostatic pressuring (HIP), cold isostatic pressing (CIP) followed by HIP in a pressure transmitting medium, CIP followed by sintering, and CIP followed by sintering followed by HIP. Evaluation of density, tensile properties, microyield strength, and microstructure was carried out. Economic comparisons between consolidation techniques were also drawn. An example of the application of a NNS process to make a component such as a lightweighted airborne infrared mirror is presented.

Aerosol Resuspension from Fabric: Implications for Personal Monitoring in the Beryllium Industry

The fabric used for work clothing at an industrial site can significantly influence personal monitor (PM) exposure estimates because dust resuspension from clothing can increase the concentration at the sampler inlet. The magnitude of the effect depends on removal forces and on the interaction of the contaminant particles with work garments. Aerosol deposition and resuspension on cotton and Nomex® aramid fabrics was evaluated at a beryllium refinery. Electrostatically charged cotton backdrops collected more beryllium than neutral controls, but electronegative Nomex backdrops did not. Moving fabrics collected more beryllium than did stationary controls. When contaminated fabrics were agitated, PMs mounted 2.5 cm in front of the fabric collected more beryllium than monitors above the fabric, positioned to simulate the nose or mouth. The difference between the air concentrations measured by these PMs increased with Be loading and tended to level off for highly contaminated fabric. Cotton resuspended a larger fraction of its contaminant load than Nomex. These results are consistent with current knowledge of the behavior of particles on fabric fibers. Aerosol resuspension from garments is an important consideration in assessing inhalation exposure to toxic dusts. A garment may attract and retain toxic particles. This contamination is then available for later resuspension.

Aerosol resuspension from fabric: implications for personal monitoring in the beryllium industry.

The fabric used for work clothing at an industrial site can significantly influence personal monitor (PM) exposure estimates because dust resuspension from clothing can increase the concentration at the sampler inlet. The magnitude of the effect depends on removal forces and on the interaction of the contaminant particles with work garments. Aerosol deposition and resuspension on cotton and Nomex aramid fabrics was evaluated at a beryllium refinery. Electrostatically charged cotton backdrops collected more beryllium than neutral controls, but electronegative Nomex backdrops did not. Moving fabrics collected more beryllium than did stationary controls. When contaminated fabrics were agitated, PMs mounted 2.5 cm in front of the fabric collected more beryllium than monitors above the fabric, positioned to simulate the nose or mouth. The difference between the air concentrations measured by these PMs increased with Be loading and tended to level off for highly contaminated fabric. Cotton resuspended a larger fraction of its contaminant load than Nomex. These results are consistent with current knowledge of the behavior of particles on fabric fibers. Aerosol resuspension from garments is an important consideration in assessing inhalation exposure to toxic dusts. A garment may attract and retain toxic particles. This contamination is then available for later resuspension.