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Objective: To establish a inductively coupled plasma mass spectrometry method for the determination of trace cobalt and tungsten in human urine. Methods: The authors used 1% nitric acid solution as diluent in October-December 2021, the sample dilution factor and internal standard element were optimized by single factor rotation experiment, and the difference between the working curve and the standard curve was compared. Results: The method uses working curve to determine cobalt and tungsten in urine, the linear range of this method was 0.0~10.0 μg/L, the correlation coefficient was 0.999 9, the detection limits respectively were 0.005 μg/L (cobalt) and 0.09 μg/L (tungsten), the recoveries of samples respectively were 87.0%~100.2% (cobalt) and 89.4%~104.8% (tungsten), the relative standard deviations respectively were 0.4%~4.4% (cobalt) and 0.6%~3.8% (tungsten) . Conclusion: A simple and rapid method for determination of cobalt and tungsten in urine has been established. This method has the advantages of simple operation, high sensitivity, low detection limit and good stability. It is suitable for determination of cobalt and tungsten in urine of all kinds of people.

Purpose: To study the relationship between inhalation of airborne particles and cobalt in the Swedish hard metal industry and markers of inflammation and coagulation in blood., Methods: Personal sampling of inhalable cobalt and dust were performed for subjects in two Swedish hard metal plants. Stationary measurements were used to study concentrations of inhalable, respirable, and total dust and cobalt, PM 10 and PM 2.5 , the particle surface area and the particle number concentrations. The inflammatory markers CC16, TNF, IL-6, IL-8, IL-10, SAA and CRP, and the coagulatory markers FVIII, vWF, fibrinogen, PAI-1 and D-dimer were measured. A complete sampling was performed on the second or third day of a working week following a work-free weekend, and additional sampling was taken on the fourth or fifth day. The mixed model analysis was used, including covariates., Results: The average air concentrations of inhalable dust and cobalt were 0.11 mg/m 3 and 0.003 mg/m 3 , respectively. For some mass-based exposure measures of cobalt and total dust, statistically significant increased levels of FVIII, vWF and CC16 were found., Conclusions: The observed relationships between particle exposure and coagulatory biomarkers may indicate an increased risk of cardiovascular disease.

Background: Mortality pattern was determined in a cohort of 16,999 white and blue-collar workers in the Swedish hardmetal industry. Exposure assessment for cobalt is presented., Methods: A historical database (1970 to 2012) of personal and area measurements of cobalt, tungsten, and nickel in the Swedish hardmetal industry was created. Log linear and exponential modeling of cobalt concentrations based on time period, job, and site was performed, and cumulative and mean exposures were calculated., Results: Some 37% of the personal cobalt measurements exceeded 0.02 mg/m, mostly for powder production, pressing, and shaping. The log linear regression showed statistical differences (P < 0.05) between sites, time periods, and jobs. Some 1.6% of the cobalt cumulative exposures for blue-collar workers exceeded 0.4 mg/m years., Conclusion: Low levels of cumulative and mean exposures were determined.

Objective: To generate quantitative exposure estimates for use in retrospective occupational cohort mortality studies of the hardmetal industry., Methods: Job-exposure matrices (JEMs) were constructed for cobalt, tungsten, and nickel over the time period 1952 to 2014. The JEMs consisted of job class categories, based on job titles and processes performed, and exposure estimates calculated from available company industrial hygiene measurements., Results: Exposure intervals of one-half order magnitude were established for all three agents. Eight job classes had significantly decreasing time trends for cobalt exposure; no significant time trends were detected for tungsten or nickel exposures., Conclusions: The levels of exposures determined for this study were similar to or lower than those previously reported for the hardmetal industry during the 1952 to 2014 study period.

Objective: To establish the inductively coupled plasma optical emission spectrometry (ICP-OES) method for determination of cobalt and tungsten in the air of workplace. Methods: The cobalt and tungsten were collected by filter membrane and then digested by nitric acid, inductively coupled plasma optical emission spectrometry (ICP-OES) was used for the detection of cobalt and tungsten. Results: The linearity of tungsten was good at the range of 0.01-1 000 μg/ml with a correlation coefficient of 0.999 9, the LOD and LOQ were 0.006 7 μg/ml and 0.022 μg/ml, respectively. The recovery was ranged from 98%-101%, the RSD of intra-and inter-batch precision were 1.1%-3.0% and 2.1%-3.8%, respectively. The linearity of cobalt was good at the range of 0.01-100 μg/ml with a correlation coefficient of 0.999 9, the LOD and LOQ were 0.001 2 μg/ml and 0.044 μg/ml, respectively. The recovery was ranged from 95%-97%, the RSD of intra-and inter-batch precision were 1.1%-2.4% and 1.1%-2.9%, respectively. The sampling efficiency of tungsten and cobalt were higher than 94%. Conclusion: The linear range, sensitivity and precision of the method was suitable for the detection of tungsten and cobalt in the air of workplace.

Objective: To establish a rapid detection method regarding the air conditions of workplace and the workers' urine included Tungsten, Cobalt, Nickel, Titanium, Cadmium, Manganese, Lead and its compounds based on inductively coupled plasma mass spectrometry (ICP-MS) . Methods: The experiment adopts ICP-MS to deter-mine those metals in workshop air and workers urine, evaluate the detection's limitation, the precision and accuracy of the method. Using the membrane filter and urine freeze - dried metal standard material to verify this method. Results: Each element of correlation coefficient was greater than 0.999. The recovery rate of air samples was 91.6%~104.6%, within-batch RSD precision was 1.41%~3.50%, between-run precision was 1.28%~4.31%, urine samples recovery rate was 93.0%~102.6%, within - batch RSD precision was 1.25%~3.56%, between - run precision was 1.58%~4.67%, According to the method every element was within the scope of the standard reference, it was also showed that the established method is accurate and reliable. Conclusion: ICP-MS is an effective and feasible method to detect the workshop air and the workers' urine which included Tungsten, Cobalt, Nickel, Titanium, Cadmium, Manganese, Lead and its compounds.

Exposure to cobalt in the hard metal industry entails severe adverse health effects, including lung cancer and hard metal fibrosis. The main aim of this study was to determine exposure air concentration levels of cobalt and tungsten for risk assessment and dose-response analysis in our medical investigations in a Swedish hard metal plant. We also present mass-based, particle surface area, and particle number air concentrations from stationary sampling and investigate the possibility of using these data as proxies for exposure measures in our study. Personal exposure full-shift measurements were performed for inhalable and total dust, cobalt, and tungsten, including personal real-time continuous monitoring of dust. Stationary measurements of inhalable and total dust, PM2.5, and PM10 was also performed and cobalt and tungsten levels were determined, as were air concentration of particle number and particle surface area of fine particles. The personal exposure levels of inhalable dust were consistently low (AM 0.15mg m(-3), range <0.023-3.0mg m(-3)) and below the present Swedish occupational exposure limit (OEL) of 10mg m(-3) The cobalt levels were low as well (AM 0.0030mg m(-3), range 0.000028-0.056mg m(-3)) and only 6% of the samples exceeded the Swedish OEL of 0.02mg m(-3) For continuous personal monitoring of dust exposure, the peaks ranged from 0.001 to 83mg m(-3) by work task. Stationary measurements showed lower average levels both for inhalable and total dust and cobalt. The particle number concentration of fine particles (AM 3000 p·cm(-3)) showed the highest levels at the departments of powder production, pressing and storage, and for the particle surface area concentrations (AM 7.6 µm(2)·cm(-3)) similar results were found. Correlating cobalt mass-based exposure measurements to cobalt stationary mass-based, particle area, and particle number concentrations by rank and department showed significant correlations for all measures except for particle number. Linear regression analysis of the same data showed statistically significant regression coefficients only for the mass-based aerosol measures. Similar results were seen for rank correlation in the stationary rig, and linear regression analysis implied significant correlation for mass-based and particle surface area measures. The mass-based air concentration levels of cobalt and tungsten in the hard metal plant in our study were low compared to Swedish OELs. Particle number and particle surface area concentrations were in the same order of magnitude as for other industrial settings. Regression analysis implied the use of stationary determined mass-based and particle surface area aerosol concentration as proxies for various exposure measures in our study., (© The Author 2016. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.)

A baseline investigation into heavy metal status in the mangrove sediments was conducted in Shenzhen, China where rapid urban development has caused severe environmental contamination. It is found that heavy metal contamination in this mangrove wetland is characterized by the dominant presence of tungsten and cobalt, which is markedly different from the neighboring Hong Kong and other parts of the world. The vertical variation pattern of these two metals along the sediment profile differed from other heavy metals, suggesting an increasing influx of tungsten and cobalt into the investigated mangrove habitat, as a result of uncontrolled discharge of industrial wastewater from factories that produce or use chemical compounds or alloys containing these two heavy metals. Laboratory simulation experiment indicated that seawater had a stronger capacity to mobilize sediment-borne tungsten and cobalt, as compared to deionized water, diluted acetic, sulfuric and nitric acids., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Background: Many daily contacts with metallic items are short and repetitive, and result in metal release; material, sweat, friction and wear may all be important., Objectives: To study cobalt release and skin deposition as a result of many short and repetitive contacts with two cobalt-containing materials., Materials/methods: Study participants (n = 5) handled two types of hard metal disc (Co 6% and Co 15% Cr 0.6%) for 30 min. Deposited cobalt skin doses were measured with acid wipe sampling and chemical analysis. Cobalt release from the hard metal discs in artificial sweat was measured under conditions simulating those present during the handling of discs., Results: Average cobalt skin doses from discs containing 6% Co and 15% Co 0.6% Cr were 1.1 µg/cm(2) [standard deviation (SD) 0.4 µg/cm(2) ] and 0.7 µg/cm(2) (SD 0.5 µg/cm(2) ), respectively. More cobalt was released from hard metal discs containing 6% Co [11.4 µg/cm(2) (SD 1.2 µg/cm(2) )] than from discs containing 15% Co 0.6% Cr [4.8 µg/cm(2) (SD 0.6 µg/cm(2) )]. 10% to 15% of the potentially available cobalt was deposited on the skin during handling., Conclusions: It is likely that the cobalt deposited as a result of short and repetitive contact with hard metals may cause harm. Research regarding cobalt exposure, metal release and the deposition of skin-sensitizing metals resulting from short and repetitive contact is needed for a better understanding of the allergy risk., (© 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Previously reported dendrochemical data showed temporal variability in concentration of tungsten (W) and cobalt (Co) in tree rings of Fallon, Nevada, US. Criticism of this work questioned the use of the Mann-Whitney test for determining change in element concentrations. Here, we demonstrate that Mann-Whitney is appropriate for comparing background element concentrations to possibly elevated concentrations in environmental media. Given that Mann-Whitney tests for differences in shapes of distributions, inter-tree variability (e.g., "coefficient of median variation") was calculated for each measured element across trees within subsites and time periods. For W and Co, the metals of highest interest in Fallon, inter-tree variability was always higher within versus outside of Fallon. For calibration purposes, this entire analysis was repeated at a different town, Sweet Home, Oregon, which has a known tungsten-powder facility, and inter-tree variability of W in tree rings confirmed the establishment date of that facility. Mann-Whitney testing of simulated data also confirmed its appropriateness for analysis of data affected by point-source contamination. This research adds important new dimensions to dendrochemistry of point-source contamination by adding analysis of inter-tree variability to analysis of central tendency. Fallon remains distinctive by a temporal increase in W beginning by the mid 1990s and by elevated Co since at least the early 1990s, as well as by high inter-tree variability for W and Co relative to comparison towns., (Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.)

We present a 54-year-old man employed in the field of hard metal manufacturing who complained of progressive dyspnea and weight loss. His chest radiograph showed bilateral fibrosis predominantly distributed in the upper lobes with bilateral pleural effusions, and a strong reduction in lung volume. Lung histopathology showed apical cap-like fibrosis but no giant cell interstitial pneumonia. Electron probe microanalysis detected tungsten deposits in the fibrotic region: we therefore considered this to be a case of hard metal disease. Hard metal disease should be considered as one possibility in the differential diagnosis of upper lobe-dominant pulmonary fibrosis.

Inhalation of cobalt (Co) and tungsten carbide (WC) particles, but not Co or WC alone, may cause hard metal disease, risk of which does not appear to be uniform across cemented tungsten carbide (CTC) production processes. Inhalation of Co alone or in the presence of WC may cause asthma. Hypothesizing that aerosol size, chemical content, heterogeneity, and constituent compaction may be important exposure factors, we characterized aerosols from representative CTC manufacturing processes. Six work areas were sampled to characterize aerosol size distributions (dust, Co) and 12 work areas were sampled to characterize physicochemical properties (using scanning electron microscopy with energy dispersive x-ray spectrometry [SEM-EDX]). Bulk feedstock and process-generated powders were characterized with SEM-EDX and x-ray diffraction. The dust mass median diameter was respirable and the cobalt respirable mass fraction was highest (37%) in grinding. Morphology of particles changed with processing: individual, agglomerate, or aggregates (pre-sintered materials), then mostly compacted particles (subsequent to sintering). Elemental composition of particles became increasingly heterogeneous: mostly discrete Co or W particles (prior to spray drying), then heterogeneous W/Co particles (subsequent work areas). Variability in aerosol respirability and chemical heterogeneity could translate into differences in toxicity and support detailed characterization of physicochemical properties during exposure assessments.

Spatial patterns of tungsten and cobalt are described for surface dust of Fallon, Nevada, where a cluster of childhood leukemia has been ongoing since 1997. In earlier research, airborne tungsten and cobalt was shown to be elevated in total suspended particulates in Fallon. To fine-tune the spatial patterns of tungsten and cobalt deposition in Fallon, surface dust was collected in a grid pattern within as well as outside of Fallon to establish background concentrations of metals. In surface dust, tungsten and cobalt show sharp peaks (934 ppm and 98 ppm, respectively) within Fallon just north of highway 50 and west of highway 95. These two peaks overlap spatially, and given the grid pattern used for collecting surface dust, the source area of these two airborne metals can be pinpointed to the vicinity of hard-metal industry located north of highway 50 and west of highway 95. Fallon is distinctive in west central Nevada because of high airborne tungsten and cobalt particulates, and given its cluster of childhood leukemia, it stands to reason that additional biomedical research is in order to test directly the leukogenicity of combined airborne tungsten and cobalt particulates.

This paper describes the use of lichen chemistry to assess airborne tungsten and cobalt in Fallon, Nevada, where a cluster of childhood leukemia has been on going since 1997. Lichens and their rock substrates were collected from Rattlesnake Hill within Fallon as well as from four different rock outcrops located north, east, south, and west of Fallon and at least 20 km away from the town center. In the lichens themselves, W and Co are significantly higher within Fallon than in the combined control site outside of Fallon. In the rock substrates of the lichens, no differences exist in W and Co. The W and Co differences in lichens cannot be attributed to substrate geochemistry. Fallon is distinctive in west central Nevada for high airborne W and Co, and given its cluster of childhood leukemia, it stands to reason that additional biomedical research is in order to test directly the leukogenicity of combined airborne W and Co.

Background: Since 1997, Fallon, Nevada, has experienced a cluster of childhood leukemia that has been declared "one of the most unique clusters of childhood cancer ever reported." Multiple environmental studies have shown airborne tungsten and cobalt to be elevated within Fallon, but the question remains: Have these metals changed through time in correspondence with the onset of the leukemia cluster?, Methods: We used dendrochemistry, the study of element concentrations through time in tree rings, in Fallon to assess temporal variability of airborne tungsten and cobalt since the late 1980s. The techniques used in Fallon were also tested in a different town (Sweet Home, OR) that has airborne tungsten from a known source., Results: The Sweet Home test case confirms the accuracy of dendrochemistry for showing temporal variability of environmental tungsten. Given that dendrochemistry works for tungsten, tree-ring chemistry shows that tungsten increased in Fallon relative to nearby comparison towns beginning by the mid-1990s, slightly before the onset of the cluster, and cobalt has been high throughout the last approximately 15 years. Other metals do not show trends through time in Fallon., Discussion: Results in Fallon suggest a temporal correspondence between the onset of excessive childhood leukemia and elevated levels of tungsten and cobalt. Although environmental data alone cannot directly link childhood leukemia with exposure to metals, research by others has shown that combined exposure to tungsten and cobalt can be carcinogenic to humans., Conclusion: Continued biomedical research is warranted to directly test for linkage between childhood leukemia and tungsten and cobalt.

These tests were conducted to develop a database that could be used to assess risks to soldiers from exposure to aerosolized metallic particulates when the crew compartment of an Abrams tank is perforated by a kinetic energy penetrator. Quantitative data are reported for aerosols produced by kinetic energy penetrators containing tungsten, nickel, and cobalt. The following are addressed: (1) concentrations and rates of particle settling inside the vehicle, (2) particle size distribution, (3) inhalable and respirable particulates, (4) distribution of aerosol particles by mass, and (5) particle shapes. The scenario described in this report simulates a rare occurrence. The lessons learned, however, highlight a requirement for developing protocols for analyses of metals in body fluids and urine as soon as practical, and also for implementing targeted postdeployment medical surveillance programs that monitor both body burden for respired metals and pulmonary function.

The aim of the present study was to investigate whether exhaled breath condensate (EBC), a fluid formed by cooling exhaled air, can be used as a suitable matrix to assess target tissue dose and effects of inhaled cobalt and tungsten, using EBC malondialdehyde (MDA) as a biomarker of pulmonary oxidative stress. Thirty-three workers exposed to Co and W in workshops producing either diamond tools or hard-metal mechanical parts participated in this study. Two EBC and urinary samples were collected: one before and one at the end of the work shift. Controls were selected among nonexposed workers. Co, W, and MDA in EBC were analyzed with analytical methods based on mass spectrometric reference techniques. In the EBC from controls, Co was detectable at ultratrace levels, whereas W was undetectable. In exposed workers, EBC Co ranged from a few to several hundred nanomoles per liter. Corresponding W levels ranged from undetectable to several tens of nanomoles per liter. A parallel trend was observed for much higher urinary levels. Both Co and W in biological media were higher at the end of the work shift in comparison with preexposure values. In EBC, MDA levels were increased depending on Co concentration and were enhanced by coexposure to W. Such a correlation between EBC MDA and both Co and W levels was not observed with urinary concentration of either element. These results suggest the potential usefulness of EBC to complete and integrate biomonitoring and health surveillance procedures among workers exposed to mixtures of transition elements and hard metals. Key words: cobalt, exhaled breath condensate, hard metals, lung, malondialdehyde, oxidative stress, tungsten.

A series of inorganic polyanions (viz. heteropolytungstates) has been shown to have antiviral activity but there was no evidence to indicate that the drugs reached their site of antiviral (HIV) activity intact. We have shown that with a scanning proton microprobe it is possible to analyse the metal content of individual cells (PBLs) treated with such a polyoxometalate drug and to determine the atomic ratio of the metals within the cell. This was found to be near that in the drug. The distribution of the metals (tungsten and cobalt) within the cell was measured and it was shown that both metals were located in the same region within the cell. These findings would suggest that the drug had entered the cells intact.

The results of 30 years screening of exposed workers in the hard metal industry are presented in a retrospective study. There were 11 workers who had radiographic signs of pulmonary fibrosis. No correlation was found between intensity and/or duration of exposure and the stage and progression of pulmonary fibrosis. In 45% of the cases there was progression of the fibrosis after cessation of the exposure. Steroid therapy in three cases relieved the subjective symptoms but there was no regression of the fibrosis.

Experimental pneumoconiosis was induced by intratracheal injection of dusts of presintered cemented tungsten carbide, G2 (WC : Co=98 : 2) and TX20 (WC : Co : TiC : TaC=64 : 16 : 6 : 14) into the lungs of rats in order to document the pathological changes in lung tissues associated with environmental cobalt and tungsten. The following results were obtained. 1) Six months after the administration of G2 and TX20 dusts, marked fibrotic foci were noted and tungsten was detected in the lung tissues of all of the experimental animals. 2) Twelve months after the administration of both dusts, both the fibrotic changes and the tungsten levels were reduced in both test groups, but the reduction was more notable in the G2 group. The cases with fibrotic changes were relatively concomitant with the cases in which tungsten was detected. 3) On examination of tissue levels of cobalt derived from the dust, the cobalt levels in the lungs and bone tissues were less influenced by the dust of the G2 group at any point of investigation, whereas only the pulmonary cobalt levels at six months after the administration of the TX20 group showed a remarkable influence from the dust cobalt (p less than 0.01). 4) In the cases where tungsten was detected six months after the administration of both groups and twelve months after the administration of the TX20 group, pulmonary cobalt levels had not reached the value that should have been gained by the addition of expected values (dust cobalt levels calculated from the tungsten levels) to the control values. 5) The above results indicate that both G2 and TX20 dusts induced marked fibrotic changes in rat pulmonary tissues. However, these changes were reversible to some extent. In addition, a portion of the dust cobalt was dissolved in the body fluid and disappeared from the pulmonary fields.