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Tungsten (W), a toxic and hazardous pollutant, poses substantial risks to both aquatic life and human health. However, the available understanding of the migration properties of W in lake sediments under various habitats is still limited. This study was designed to evaluate variations in the concentrations of soluble W, manganese (Mn), and iron (Fe) in the summer season by applying a high-resolution Peeper sampling device. According to the results, soluble W concentrations and release fluxes were higher in the pore water of sediments in algae-dominated lake areas than in areas dominated by aquatic plants. This result indicates that the competition for adsorption between algae-derived dissolved organic matter and W, as well as the reductive dissolution caused by dissolved organic matter on Fe (III)/Mn (IV) (hydroxyl) oxides, contributes to the release of W from lake sediments. W uptake by aquatic plants and in-situ formation of Fe (III)/Mn (IV) (hydroxyl) oxides might be the primary factor that controls W release from lake sediments. Aquatic plants can effectively control W release from sediments. The findings of this work provide a scientific basis for the effective control of W release from shallow lake sediments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Mining operations contribute to higher environmental contaminant levels, such as particulate matter (PM) hosting potentially toxic elements (PTE). This study aimed to comprehensively characterise atmospheric PM in an environment impacted by former tungsten-tin mining exploration at Regoufe mine (Arouca, Portugal). Although this is a deactivated mine, its location near population clusters and integration into a Geopark belonging to the "World Geoparks Network" with frequent presence of hikers highlight the importance of air quality monitoring to keep its Geopark classification. A seasonal and cumulative sampling approach was used, with samples collected over a seasonal period, between April 2022 and April 2023, through passive sampling, wet and dry sedimentation, and air mass filtration. All samples were analysed using SEM-EDS for detailed imaging. Samples from wet deposition and filtration were also analysed with ICP-MS to determine the concentration of the inorganic elements. The PTE determined in the atmospheric particulate matter of the studied area occurs in variable concentrations as a function of the sampling period. The mineralogy of the PM sampled includes Sn- and W-minerals, pyrite, quartz, phosphates, sulfates, and As-oxides. These materials are typical in the site's soils, suggesting their resuspension by the wind and transported to nearby areas. Angular to sub-angular dense particles indicate limited transportation, depositing closer to their emission source. The smaller particles (<25 μm) tended to be angular with sharp edges. Our results emphasise the importance of monitoring potentially toxic elements in atmospheric particulate matter of abandoned mining areas for developing mitigation strategies to reduce impacts on human health and surrounding environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Tungsten (W) contamination presents emerging environmental challenges, necessitating the need to establish soil screening levels (SSLs), especially for residential soils. This study assessed the health exposure risk and derived national and regional residential SSLs for W in Chinese residential soils, incorporating machine-learning prediction of in-vitro soil W bioaccessibility. We analyzed 204 residential soil samples collected across 24 provinces, recording a wide range of W concentrations (0.01-3063.2 mg/kg). Synchrotron-based X-ray fluorescence spectroscopy, chemical extractions, and random forest modeling indicated that the key determinants of soil W bioaccessibility were soil pH, cation exchange capacity, organic matter, and clay contents. Monte Carlo simulations demonstrated that soil W contamination predominantly results in noncarcinogenic health risks to residents via oral exposure, especially in mining-affected regions. A national residential SSL (NRSSL) of 35.5 mg/kg and regional residential SSLs (RRSSLs) of 34.5-49.2 mg/kg were established. Incorporating predicted bioaccessibility increased the NRSSL to 73.8 mg/kg and the RRSSLs to 69.8-112.5 mg/kg. Southern China, which is rich in W ore, exhibited lower RRSSLs, underscoring a need for enhanced safety management. Our framework and findings provide a robust scientific foundation for future soil contamination risk assessment studies, and we present customized SSLs that can guide targeted W risk control strategies., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Huihui Du reports financial support was provided by National Key Research and Development Program of China. Huihui Du reports financial support was provided by Science and Technology Innovation Program of Hunan Province. Huihui Du reports financial support was provided by National Natural Science Foundation of China. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: Dayu County, a major tungsten producer in China, experiences severe heavy metal pollution. This study evaluated the pollution status, the accumulation characteristics in paddy rice, and the potential ecological risks of heavy metals in agricutural soils near tungsten mining areas of Dayu County. Furthermore, the impacts of soil properties on the accumulation of heavy metals in soil were explored., Methods: The geo-accumulation index (I geo ), the contamination factor (CF), and the pollution load index (PLI) were used to evaluate the pollution status of metals (As, Cd, Cu, Cr, Pb, Mo, W, and Zn) in soils. The ecological risk factor (RI) was used to assess the potential ecological risks of heavy metals in soil. The health risks and accumulation of heavy metals in paddy rice were evaluated using the health risk index and the translocation factor (TF), respectively. Pearson's correlation coefficient was used to discuss the influence of soil factors on heavy metal contents in soil., Results: The concentrations of metals exceeded the respective average background values for soils (As: 10.4, Cd: 0.10, Cu: 20.8, Cr: 48.0, Pb: 32.1, Mo: 0.30, W: 4.93, Zn: 69.0, mg/kg). The levels of As, Cd, Mo, and tungsten(W) exceeded the risk screening values for Chinese agricultural soil contamination and the Dutch standard. The mean concentrations of the eight tested heavy metals followed the order FJ-S > QL > FJ-N > HL > CJ-E > CJ-W, with a significant distribution throughout the Zhangjiang River basin. Heavy metals, especially Cd, were enriched in paddy rice. The I geo and CF assessment indicated that the soil was moderately to heavily polluted by Mo, W and Cd, and the PLI assessment indicated the the sites of FJ-S and QL were extremely severely polluted due to the contribution of Cd, Mo and W. The RI results indicated that Cd posed the highest risk near tungsten mining areas. The non-carcinogenic and total carcinogenic risks were above the threshold values (non-carcinogenic risk by HQ > 1, carcinogenic risks by CR > 1 × 10 -4 a -1 ) for As and Cd. Correlation analysis indicated that K 2 O, Na 2 O, and CaO are main factors affecting the accumulation and migration of heavy metals in soils and plants. Our findings reveal significant contamination of soils and crops with heavy metals, especially Cd, Mo, and W, near mining areas, highlighting serious health risks. This emphasizes the need for immediate remedial actions and the implementation of stringent environmental policies to safeguard health and the environment., Competing Interests: The authors declare that they have no competing interests., (© 2024 Lai et al.)

Tungsten ore processing residue (TOPR) poses a potential risk due to tungsten (W) leaching. However, the leachability of W in TOPR is not well understood. Herein, the mechanism of W leachability from TOPR was investigated using complementary characterization techniques and leaching experiments. Our X-ray absorption near edge structure (XANES) analysis resolved wolframite in TOPR with a distorted octahedral coordination. The sequential extraction procedure showed that 78% of mobile fraction W in TOPR were bound to Fe oxides, and consequently W leachability was positively correlated with dissolved Fe concentration as evidenced by the general acid neutralizing capacity (GANC) test. The GANC results showed that the W release was negatively correlated with Ca concentration due to CaWO 4 precipitation. The in vitro gastrointestinal procedure (IVG) results indicated that organic acids, abundant in fruits and vegetables, significantly improved the bioaccessibility of W from 10% to 20% of total W in TOPR. As a consequence, accidental ingestion of TOPR with a chemical daily intake at 0.8 mg kg -1 day -1 evidenced its emerging concern in the environment and human health., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Establishing when, and from where, carbon, nitrogen and water were delivered to Earth is a fundamental objective in understanding the origin of habitable planets such as Earth. Yet, volatile delivery to Earth remains controversial 1-5 . Krypton isotopes provide insights on volatile delivery owing to their substantial isotopic variations among sources 6-10 , although pervasive atmospheric contamination has hampered analytical efforts. Here we present the full suite of krypton isotopes from the deep mantle of the Galápagos and Iceland plumes, which have the most primitive helium, neon and tungsten isotopic compositions 11-16 . Except for 86 Kr, the krypton isotopic compositions are similar to a mixture of chondritic and atmospheric krypton. These results suggest early accretion of carbonaceous material by proto-Earth and rule out any combination of hydrodynamic loss with outgassing of the deep or shallow mantle to explain atmospheric noble gases. Unexpectedly, the deep-mantle sources have a deficit in the neutron-rich 86 Kr relative to the average composition of carbonaceous meteorites, which suggests a nucleosynthetic anomaly. Although the relative depletion of neutron-rich isotopes on Earth compared with carbonaceous meteorites has been documented for a range of refractory elements 1,17,18 , our observations suggest such a depletion for a volatile element. This finding indicates that accretion of volatile and refractory elements occurred simultaneously, with krypton recording concomitant accretion of non-solar volatiles from more than one type of material, possibly including outer Solar System planetesimals., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

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.

Raman spectroscopy was used for the quantitative determination of Mo and W in Mo- and W-supported mesoporous silica (Mo/SBA-15 and W/SBA-15, respectively) and Mo-supported beta zeolite (Mo-BEA). Three Raman quantitative models were developed and optimized for the metal contents of Mo/SBA-15, W/SBA-15, and Mo/BEA. Subsequently, the models were characterized using the root mean square error of calibration (RMSEC), root mean square error of cross-validation (RMSECV), root mean square error of prediction (RMSEP), correlation coefficient, and predicted residual error sum of squares (PRESS) diagnostic function. The calibration range of the models were in the range of approximately 2-40 wt% for the SBA-15 support and 1-21 wt% for the BEA support because the BEA support presented lower Mo absorption than the SBA-15 support. The RMSEC, RMSECV, and RMSEP values were below 1.80% for all developed models. The highest and lowest correlation coefficients corresponded to the W/SBA-15 (0.9984) and Mo/BEA (0.9777) models, respectively. The change in catalyst support affected the mentioned chemometric parameters (Mo/SBA-15 vs. Mo/BEA). Subsequently, Raman spectroscopy combined with the temperature control stage was used to study the calcination of Mo/BEA, Mo/SBA-15, and W/SBA-15 using three-dimensional diagrams, in which the changes in catalyst structure were analyzed as functions of the temperature and time. Raman spectroscopy was determined to be a suitable analytical tool for the quantitative analysis of the metal contents of the catalyst and optimization of the calcination process. Therefore, Raman spectroscopy can be used during catalyst manufacturing.

In this study, a photocatalytic reactor with a novel engineering design has been used for the extended degradation of sulfamethazine (SMZ). The reactor employed four consecutive stainless-steel plates immobilized by tungsten-dope TiO 2 (W-TiO 2 ) using polysiloxane. The characterization of W-TiO 2 by X-ray diffraction (XRD), Raman spectroscopy, and energy-dispersive X-ray (EDX) denoted successful doping of tungsten in the lattice of anatase crystals of TiO 2 suggesting a high photocatalytic activity under UV and visible light. A Box-Behnken experimental design was employed for the optimization of the operating parameters such as solution pH, flow rate, and the initial SMZ concentration. The residual SMZ concentration was below the detection limit after 30 min of the photocatalytic reaction under the optimum operating conditions. A highly remarkable degradation of SMZ was observed in five consecutive cycles, which reveals an extended stable photocatalytic activity offered by the reactor design. The transformation products were identified by tandem mass spectrometry, and they were employed to propose the degradation pathway. These results highlight the importance of using the photocatalysts in retained forms and open additional avenues for the practical application of photocatalysis in wastewater treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

At high concentrations, tungsten can be toxic to humans, animals, and the environment, though little is known about natural, aqueous tungsten in surface waters. To improve understanding and develop a model predicting tungsten concentrations, we collected water and sediment from 77 water bodies in 20 watersheds in Washington State, USA. We found aqueous tungsten concentrations spanning two orders of magnitude (10.3 ng L -1 - 2.05 μg L -1 ) with average tungsten concentrations in both water and sediments more than two-fold higher in watersheds with tungsten-bearing underlying rock types (average: 0.217 μg L -1 , 0.669 mg kg -1 ; range: 0.010-2.05 μg L -1 , 0.0713-4.691 mg kg -1 for surface waters and sediments, respectively) than in watersheds without such underlying geology (average: 0.068 μg L -1 , 0.352 mg kg -1 ; range: 0.010-0.211 μg L -1 , 0.0349-2.399 mg kg -1 for surface waters and sediments, respectively). Aqueous concentrations of tungsten significantly correlated with beryllium (Be) and copper (Cu) (R 2  = 0.31, 0.41, respectively) and a multiple linear regression model using Be and Cu explained 65% of the variance in measured aqueous tungsten concentrations. Applying this model to existing Be and Cu data from 19 sites across the Pacific Northwest resulted in predicted tungsten concentrations ranging from 0.116 to 0.458 μg L -1 . These predicted concentrations along with our measured concentrations indicate none of these sites were close to the drinking water standard for tungsten set by the former Soviet Union-the only country so far to set limits for tungsten in drinking water (50 μg L -1 )., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Synchrotron radiation micro-X-ray fluorescence (SR-μXRF) is a powerful elemental mapping technique that has been used to map tungsten and zinc distribution in bone tissue. However, the heterogeneity of the bone samples along with overlap of the tungsten L-edge with the zinc K-edge signals complicates SR-μXRF data analysis, introduces minor artefacts into the resulting element maps, and decreases image sensitivity and resolution. To confirm and more carefully delineate these SR-μXRF results, we have employed laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to untangle the problem created by the K/L-edge overlap of the tungsten/zinc pair. While the overall elemental distribution results are consistent between the two techniques, LA-ICP-MS provides significantly higher sensitivity and image resolution compared with SR-μXRF measurements in bone. These improvements reveal tissue-specific distribution patterns of tungsten and zinc in bone, not observed using SR-μXRF. We conclude that probing elemental distribution in bone is best achieved using LA-ICP-MS, though SR-μXRF retains the advantage of being a non-destructive method with the capability of being paired with X-ray techniques, which determine speciation in situ. Since tungsten is an emerging contaminant recently found to accumulate in bone, accurately determining its distribution and speciation in situ is essential for directing toxicological studies and informing treatment regimes. Graphical abstract Tungsten and zinc localization and uptake in mouse femurs were imaged by synchrotron radiation, left, and by laser ablation ICP-MS, right. The increased resolution of the LA-ICP-MS technique resolves the problem of the overlap in tungsten's L-edge and zinc's K-edge.

The performance of the first direct digital mammography unit in Gozo General Hospital, the Hologic Selenia Dimensions 2D, was assessed by applying the European Protocol for quality control in mammography screening. This system employs a Tungsten anode in association with a Rhodium or Silver filter, depending on the compressed breast thickness. The objective of this article was to apply the European Protocol in the evaluation of this system in terms of dose, image quality and detector performance and determine whether this system is suitable for use in the national breast-screening program., (© The Author(s) 2019. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

The mobility of heavy metalloids including As, Sb, Mo, W, and Cr in soil was investigated under both reducing and oxidizing conditions. The effects of soil mineralogy and the presence of competitive anions were studied as important factors affecting the mobility of these contaminants. Batch experiments conducted with the addition of oxidized and fresh FeS exhibited enhanced sorption rates for As and W under oxidizing conditions, and for Mo under reducing conditions. The inhibitory effect of phosphate on the sorption rates was most apparent for As and Mo under both oxidizing and reducing conditions, while only a small phosphate effect was observed for Sb and W. For Sb and W mobility, pH was determined to be the most important controlling factor. The results of long-term batch experiments revealed that differences in the mobility of metalloids, particularly As, were also influenced by microbial activity in the oxidizing and reducing conditions., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

As the largest man-made reservoir in China, the Three Gorges Reservoir (TGR) has significant influence on national drinking water safety. The geochemical behavior of trace elements at the sediment-water interface (SWI) is still unknown. The mobilization characteristics of trace elements (As, Mo and W)-determined by diffusive gradients in thin films (DGT)-were studied to quantitatively calculate the release trends in the SWI in three typical tributaries and the mainstream of the TGR in the summer. The results showed that concentrations of DGT-labile As, Mo and W in the overlying water and sediment cores showed significant variations in the ranges of 0.05-50.90, 0.30-1.63 and 0.01-0.42μgL -1 , respectively. The apparent net diffusive fluxes were significantly positive in most sampling sites (77.8% for As, 88.8% for Mo and 66.6% for W), suggesting that the sediment was the source of these three elements. It was noteworthy that the maximum net diffusive fluxes of As and W were found in the upstream of Meixi tributary, which may be attributed to anthropogenic activities. In addition, As, Mo and W may be incorporated in Fe and Mn oxyhydroxides and these three elements simultaneously remobilized with Fe and Mn., (Copyright © 2017 Elsevier Inc. All rights reserved.)

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.

Background: Welders are exposed to a number of metallic elements during work. Bioaccessability, that is important for element uptake, has been little studied. This study addresses bioaccessability and uptake of chromium (Cr), molybdenum (Mo), tungsten (W) and vanadium (V) among welders., Methods: Bioaccessability of Cr, Mo, V and W was studied in airborne particulate matter collected by personal sampling of the workroom air among shipyard welders by using the lung lining fluid simulant Hatch solution. Associations between concentrations of Hatch soluble and non-soluble elements (Hatch sol and Hatch non-sol ) and concentrations of the four elements in whole blood, serum, blood cells and urine were studied., Results: Air concentrations of the four elements were low. Only a small fraction of Cr, V and W was Hatch sol , while similar amounts of Mo were Hatch sol and Hatch non-sol . Welders (N=70) had statistically significantly higher concentrations of all four elements in urine and serum when compared to referents (N=74). Highly statistically significant associations were observed between urinary W and Hatch sol W (p<0.001) and serum V and Hatch sol V (p<0.001), in particular when air samples collected the day before collection of biological samples were considered., Conclusions: Associations between Hatch sol elements in air and their biological concentrations were higher than when Hatch non-sol concentrations were considered. Associations were generally higher when air samples collected the day before biological sampling were considered as compared to air samples collected two days before., (Copyright © 2017 Elsevier GmbH. All rights reserved.)

We aimed to evaluate the elemental (W, Mo, Zn, Fe, Cu, Co, Bi, Mn, Cd, Cr, As) composition of some plant species spread around the abandoned tungsten mining area of Uludağ Mountain. The plant species tested were Anthemis cretica and Trisetum flavescens which are grown in this area and they are pioneer species on these contaminated sites. W levels in soils were found up to 1378.6 ± 672.3 mg/kg dry weight in contaminated areas. The leaf W contents of the selected plant species were found 41.1 ± 24.4 and 31.1 ± 15.5 mg/kg dry weight for A. cretica and T. flavescens, respectively. Our results indicate that the elemental composition of species changed by the increased tungsten and some element concentrations in soil without detrimental effect. So, these species can be useful tungsten removal and some elements from contaminated sites.

Pure Ti and Ti-5%W foams were prepared via freeze casting. The porosity and grain size of both the materials were 32-33% and 15-17µm, respectively. The mechanical behavior of the foams was investigated by uniaxial compression up to a plastic strain of ~0.26. The Young׳s moduli of both foams were ~23GPa, which was in good agreement with the value expected from their porosity. The Young׳s moduli of the foams were similar to the elastic modulus of cortical bones, thereby eliminating the osteoporosis-causing stress-shielding effect. The addition of W increased the yield strength from ~196MPa to ~235MPa. The microstructure evolution in the grains during compression was studied using electron backscatter diffraction (EBSD) and X-ray line profile analysis (XLPA). After compression up to a plastic strain of ~0.26, the average dislocation densities increased to ~3.4×10(14)m(-2) and ~5.9×10(14)m(-2) in the Ti and Ti-W foams, respectively. The higher dislocation density in the Ti-W foam can be attributed to the pinning effect of the solute tungsten atoms on dislocations. The experimentally measured yield strength was in good agreement with the strength calculated from the dislocation density and porosity. This study demonstrated that the addition of W to Ti foam is beneficial for biomedical applications, because the compressive yield strength increased while its Young׳s modulus remained similar to that of cortical bones., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Objectives: Exposure to stainless steel (SS) welding aerosol that contain toxic heavy metals, chromium (Cr), manganese (Mn), and nickel (Ni), has been associated with numerous adverse health effects. The gas tungsten arc welding (GTAW) is commonly applied to SS and produces high number concentration of substantially smaller particles compared with the other welding techniques, although the mass emission rate is low. Here, a field study in a workshop with the GTAW as principal welding technique was conducted to determine the physicochemical properties of the airborne particles and to improve the understanding of the hazard the SS welding aerosols pose to welders., Methods: Particle number concentration and number size distribution were measured near the breathing zone (50cm from the arc) and in the middle of the workshop with condensation particle counters and electrical mobility particle sizers, respectively. Particle morphology and chemical composition were studied using scanning and transmission electron microscopy and energy-dispersive X-ray spectroscopy., Results: In the middle of the workshop, the number size distribution was unimodal with the geometric mean diameter (GMD) of 46nm. Near the breathing zone the number size distribution was multimodal, and the GMDs of the modes were in the range of 10-30nm. Two different agglomerate types existed near the breathing zone. The first type consisted of iron oxide primary particles with size up to 40nm and variable amounts of Cr, Mn, and Ni replacing iron in the structure. The second type consisted of very small primary particles and contained increased proportion of Ni compared to the proportion of (Cr + Mn) than the first agglomerate type., Conclusions: The alterations in the distribution of Ni between different welding aerosol particles have not been reported previously., (© The Author 2016. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.)

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.)

Tungsten inert gas welding (TIG) represents one of the most widely used metal joining processes in industry. Its propensity to generate a greater portion of welding fume particles at the nanoscale poses a potential occupational health hazard for workers. However, current literature lacks comprehensive characterization of TIG welding fume particles. Even less is known about welding fumes generated by welding apprentices with little experience in welding. We characterized TIG welding fume generated by apprentice welders (N = 20) in a ventilated exposure cabin. Exposure assessment was conducted for each apprentice welder at the breathing zone (BZ) inside of the welding helmet and at a near-field (NF) location, 60cm away from the welding task. We characterized particulate matter (PM4), particle number concentration and particle size, particle morphology, chemical composition, reactive oxygen species (ROS) production potential, and gaseous components. The mean particle number concentration at the BZ was 1.69E+06 particles cm(-3), with a mean geometric mean diameter of 45nm. On average across all subjects, 92% of the particle counts at the BZ were below 100nm. We observed elevated concentrations of tungsten, which was most likely due to electrode consumption. Mean ROS production potential of TIG welding fumes at the BZ exceeded average concentrations previously found in traffic-polluted air. Furthermore, ROS production potential was significantly higher for apprentices that burned their metal during their welding task. We recommend that future exposure assessments take into consideration welding performance as a potential exposure modifier for apprentice welders or welders with minimal training., (© The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.)

Determination of the (182)W/(184)W ratio to a precision of ± 5 ppm (2σ) is desirable for constraining the timing of core formation and other early planetary differentiation processes. However, WO3(-) analysis by negative thermal ionization mass spectrometry normally results in a residual correlation between the instrumental-mass-fractionation-corrected (182)W/(184)W and (183)W/(184)W ratios that is attributed to mass-dependent variability of O isotopes over the course of an analysis and between different analyses. A second-order correction using the (183)W/(184)W ratio relies on the assumption that this ratio is constant in nature. This may prove invalid, as has already been realized for other isotope systems. The present study utilizes simultaneous monitoring of the (18)O/(16)O and W isotope ratios to correct oxide interferences on a per-integration basis and thus avoid the need for a double normalization of W isotopes. After normalization of W isotope ratios to a pair of W isotopes, following the exponential law, no residual W-O isotope correlation is observed. However, there is a nonideal mass bias residual correlation between (182)W/(i)W and (183)W/(i)W with time. Without double normalization of W isotopes and on the basis of three or four duplicate analyses, the external reproducibility per session of (182)W/(184)W and (183)W/(184)W normalized to (186)W/(183)W is 5-6 ppm (2σ, 1-3 μg loads). The combined uncertainty per session is less than 4 ppm for (183)W/(184)W and less than 6 ppm for (182)W/(184)W (2σm) for loads between 3000 and 50 ng.

Unlabelled: Glass prefilled syringes are increasingly becoming a container of choice for storing and administering therapeutic protein products to patients. Tungsten leaching from a PFS is known to induce protein particle formation, and the source was traced to the tungsten pins used in the manufacturing process of the syringe barrels. Study of the tungstates present in extracts from both tungsten pins used in the syringe manufacturing process and from single syringes from various suppliers was undertaken. Electrospray mass spectrometry was chosen as a technique with the sensitivity to characterize tungstates at levels (∼1 ppm of elemental tungsten) observed in single syringes. Extraction solvents were chosen to simulate the range (pH 4.0-7.0) typically used for therapeutic protein formulation. A commercial product formulation buffer was also used as an extraction solution to characterize tungstate species used for tungsten spiking studies of protein. All pin and syringe extracts from various manufacturers were similar in regards to containing stable Na/K containing lacunary polytungstate ([W11O39](7-)) species, which were the main species present in syringe extracts and are different than the metatungstate ([W12O39](6-)) species identified in commercially available sodium polytungstate and as the main species in pin extracts. These stable Na/K containing polytungstates species present in pin and syringe extracts are likely formed during the glass manufacturing process at >400 °C and may have the capability to subsequently form larger polytungstate complexes., Lay Abstract: Glass prefilled syringes are a type of container used for storing and administering biotechnology medicines to patients. The manufacturing process for the syringes may lead to very low levels of the metal tungsten being present in the syringes, and thus in the medicine stored in the syringes. The presence of tungsten in certain biotechnology medicines has been shown to cause changes to the medicine. Understanding something that can cause a medicine to change is an important part of producing safe and effective medicines for patients. The study described in this article sought to increase understanding by characterizing the form of tungsten observed in syringes from a number of vendors. Study of the tungsten present in syringes from four vendors indicates the same form of tungsten is observed regardless of the vendor. The study also found that the form of tungsten differed from that expected., (© PDA, Inc. 2016.)

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.)

We evaluated the relationship between the risk of childhood acute lymphoblastic leukemia (ALL) and the levels of metals in carpet dust. A dust sample was collected from the homes of 142 ALL cases and 187 controls participating in the California Childhood Leukemia Study using a high volume small surface sampler (2001-2006). Samples were analyzed using microwave-assisted acid digestion in combination with inductively coupled plasma mass spectrometry for arsenic, cadmium, chromium, copper, lead, nickel, tin, tungsten, and zinc. Eight metals were detected in at least 85% of the case and control homes; tungsten was detected in <15% of homes. Relationships between dust metal loadings (μg metal per m(2) carpet) and ALL risk were modeled using multivariable logistic regression, adjusting for the child's age, sex, and race/ethnicity and confounders, including household annual income. A doubling of dust metal loadings was not associated with significant changes in ALL risk (odds ratio (95% confidence interval): arsenic: 0.96 (0.86, 1.07), cadmium: 0.92 (0.81, 1.05), chromium: 1.01 (0.90, 1.14), copper: 0.97 (0.91, 1.03), lead: 1.01 (0.93, 1.10), nickel: 0.95 (0.82, 1.09), tin: 0.96 (0.86, 1.08), and zinc: 0.94 (0.84, 1.05)). Our findings do not support the hypothesis that metals in carpet dust are risk factors for childhood ALL.

There is a dearth of dental scientific literature on the effect of different oxidation heat treatments (OHTs) (as surface pretreatments) on the bonding performance of cast and milled cobalt-chromium (CoCr) alloys. The objective of this study was to evaluate the effect of different OHTs on the bond strength between a ceramic and cast and milled CoCr alloys. Cobalt-chromium metallic specimens were prepared using either a cast or a milled method. Specimens were subjected to four different OHT methods: without OHT; OHT under normal atmospheric pressure; OHT under vacuum; and OHT under vacuum followed by sandblasting. The metal-ceramic bond strength was evaluated using a three-point bending test according to ISO9693. Scanning electron microscopy and energy-dispersive spectroscopy were used to study the specimens' microstructure and elemental composition. The bond strength was not affected by the CoCr manufacturing method. Oxidation heat treatment performed under normal atmospheric pressure resulted in the highest bond strength. The concentration of oxygen on the alloy surfaces varied with the different pretreatment methods in the following order: OHT under normal atmospheric pressure > OHT under vacuum > without OHT ≈ OHT under vacuum followed by sandblasting., (© 2015 Eur J Oral Sci.)

Recent legislation has focused attention on the supply chains of tin, tungsten, tantalum, and gold (3TG), specifically those originating from the eastern part of the Democratic Republic of Congo. The unique properties of these so-called “conflict minerals” lead to their use in many products, ranging from medical devices to industrial cutting tools. This paper calculates per product use of 3TG in several information, communication, and technology (ICT) products such as desktops, servers, laptops, smart phones, and tablets. By scaling up individual product estimates to global shipment figures, this work estimates the influence of the ICT sector on 3TG mining in covered countries. The model estimates the upper bound of tin, tungsten, tantalum, and gold use within ICT products to be 2%, 0.1%, 15%, and 3% of the 2013 market share, respectively. This result is projected into the future (2018) based on the anticipated increase in ICT device production.

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.)

There is an increasing likelihood of interactions between nanomaterials and munitions constituents in the environment resulting from the use of nanomaterials as additives to energetic formulations and potential contact in waste streams from production facilities and runoff from training ranges. The purpose of the present research was to determine the ability of nano-aluminum oxide (Al(2)O(3)) and multiwalled carbon nanotubes (MWCNTs) to adsorb the munitions constituents cyclotrimethylenetrinitramine (RDX) and tungsten (W) from aqueous solution as a first step in determining the long-term exposure, transport, and bioavailability implications of such interactions. The results indicate significant adsorption of RDX by MWCNTs and of W by nano-Al(2)O(3) (but not between W and MWCNT or RDX and nano-Al(2)O(3)). Kinetic sorption and desorption investigations indicated that the most sorption occurs nearly instantaneously (<5 min), with a relatively slower, secondary binding leading to statistically significant but relatively smaller increases in adsorption over 30 d. The RDX sorption that occurred during the initial interaction was irreversible, with long-term, reversible sorption likely the result of a secondary interaction; as interaction time increased, however, the portion of W irreversibly sorbed onto nano-Al(2)O(3) also increased. The present study shows that strong interactions between some munitions constituents and nanomaterials following environmental release are likely. Time-dependent binding has implications for the bioavailability, migration, transport, and fate of munitions constituents in the environment., (© 2014 SETAC.)

The objective of this study is to investigate tungsten (W) contamination in soil and its enrichment in rice in the area of the world's largest and longest-operating W mines in China. Root zone soil and rice plants were sampled at 15 sites in the agricultural field adjacent to W mines and analyzed for Al, Fe, Mn, Sc, and W contents and W chemical forms in the soil samples and W contents in the rice root, stem, leaf, and grain samples. Results showed that W content in the soil ranged from 3.99 to 43.7 mg kg(-1), with more than 90% of W in the residual fraction, showing its low mobility and bioavailability. Average W contents in the rice root, stem, leaf, and grain were 7.06, 2.34, 4.76, 0.17 mg kg(-1), respectively. In addition, they were linearly independent of W content and chemical forms in the soil. Average enrichment factor values were 0.39, 0.13, 0.28, and 0.01 for the root, stem, leaf, and grain, respectively. In can be concluded that W mining activity in the Dayu county contaminated the nearby agricultural soil and led to W bioaccumulation in the rice. This may pose a health risk to residents via food and soil ingestion, which should be a focus of scrutiny.

Background: The majority of modern war wounds are characterized by high-energy blast injuries containing a wide range of retained foreign materials of a metallic or composite nature. Health effects of retained fragments range from local or systemic toxicities to foreign body reactions or malignancies, and dependent on the chemical composition and corrosiveness of the fragments in vivo. Information obtained by chemical analysis of excised fragments can be used to guide clinical decisions regarding the need for fragment removal, to develop therapeutic interventions, and to better anticipate future medical problems from retained fragment related injuries. In response to this need, a new U.S Department of Defense (DoD) directive has been issued requiring characterization of all removed fragments to provide a database of fragment types occurring in combat injuries., Objectives: The objective of this study is to determine the chemical composition of retained embedded fragments removed from injured military personnel, and to relate results to histological findings in tissue adjacent to fragment material., Methods: We describe an approach for the chemical analysis and characterization of retained fragments and adjacent tissues, and include case examples describing fragments containing depleted uranium (DU), tungsten (W), lead (Pb), and non-metal foreign bodies composed of natural and composite materials. Fragments obtained from four patients with penetrating blast wounds to the limbs were studied employing a wide range of chemical and microscopy techniques. Available adjacent tissues from three of the cases were histologically, microscopically, and chemically examined. The physical and compositional properties of the removed foreign material surfaces were examined with energy dispersive x-ray fluorescence spectrometry (EDXRF), scanning electron microscopy (SEM), laser ablation inductively-coupled plasma mass-spectrometry (LA-ICP-MS), and confocal laser Raman microspectroscopy (CLRM). Quantitative chemical analysis of both fragments and available tissues was conducted employing ICP-MS., Results: Over 800 fragments have been characterized and included as part of the Joint Pathology Center Embedded Fragment Registry. Most fragments were obtained from penetrating wounds sustained to the extremities, particularly soft tissue injuries. The majority of the fragments were primarily composed of a single metal such as iron, copper, or aluminum with traces of antimony, titanium, uranium, and lead. One case demonstrated tungsten in both the fragment and the connected tissue, together with lead. Capsular tissue and fragments from a case from the 1991 Kuwait conflict showed evidence of uranium that was further characterized by uranium isotopic ratios analysis to contain depleted uranium., Conclusions: The present study provides a systematic approach for obtaining a full chemical characterization of retained embedded fragments. Given the vast number of combat casualties with retained fragments, it is expected that fragment analysis will have significant implications for the optimal short and long-term care of wounded service members.

A 63-year-old man employed in a hard metal manufacturing company for 40 years presented with a chronic dry cough and exertional dyspnea 20 years after the onset of recurrent exanthemas. A chest radiograph revealed bilateral reticular shadows in the upper lung field. Pathological specimens in which tungsten was detected were obtained via a transbronchial lung biopsy. Patch tests were positive for cobalt and other metals. The patient was diagnosed with hard metal lung disease (HMLD) concurrent with contact dermatitis and treated with corticosteroids. This case suggests that allergies to metal may play a role in the onset of HMLD.

A number of gaseous oxyacid salts have been identified by Knudsen effusion mass spectrometry by vaporizing In2O3 from molybdenum or tungsten double two-temperature cells. The stability of gaseous molecules In2MoO4, In2WO4, and In2W2O7 was deduced from the measurements. The structures and molecular parameters of all investigated salts were obtained using quantum chemical calculations. On the basis of equilibrium constants measured for gas-phase reactions, the standard enthalpies of formation were determined to be -855 ± 33, -773 ± 30, and -1565 ± 30 kJ mol(-1) for In2MoO4, In2WO4, and In2W2O7 respectively. Overall the results obtained allowed us to estimate the standard formation enthalpy of In2MoO3, In2WO3, and In2Mo2O7 to be -519, -467 and -1530 kJ mol(-1), respectively, with an accuracy of ±40 kJ mol(-1).

A test procedure was developed and verified to measure the airborne concentrations of particles of different sizes (0.5-20 μm) within the vicinity of a dropped container when a significant portion of the tungsten oxide powder (simulating uranium oxide) is ejected from the container. Tests were carried out in a full-scale stainless steel environmental chamber with an interior volume of 24.1 m(3). Thirty-two drop tests were performed, covering variations in dropping height, room air movement, landing scenario, and lid condition. Assuming a breathing rate of 1.2 m(3)/hr, the uptake factor during the first 10 min was calculated to be between 1.13 × 10(-9) and 1.03 × 10(-7) in reference to the amount loaded; or between 6.44 × 10(-8) and 3.55 × 10(-4) in reference to the amount spilled. Results provide previously unavailable data for estimating the exposure and associated risk to building occupants in the case of an accidental dropping of heavy powder containers. The test data show that for spills larger than 0.004 g, the power-law correlation between the spill uptake factor and the spilled mass (i.e., SUF = 2.5 × 10(-5) × Spill&#95;Mass(-0.667)) established from the test data is smaller and a more accurate estimate than the constant value of 10(-3) assumed in the Department of Energy Nuclear Material Packaging Manual. [Supplementary materials are available for this article. Go to the publisher's online edition of Journal of Occupational and Environmental Hygiene for the following free supplementary resource: an online supplementary table of all cumulative uptake amounts at 10 min for all test data.].

Metallic tungsten has civil and military applications and was considered a green alternative to lead. Recent reports of contamination in drinking water and soil have raised scrutiny and suspended some applications. This investigation employed the cabbage Brassica oleracae and snail Otala lactea as models to determine the toxicological implications of sodium tungstate and an aged tungsten powder-spiked soil containing monomeric and polymeric tungstates. Aged soil bioassays indicated cabbage growth was impaired at 436 mg of W/kg, while snail survival was not impacted up to 3793 mg of W/kg. In a dermal exposure, sodium tungstate was more toxic to the snail, with a lethal median concentration of 859 mg of W/kg. While the snail significantly bioaccumulated tungsten, predominately in the hepatopancreas, cabbage leaves bioaccumulated much higher concentrations. Synchrotron-based mapping indicated the highest levels of W were in the veins of cabbage leaves. Our results suggest snails consuming contaminated cabbage accumulated higher tungsten concentrations relative to the concentrations directly bioaccumulated from soil, indicating the importance of robust trophic transfer investigations. Finally, synchrotron mapping provided evidence of tungsten in the inner layer of the snail shell, suggesting potential use of snail shells as a biomonitoring tool for metal contamination.

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.)

By increasing the usage of radiation in all aspects of lives, the human body is becoming more exposed to ionising radiation. The purpose of this study is to find the optimal radiation shielding materials to protect humans from the radiation hazards of radiation. Some elements and compounds such as Ag, Bi, Pb, W, BaSO(4) were chosen on the basis of their attenuation coefficients and other characteristics to produce optimised radiation shielding compounds. Multi-objective non-dominated sorting genetic algorithm-II was used to optimise the weight fraction of the elements in compounds based on the dose equivalent rate, shield weight and cost. Consequently, sets of suitable compounds were obtained depending on various applications for energy 0.06 and 0.15 MeV. In addition, optimised lead free compounds were obtained. The results presented in a series of graphs should enable radiation shield designers to choose an appropriate combination according to their requirements.

This study investigates the dissolution, sorption, leachability, and plant uptake of tungsten and alloying metals from canister round munitions in the presence of model, well characterized soils. The source of tungsten was canister round munitions, composed mainly of tungsten (95%) with iron and nickel making up the remaining fraction. Three soils were chosen for the lysimeter studies while four model soils were selected for the adsorption studies. Lysimeter soils were representatives of the typical range of soils across the continental USA; muck-peat, clay-loamy and sandy-quartzose soil. Adsorption equilibrium data on the four model soils were modeled with Langmuir and linear isotherms and the model parameters were obtained. The adsorption affinity of soils for tungsten follows the order: Pahokee peat>kaolinite>montmorillonite>illite. A canister round munition dissolution study was also performed. After 24 d, the measured dissolved concentrations were: 61.97, 3.56, 15.83 mg L(-1) for tungsten, iron and nickel, respectively. Lysimeter transport studies show muck peat and sandy quartzose soils having higher tungsten concentration, up to 150 mg kg(-1) in the upper layers of the lysimeters and a sharp decline with depth suggesting strong retardation processes along the soil profile. The concentrations of tungsten, iron and nickel in soil lysimeter effluents were very low in terms of posing any environmental concern; although no regulatory limits have been established for tungsten in natural waters. The substantial uptake of tungsten and nickel by ryegrass after 120 d of exposure to soils containing canister round munition suggests the possibility of tungsten and nickel entering the food chain., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

A highly selective and low cost extractive spectrofluorimetric method was developed for determination of trace concentrations of tungsten (VI) in water. The method was based upon solvent extraction of the developed ion associate [(PQH(+))(2)·WO(4)(2-)] of the fluorescent ion-pairing reagent [2-(diethylamino)ethyl 4 aminobenzoate] hydrochloride namely procaine hydrochloride, PQH(+)·Cl(-) and tungstate (WO(4)(2-)) in aqueous solution of pH 6-7 followed by measuring the resulting fluorescence enhancement in n-hexane at λ(ex/em)=270/320nm. The fluorescence intensity of PQH(+)·Cl(-) increased linearly on increasing tungstate concentration in the range 25-250μgL(-1). The limits of detection (LOD) and quantification (LOQ) of tungsten (VI) were found 7.51 and 24.75μgL(-1), respectively. Chemical composition of the developed ion associate and the molar absorptivity at 270nm were found to be [(PQH(+))(2)·WO(4)(2-)] and 2.7×10(4)Lmol(-1)cm(-1), respectively. Other oxidation states (III, IV, V) of tungsten species could also be determined after oxidation with H(2)O(2) in aqueous solution to tungsten (VI). The method was applied for analysis of tungsten in certified reference material (IAEA Soil-7) and wastewater samples. The results were compared successfully (>95%) with the data of inductively coupled plasma-mass spectrometry (ICP-MS)., (Copyright © 2011 Elsevier B.V. All rights reserved.)

To improve understanding of possible connections between airborne tungsten and public health, size and geography of airborne tungsten particles collected in Fallon, Nevada, and Sweet Home, Oregon, were compared. Both towns have industrial tungsten facilities, but only Fallon has experienced a cluster of childhood leukemia. Fallon and Sweet Home are similar to one another by their particles of airborne tungsten being generally small in size. Meteorologically, much, if not most, of residential Fallon is downwind of its hard metal facility for at least some fraction of time at the annual scale, whereas little of residential Sweet Home is downwind of its tungsten facility. Geographically, most Fallon residents potentially spend time daily within an environment containing elevated levels of airborne tungsten. In contrast, few Sweet Home residents potentially spend time daily within an airborne environment with elevated levels of airborne tungsten. Although it cannot be concluded from environmental data alone that elevated airborne tungsten causes childhood leukemia, the lack of excessive cancer in Sweet Home cannot logically be used to dismiss the possibility of airborne tungsten as a factor in the cluster of childhood leukemia in Fallon. Detailed modeling of all variables affecting airborne loadings of heavy metals would be needed to legitimately compare human exposures to airborne tungsten in Fallon and Sweet Home.

Purpose: Target tracking is a promising method for motion compensation in radiotherapy. For image-based dynamic multileaf collimator (DMLC) tracking, latency has been shown to be the main contributor to geometrical errors in tracking of respiratory motion, specifically due to slow transfer of image data from the image acquisition system to the tracking system via image file storage on a hard disk. The purpose of the current study was to integrate direct image access with a DMLC tracking system and to quantify the tracking latency of the integrated system for both kV and MV image-based tracking., Method: A DMLC tracking system integrated with a linear accelerator was used for tracking of a motion phantom with an embedded tungsten marker. Real-time target localization was based on x-ray images acquired either with a portal imager or a kV imager mounted orthogonal to the treatment beam. Images were processed directly without intermediate disk access. Continuous portal images and system log files were stored during treatment delivery for detailed offline analysis of the tracking latency., Results: The mean tracking system latency for kV and MV image-based tracking as function of the imaging interval ΔT(image) increased linearly with ΔT(image) as 148 ms + 0.58 * ΔT(image) (kV) and 162 ms + 1.1 * ΔT(image) (MV). The latency contribution from image acquisition and image transfer for kV image-based tracking was independent on ΔT(image) at 103 ± 14 ms. For MV-based tracking, it increased with ΔT(image) as 124 ms + 0.44 * ΔT(image). For ΔT(image) = 200 ms (5 Hz imaging), the total latency was reduced from 550 ms to 264 ms for kV image-based tracking and from 500 ms to 382 ms for MV image-based tracking as compared to the previously used indirect image transfer via image file storage on a hard disk., Conclusion: kV and MV image-based DMLC tracking was successfully integrated with direct image access. It resulted in substantial tracking latency reductions compared with image-based tracking without direct image access.

Through analyses of water and sediments, we investigate tungsten and 14 other heavy metals in a stream receiving treated effluents from a semiconductor manufacturer-clustered science park in Taiwan. Treated effluents account for ∼ 50% of total annual river discharge and <1% of total sediment discharge. Dissolved tungsten concentrations in the effluents abnormally reach 400 μg/L, as compared to the world river average concentration of <0.1 μg/L. Particulate tungsten concentrations are up to 300 μg/g in suspended and deposited sediments, and the corresponding enrichment factors are three orders of magnitude higher than average crust composition. Surprisingly, the estimated amount of tungsten exported to the adjacent ocean is 23.5 t/yr, which can approximate the amount from the Yangtze River should it be unpolluted. This study highlights the urgency of investigating the biological effect of such contamination., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Physical changes that occur on the surface of fired shots due to firing and impact with soil may increase the dissolution of muniton metals. Increased metal dissolution could potentially increase metal transport and leaching, affecting metal concentrations in surface and groundwater. This research describes the relationship between the surface changes on fired tungsten-nickel-iron (94% W:2% Ni:4% Fe) composite shots and metals leaching from those shots. Tungsten composite shot was fired into, and aged in, three soil types (Silty Sand, Sandy Clay, and Silt) in mesoscale rainfall lysimeters to simulate live-fire conditions and subsequent interactions between the metals of the composite and soil. Leachate, runoff, and soil samples were collected from the lysimeters and analyzed for metal content. The shots were analyzed using scanning electron microscopy (SEM) to evaluate surface changes. SEM results indicated that a soil's particle size distribution initially affected the amount of metal that was sheared from the surface of the fired W-composite shots. Shearing was greatest in soils with larger soil particles (sand and gravel); shearing was least in soils composed of small soil particles (fines). Increased metallic shearing from the shot's surface was associated with increased W dissolution, compared to controls, following a simulated 1 year soil aging., (Published by Elsevier Ltd.)

A microfluidic dielectrophoresis platform consisting of curved microelectrodes was developed and integrated with a Raman spectroscopy system. The electrodes were patterned on a quartz substrate, which has insignificant Raman response, and integrated with a microfluidic channel that was imprinted in poly-dimethylsiloxane (PDMS). We will show that this novel integrated system can be efficiently used for the determination of suspended particle types and the direct mapping of their spatial concentrations. We will also illustrate the system's unique advantages over conventional optical systems. Nanoparticles of tungsten trioxide (WO(3)) and polystyrene were used in the investigations, as they are Raman active and can be homogeneously suspended in water.

Background: During the manufacture of tungsten metal for non-sag wire, tungsten oxide powders are produced as intermediates and can be in the form of tungsten trioxide (WO3) or tungsten blue oxides (TBOs). TBOs contain fiber-shaped tungsten sub-oxide particles of respirable or thoracic size. The aim of this research was to investigate whether fiber-containing TBOs had prolonged biodurability in artificial lung fluids compared to tungsten metal or WO3 and therefore potentially could pose a greater inhalation hazard., Methods: Dissolution of tungsten metal, WO3, one fiber-free TBO (WO2.98), and three fiber-containing TBO (WO2.81, WO2.66, and WO2.51) powders were measured for the material as-received, dispersed, and mixed with metallic cobalt. Solubility was evaluated using artificial airway epithelial lining fluid (SUF) and macrophage phagolysosomal simulant fluid (PSF)., Results: Dissolution rates of tungsten compounds were one to four orders of magnitude slower in PSF compared to SUF. The state of the fiber-containing TBOs did not influence their dissolution in either SUF or PSF. In SUF, fiber-containing WO2.66 and WO2.51 dissolved more slowly than tungsten metal or WO3. In PSF, all three fiber-containing TBOs dissolved more slowly than tungsten metal., Conclusions: Fiber-containing TBO powders dissolved more slowly than tungsten metal and WO3 powders in SUF and more slowly than tungsten metal in PSF. Existing pulmonary toxicological information on tungsten compounds indicates potential for pulmonary irritation and possibly fibrosis. Additional research is needed to fully understand the hazard potential of TBOs.

In an extensive environmental study, field samples, including soil, water, rice, vegetable, fish, human hair and urine, were collected at an abandoned tungsten mine in Shantou City, southern China. Results showed that arsenic (As) concentration in agricultural soils ranged from 3.5 to 935 mg kg(-1) with the mean value of 129 mg kg(-1). In addition, As concentration reached up to 325 microg L(-1) in the groundwater, and the maximum As concentration in local food were 1.09, 2.38 and 0.60 mg kg(-1) for brown rice, vegetable and fish samples, respectively, suggesting the local water resource and food have been severely contaminated with As. Health impact monitoring data revealed that As concentrations in hair and urine samples were up to 2.92 mg kg(-1) and 164 microg L(-1), respectively, indicating a potential health risk among the local residents. Effective measurements should be implemented to protect the local community from the As contamination in the environment., (Copyright (c) 2009 Elsevier Ltd. All rights reserved.)

Tungsten is a widely used transition metal for which very limited information on environmental and toxicological effects is available. Of particular interest is the lack of information linking tungsten speciation and environmental effects. Tungsten anions may polymerize (depending upon concentration, pH, and aquatic geochemistry) in aquatic and soil systems. However, to this date, of all soluble tungstate species only monotungstates have been scrutinized to a fair extent in toxicological studies. The objective of this work is a comparative assessment of the acute toxicity of monotungstates (sodium tungstate, Na(2)WO(4)) and polytungstates (sodium metatungstate, 3Na(2)WO(4).9WO(3)) to Poecilia reticulate. The experiments have been performed according to the OEDC protocols 203 and 204. LD50 values for 1-14 days show that sodium metatungstate is significantly more toxic to fish than sodium tungstate. Based on LD50 (0.86-3.88gL(-1) or 4.67-21.1x10(-3)molNa(2)WO(4)L(-1)), sodium tungstate may be classified as a chemical of low toxicity to fish. Sodium metatungstate caused similar fish mortality to sodium tungstate when it was introduced in 55-80 times lower concentrations (in terms of molL(-1)) than sodium tungstate. LD50 values for sodium metatungstate range from 0.13 to 0.85gWL(-1) or 5.69 to 38.71x10(-5)mol 3Na(2)WO(4).9WO(3)L(-1). Based on these values sodium metatungstate can be classified as a moderate toxic agent to fish.

Interest in tungsten occurrence and geochemistry is increasing due to increased use of tungsten compounds and its unknown biochemical effects. Tungsten has a complex geochemistry, existing in most environmental matrices as the soluble and mobile tungstate anion, as well as poly- and heteropolytungstates. Because the geochemistry of tungsten is substantially different than most trace metals, including the formation of insoluble species under acidic conditions, it is not extracted from soil matrices using standard acid digestion procedures. Therefore, the current work describes a modification to a commonly used acid digestion procedure to facilitate quantification of tungsten in soil matrices. Traditional soil digestion procedures, using nitric and hydrochloric acids with hydrogen peroxide yield <1 up to 50% recovery on soil matrix spike samples, whereas the modified method reported here, which includes the addition of phosphoric acid, yields spike recoveries in the 76-98% range. Comparison of the standard and modified digestion procedures on National Institute of Standards and Technology Standard Reference Materials yielded significantly improved tungsten recoveries for the phosphoric acid modified method. The modified method also produces comparable results for other acid extractable metals as the standard methods, and therefore can be used simultaneously for tungsten and other metals of interest.

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.