Metal determinations in biological specimens of diseased and non-diseased hard metal workers

Biological monitoring of Co, Ta and W, using mainly neutron activation analysis, was carried out on the urine, blood, pubic hair and toe nails of 251 subjects occupationally exposed to hard metal dusts (23 individuals were diagnosed as ‘diseased subjects’, affected by asthma and/or lung fibrosis). Airborne dust at hard metal workplaces were also analyzed for Co and W content. Cobalt and tungsten exposure at workplaces varied widely and frequently exceeded the TLV (0.05 mg Co/m³). Cobalt in urine (CoU), which is better than Co in blood (CoB), could represent a valuable indicator in discriminating between exposed groups, but is of little value as an indicator of exposure for single individuals. The high concentrations of cobalt in pubic hair (CoH) and toe nails (CoN) could also be valuable indicators of exposure although they are not useful, however, in establishing quantitatively the levels of cobalt accumulation. Tungsten and tantalum in pubic hair (WH and TaH) and toe nails (WN and TaN) also seem to be useful indicators in proving hard metal exposure qualitatively. The determination of these two elements, rather than cobalt, in the bronchoalveolar lavage (BAL) is very useful in complementing the diagnosis of hard metal disease proving hard metal exposure. The analysis of the BAL subfractions showed that W and Ta were firmly incorporated into the macrophage fraction while Co was distributed between cellular fraction and supernatant, which suggests a different mobility of hard metals in pulmonary tissue. The metal concentrations determined when submitted to statistical analysis indicated a positive correlation with P < 0.001 for the pairs (CoB---CoU), (Co---W) in urine, and (Co---W) in toe nails. Multielement analysis of biological specimens from diseased subjects suggests that hard metal disease does not relate to Co, W and Ta levels in the specimens considered. The disease does not depend on sex, age, working age and length of hard metal exposure. These findings support the theory on the possible haptenic properties of Co which may induce hypersensitivity and immuno-related toxic effects.     

Bronchoalveolar lavage and its role in diagnosing cobalt lung disease

The bronchoalveolar lavage (BAL) of two groups of hard metal workers (11 subjects) were examined and compared with BALs of 14 unexposed individuals as controls. The first group of workers included five asymptomatic subjects (2 females and 3 males) with normal lung function tests and chest X-rays. All the workers had been exposed daily to hard metal dust for 5 years before fiberoptic bronchoscopy. The second group of workers included six individuals (1 female and 5 males) with cobalt lung disease at biopsy. The BAL's cytology at the deep lung level is in agreement with a possible immunologic pathogenesis of the lung disease, similar to hypersensitivity pneumonitis (lymphocytosis with helper-suppressor ratio reduction). In order to identify diagnostic key-parameters, the data presented here are compared with data reported in literature for workers with a history of hard metal or cobalt (alone) exposure. Although the BAL can be useful, for a better definition of the reaction at the deep lung level, it seems insufficient per se for the diagnosis of hard metal lung disease.     

On the potential of combining neutron activation analysis and particle induced X-ray emission (PIXE) for micro- and microdistribution analysis of hard metals in human tissues

Tungsten carbide and cobalt are the main components of hard metal alloy while other metals such as chromium, niobium, tantalum, titanium and vanadium are sometimes added in smaller amounts. Exposure to hard metal dusts can induce a lung fibrosis with cobalt playing a major role. In order to provide information on the role that each metal may have in causing this disease, determination of the total content and the distribution of inhaled metals in lung tissue of hard metal workers is of paramount importance. However, samples such as transbronchial biopsy and bronchoalveolar lavage (BAL), often used in the medical diagnosis of pneumoconiosis, only allow for a small amount of material. This calls for sensitive and accurate analytical procedures for microdetermination and distribution of metals in pulmonary tissue and cellular material, such as macrophages. This work proposes a combination of sophisticated analytical techniques such as neutron activation analysis (NAA), currently applied to the determination of the total concentration of more than 30 elements in biological specimens, and PIXE analysis, particularly microPIXE, which has a great potential for microdistribution analysis in small biological samples. Principles and perspectives for the combined use of these techniques for the analysis of human tissue are outlined and discussed. NAA: determination of hard metals in lung tissue are carried out by neutron irradiation (2 × 10¹⁴ neutrons cm⁻² s⁻¹) in the HFR reactor of Petten. After neutron activation, radiochemical separations of ⁶⁰Co, ¹⁸⁷W, ¹⁸²Ta, ⁵¹Cr followed by computer-based high resolution gamma ray spectrometry allow the measurement of these elements in pulmonary tissues with sensitivities ranging from 10⁻⁴ μg (Cr) to 10⁻⁶ μg (W). PIXE: this technique is multielemental and of relatively high sensitivity (μg/g) even in small total sample masses of from 10 to 100 μg, thus allowing the analysis of parts of needle biopsies. Whereas PIXE has been successfully applied to many medical problems, its usefulness is limited in the total samples analysis for cobalt-related hard metal disease, due to the low levels of cobalt in tissue combined with severe element interferences from the generally more abundant metal, iron. Nevertheless, microPIXE, a special variety of the method scanning over the sample with a focussed ion beam of about 2 × 2 μm², could complement the NAA findings in total samples in the sense of achieving a microdistribution analysis of hard metals (including cobalt) in suitable thin tissue sections.The availability of specialized facilities at the JRC such as the powerful HFR reactor (Petten), the NAA laboratories (Ispra) and the microPIXE facility (Geel) could represent a European ‘reference pole’ for the study of metals in tissues of hard metal diseased subjects.     

Cobalt speciation in urine of hard metal workers. A study carried out by nuclear and radioanalytical techniques

A method for the determination of inorganic and organically-bound cobalt in human urine has been developed and applied to the urine of hard metal workers. The development was based on the use of the radionuclides ⁵⁷Co, ⁵⁸Co and ⁶⁰Co-labelled Co compounds such as Co-Vitamin B12 and CO²⁺ ions which allowed the study of their biotransformations in human and rat urine. The proposed procedure is based on the use of Chelex 100 resin which retains quantitatively the inorganic Co from the urine while the organic complexed form of the element is eluted. Cobalt is detected in both column and eluate by neutron activation analysis (NAA). The method has been applied to speciate inorganic and organically-bound Co in the urine of hard metal workers. There is a significant increase (P < 0.02) of the ratio inorganic/organic Co (2.3) in the urine of workers compared with controls (1.01), showing an increase of the inorganic fraction of Co in the urine of workers. The ratio was constant for the wide range of urinary Co analyzed (from 180 μg to 1254 μg Co/l). Therefore, the discrimination between inorganic and organic Co in urine should not represent progress in the biological monitoring of Co compared with the determination of total urinary Co. However, a large amount of organically-complexed Co is formed in the body of hard metal workers and excreted in urine, thus, investigationsof the nature of the organocobalt compounds are of fundamental importance in establishing their possible clinical significance.     

Absorption and excretion of cobalt in the hard metal industry

Absorption and excretion of cobalt in the hard metal industry was investigated by means of ambient air and urine measurements in three factories with high levels of environmental cobalt pollution. In the presence of poor hygiene conditions and permission to smoking during work, there was no relationship between cobalt ambient air and cobalt urine concentrations. Such a finding was therefore attributed to a substantial skin contact. A simple experiment of skin exposure to freshly mixed or waste powder on volunteers identified a ten-fold increase of cobalt in urine in the post-exposure samples, thus confirming the contribution of dermal exposure as a route of entry. An improvement in the hygiene of the working conditions helped to investigate the relationship between exposure and excretion level. Cobalt uptake through the different routes of entry may be substantial, and requires a more prolonged exposure-free period so that the excretion rate can be reduced to the reference population level.     

Cobalt excretion in urine: results of a study on workers producing diamond grinding tools and on a control group

A study was carried out on cobalt (Co) excretion in the urine of 12 workers exposed to known cobalt concentrations in the stone cutting diamond wheel production and in six volunteers: four of these were exposed in the same work environment for a whole workshift and the other two were exposed to cobalt in a cabin under experimental conditions. The kinetics of the urinary excretion was multiphase: (i) a first stage of rapid elimination ( ); (ii) a second phase of slower elimination ( ); (iii) a longer period of retention, of the order of years, in subjects with higher exposure. In the control group (4 subjects), the excretion proved to be much faster in the first stage ( h). The different behaviour of the two groups could be related to the different body burden, of cobalt and/or to the possibility of different kinetics induced by continuous exposure to the metal. Moreover, 3 weeks after the removal of the workers from exposure the urinary cobalt concentrations were not within the normal limits of CoU for the general population, (even for workers exposed to cobalt levels of the same order as the TLV). The increase of CoU concentrations in the first 3 h after the end of exposure, stresses the problem of when urine samples for biological monitoring of the workers should be collected. The present study confirms the utility of CoU in discriminating between exposed and non-exposed subjects as well as in assessing high and low level exposure.     

Hard metal lung disorders: analysis of a group of exposed workers

The experience gained during the last 5 years in the study of 36 male workers exposed to hard metal dusts (10 engaged in mixing, 12 in presintering, three in sintering and 11 in grinding) is presented. The mean age was 33.2 years (S.D., 11.8) and the mean number of years of exposure was 9.4 (S.D., 7.6). All subjects received a physical examination, chest X-rays, pulmonary function test (VC, FEV₁, expiratory flows, RV, DLco, and metacholine bronchial provocation test), skin tests, brochoalveolar lavage (BAL) and determination of trace metals in BAL, blood, uring, pubic hair and toe nails. Two cases of bronchial asthma, six cases of interstitial lung disease and one case with both disorders were identified; eight of these cases presented at BAL signs of alveolitis with different cytologic features. Among the other 27 asymptomatic subjects, two showed an aspecific bronchial hyperreactivity, four showed a reduced DLco, 12 showed an inverted ratio of CD4/CD8 lymphocytes in BAL without signs of alveolitis while one subject presented both an aspecific bronchial reactivity and a reduced DLco. The presence of aspecific bronchial hyperreactivity in asymptomatic subjects might represent a preclinal indicator of a possible evolution towards bronchial asthma. An altered DLco, alone or associated with an inverted CD4/CD8 ratio of BAL lymphocytes, might constitute an early sign of a possible evolution towards interstitial lung disease. The association of aspecific bronchial reactivity and reduced DLco might indicate the possible evolution towards a mixed form. Only to follow up of these subjects might confirm or exclude these hypotheses. The nine symptomatic subjects have been followed up in time; three have continued their job in better hygienic conditions, six have completely discontinued the exposure; five were treated with corticosteroids. The clinical evolution of both asthma and interstitial diseasehas been variable and poorly influenced by changed working conditions and steroid treatment (two cases improved, two worsened, and five remained stationary). In consideration of the possible evolution of hard metal disorders towards a respiratory insufficiency and because of the unpredictable and questionable response to treatment, a thorough periodical surveillance of the exposed seems necessary in order to make early diagnoses in those still in an asymptomatic phase.     

Hard metal disease: clinical aspects

On the basis of the data available in the literature and of our experience, the clinical patterns of respiratory troubles which can be observed in workers exposed to inhalation of hard metal dusts can be schematized as follows: Irritation forms, mild and transient, or severe up to pulmonary oedema, dose-correlated, which occur in all subjects exposed to sufficiently high atmospheric concentrations; Asthmatic factors, either reversible after cessation of exposure or persistent after stopping the exposure, which occur in a relatively low percentage of exposed subjects and also apply to the states quoted below; Dyspnoic patterns due to alveolitis (lymphocytic alveolitis with inverted helper/suppressor ratio, or giant cell-eosinophilic alveolitis, with or without fibrotic changes of pulmonary interstitium); Interstitial sclerotics lung disease, associated with or without an alveolitic component. The present diagnostic potentialities, particularly bronchoalveolar lavage (BAL), have helped in defining the clinical patterns and have confirmed the fundamental role of individual susceptibility in the occurrence of clinical manifestations (with the exception of the irritation forms), but so far have not yet enabled us to clarify whether the different clinical patterns are the results of a single pathogenetic mechanism or constitute pathogenetically distinct entities.     

Assessment of nickel and cobalt release from 200 unused hand-held work tools for sale in Denmark - Sources of occupational metal contact dermatitis?

Introduction

Nickel and cobalt allergy remain frequent in dermatitis patients. It is important to determine possible nickel and cobalt exposures at work as these may offer important information to regulators and physicians who perform patch testing. Clinical relevance of metal exposure is usually assessed by the treating physician via the medical history and by presentation of allergic contact dermatitis.

Objectives

To screen unused non-powered hand-held work tools for nickel and cobalt release by using colorimetric spot tests.

Materials & methods

A random selection of 200 non-powered hand-held work tools for sale in 2 retailers of home improvement and construction products were analyzed qualitatively for metal release using the colorimetric nickel and cobalt spot tests.

Results

Nickel release was identified from 5% of 200 work tools using the dimethylglyoxime (DMG) test. In 8 of 10, positive results were located to the metal ring that acts like a cuff and is located at the end of the grip. The positive DMG test results were not related to specific categories of work tools. The cobalt spot test gave no positive test reactions.

Conclusions

It appears that the proportion of work tools that release nickel, in amounts that may result in allergic nickel dermatitis, has decreased markedly, when results were compared with a Swedish study performed more than a decade ago. No cobalt release was detected but it should be underscored that hard-metal tools were not examined. Other sources of cobalt may explain the relatively high levels of cobalt allergy in dermatitis patients.     

Cobalt powdersintering industry (stone cutting diamond wheels): a study of environmental-biological monitoring, workplace improvement and health surveillance

This communication deals with an aspect of occupational hygiene in a factory producing granite cutting diamond wheels by sintering, in moulds, of fine cobalt powder. The factory has been studied between 1988 and 1991; the Department of Preventive and Occupational Medicine of the Local Sanitary Unit of Reggio Emilia has followed the evolution of the local exhaust ventilation equipment supplied by the employer in that period. At the same time, the following measurements and observations were carried out: (a) cobalt exposure by personal sampling, (b) airborne cobalt measurements by area sampling, (c) biological monitoring of cobalt in urine, (d) health surveillance.     

Degradation of atrazine by cobalt-mediated activation of peroxymonosulfate: Different cobalt counteranions in homogenous process and cobalt oxide catalysts in photolytic heterogeneous process

The degradation of atrazine (ATZ) by cobalt-mediated activation of peroxymonosulfate (PMS) has been studied in this work. For the homogenous process, different cobalt counteranions: cobalt(II) nitrate Co(NO₃)₂, cobalt(II) sulfate CoSO₄, cobalt(II) chloride CoCl₂, and cobalt(II) acetate Co(CH₃COO)₂, have been examined. The inhibitory effect was observed in the process initiated by CoCl₂. For the pH test, wide range of pH level (2-10) has been investigated. It was found that the higher rates were obtained in the normal pH levels. At extreme pH levels, the process was impeded by inactivation of PMS at acidic pH and prohibited by precipitation at basic pH. On the other hand, the recycling capability of cobalt oxide and the oxidative potential of cobalt-immobilized titanium dioxide Co-TiO₂ catalyst were analyzed in the heterogeneous process. It was found that the higher the cobalt content in the catalyst, the better the removal performance was resulted. At last, the Co-TiO₂ catalyst synthesized in this work was found to be very effective in transforming ATZ as well as its intermediate in the presence of UV-vis irradiation.     

Life style and home environment are associated with racial disparities of asthma and allergy in Northeast Texas children

A high prevalence and racial disparities in asthma and allergy have been observed in American children. This study aimed to identify risk factors for asthma and allergy among children, and their contribution to racial disparities in allergy prevalence. A population-based cross-sectional study was carried out among children aged 1-8 years in Northeast Texas 2008-2009. The health conditions, life style and home environment of 3766 children were surveyed by parental questionnaires through e.g. daycares, elementary school, and medical clinics. Among participants who indicated their ethnicity, 255 were Mexican-Americans, 178 Afro-Americans and 969 Caucasians. Afro-American children had a significantly higher prevalence of asthma and eczema. Caucasian had the highest prevalence of rhinitis. Compared to Mexican-American children, Afro-American and Caucasian children were breast fed shorter time, more often went to day care center, had pets and environmental tobacco smoke exposure at home more often. For all children, being at a day care center, being exposed to dampness and environmental tobacco smoke at home were strong risk factors for asthma and allergy. Central air conditioning system was associated with an increased prevalence of wheeze among Mexican-American children, while pets were associated with an increased risk of rhinitis among Afro-American and Caucasian children. Caucasian children were generally not healthier than relatively poor Mexican-American children. Differences in the prevalence of asthma and allergy between races cannot be explained by socioeconomic status only. Life style and home environmental exposures are important risk factors for asthma and allergy in Northeast Texas children.     

Removal of Co2+ from aqueous solutions by hydroxyapatite

A study on the removal of cobalt ions from aqueous solutions by synthetic hydroxyapatite was conducted in batch conditions. The influence of different sorption parameters, such as: initial metal concentration, equilibration time, solution pH and presence of EDTA on the amount of Co(2+) sorbed was studied and discussed. The sorption process followed pseudo-second-order kinetics with necessary time of 24 h to reach equilibrium. Cobalt uptake was quantitatively evaluated using the Langmuir and Dubinin-Kaganer-Radushkevich (DKR) model. The Langmuir adsorption isotherm constant corresponding to adsorption capacity, Xm, was found to be 20.92 mg/g. Sorption of Co(2+) is constant in the initial pH range 4-8, because HAP surface buffers these solutions to the constant final pH value of 5.1. In the presence of EDTA, sorption of Co(2+) decreases due to formation of complex with lower sorption affinities. Cobalt desorption depends on the composition of the extracting solution. The desorbed amount of cobalt decreased continuously with increasing pH, and increased with increasing Ca(2+) concentration in leaching solution.     

Removal of some divalent cations from water by membrane-filtration assisted with alginate

The removal of divalent metal ions from hard waters or galvanic wastewater by polymer-assisted membrane filtration using alginate was investigated. The ability of this natural polymer to form aggregates and gels in presence of metal ions was studied, in order to carry out metal removal by ultra or micro-filtration. Alginate titrations have shown the presence of amine groups in addition to carboxylates onto the polymer backbone. The binding properties of alginate with divalent cations have been studied, showing an increasing affinity for Ca2+ over Mg2+ as polymer concentration increases, and the relative affinity Pb2+ > or = Cu2+ > Zn2+ > Ni2+. The softening of hard natural waters was achieved successfully and easily, but needs an optimal alginate concentration approximately 4 x 10(-2) M. The alginate powder can be directly added to hard waters. Except for Ni2+, metal-removal was efficient. Polymer regeneration has shown that Cu2+-complexes are labiles.     

Impact of nickel and cobalt on biogas production and process stability during semi-continuous anaerobic fermentation of a model substrate for maize silage

The importance of nickel and cobalt on anaerobic degradation of a defined model substrate for maize was demonstrated. Five semi-continuous reactors were operated for 250 days at 35 °C and a well-defined trace metal solution was added to all reactors. Two reactors each were limited regarding the concentration of Ni²⁺ and Co²⁺, respectively, for certain time intervals. The required nickel concentration was depending on the organic loading rates (OLR) while, for example, above 2.6 g ODM L⁻¹ d⁻¹ nickel concentrations below 0.06 mg kg⁻¹ FM in the process significantly decreased biogas production by up to 25% compared to a control reactor containing 0.8 mg Ni²⁺ kg⁻¹ FM. Similarly, limitation of cobalt to 0.02 mg kg⁻¹ FM decreased biogas production by about 10%. Limitations of nickel as well as cobalt lead to process instability. However, after gradual addition of nickel till 0.6 mg and cobalt till 0.05 mg kg⁻¹ FM the OLR was again increased to 4.3 g ODM L⁻¹ d⁻¹ while process stability was recovered and a fast metabolisation of acetic and propionic acid was detected. An increase of nickel to 0.88 mg kg⁻¹ FM did not enhance biogas performance. Furthermore, the increase of cobalt from 0.05 mg kg⁻¹ FM up to 0.07 mg kg⁻¹ FM did not exhibit a change in anaerobic fermentation and biogas production.     

Toxicity bioassay of heavy metals in water using Tetrahymena pyriformis

The toxicities of five heavy metal compounds on the survival of the ciliated protozoan Tetrahymena pyriformis were determined. Three-day old cultured cells were exposed to five concentrations of each test compound in one or more of three water series; distilled, soft, and hard water. A culture of each sample was placed in a plastic petri dish and covered with mineral oil to prevent evaporation. The cells were counted initially, then again at 0·5 h, 1 h, 2 h, 1 day, 2 days, 3 days, and on the fourth day. Lethal threshold concentrations and tolerance limit medians were determined by graphic methods. On a weight bases cadmium was most toxic, followed in decreasing toxicity by mercury, cobalt, zinc, and lead. Compared to similar fish data, all heavy metals were more toxic to T. pyriformis except lead. The toxicity of lead in soft versus hard water exemplified an antagonistic effect with greater than seven times the amount of lead necessary in hard water to produce comparable mortality as lead in soft water. On the other hand, the toxicity of mercury is about twice as great in hard water as in soft water (a synergistic effect). T. pyriformis appears to be a more sensitive indicator than fish of heavy metal contamination of water. T. pyriformis bioassay should prove a good means of determining the existence of many water pollutants.     

Persistence and decontamination of surrogate radioisotopes in a model drinking water distribution system

Contamination of a model drinking water system with surrogate radioisotopes was examined with respect to persistence on and decontamination of infrastructure surfaces. Cesium and cobalt chloride salts were used as surrogates for cesium-137 and cobalt-60. Studies were conducted in biofilm annular reactors containing heavily corroded iron surfaces formed under shear and constantly submerged in drinking water. Cesium was not detected on the corroded iron surface after equilibration with 10 and 100 mg L⁻¹ solutions of cesium chloride, but cobalt was detected on corroded iron coupons at both initial concentrations. The amount of adhered cobalt decreased over the next six weeks, but was still present when monitoring stopped. X-ray absorption near-edge spectroscopy (XANES) showed that adhered cobalt was in the III oxidation state. The adsorbed cobalt was strongly resistant to decontamination by various physicochemical methods. Simulated flushing, use of free chlorine and dilute ammonia were found to be ineffective whereas use of aggressive methods like 14.5 M ammonia and 0.36 M sulfuric acid removed 37 and 92% of the sorbed cobalt, respectively.     

Toxicity of cadmium, cobalt, uranium and zinc to Zoogloea ramigera

The toxic effects of cadmium, cobalt, uranium and zinc to the bacterium Zoogloea ramigera have been studied. This organism, which is abundant in sewage-treatment plants, responded to media supplemented with heavy metals by showing a prolonged lag phase and by decreasing its growth rate. The length of the lag phase was proportional to the metal concentration when Z. ramigera was exposed to cadmium, cobalt and zinc. When exposed to uranium (uranyl ions) the organism altered its growth behavior by showing an extended lag phase almost independent of the metal concentration. The order of toxicity of the metals to Z. ramigera was Cd²⁺ = Zn²⁺ > Co²⁺ > UO₂²⁺.     

The efficiency of heavy metal removal by a conventional activated sludge treatment plant

The total and dissolved concentration of cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, nickel and zinc at various points in a conventional activated sludge treatment plant have been measured. The analysis of raw sewage samples collected hourly over a 3-day period showed that metal input to the sewage treatment plant was not a continuous process but consisted of slugs of metal lasting for a discrete time. The efficiency of heavy metal removal by this model treatment plant was determined by monitoring the influent and effluent metal levels over a 4-week period.