Chemical Composition of Thoracic Dust at Workplaces During Cement Production.

OBJECTIVES: Cement belongs to the most used building materials. Clinker is the major constituent of cement, and it is believed that the strong increase of pH after hydration of clinker minerals is responsible for the observed decline in lung function of cement production workers. Information on clinker exposure at workplaces in the cement production industry is scarse. The aims of this study are to determine the chemical composition of thoracic dust and to quantify workplace exposure to clinker in cement production. METHODS: The elemental composition of 1250 personal thoracic samples collected at workplaces in 15 plants located in 8 different countries (Estonia, Greece, Italy, Norway, Sweden, Switzerland, Spain, Turkey) was determined by inductively coupled plasma optical emission spectrometry (ICP-OES), separately for water- and acid-soluble fraction. Positive matrix factorization (PMF) was used to determine the contribution of different sources to the dust composition and to quantify the clinker content in 1227 of the thoracic samples. In addition, 107 material samples were analysed to facilitate interpretation of the factors obtained by PMF. RESULTS: The median thoracic mass concentrations varied for individual plants between 0.28 and 3.5 mg/m3. PMF with 8 water-soluble and 10 insoluble (i.e., acid-soluble) element concentrations yielded a five-factor solution: Ca, K, Na sulfates; silicates; insoluble clinker; soluble clinker-rich; and soluble Ca-rich. The clinker content of the samples was calculated as sum of the insoluble clinker and soluble clinker-rich factors. The median clinker fraction of all samples was 45% (range 0-95%), and varied between 20% and 70% for individual plants. DISCUSSION: The 5-factor solution of PMF was selected on the basis of several mathematical parameters recommended in the literature as well as the mineralogical interpretability of the factors. In addition, interpretation of the factors was supported by the measured apparent solubility of Al, K, Si, Fe, and to a lesser extent Ca in material samples. The total clinker content obtained in the present study is considerably lower than estimates based on the Ca concentrations in a sample, and somewhat lower than estimates based on Si concentrations after selective leaching with a methanol/maleic acid mixture. The clinker abundance in workplace dust of one plant investigated in the present contribution was also estimated in a recent study by electron microscopy, and the good agreement between both studies gives confidence in the results of PMF. CONCLUSIONS: The clinker fraction in personal thoracic samples could be quantified from the chemical composition by positive matrix factorization. Our results allow for further epidemiological analyses of health effects in the cement production industry. As these estimates are more accurate for clinker exposure than aerosol mass, stronger associations with respiratory effects are expected if clinker is the main cause of these effects.

Elemental Carbon and Nitrogen Dioxide as Markers of Exposure to Diesel Exhaust in Selected Norwegian Industries.

Elemental carbon (EC) and nitrogen dioxide (NO2) in air as markers for diesel exhaust (DE) emission exposure were measured in selected work environments in Norway where diesel-powered engines are in use. Two hundred and ninety personal full-shift air samples were collected in primary aluminium production, underground and open-pit mining, road tunnel finishing, transport of ore, and among airport baggage handlers. EC was determined in the samples by a thermo-optical method, while NO2 was determined by ion chromatography. Highest EC air concentrations (geometric mean, GM) were found in aluminium smelters (GM = 45.5 µg m-3) followed by road tunnel finishing (GM = 37.8 µg m-3) and underground mining activities (GM = 18.9 µg m-3). Low EC air concentrations were measured for baggage handling at an international airport (GM = 2.7 µg m-3) and in an open-pit mine (GM = 1.2 µg m-3). Air concentrations of NO2 were similar in road tunnel finishing (GM = 128 µg m-3) and underground mining (GM = 108 µg m-3). Lower NO2 values were observed in open-pit mining (GM = 50 µg m-3), at the airport (GM = 37 µg m-3), and in the aluminium smelters (GM = 27 µg m-3). Highly significant (P < 0.001) positive correlations between NO2 and EC air concentrations in underground mining (r = 0.54) and road tunnel finishing (r = 0.71) indicate a common source of these pollutants. NO2 and EC were also correlated (P < 0.01) positively at the airport. However, due to the complex air chemistry and a potential contribution of various sources, the correlation between EC and NO2 cannot be regarded as unambiguous hint for a common source. The association between EC and NO2 was not of statistical significance in open-pit mining. In the aluminium smelters, EC and NO2 were negatively correlated, although not reaching statistical significance. The substantial differences in NO2/EC ratios across the investigated industries, ranging from around 0.2 in the primary aluminium production to around 25 during spring at the airport, clearly show that exposure to DE cannot be estimated based on NO2 concentrations, at least for outdoor environments. Results in the primary aluminium production suggest that the measured EC concentrations are related to DE emissions, although the NO2 concentrations were low. Further studies are required to assess the magnitude of exposure in primary aluminium production.

Multi-elemental bio-imaging of rat tissue from a study investigating the bioavailability of bismuth from shotgun pellets.

In recent years, bismuth has been promoted as a "green element" and is used as a substitute for the toxic lead in ammunition and other applications. However, the bioavailability and toxicity of bismuth is still not very well described. Following a hunting accident with bismuth-containing shots, a bioavailability study of bismuth from metal pellets inoculated into rat limb muscles was carried out. Bismuth could be found in urine and blood of the animals. Bio-imaging using laser ablation ICP-MS of thin sections of the tissue around the metal implant was carried out to find out more about the distribution of the metal diffusing into the tissue. Two laser ablation systems with different ablation cell designs were compared regarding their analytical performance. Low concentrations of bismuth showing a non-symmetrical pattern were detected in the tissue surrounding the metal implant. This was partly an artefact from cutting the thin sections but also bio-mobilisation of the metals of the implant could be seen. An accumulation of zinc around the implant was interpreted as a marker of inflammation. Challenges regarding sample preparation for laser ablation and bio-imaging of samples of diverse composition became apparent during the analysis.

The fate of Gd and chelate following intravenous injection of gadodiamide in rats.

OBJECTIVE: The biodistribution of gadolinium (Gd) and chelate was studied in rats injected intravenously with a commercially available gadodiamide magnetic resonance contrast agent spiked with trace amounts of (14)C-labelled GdDTPA-BMA. METHODS: Biodistribution of the (14)C-labelled ligand in whole animals was visualised using quantitative whole-body autoradiography, and quantified in individual tissue samples by analysing for radioactivity using beta-counting. Biodistribution of Gd was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and inductively coupled plasma sector field mass spectrometry (ICP-SF-MS). RESULTS: The injected dose was rapidly excreted, with only 1.0% remaining in the body at 24 h. The radioactivity thereafter was mainly associated with kidney cortex, liver, lung, muscle and skin, with a similar rate of clearance for both ligand and Gd from these tissues. The ratio between (14)C-labelled substance and Gd was not significantly different from that of the injected substance in most tissue samples up to 24 h after injection; the ratio then slowly decreased. CONCLUSIONS: The data clearly show that measurements of Gd concentration alone in tissue samples from animals injected with Gd-based contrast agents (GBCAs) cannot be used as a measure of Gd released from the ligand. To our knowledge, such measurements comparing Gd and ligand concentrations and distribution in tissue samples have not been published previously for any of the commercial GBCAs.

Nc100668, a new tracer for imaging of venous thromboembolism: disposition and metabolism in rats.

The 99mTc-complex of NC100668 [Acetyl-Asn-Gln-Glu-Gln-Val-Ser-Pro-Tyr(3-iodo)-Thr-Leu-Leu-Lys-Gly-NC100194] is being evaluated for nuclear medical imaging of venous thromboembolism. NC100668 is a 13-amino acid peptide with a Tc-binding chelator [NC100194; -NH-CH2-CH2-N(CH2-CH2-NH-C(CH3)2-C(CH3)=N-OH)2] linked to the C-terminal end. Following injection in rats of [Asn-U-14C]NC100668 (labeling of the N-terminal amino acid), approximately 70% of the radioactivity was recovered in urine within 3 days. Following injection of [Lys-U-14C]NC100668 (labeling close to the C-terminal amino acid), radioactivity was cleared more slowly, with only 8% recovered in urine and approximately 80% of the radioactivity present in the body after 3 days. The highest concentration of radioactivity in the body following injection of [Lys-U-14C]NC100668 was observed in the kidney inner cortex; this probably represents 14C-labeled Lys, which is reabsorbed in the kidney tubules and incorporated into protein metabolism. Metabolite profiling by high-performance liquid chromatography with radiochemical detection revealed that following injection of [Asn-U-14C]NC100668, there is a rapid appearance in blood of one peak containing radioactive metabolite(s) originating from the N-terminal part of the molecule. In urine samples, only this radioactive peak was observed with no intact NC100668 remaining; this very hydrophilic N-terminal metabolite was probably either the N-terminal amino acid or a very short peptide. Liquid chromatography-mass spectrometry analyses of rat urine samples obtained after injection of nonlabeled NC100668 confirmed the identity of two metabolites generated from the C-terminal end of the molecule; Gly-NC100194 was identified as the major of these metabolites and NC100194 as a minor metabolite present at approximately one-tenth the amount of Gly-NC100194. No other metabolites were identified.