Exposure and inhalation risk assessment in an aluminium cast-house

To date the exposure, absorption and respiratory health effects of cast-house workers have not been described since most studies performed in the aluminium industry are focused on exposure and health effects of potroom personnel. In the present study, we assessed the external exposure and the absorbed dose of metals in personnel from the aluminium cast house. This was combined with an evaluation of respiratory complaints and the lung function of the personnel. 30 workers from an aluminium casting plant participated and 17 individuals of the packaging and distribution departments were selected as controls. The exposure was assessed by the quantification of total inhalable fume with metal fraction and by the determination of urinary aluminium, chromium, beryllium, manganese and lead concentration. Carbon monoxide (CO), carbon dioxide (CO2), aldehydes and polyaromatic hydrocarbons and man-made mineral fibres concentration were assessed as well. In order to evaluate their respiratory status each participant filled out a questionnaire and their lung function was tested by forced spirometry. Total inhalable fume exposure was maximum 4.37 mg m(-3). Exposure to the combustion gases, man-made mineral fibres and metal fume was well below the exposure limits. Beryllium could not be detected in the urine. The values of aluminium, manganese and lead in the urine were all under the respective reference value. One individual had a urinary chromium excretion above the ACGIH defined biological exposure index (BEI) of 30 microg g(-1) creatinine. There was no significant difference in any of the categories of the respiratory questionnaire and in the results of the spirometry between cast house personnel and referents (Chi-square, all p > 0.05). Exposure in cast houses seem to be acceptable under these conditions. However, peak exposure to fumes cannot be excluded and the potential risk of chromium and beryllium exposure due to the recycling of aluminium requires further attention.     

Seasonal variations in nickel and vanadium in Mont Blanc snow and ice dated from the 1960s and 1990s

Ni and V have been determined in snow and ice collected at a high altitude location (Col du D?me) near the summit of Mont Blanc on the French-Italian border; dated from the 1960s and 1990s. Ni and V were simultaneously determined by inductively coupled plasma sector field mass spectrometry. Measured concentrations range from 6 to 700 pg g(-1) and 4 to 1,100 pg g(-1) for Ni and V, respectively. The results show pronounced seasonal variations in the concentrations of both metals, with high concentration values in summer layers and much lower values for winter layers. These seasonal variations are linked especially with the existence of inversion layers during winter months. Ni and V concentrations in excess of the contributions from rock and soil dust (Ni(excess), V(excess)) appear to be mainly associated with anthropogenic inputs, with pronounced seasonal variations. Large variations in the V(excess)/Ni(excess) ratio are observed, with a higher ratio in summer than in winter. This shows differences in anthropogenic inputs at Col du D?me during the different parts of the year. The above ratio was compared with the corresponding ratios for oil combustion from stationary sources and the exhaust from gasoline and diesel engines. It appears that Ni and V concentrations at Col du D?me are probably the result of changing combinations of contributions from oil combustion for power generation, industrial and residential uses, on one side, and automobile and truck traffic, on the other side, with possibly a significant contribution from Ni smelters in Russia during winter months.     

Should foliar cadmium concentrations be expressed on a dry weight or dry ash weight basis?

Foliar analysis is a valuable tool for evaluating the pollution status of forests. However, the use of foliar diagnosis in large-scale surveys is a complicated process owing to the high variability within the crown. The method used to express foliar concentrations has often been found to diminish the variability. The effect of the method used to express element concentrations on the spatial variability of cadmium (Cd) in the leaves of crack willow (Salix fragilis L.) was investigated by sampling the leaves of one willow at 292 locations in the crown, each sampling location having a volume of 0.027 m3 (0.3 m x 0.3 m x 0.3 m). Cadmium showed a distinct spatial trend in the crown of the tree. Concentrations as low as 2.4 mg kg(-1) dry weight (DW) or 23.1 mg kg(-1) dry ash weight (DAW) were obtained in the top of the crown, and 10.6 mg kg(-1) DW or 73.0 mg kg(-1) DAW in the bottom of the crown. The lower relative standard deviation and weaker correlation with the sampling height support the use of DAW in large-scale surveys especially. The lower variability of the DAW Cd concentration makes this variable less sensitive to fluctuations caused by differences in growing conditions and sampling methodology. However, the majority of publications in this field report metal concentrations on a DW basis. Therefore, the restrictions set on the use of results expressed on a DAW basis in large-scale surveys of foliar metal concentrations have to be offset against the advantages offered by a reduction of the variability in metal concentrations.     

Nitrogen isotope ratios in pine bark as an indicator of N emissions from anthropogenic sources

The article describes the use of Scots pine bark to identifynitrogen sources in eastern Germany, as well as background areas in Russia and Bulgaria, by using natural isotope ratios of total nitrogen (N_t) and individual N compoundssuch as ammonium (NH₄ ⁺), nitrate (NO₃ ^-)and amid nitrogen (amide-N). The samples collected were analysed using an elemental analyser in connection with a gas isotope mass spectrometer (EA-IRMS). Natural ¹⁵N abundances in pine bark from impact areas suggest that the ammonium accumulated on the surface of the bark is releasedfrom livestock management. Bark of Scots pines growing near agricultural land had highly depleted ¹⁵N_t values (between –8 and –12), while bark from background areas (unpolluted areas) displayed slightly negative ¹⁵N_t values (mean ¹⁵N_t = –3.8). It is assumed that part of the N adsorbed on the bark surface is mainly derived from ammonia(mean ¹⁵N_t = –40.3) escaping from livestock housing and during the application of manure. This assumption is confirmed by experiments under controlled conditions in which manure samples were spread on soil. In addition, temporal and spatial variations of ¹⁵N_t abundances in pine bark from various locations in eastern Germany as wellas pine stands in Nature Park Dübener Heath are discussed.     

Measurements of fractionated gaseous mercury concentrations over northwestern and central Europe, 1995-99

Although it makes up only a few per cent. of total gaseous mercury (TGM) in the atmosphere, the fraction of oxidised (divalent) mercury plays a major role in the biogeochemical cycle of mercury due to its high affinity for water and surfaces. Quantitative knowledge of this fraction present in mixing ratios in the parts-per-10(15) (ppq) range is currently very scarce. This work is based on approximately 220 data for divalent gaseous mercury (DGM) collected during 1995-99 in ambient air. Over the course of the measurements, the sampling and analytical methods were modified and improved. This is described here in detail and includes transition from wet leaching and reduction procedures to thermo-reductive desorption, the use of annular as well as tubular denuders and adoption of an automated sampling system. The concentration of DGM exhibited a strong seasonal behaviour in contrast to atomic gaseous mercury, with low values in winter and maximum values in summer. The DGM/TGM ratios were frequently found to be below the detection limit (< or = 1%) and in the range 1-5%. A trend of diurnal DGM patterns was observed and implies photolytically induced sources. Scavenging of DGM during rain events was also noticed.     

Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air

Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.     

Preliminary studies of a fast screening method for polycyclic aromatic hydrocarbons in soil by using solvent microextraction-gas chromatography

Solvent microextraction (SME) was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from spiked and real environmental soil samples with different matrices. Soil sample was mixed with 7 mL of acetone and 14 mL of water to allow partitioning of the PAHs from the soil to the liquid phase. A 2 microL octane drop suspended from a microsyringe needle tip was then immersed into the stirred solution-soil mixture for extraction. After an 11 min extraction, the octane drop was withdrawn into the syringe and injected directly into the GC for identification and quantification. The whole analysis procedure took 27 min, with an extraction time of 11 min, and a GC separation time of 16 min. A second extraction could be undertaken whilst the GC is running, hence the GC run time currently limits the sample throughput. In this method, a small amount of organic solvent was used for the extraction process, which produced little waste. The limits of detection for lower molecular weight (< 230) PAHs range from 0.13 to 0.36 mg kg-1, and for higher molecular weight (> 250) PAHs are estimated to be between 0.5 and 1.0 mg kg-1, with RSD values generally under 20%. Due to the small volumes of organic solvent used, the consumable cost per extraction is only US$ 0.12. This is the first report of the application of SME to solid samples, and the first report of the use of SME for the analysis of PAHs.     

Water quality test based on dielectrophoretic measurements of fresh water algae Selenastrum capricornutum

A method is described whereby dielectrophoresis of algal cells is used to perform rapid water quality analysis, specifically detecting the presence of CuSO4. The dielectric collection spectrum of the fresh water alga Selenastrum capricornutum was determined for a range of concentrations of CuSO4 from 25 mg L(-1) to 0.25 mg L(-1) for exposure times of 15 min and 18 h. In all cases increasing the concentration of CuSO4 reduced cell collection, but a step reduction was observed in collection between 2 mg L(-1) and 5 mg L(-1). This method has potential for forming a rapid, low-cost test for water quality with broad specificity and significantly reduced analysis time compared to current methods.