Characterization of individual aerosol particles in workroom air of aluminium smelter potrooms

Aerosol particles with aerodynamic diameters between 0.18 and 10 microm were collected in the workroom air of two aluminium smelter potrooms with different production processes (Soderberg and Prebake processes). Size, morphology and chemical composition of more than 2000 individual particles were determined by high resolution scanning electron microscopy and energy-dispersive X-ray microanalysis. Based on chemical composition and morphology, particles were classified into different groups. Particle groups with a relative abundance above 1%(by number) include aluminium oxides, cryolite, aluminium oxides-cryolite mixtures, soot, silicates and sea salt. In both production halls, mixtures of aluminium oxides and cryolite are the dominant particle group. Many particles have fluoride-containing surface coatings or show agglomerations of nanometer-sized fluoride-containing particles on their surface. The phase composition of approximately 100 particles was studied by transmission electron microscopy. According to selected area electron diffraction, sodium beta-alumina (NaAl(11)O(17)) is the dominant aluminium oxide and cryolite (Na(3)AlF(6)) the only sodium aluminium fluoride present. Implications of our findings for assessment of adverse health effects are discussed.     

Theoretical aspects of fluoride air contaminant formation in aluminium smelter potrooms

The amount of particulate fluorides evolved from aluminium electrolysis cells is not entirely accounted for by the fluorides entrained in the anode gas. The largest additional source of particulate fluoride formation is by direct evaporation of fluorides into the anode gas stream and subsequent condensation on the drops of electrolyte generated in the process of bubble burst. A theoretical model was used for the calculation of the main physical parameters responsible for the formation of particle nuclei when the hot anode-gas is mixed with ambient air. The results of these calculations are in agreement with experimental observations reported in the literature. In particular, the size distribution, composition and morphology of the nano-particles support the theory of a vapour condensation mechanism under conditions of extreme supersaturation, but further studies are necessary.     

Occupational exposure to beryllium in primary aluminium production

Alumina used in the production of primary aluminium contains Be which partly vaporises from the cryolite bath into the workroom atmosphere. Since Be may be toxic at lower exposure levels than previously thought, the personal exposure to Be among workers in 7 Norwegian primary smelters has been assessed. In total, 480 personal Respicon? virtual impactor full shift air samples have been collected during 2 sampling campaigns and analysed for water soluble Be, Al and Na using inductively coupled plasma optical emission spectrometry. In addition, water soluble F(-) has been measured by ion chromatography. The Be air concentrations in the inhalable, thoracic and respirable aerosol fractions have been calculated. The Be concentrations in the inhalable aerosol fraction vary between the different smelters. The highest GM concentration of Be in the inhalable fraction (122 ng m(-3), n = 30) was measured in the prebake pot room of a smelter using predominantly Jamaican alumina where also the highest individual air concentration of 270 ng m(-3) of Be was identified. The relative distribution of Be in the different aerosol fractions was fairly constant with the mean Be amount for the two sampling campaigns between 44-49% in the thoracic fraction expressed as % of the inhalable amount. Linear regression analysis shows a high correlation between water soluble Be, Al, F and Na describing an average measured chemical bulk composition of the water soluble thoracic fraction as Na(5.7)Al(3.1)F(18). Be is likely to be present as traces in this particulate matter by replacing Al atoms in the condensed fluorides and/or as a major element in a nanoparticle sized fluoride. Thus, the major amount of Be present in the work room atmosphere of Al smelter pot rooms will predominantly be present in combination with substantial amounts of water soluble Al, F and Na.     

Exposure to airborne isocyanates and other thermal degradation products at polyurethane-processing workplaces

The thermal degradation products of polyurethanes (PURs) and exposure to isocyanates were studied by stationary and personal measurements in five different occupational environments. Isocyanates were collected on glass fibre filters impregnated with 1-(2-methoxyphenyl)piperazine (2MP) and in impingers containing n-dibutylamine (DBA) in toluene. connected to a glass fibre postfilter. The derivatives formed were analysed by liquid chromatography: 2MP derivatives with UV and electrochemical detection and DBA derivatives with mass spectrometric detection. The release of aldehydes and other volatile organic compounds into the air was also studied. In a comparison of the two sampling methods, the 2MP method yielded about 20% lower concentrations for 4,4'-methylenediphenyl diisocyanate (MDI) than did the DBA method. In car repair shops, the median concentration of diisocyanates (given as NCO groups) in the breathing zone was 1.1 microg NCO m(-3) during grinding and 0.3 microg NCO m(-3) during welding, with highest concentrations of 1.7 and 16 pg NCO m(-3), respectively. High concentrations of MDI, up to 25 and 19 microg NCO m(-3), respectively, were also measured in the breathing zone during welding of district heating pipes and turning of a PUR-coated metal cylinder. During installation of PUR-coated floor covering, small amounts of aliphatic diisocyanates were detected in the air. A small-molecular monoisocyanate, methyl isocyanate, and isocyanic acid were detected only during welding and turning operations. The diisocyanate concentrations were in general higher near the emission source than in the workers' breathing zone. A sampling strategy to evaluate the risk of exposure to isocyanates is presented.     

Long-term fate of polycyclic aromatic hydrocarbons (PAH) in sediments from Loch Leven after closure of an aluminium smelter

An aluminium smelter discharged polycyclic aromatic hydrocarbons (PAHs) into Loch Leven on the west of Scotland from 1907 until it closed in 2000, resulting in elevated PAH concentrations in the sediment. A temporal monitoring programme to investigate any recovery in sediment concentrations began in 2004, with sampling each year until 2008 and again in 2010. Cores were also collected to investigate temporal trends over a longer time scale and to estimate the sedimentation rate in the loch. The loch is divided into two basins, and PAH concentrations were significantly higher in the upper basin, closer to the smelter, than in the lower basin. The PAH distribution and concentration ratios were consistent with a pyrolytic source of PAHs, with a high proportion of heavier parent PAHs. There was no evidence of any recovery in PAH concentrations, perhaps due to the mixing and disturbances of the sediment, and the persistence of PAHs. Concentrations of all PAHs were above the Background Assessment Concentrations (BACs) in both basins. In the lower basin only the 5- and 6-ring PAHs were above the Effects Range Low (ERL) values, but in the upper basin all but naphthalene were above the ERLs. There is therefore still an unacceptable risk of chronic effects in marine species. Concentrations decreased down the cores, falling below BACs in the deepest sections. However, ERLs were exceeded as far down the core as 30 cm for some PAHs.     

Characterization of airborne particles at a high-btu coal-gasification pilot plant

Airborne particles in fugitive emissions have been measured at a slagging fixed-bed coal-gasification pilot plant using lignite. Sampling was conducted during shutdown operations and opening of the gasifier following an aborted startup. Aerosol collected with a Sierra high-volume impactor was subjected to analysis by gas chromatography, mass spectrometry, and scanning electron microscopy; aerosol collected with an Andersen low-volume impactor was subjected to flameless atomic absorption analysis. The data show that the bulk of the trace organic material is associated with small particles: these data are similar to data on ambient air reported in the literature. Particle morphologies resemble those of fly ash from coal combustion, including smooth spheres, vesicular spheres, and crystalline material. Trace element size distributions are bimodal and resemble data for ambient air. Pb-containing particles are generally submicron, while particles containing Al, Fe, and other crustal species are mostly of supermicron size. Aluminum-based aerosol enrichment factors calculated from the lignite composition show that the composition of the aerosol resembles that of the coal, with the exception of modest enrichments of Mg, Na, As, and Pb in the submicron size range. Aerosol enrichment factors based on the earth's crustal composition are somewhat greater than those based on coal composition for several elements, suggesting potential errors in using crustal enrichment data to investigate chemical fractionation during aerosol formation.     

Wipe sampling as a tool for monitoring aerosol deposition in workplaces

As a complement to traditional exposure assessment, monitoring deposition of aerosols can be a simple and quick screening method for identifying deposited aerosols. In this presentation examples of screening studies, based on wipe sampling in combination with adequate analytical techniques, are described. These screening methods are rapid, simple and easy to carry out. The examples given in this presentation show a broad applicability and the methods are proven useful for assessing aerosol distribution in the workplace as well as to identify target spots for more extensive assessment of a worker's exposure situation.     

Polycyclic aromatic hydrocarbon (PAH) concentration and composition determined in farmed blue mussels (Mytilus edulis) in a sea loch pre- and post-closure of an aluminium smelter

Concentrations of polycyclic aromatic hydrocarbons (2- to 6-ring parent and branched PAH) from an actively producing commercial shellfish farm in Loch Leven, Scotland, were found in excess of 4000 ng g(-1) wet weight tissue. These concentrations were considerably greater than had been recorded from mussels sampled elsewhere around the Scottish mainland. The PAH composition of the mussels from Loch Leven was dominated by the 5-ring, parent compounds; benzo[b]fluoranthene was the dominant compound. This data was consistent with the source being a discharge from an aluminium smelter. The individual compounds benz[a]anthracene, benzo[a]pyrene and dibenz[a,h]anthracene returned values of 304 ng g(-1), 446 ng g(-1) and 39 ng g(-1) respectively; these were well above the 15 ng g(-1) pragmatic guideline limit. Over the two year monitoring period, the concentrations of these compounds in mussels from Loch Etive, a reference location, ranged between 'not detected' and 4 ng g(-1)(for benz[a]anthracene). Mussels were transferred from a clean location to Loch Leven which demonstrated that the rate of uptake of PAH was rapid. Following closure of the aluminium smelter, the PAH concentrations in mussels decreased. Differences between the two sites within Loch Leven were noted with the longer-term impact remaining greater for the mussels closer to the original point discharge.     

Aluminium contamination via assisted leaching from metallic aluminium utensils at neutral pH

Fluoride ion in trace concentrations is found to leach metallic aluminium from utensils even at neutral pH, releasing aluminium hydroxide which is readily soluble in dilute acids. The levels of leaching at different F^- concentrations are given and compared with leaching levels with equivalent concentrations of Cl^-. It is suggested that consumption of water boiled in aluminium utensils may contribute to cumulative aluminium toxicity.     

Lead,cadmium, arsenic and zinc in the ecosystem surrounding a lead smelter

A lead smelter has been operating at Belledune in the province of New Brunswick, in eastern Canada, since 1966. This paper presents data on the concentrations of the four primary metals emitted from the smelter — lead, cadmium, arsenic and zinc — which were measured in the terrestrial environment near the smelter and the concentrate transport route. Deposition of these metals to the snowpack and the uptake by grass forage are discussed in relation to non-regulatory guidelines, toxicity and atmospheric emissions. A 1992 snowpack transect survey extending 0.5–40 km northwest, southeast and south of the smelter revealed lead concentrations of 2–3193 ppb, cadmium <0.10–49.7 ppb, arsenic <3.0–72.0 ppb, and zinc 3–401 ppb. Deposition estimates within this zone for lead were between 0.046 and 20.1 kg/ha/yr, cadmium <0.007 and 313 g/ha/yr, arsenic <0.016 and 453 g/ha/yr and zinc 0.020 and 2.52 kg/ha/yr. Concentrations of these metals in the snowpack were highest within 3 km of the smelter and were detectable at greater distances SE of the smelter. Lead was dispersed greater distances from the smelter than cadmium or arsenic. Snowpack samples collected within 5–20 m of the railway contained 140–7270 ppb of lead, 0.4–36.9 ppb of cadmium, <3.0–72.0 ppb of arsenic and 41–13100 ppb of zinc. Grass forage sampled within 0.6–16 km of the smelter contained lead 5–152 ppm, cadmium 0.10–4.1 ppm, and zinc 22–154 ppm. Highest concentrations of lead, cadmium and zinc in grass forage were found were found within 2.2 km of the smelter. Grass forage collected within 10–70 m of the railway contained lead 13–288 ppm, cadmium 0.4–1.3 ppm and zinc 98–831 ppm.     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

Macroalgae and DGT as indicators of available trace metals in marine coastal waters near a lead–zinc smelter

The levels of Cd, Cu, Pb, and Zn were determined in the commonest species of green, red, and brown algae collected from five coastal sites in south-western Sardinia (Italy), an area with a long history of mining and smelting. The usefulness of employing Enteromorpha sp. and Padina pavonica (L.) Thivy to monitor metal pollution was evaluated, while diffusive gradients in thin films (DGT) devices were used to measure dissolved metals in seawater. Levels of Cd and Pb were high enough to be of environmental concern in the whole study area. A significant relationship was found between the content of Pb in P. pavonica and DGT-labile Pb in seawater, suggesting that gross elemental concentrations of nonessential metals such as Pb in algal tissues are apparently controlled by the abundance of dissolved metal species in the ambient seawater. The results pointed out the usefulness of using both DGT and algal methods for a better understanding of trace metal availability in coastal waters.     

Exposure to methylhexahydrophthalic anhydride (MHHPA) in two workplaces of the electric industry

Methylhexahydrophthalic anhydride (MHHPA) is a hardener for hot-cured epoxy resins employed as insulators in the electric industry. MHHPA has only been measured as an ingredient with other alicyclic anhydrides, albeit there are also large processes which use only MHHPA. We collected MHHPA vapour in a set of devices: Teflon filter, glass spiral, TenaxTA tube connected consecutively together. Elution was performed with a solvent mixture of methyl-tert-butyl ether (70%), acetonitrile (30%), and acetic anhydride (0.5%). By capillary GC-ECD, the regression was linear (0.9994) in the practical low concentration range of 0.04-1 microg ml(-1) being equal to 0.001-0.035 mg m(-3) in 30 l of air. The exposure was measured in two factories manufacturing electric appliances. The assembled objects were first impregnated with a liquid epoxy/hardener mixture, and then the resin hardened at elevated temperature. In condenser manufacturing, the operators' 8 h exposure ranged from 0.068 to 0.118 mg m(-3), and the short-term exposure was during operation at ovens mean 1.90 mg m(-3). The impregnation of coiled resistors and transfer of them to ovens caused the worst exposures, short-term mean 3.846 mg m(-3) and long-term mean 2.191 mg m(-3). During the 'baking', the ovens were closed and evacuated, but when the hot objects were moved out of the ovens, they continued during chilling to emit MHHPA, mean 0.366 mg m(-3). In the adjacent areas, assembling, control rooms, offices, the exposure was still significant, 0.017-0.043 mg m(3), due to leaks from the high exposure areas. Mechanical general ventilation and local exhausts were functioning. Respirators were available for short supervising of the hot equipment.     

Emissions of reduced sulphur compounds from the surface of primary and secondary wastewater clarifiers at a Kraft Mill

Emissions of reduced sulphur compounds (RSCs) from the primary and secondary clarifiers at a Kraft mill were measured for respectively 8 and 22 days using a floating flux chamber. In the primary clarifier, dimethyl disulphide (DMDS) had the highest mean flux (0.83 microg s(-1) m(-2)) among all RSCs, and the mean flux of total reduced sulphur (TRS) was 1.53 microg s(-1) m(-2). At the secondary clarifier, dimethyl sulphide (DMS) had the highest mean flux (0.024 microg s(-1) m(-2)), and the mean flux of total reduced sulphur (TRS) was 0.025 microg s(-1) m(-2). Large variations in fluxes as a function of sampling date were observed in both clarifiers. Emission fluxes of DMS from the secondary clarifier were correlated with temperature in the flux chamber and with the biological and chemical oxygen demands (BOD and COD) of the wastewater. Emission rates of RSCs from the clarifiers were found to be insignificant by comparison with other mill sources.     

Airbone particles dynamics: towards a theoretical approach

Wind-tunnel simulations and field experiments for dust transport by air show that deposition is predominant on the windward side of hills whereas sans deposition is mainly observed on the lee side. That and other aspects such as the existence of several deposition regimes depending on wind intensity call for theoretical explanations. We present some preliminary considerations leading to such a theoretical framework.     

Determination of aluminium in groundwater samples by GF-AAS, ICP-AES, ICP-MS and modelling of inorganic aluminium complexes

The paper presents the results of aluminium determinations in ground water samples of the Miocene aquifer from the area of the city of Poznań (Poland). The determined aluminium content amounted from <0.0001 to 752.7 μg L(-1). The aluminium determinations were performed using three analytical techniques: graphite furnace atomic absorption spectrometry (GF-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of aluminium determinations in groundwater samples for particular analytical techniques were compared. The results were used to identify the ascent of ground water from the Mesozoic aquifer to the Miocene aquifer in the area of the fault graben. Using the Mineql+ program, the modelling of the occurrence of aluminium and the following aluminium complexes: hydroxy, with fluorides and sulphates was performed. The paper presents the results of aluminium determinations in ground water using different analytical techniques as well as the chemical modelling in the Mineql+ program, which was performed for the first time and which enabled the identification of aluminium complexes in the investigated samples. The study confirms the occurrence of aluminium hydroxy complexes and aluminium fluoride complexes in the analysed groundwater samples. Despite the dominance of sulphates and organic matter in the sample, major participation of the complexes with these ligands was not stated based on the modelling.     

A new method for the characterisation and quantitative speciation of base metal smelter stack particulates

Base metal smelters may be a source of particulates containing metals of environmental concern released to the atmosphere. Knowledge of the quantitative chemical speciation of particulate releases from base metal smelters will be of value in smelter emission fingerprinting, site-specific risk assessments, predictions of the behaviour of smelter stack particulates released to the environment and in resolving liability issues related to current and historic releases. Accordingly, we have developed an innovative approach comprising bulk chemical analysis, a leaching procedure, X-ray diffraction analysis and scanning electron microscopy/electron probe microanalysis characterisation in a step-wise apportioning procedure to derive the quantitative speciation of particulate samples from the stacks of three copper smelters designated as A, B and C. For the A smelter stack particulates, the major calculated percentages were 29 CuSO₄, 20 ZnSO₄.H₂O, 13 (Cu_0.94Zn_0.06)₂(AsO₄)(OH), 11 PbSO₄ and four As₂O₃. For the B smelter stack particulates, the primary calculated percentages were 20 ZnSO₄.H₂O, 20 PbSO₄, 12 CuSO₄ and nine As₂O₃. Finally, we calculated that the C smelter stack particulates mostly comprised 34 ZnSO₄.H₂O, 19 (Cu_0.84Zn_0.16)(AsO₃OH), 11 PbSO₄, 10 As₂O₃ and nine Zn₃(AsO₄)₂. Between 56% and 67% by weight of the smelter stack particulates, including the As, was soluble in water. For these and other operations, the data and approach may be useful in estimating metals partitioning among water, soil and sediment, as well as predictions of the effects of the stack particulates released to the environment.     

The lichen transplant methodology in the source apportionment of metal deposition around a copper smelter in the former mining town of Karabash, Russia

The lichen transplant monitoring methodology has been tested for source apportionment of metal deposition around the Cu smelter and former mining town of Karabash. Transplants of the lichen Hypogymnia physodes (L.) Nyl., collected from a ‘control’ site in July 2001, were set up at 10 stations along a 60 km NE–SW transect centred on Karabash. Samples were collected after 2 and 3 month monitoring periods and analysed using established wet-chemical techniques. The sources of particulate investigated were the smelter blast furnace and converter, floatation tailings, metallurgical slags, local road dusts, top soils and ambient airborne total suspended particulate. From multi-element least-squares modelling the blast furnace was the main source of particulate in transplants close to the smelter (<10 km). Particulate from the converter, with relatively high Pb and Zn, was found to be more widely dispersed, being finer-grained and so having a longer atmospheric residence time. Ambient airborne particulate, sampled in Karabash town using air-pump apparatus, was almost entirely derived from the converter, very different to the lichen transplants from the same area which mainly contained blast furnace particulate. It is proposed that lichens close to the smelter mainly trapped larger blast furnace-derived particulate as they have a low capture efficiency for smaller (converter) particles. The study demonstrates the utility of lichen transplants for monitoring atmospheric deposition and highlights the caution required in their use to assess ambient air quality in human health studies.     

Characterisation of particulate matter emissions from the Zimbabwe Mining and Smelting Company (ZIMASCO) Kwekwe Division (Zimbabwe): a ferrochrome smelter

Particulate matter emissions from stack number 2 of a majorferrochrome smelter, Zimbabwe Mining and Smelting Company(ZIMASCO) were characterized and the rates at which the elementsCr, Fe, Cu and Zn and total ferrochrome dust are emitted into theatmosphere were determined. The extent of soil contamination bythe dust deposited around the smelter in the generally prevailingsoutheasterly wind direction around the smelter was carried out.The highest concentrations of Cr and Fe occurred in the fineparticulates of sizes less than 59 m whilst that of Cu and Znoccurred in the coarse particulates of size range 70-100 m.The emission rates from stack 2 were; total ferrochromeparticulates 62.17 kg h^-1, Cr 6.217 kg h^-1, Fe 2.423 kg h^-1, Zn42 mg h^-1 and 6 mg h^-1 for Cu. Particulate matter was emitted at arate of 289 mg m^-3 from stack number 2. This value exceeds thelegal limit of 200 mg m^-3. Chromium and iron are the metalsin the largest amounts. The particles that constitute the largestproportion of the dust were in the range of 58-107.5 m. Thisis a characteristic feature of the particulate matter emissionsfrom ZIMASCO. Soils in the downwind direction from the smelterwere polluted with Cr up to a distance of about 700 m outward fromthe perimeter of the boundary of the smelter.     

Sulfuric acid at workplaces--applicability of the new Indicative Occupational Exposure Limit Value (IOELV) to thoracic particles

Until 2009, the limit values for airborne sulfuric acid in Europe were based on the inhalable particle fraction (e.g. MAK (Maximum allowed concentration at workplace) value 0.1 mg m(-3) as the inhalable fraction). With the publication of the Commission Directive 2009/161/EU, an Indicative Occupational Exposure Limit Value (IOELV) of 0.05 mg m(-3) for sulfuric acid aerosols was based for the first time on the thoracic particle fraction. To permit a comparison of the measured values for the inhalable fraction with those of the thoracic fraction and to quantify the thoracic fraction, a cyclone was fabricated out of sulfuric-acid-resistant stainless steel that achieves suitable collection characteristics (PM(10)) at a flow rate of 5.34 L min(-1). 49 measurements were carried out in parallel in 21 companies. At concentrations well below the IOELV, there is little difference between the thoracic and inhalable particle concentrations. At higher concentrations (>0.1 mg m(-3) inhalable aerosol), larger droplets have a marked effect on the measured values and the thoracic fraction accounts for only 32.1 ± 12.5% of the inhalable fraction. The EU's IOELV and the proposal of the MAK Commission therefore provide a comparable level of protection. In the transposition of the IOELV into national law, an air limit of 0.1 mg m(-3) could therefore be implemented for the inhalable fraction.