Chemical composition of individual aerosol particles from working areas in a nickel refinery

Individual aerosol particles (n = 1170) collected at work stations in a nickel refinery were analyzed by wavelength-dispersive electron-probe microanalysis. By placing arbitrary restrictions on the contents of sulfur and silicon, the particles could be divided into four main groups. Scanning electron images indicated that most of the particles examined were relatively small (< or = 2 microm, equivalent projected area diameter), and that their morphology suggested formation from a melt. There was an absence of well-defined phases and simple stoichiometries, indicating that exposures to pure substances such as nickel subsulfide or specific oxides appeared not to occur. Although the elemental composition of particles varied greatly, a rough association was evident with the known elemental content of the refinery intermediates. The implications of the findings for aerosol speciation measurements, toxicological studies and interpretation of adverse health effects are explored.     

Visualisation of natural aquatic colloids and particles -- a comparison of conventional high vacuum and environmental scanning electron microscopy

The applicability of environmental scanning electron microscopy (ESEM; imaging of hydrated samples) and conventional high vacuum scanning electron microscopy (SEM; imaging of dried samples at high vacuum) for the observation of natural aquatic colloids and particles was explored and compared. Specific attention was given to the advantages and limitations of these two techniques when used to assess the sizes and morphologies of complex and heterogeneous environmental systems. The observation of specimens using SEM involved drying and coating, whereas ESEM permitted their examination in hydrated form without prior sample preparation or conductive coating. The two techniques provided significantly different micrographs of the same sample. SEM provided sharper images, lower resolution limits (10 nm or lower), but more densely packed particles, suggesting aggregation, and different morphological features than ESEM, suggesting artefacts due to drying. ESEM produced less easily visualised materials, more complex interpretation, slightly higher resolution limits (30-50 nm), but these limitations were more than compensated for by the fact that ESEM samples retained, at least to some extent, their morphological integrity. The results in this paper show that SEM and ESEM should be regarded as complementary techniques for the study of aquatic colloids and particles and that ESEM should be more widely applied to aquatic environmental systems than hitherto.     

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.     

Chemical composition of individual aerosol particles in workplace air during production of manganese alloys

Aerosol particle samples were collected at ELKEM ASA ferromanganese (FeMn) and silicomanganese (SiMn) smelters at Porsgrunn, Norway, during different production steps: raw material mixing, welding of protective steel casings, tapping of FeMn and slag, crane operation moving the ladles with molten metal, operation of the Metal Oxygen Refinement (MOR) reactor and casting of SiMn. Aerosol fractions were assessed for the analysis of the bulk elemental composition as well as for individual particle analysis. The bulk elemental composition was determined by inductively coupled plasma atomic emission spectrometry. For individual particle analysis, an electron microprobe was used in combination with wavelength-dispersive techniques. Most particles show a complex composition and cannot be attributed to a single phase. Therefore, the particles were divided into six groups according to their chemical composition: Group I, particles containing mainly metallic Fe and/or Mn; Group II, slag particles containing mainly Fe and/or Mn oxides; Group III, slag particles consisting predominantly of oxidized flux components such as Si, Al, Mg, Ca, Na and K; Group IV, particles consisting mainly of carbon; Group V, mixtures of particles from Groups II, III and IV; Group VI, mixtures of particles from Groups II and III. In raw material mixing, particles originating from the Mn ores were mostly found. In the welding of steel casings, most particles were assigned to Group II, Mn and Fe oxides. During the tapping of slag and metal, mostly slag particles from Group III were found (oxides of the flux components). During movement of the ladles, most particles came from Group II. At the MOR reactor, most of the particles belonged to the slag phase consisting of the flux components (Group III). The particles collected during the casting of SiMn were mainly attributed to the slag phase (Groups III and V). Due to the compositional complexity of the particles, toxicological investigations on the kinetics of pure compounds may not be easily associated with the results of this study.     

Evaluation of confocal laser scanning microscopy for enumeration of virus-like particles in aquatic systems

Abundances of virus-like particles (VLPs, mostly bacteriophages) are high in aquatic environments; therefore, techniques for precise enumeration are essential in ecological monitoring. VLPs were determined after staining with SYBR Gold by conventional epifluorescence microscopy and compared to enumerations performed by confocal laser scanning microscopy (CLSM). In order to assess the potential of CLSM for viral direct counts (VDCs), we processed samples from different freshwater and marine systems. Optical sectioning by CLSM and production of an overlay picture of multiple scans enables the often uneven whole investigated filter area to be brought to the plane of focus. This allows for subsequent image analysis of digitally created high-quality images. Another advantage using the CLSM was that the short spot excitation of the stain via laser beam minimized fading of the stain. The VDC results show that there is no significant difference between the two methods. Regarding the known difficulties of viral abundance estimates on particulate material, CLSM was further applied to enumerate VLPs on a small set of marine transparent exopolymeric particles sampled from the Atlantic Ocean. Our data suggest that CLSM is a useful tool to count viruses in water samples as well as attached to certain types of aquatic aggregates.     

The heterogeneous composition of working place aerosols in a nickel refinery: a transmission and scanning electron microscope study

Size, morphology and chemical composition of individual aerosol particles collected in a nickel refinery were analyzed by scanning electron microscopy and energy-dispersive X-ray microanalysis (EDX). The phase composition was determined by selected area electron diffraction and EDX in a transmission electron microscope. Most particles are heterogeneous on a nanometer scale and consist of various phases. Nickel phases observed in the roasting and anode casting departments include metallic nickel, bunsenite (NiO), trevorite (Ni,Cu)Fe2O4, heazlewoodite Ni3S2, godlevskite (Ni,Cu)9S8, orthorhombic NiSO4 and an amorphous Ni,Cu.Al,Pb sulfate of variable composition. Additional phases encountered include corundum (Al2O3), murdochite (PbCu6O8), hexagonal Na2SO4, anhydrite (CaSO4), graphite (C) and amorphous carbon. The implications of the occurrence of the different Ni phases and their nanometer size for the study of adverse health effects are explored.     

Classification of particles from the farm environment by automated sizing, counting and chemical characterisation with scanning electron microscopy-energy dispersive spectroscopy

About 60,000 particles in 288 aerosol samples collected during farm work have been characterised with automated particle analysis using scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). Based on EDS-analysis of materials with known composition (potato flour, alpha-quartz, K-feldspar and beta-wollastonite), criteria were developed for classification of particles as: (1) organic, (2) silicon-rich (silica), and (3) other inorganic particles. The reproducibility of the relative mass proportions in dust samples collected during farm work was 0.078 when approximately 200 particles were characterised per sample. Field samples from the farm environment showed clear differences in composition. Generally, inorganic particles dominated the particle mass. The proportion of the organic particle mass was highest for tending of swine and poultry, 55 and 38% respectively. Silica particles amounted to 10 to 20% of the total mass during handling crops, e.g. grain, straw, hay, potatoes, and onions. It seems likely that the results can be used in etiologic studies, but further validation would be needed for quantitative purposes.     

Detection of phenol-induced subcellular alteration by electron microscopy in the liver and panceres of carp

A sublethal dose (5 mg L^-1) of phenol was applied in the experiment. Liver and pancreas samples were taken at 24, 48, 72, and 96 hr for electron microscopy. The following alterations were manifested during the experiment: amitosis, irregular nuclear forms, decrease of chromatin, nucleolar segregation and numerous phagosomes and autophagic vacuoles in the cytoplasm. After 72 hr, large empty vacuoles also developed in the cells. The rEr was often dilated, and the accumulation of paraprotein crystals in their lumen was also common. All these alterations prove the serious cytopathological effects of phenol on the metabolism of parenchymal cells.     

Magnetic microsphere confined ionic liquid as a novel sorbent for the determination of chlorophenols in environmental water samples by liquid chromatography

Magnetic microsphere confined ionic liquid was synthesized by covalently bonding N-methylimidazolium on magnetic microspheres. The functionalized magnetic microspheres were characterized by Fourier transform infrared (FT-IR) spectrometry, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The prepared material was used for the preconcentration of three chlorophenols (CPs) in water combined with high-performance liquid chromatography (HPLC). Several conditions that probably affected the extraction efficiency such as standing time, eluent and its volume, sample pH and volume, were optimized. Under the optimal conditions, good recoveries (70.3-88.8%) were achieved with satisfactory relative standard deviations (RSDs) of less than 6.0%. The limits of detection for the three CPs were 0.20-0.35 μg L(-1). The results indicated that the ionic liquid-functionalized magnetic microspheres show significant promise for the analysis of CPs in environmental samples.     

The biological behaviour and bioavailability of aluminium in man, with special reference to studies employing aluminium-26 as a tracer: review and study update

Until 1990 biokinetic studies of aluminium metabolism and biokinetics in man and other animals had been substantially inhibited by analytical and practical difficulties. Of these, the most important are the difficulties in differentiating between administered aluminium and endogenous aluminium-especially in body fluids and excreta and the problems associated with the contamination of samples with environmental aluminium. As a consequence of these it was not possible to detect small, residual body burdens of the metal following experimental administrations. Consequently, many believed aluminium to be quantitatively excreted within a short time of uptake in all, but renal-failure patients. Nevertheless, residual aluminium deposits in a number of different organs and tissues had been detected in normal subjects using a variety of techniques, including histochemical staining methods. In order to understand the origins and kinetics of such residual aluminium deposits new approaches were required. One approach taken was to employ the radioisotope (67)Ga as a surrogate, but this approach has been shown to be flawed-a consequence of the different biological behaviours of aluminium and gallium. A second arose from the availability, in about 1990, of both (26)Al-a rare and expensive isotope of aluminium-and accelerator mass spectrometry for the ultra-trace detection of this isotope. Using these techniques the basic features of aluminium biokinetics and bioavailability have been unravelled. It is now clear that some aluminium is retained in the body-most probably within the skeleton, and that some deposits in the brain. However, most aluminium that enters the blood is excreted in urine within a few days or weeks and the gastrointestinal tract provides an effective barrier to aluminium uptake. Aspects of the biokinetics and bioavailability of aluminium are described below.     

Study on determination of iron,cobalt, nickel,copper, zinc and manganese in drinking water by solid-phase extraction and RP-HPLC with 2-(2-quinolinylazo)-5-diethylaminophenol as precolumn derivatizing reagent

A new method for the determination of iron, cobalt, nickel, copper, zinc and manganese in drinking water by the reversed-phase high-performance liquid chromatography (RP-HPLC) with 2-(2-quinolinylazo)-5-diethylaminophenol (QADEAP) as precolumn derivatizing reagent was studied in this paper. The iron, cobalt, nickel, copper, zinc, and manganese ions react with QADEAP to form color chelates in the presence of cetyl trimethylammonium bromide (CTMAB) and acetic acid-sodium acetic buffer solution medium of pH 4.0. These chelates were enriched by solid-phase extraction with a Waters Nova-Pak C18 cartridge and eluted the retained chelates from the cartridge with tetrahydrofuran (THF). The enrichment factor of 100 was achieved. Then the chelates were separated on a Waters Nova-Pak C18 column (3.9 x 150 mm, 5 microm) by gradient elution with methanol (containing 0.2% of acetic acid and 0.1% of CTMAB) and 0.05 mol L(-1) acetic acid-sodium acetic buffer solution (containing 0.1% of CTMAB) (pH 4.0) as mobile phase at a flow rate of 0.5 ml min(-1), and monitored with a photodiode array detector from 450 approximately 700 nm. The detection limits (S/N = 3) of iron, cobalt, nickel, copper, zinc and manganese are 0.8, 1.1, 0.9, 1.1, 1.5 and 2.0 ng L(-1), respectively, in the original sample. This method can be applied to determination at the microg L(-1) level of iron, cobalt, nickel, copper, zinc and manganese in drinking water with good results.     

The Composition of PM10 as collected by a Conventional TEOM, a Modified TEOM and a Partisol Gravimetric Monitor at a Kerbside Site in the North East of England

The composition of airborne particulate matter sampled by a conventional TEOM^®, an experimental modified TEOM, operated at a lower temperature but fitted with a drier to remove moisture and a Partisol^®, installed at a kerbside site in the North East of England, has been investigated. The results indicate that there is a seasonal variation in the composition of PM₁₀ as sampled by the three monitors, with chloride concentration being significantly higher in the winter. The Partisol was found to sample a higher mass of chloride and nitrate, however the differences between the monitors was only significant for chloride. Both TEOM's were found to sample a greater mass of sulphate, although the variability in the data collected meant that significance of the results was not proven statistically. The range of artifacts associated with PM₁₀ monitors is reviewed. Difficulties in the interpretation of results due to the variable nature of airborne particulate matter and the ability of filter based systems to accurately represent the composition of atmospheric particles are considered.     

The composition of PM10 as collected by a conventional TEOM, a modified TEOM and a Partisol gravimetric monitor at a kerbside site in the North East of England

The composition of airborne particulate matter sampled by a conventional TEOM, an experimental modified TEOM, operated at a lower temperature but fitted with a drier to remove moisture and a Partisol, installed at a kerbside site in the North East of England, has been investigated. The results indicate that there is a seasonal variation in the composition of PM(10) as sampled by the three monitors, with chloride concentration being significantly higher in the winter. The Partisol was found to sample a higher mass of chloride and nitrate, however the differences between the monitors was only significant for chloride. Both TEOM's were found to sample a greater mass of sulphate, although the variability in the data collected meant that significance of the results was not proven statistically. The range of artifacts associated with PM(10) monitors is reviewed. Difficulties in the interpretation of results due to the variable nature of airborne particulate matter and the ability of filter based systems to accurately represent the composition of atmospheric particles are considered.