Improved identification of transition metals in airborne aerosols by SEM-EDX combined backscattered and secondary electron microanalysis.

The SEM EDX backscattered electron (BSE) atomic number contrast has been largely used in this work, in combination with conventional secondary electron microanalysis, to investigate the presence of metal particles in airborne particulate collected at three sites (industrial, residential, and rural background) in the Po Valley (Italy). Individual particle x-ray microanalysis was used for this aim. In many cases, the presence of metal particles was not evident by secondary electron imaging and it was instead revealed by BSE detection. Metal particles were observed either as isolated (not clustered to other particles), or gathered together (homogeneous clusters). In addition, the BSE microanalysis put on evidence two main types of association of metals to other particulate components: heterogeneous clusters and metals embedded or enclosed in other materials. In this study, the first association (heterogeneous clusters) was observed mostly between Fe-bearing metallic particles and soot aggregates (or other carbonaceous particles) and it was found in the particulate matter (PM) of all studied sites. The second association, conversely, seems to be characterized by more selective relationships between composition/size of metal particles and type of other particulate components. These associations could be evidenced only when using the BSE Z-contrast and mainly concern three cases: (1) unusual silicate-carbonate mixed aggregates were observed at the industrial site only. In these aggregates, embedded Mn, Cr, Co, Bi, W, and Zr fine particles were selectively observed. (2) Ni and V rich ultrafine particles were only observed as embedded particles in the surface structure of carbon cenospheres. (3) Pb or Pb-Zn bearing fine and ultrafine particles were largely detected only in oxygenated organic aerosols in the ultrafine PM.

Determination of metals, metalloids and non-volatile ions in airborne particulate matter by a new two-step sequential leaching procedure Part A: Experimental design and optimisation.

The optimisation of a micro-analytical two-step sequential leaching procedure for the determination of non-volatile ions (NO(3)(-), SO(4)(2-), Cl(-), Na(+), Mg(2+), NH(4)(+) and Ca(2+)) and of 17 elements (Al, As, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, S, Se, V, Zn, Sb, Si and Ti) in two fractions-extract and residue-on the same sample of air particulate matter is described. The two-step method was tested on the SRM NIST 1648 for equivalence with two reference methods, the EMEP procedure for ions extraction and the EN 12341 standard for the elemental determination of the PM(10) and is suitable for application to small sample amounts (less than 1mg of particulate matter is needed), i.e. those collected by daily low volume filter-sampling. Performance times of the procedure were optimised to meet the target of routine application for large scale monitoring samples. A single ultrasonic-assisted extraction of air particulate matter is performed in 0.01M acetate buffer at pH 4.5, followed by IC ions analysis and ICP-OES elemental analysis of the extract and by ICP-OES elemental analysis of the mineralized residue after dissolution by microwave-assisted digestion with a HNO(3)/H(2)O(2) mixture. Using a pH buffered extracting solvent was preferred to water or diluted acid solutions to improve the reproducibility of metals extraction with respect to existing leaching methods; the influence of pH, nature and concentration of the buffer solution and extraction time on analytes concentration in the extract is discussed. Values of ions extraction and elements recoveries resulted fairly equivalent with those obtained by the reference methods. The study was also extended to some non-certified elements (Mg, S, Sb, Si and Ti) for their environmental significance. Elements recoveries were obtained as sum of the extract and residue fractions and were comparable with those obtained by direct dissolution. Standard deviations were within 10% for almost all detected ions and elements.

Determination of metals, metalloids and non-volatile ions in airborne particulate matter by a new two-step sequential leaching procedure Part B: Validation on equivalent real samples.

Due to the lack of proper standard materials for airborne particulate matter collected on filters, a validation scheme was developed, which is here described, to the aim of testing the application of leaching procedures performing both ions and elemental determinations on real samples of airborne particulate matter collected on filters. The scheme has been developed on a two-step leaching method (extraction in acetate buffer and acid dissolution of residue) previously developed by authors and consists of two series of tests to be run on n pairs of equivalent parallel samples filter-collected. The first series of tests aims to assess on real samples the equivalence between results obtained by the tested procedure with those obtained by the EMEP ions extraction and the EN 12341 standard methods, whereas the second aims to evaluate the reproducibility of analytical results of elemental determination in the leached and dissolved fractions; in the latter case data reliability is also evaluated as a function of the environment-intrinsic variability of real samples. To avoid errors due to sampling differences data from filter pairs were standardized both by gravimetric determination of loaded filters, according to the EN 12341 standard and by the rate [SO(4)(2-)](A)/[SO(4)(2-)](B,) where [SO(4)(2-)] indicate the soluble sulphate concentration in the extract; in the latter case values improved for all elements and in both fractions. Results of equivalence with standard methods and reproducibility tests are evaluated as mean relative percentage differences (Delta%) and percentage elements recoveries (R%). The application of the validation scheme to the two-step leaching method is here discussed for non-volatile ions and for 17 elements detected on 22 pairs of low-volume collected PM(10) samples on Teflon filters.