Silvia Canepari

Inorganic constituents of urban air pollution in the Lazio region (Central Italy).

A field study was carried out at six locations in the Lazio region (Central Italy) aimed at characterising atmospheric particulate matter (PM10 and PM2.5) from the point of view of the chemical composition and grain size distribution of the particles, the mixing properties of the atmosphere, the frequency and relevance of natural events. The combination of four different analytical techniques (ion chromatography, X-ray fluorescence and ICP for inorganic components, thermo-optical analysis for carbon compounds) yielded sound results in terms of characterisation of the air masses. During the first three months of the study (October-December 2004), many pollution events of natural (sea-salt or desert dust episodes) or anthropogenic nature were identified and characterised. More than 90% of the collected mass was identified by chemical analysis. The central role played by the mixing properties of the lower atmosphere when pollution events occurred was highlighted. The results show a major impact of primary anthropogenic pollutants on traffic stations and a homogeneous distribution of secondary pollutants over the regional area. An evaluation of the sources of PM and an identification of possible reliable tracers were obtained using a chemical fractionation procedure.

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 soluble ions and elements in ambient air suspended particulate matter: Inter-technique comparison of XRF, IC and ICP for sample-by-sample quality control.

In this paper, we describe a validation procedure for chemical fractionation analysis of elements (Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, S, Sb, Si, Sr, Ti and V) and soluble ions (Cl(-), NO(3)(-), SO(4)(2-), Na(+), NH(4)(+), Mg(2+), Ca(2+)) in suspended particulate matter (PM). The procedure applies three distinct measurement techniques (XRF, IC and ICP-OES) to the analysis of individual samples. The techniques used generate different outputs at different stages in the procedure. This makes it possible to identify the contributions of specific parameters to measurement uncertainty. On this basis, we propose a scheme for controlling the analytical quality of data from individual samples in which inter-technique comparisons is used in the same way many analytical methods use surrogates. We apply this scheme to about 310 samples of PM(10) and PM(2.5) identifying and assessing the main factors contributing to measurement uncertainty. This procedure successfully resolved a number of difficulties frequently encountered during the analysis of PM, including lack of appropriate reference materials and the low reliability of alternative techniques of quality control. The results demonstrate the critical importance of sample treatment prior to destructive analysis by IC and ICP.

Ultrasound and microwave-assisted extraction of metals from sediment: a comparison with the BCR procedure.

In this paper we investigate alternatives to mechanical stirring for the extraction of the mobile fraction of metals from sediment, and analyze whether these techniques can reduce extraction time and improve reproducibility. We compare the quantities of metal extracted from BCR601 and BCR701 certified sediments using ultrasound bath, microwave-assisted extraction and the first step in the certified BCR sequential extraction procedure. Some environmentally important not-certified metals such as As, Mn, Co, Fe and Al have been included in this study. In the case of microwave-assisted extraction, we compare tests in which samples are exposed to constant, low power irradiation with tests using pulsed high power. In the tests using the ultrasound bath, less metal was extracted than with the other extractive techniques and standard deviations were comparable to those obtained with the BCR procedure; in assays using microwaves at constant power, extraction efficiencies were different for different metals and for different reference materials and, in some cases, standard deviations were higher than those for the reference method. In contrast, tests with microwaves and constant temperature produced encouraging results: R.S.D.s lay in the 2-4% range, both for certified and not-certified metals; these values are very low compared to those for the reference method. Extraction efficiencies for certified metals were close to 100% for Cd, Zn, Cu and Ni and around 80% for Pb and Cr.

Comprehensive profiling of carotenoids and fat-soluble vitamins in milk from different animal species by LC-DAD-MS/MS hyphenation.

This paper describes a novel and efficient analytical method to define the profile of fat-soluble micronutrients in milk from different animal species. Overnight cold saponification was optimized as a simultaneous extraction procedure. Analytes were separated by nonaqueous reversed-phase (NARP) chromatography: carotenoids on a C(30) column and fat-soluble vitamins on a tandem C(18) column system. Besides 12 target analytes for which standards are available (all-trans-lutein, all-trans-zeaxanthin, all-trans-β-cryptoxanthin, all-trans-β-carotene, all-trans-retinol, α-tocopherol, γ-tocopherol, δ-tocopherol, ergocalciferol, cholecalciferol, phylloquinone, and menaquinone-4), the DAD-MS combined detection allowed the provisional identification of other carotenoids on the basis of the expected retention times, the absorbance spectra, and the mass spectrometric data. Retinol and α-tocopherol were the most abundant fat-soluble micronutrients and the only ones found in donkeys milk along with γ-tocopherol. Ewes milk also proved to be a good source of vitamin K vitamers. Bovine milk showed a large variety of carotenoids that were absent in milk samples from other species with the only exception of all-trans-lutein and all-trans-zeaxanthin.

Seasonal variations in the chemical composition of particulate matter: a case study in the Po Valley. Part II: concentration and solubility of micro- and trace-elements

Size distribution (fine and coarse fraction) and solubility distribution (extracted and residual fraction) of 20 elements (As, Ba, Be, Cd, Co, Cu, Fe, Li, Mn, Pb, Ni, Rb, S, Sb, Se, Sn, Sr, Ti, Tl, V) in atmospheric particulate matter (PM) were determined during a 5-year field study carried out in the Po Valley (peri-urban area of Ferrara, in Northern Italy). By studying the contribution of the two size fractions and the two solubility fractions to the atmospheric concentration of each element, it was possible to obtain interesting information about the variability of PM sources, to assess the role played by atmospheric stability in determining pollution episodes, and to obtain an estimate of the bio-accessible fraction. Atmospheric stability is confirmed to be one of the main causes of atmospheric pollution in this area and is to be responsible for the pronounced winter increase in both PM and elemental concentration. Long-range transport of natural and polluted air masses caused temporary increases in PM and elemental concentration, while local industrial emission seemed to play a secondary role. Regulated elements were well below their concentration limit, but many toxic elements were in the form of fine particles and soluble chemical species, more accessible to the environment, and the human body.

Comparison of extracting solutions for elemental fractionation in airborne particulate matter.

It is here described the comparison of extraction efficiency of some solutions (acetate buffer, deionized water, diluted HNO(3) and EDTA) frequently adopted in literature for evaluating the elemental solubility in airborne particulate matter. This comparison was performed considering the distribution of As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Na, Ni, Pb, S, Si, Sb, Sn, Sr, Ti, V, Zn between the extractable and mineralized residual fractions on the NIST 1648 certified material, PM(10) real samples and size-segregated samples, collected by a 13-stage impactor. The extracting solutions were evaluated by comparing extractive efficiencies and robustness towards some factors, such as acidity and concentration of complexing species, that have great environmental variability and that could be able to modify the extractive efficiency. Furthermore, extraction methods application to size-segregated samples allowed estimating the selectivity of extracting solutions towards dimensionally characterized emission sources, as dusts originated from abrasion and road dust re-suspension. On the basis of the obtained results, it was possible to define the main advantages and disadvantages resulting from the use of different extracting solutions, necessary to make possible the comparison of environmental studies carried out in different extractive conditions and to start up a proper study for harmonizing extracting procedures.

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.

Time-resolved measurements of water-soluble ions and elements in atmospheric particulate matter for the characterization of local and long-range transport events.

Chemical composition of atmospheric PM(10) was determined at 2-h resolution during a 10-d field study carried out in the urban area of Rome, Italy. Extractable and residual fractions of elements were determined on 2-h samples by inductively coupled plasma mass spectrometry, a rather widespread analytical technique; daily chemical characterization of macro- and micro-components was also carried out and the mass closure was obtained. Interpretation of the variations in PM(10) composition was carried out in the light of the meteorological conditions and, in particular, of the mixing properties of the lower atmosphere, evaluated by monitoring natural radioactivity due to radon 222 decay. The combination of time-resolved sampling, chemical fractionation and monitoring of the dilution properties of the atmosphere allowed a reliable identification of long-range transport events and of local phenomena, which could not be detected by daily samplings. This kind of study can be effective for gathering detailed information about tracers at local scale, which are really valuable for interpreting the results of traditional low-resolution monitoring studies.

Urinary levels of trace elements among primary school-aged children from Italy: The contribution of smoking habits of family members

The aims of the present study was to investigate the role of Environmental Tobacco Smoke (ETS) exposure in domestic environment, the smoking policies adopted at home on urinary excretion of 23 trace elements present in tobacco and/or tobacco smoke (Li, Be, B, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Rb, Sr, Cd, Sn, Sb, Te, Cs, Tl, Pb, Bi, U) among a sample of healthy Italian school-aged children. The levels of monitored trace elements in urine samples from 110 children (5-11years) living in a rural area and recruited in a cross-sectional study were measured via inductively coupled plasma mass spectrometry, while information regarding demographic characteristics and ETS exposure of the participants were obtained from questionnaires. Univariate elaborations evidenced that Co and Mn levels increased in children exposed to ETS in domestic environment, but multiple linear regression analyses revealed the independent effect of the habit of cohabitant(s) smoker(s) of smoking at home when children is present on urinary concentrations of Li, Ti, V, Co, Ga and Sr. Besides, we found significant gender- and age-dependency of some monitored elements: females presented higher Cu and Pb levels, but lower Rb levels respect to males, while age displayed a significant negative independent effect on the Cr, Co, Rb, and Sn concentrations, but positive on Ga levels. Finally, u-creatinine was a significant predictor for almost all the analytes, but not for Mn, Cd, Sb, Ga.