Maria Luisa Astolfi

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.

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.

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.

Dissolution of glass wool, rock wool and alkaline earth silicate wool: Morphological and chemical changes in fibers

The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis.

Semiautomatic sequential extraction of polycyclic aromatic hydrocarbons and elemental bio-accessible fraction by accelerated solvent extraction on a single particulate matter sample

We describe the optimization and validation of a sequential extractive method for the determination of the polycyclic aromatic hydrocarbons (PAHs) and elements (Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se, V and Zn) that are chemically fractionated into bio-accessible and mineralized residual fractions on a single particulate matter filter. The extraction is performed by automatic accelerated solvent extraction (ASE); samples are sequentially treated with dichloromethane/acetone (4:1) for PAHs extraction and acetate buffer (0.01M; pH 4.5) for elements extraction (bio-accessible fraction). The remaining solid sample is then collected and subjected to acid digestion with HNO3:H2O2 (2:1) to determine the mineralized residual element fraction. We also describe a homemade ASE cell that reduces the blank values for most elements; in this cell, the steel frit was replaced by a Teflon pierced disk and a Teflon cylinder was used as the filler. The performance of the proposed method was evaluated in terms of recovery from standard reference material (SRM 1648 and SRM 1649a) and repeatability. The equivalence between the new ASE method and conventional methods was verified for PAHs and for bio-accessible and mineralized residual fractions of elements on PM10 twin filters.

Efficiency Evaluation of Food Waste Materials for the Removal of Metals and Metalloids from Complex Multi-Element Solutions

Recent studies have shown the potential of food waste materials as low cost adsorbents for the removal of heavy metals and toxic elements from wastewater. However, the adsorption experiments have been performed in heterogeneous conditions, consequently it is difficult to compare the efficiency of the individual adsorbents. In this study, the adsorption capacities of 12 food waste materials were evaluated by comparing the adsorbents’ efficiency for the removal of 23 elements from complex multi-element solutions, maintaining homogeneous experimental conditions. The examined materials resulted to be extremely efficient for the adsorption of many elements from synthetic multi-element solutions as well as from a heavy metal wastewater. The 12 adsorbent surfaces were analyzed by Fourier transform infrared spectroscopy and showed different types and amounts of functional groups, which demonstrated to act as adsorption active sites for various elements. By multivariate statistical computations of the obtained data, the 12 food waste materials were grouped in five clusters characterized by different elements’ removal efficiency which resulted to be in correlation with the specific adsorbents’ chemical structures. Banana peel, watermelon peel and grape waste resulted the least selective and the most efficient food waste materials for the removal of most of the elements.

Optimization and validation of a fast digestion method for the determination of major and trace elements in breast milk by ICP-MS

Breast milk guarantees all the nutrients required by infants during their first few months of life and remains the most important food source for their health and growth. However, the mother may transfer potentially toxic chemicals to the suckling infant through breastfeeding. The aim of this study was to optimize and validate a fast method for the determination of a total content of 34 elements (Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cs, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, Sb, Se, Si, Sn, Sr, Te, Ti, Tl, U, V, and Zn) in liquid and lyophilized breast milk. The samples were subjected to HNO3:H2O2 (2:1) digestion in an open vessel heated in a water bath (WBD; 80 °C) and subsequently analysed by quadrupole inductively coupled plasma mass spectrometry equipped with a collision-reaction interface. The performance of the proposed method was evaluated in terms of selectivity, detection and quantification limits, linearity, accuracy, and robustness by using standard reference materials and filed samples of breast milk. Compared to microwave-assisted acid digestion, the proposed open vessel digestion allows a significant reduction in treatment time and sample manipulation, while maintaining a similar analytical performance. Masses of 0.5 g of breast milk were efficiently digested with the WBD treatment allowing a residual carbon content lower than 60 mg L-1 and a residual acidity lower than 0.87 mol L-1 in final digested samples. Thus, it shows great potential for application to routine analysis. The method provides satisfactory detection limits and good performance (trueness and recovery percentages 80-111%; coefficient of variation <10%; and relative repeatability <15%) and allows a high sample throughput for multi-elemental determination in human biomonitoring studies.