Methods for Elemental Analysis of Size-Resolved PM Samples Collected on Aluminium Foils: Results of an Intercomparison Exercise.

Aluminium is the most common substrate in studies using impactors for the measurement of the number or the weight of size-segregated atmospheric particulate matter (PM), as its characteristics perfectly fit impactor requirements. However, its use is not recommended by manufacturers when one of the purposes of the study is the determination of the metal content in the sample. The aim of this work was to develop an efficient analytical procedure for the removal and acid digestion of PM samples collected on aluminium foils by a cascade impactor to perform the determination of metals. The possibility of performing the trace metal analysis of PM samples collected using aluminium foils is of great importance, as it allows the determination of an accurate size distribution and the elemental composition of the PM collected on each impactor stage. Two procedures were optimised by using different digestion and analysis techniques. Both procedures were then applied to the two halves of several Dekati low-pressure impactor (DLPI) samples, and the results were critically compared. The two procedures proved to be effective in the determination of extremely low concentrations of a large suite of analytes in different size fractions of PM emitted by a brake system.

Erratum: Illuminati et al. Determination of Cd, Pb, and Cu in the Atmospheric Aerosol of Central East Antarctica at Dome C (Concordia Station). Molecules 2021, 26, 1997.

The authors wish to make the following corrections to the paper [...].

Determination of Cd, Pb, and Cu in the Atmospheric Aerosol of Central East Antarctica at Dome C (Concordia Station).

Trace heavy metals Cd, Pb, and Cu were determined (by square wave anodic stripping voltammetry) in aerosol samples collected at Dome C (the Italo-French Station Concordia), a remote site of the Central East Antarctic plateau, for which no data are available until now. During the Austral Summer 2005-2006, three PM10 high-volume impactors were installed in two locations nearby of Concordia station: the first one very close and downwind of the station (about 50 m north), the other two (very close to each other) in a 'distant' site, upwind of the station and close to the astrophysics tent (not used in that expedition) at ~800 m south of Station Concordia. For each sample, the availability of the mass of the aerosol collected (obtained by differential weighing carried out on site), in addition to the volume of the filtered air, allowed us to express results both in terms of metal mass fractions in the aerosol and in the usual way of metal atmospheric concentrations. Metal contents increased in the order Cd < Pb < Cu with the following ranges of values: Cd 1.0-8.4 µg g-1 (0.09-3.1 pg m-3), Pb 96-470 µg g-1 (12-62 pg m-3), and Cu 0.17-20 mg g-1 (0.027-2.4 ng m-3). From the metal temporal profiles obtained we estimated the following background values for the area of Dome C, expressed both in mass fractions and in atmospheric concentrations: Cd 1.2 ± 0.2 µg g-1 (0.24 ± 0.13 pg m-3), Pb (here fixed as upper limit) 113 ± 13 µg g-1 (21 ± 8 pg m-3), and Cu 0.91 ± 0.48 mg g-1 (0.12 ± 0.07 ng m-3). The highest values were observed in the first part of the season, and particularly for the site close to the station, possibly related to sample contamination linked to intense activity at the Concordia station connected with the beginning of the expedition, including aircraft arrivals/departures. Increments of up to 10 times (and even 20 times for Cu) were recorded with respect to the background values. The metal excesses of the contaminated over background samples were found approximately, except for Cu, in the same proportion of the metal contents of the special Antarctic blend (SAB) diesel fuel, which is used almost exclusively at Concordia Station. The effect of the wind direction was also observed. Thus in the intermediate period of the campaign, when the wind direction reversed for several days with respect to the prevailing one, Cd and Pb metal contents decreased at the sampling point installed close to the station, now upwind of Concordia station, and increased at the 'clean' site astrophysics tent, turned downwind at the main station. No simple and easily interpretable effect of the wind direction was observed for Cu, which suggests that some other extemporaneous and not clearly identified factor may have intervened in this case. These results suggest that the human impact at Dome C influences mainly the zone very close to the station, but also the area in the neighborhood, including the supposed clean site of the astrophysics tent (about 800 m far from the station), when the wind direction reverses with respect to the prevailing one, leaving the site downwind of the station Concordia. Since no other data are reported for the Dome C area, our results are compared with literature data referred to the South Pole Station (the only other plateau site for which data are available) and several other coastal Antarctic sites, observing that our results (excluding Cu) are the lowest ever observed for Antarctic aerosol.

Optimization of a sequential extraction procedure for trace elements in Arctic PM10.

In this work, a two-step sequential extraction scheme for the determination of trace elements in Arctic PM10 samples was optimized by using two certified reference materials (CRMs). By means of an experimental design for qualitative variables, the five most common extracting solutions for particulate matter (PM) sequential extraction (high purity water (HPW), 0.032 M HNO3, 0.022 M HCl, 0.11 M CH3COOH, and 0.012 M CH3COOH/CH3COONH4 buffer) and two different extraction methods (stirring and ultrasounds) were compared. The purpose of the study was the identification of the procedure which gives the best estimation of the anthropogenic portion of the elements present in PM10 samples. The use of ultrasounds instead of stirring induced a low but significant decrease of the extraction of all the elements and a decrease in the repeatability of the procedure. Diluted HNO3 was the extractant which allowed to maximize the extraction of anthropogenic elements (As, Cd, Pb, Zn) with respect to crustal ones (Al, Si, Ti). The optimized procedure proved successful in avoiding contaminations and, therefore, suitable to be applied to PM samples having extremely low concentrations, such as samples collected in polar or other remote areas. The chosen procedure was applied to ten Arctic PM10 samples, allowing for a better identification of their sources. Indeed, it was possible to hypothesize that even though the concentrations of As, Cd, K, Mg, Mn, and Ni in spring and summer were different, their mobility and, therefore, their chemical form in the analyzed PM10 samples were probably similar. Graphical abstract.

Development of an easy portable procedure for on-site determination of mercury and methylmercury.

A portable measurement and speciation procedure for inorganic mercury (HgIN) and methylmercury (CH3Hg) was developed. A portable sample pretreatment was optimized to determine total mercury content. A new home-made sorbent (CYXAD, CHYPOS 101 modified Amberlite XAD), was prepared to separate HgIN and CH3Hg. Mercury species were determined using square wave anodic stripping voltammetry (SW-ASV) with a solid gold electrode (SGE) and using a portable potentiostat. A certified reference material, five freeze-dried samples and three fresh samples were analysed with conventional voltammetric analyzer, after dissolution of the samples in microwave oven, and with a portable potentiostat after the mild eating procedure. The results obtained by SW-ASV were compared with those obtained using Direct Mercury Analyser (DMA). The quantification with the portable method is comparable to that obtained with the DMA. Retention tests showed the selectivity of CYXAD for HgIN, its stability and the possibility to re-use the same aliquot of resin.

The Inorganic Component as a Possible Marker for Quality and for Authentication of the Hazelnut's Origin.

The inorganic component of hazelnuts was considered as a possible marker for geographical allocation and for the assessment of technological impact on their quality. The analyzed samples were Italian hazelnuts of the cultivar Tonda Gentile Romana and Turkish hazelnuts of the cultivars Tombul, Palaz and Çakildak. The hazelnuts were subjected to different drying procedures and different conservative methods. The concentration of 13 elements, namely Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, Sn, Sr and Zn, were quantified by inductively coupled plasma optical emission spectroscopy (ICP-OES). All the samples were previously digested in a microwave oven. Before proceeding with the analysis of the samples, the whole procedure was optimized and tested on a certified reference material. The results show that the inorganic component: (i) can represent a fingerprint, able to identify the geographical origin of hazelnuts, becoming an important quality marker for consumer protection; (ii) is strongly influenced by the treatments undergone by the investigated product during all the processing stages. A pilot study was also carried out on hazelnuts of the cultivar Tonda Gentile Trilobata Piemontese, directly harvested from the plant during early development to maturity and analyzed to monitor the element concentration over time.

Element variability in lacustrine systems of Terra Nova Bay (Antarctica) and concentration evolution in surface waters.

Major, minor and trace elements were determined in freshwater of lacustrine systems in Terra Nova Bay, along Victoria Land coast, Antarctica, as well as in algae and mosses. The samples were collected during some of the sampling campaigns between 2007 and 2011 (and the one of 2002) within the framework of the Italian National Program of Research in Antarctica (PNRA). Data were processed with chemometric techniques. Results showed that elements typically considered as potential anthropogenic pollutants (e.g. As, Pb, Zn, Cu and Ni) present a strong correlation with the lithogenic elements (e.g. Al, Si, Fe) in all matrices, suggesting that their origin is connected to natural phenomena. Metal concentrations in vegetation samples are in the same range as previously published data. The obtained results were compared with older literature data (since the early '90s) from the same lacustrine systems, in order to present a historical overview of element concentrations. This approach furnishes important information on surface water evolution as a function of time. A considerable variability was observed in metal concentrations but no clear trend was identified. This suggests that their concentration evolution is hardly correlated to specific natural or anthropic phenomena. No evidence of an increase of concentrations over time was apparent. Our results represent new important data about metal concentrations in lacustrine systems in Antarctica, furnishing ranges of values that can be considered as a reference. These data, therefore, could be used to detect or monitor future local and/or global anthropogenic contaminations.