Daniela Varrica

Volcanic and anthropogenic contribution to heavy metal content in lichens from Mt. Etna and Vulcano island (Sicily).

Major and trace element concentrations were determined in two lichen species (Parmelia conspersa and Xanthoria calcicola) from the island of Vulcano and all around Mt. Etna. In both areas, the average concentrations of Al, Ca, Mg, Fe, Na, K, P and Ti are substantially greater than those of other elements. Several elements (Br, Pb, Sb, Au, Zn, Cu) resulted enriched with respect to the local substrates. The Br and Pb enrichment factors turned out to be the highest among those calculated in both areas. Data indicate that mixing between volcanic and automotive-produced particles clearly explains the range of Pb/Br shown by lichen samples. Sb is also enriched, revealing a geogenic origin at Vulcano and a prevailing anthropic origin at Mt. Etna. Distribution maps of the enrichment factors show a generalized enrichment of Au and Zn near Mt. Etna, whereas Cu appears to be enriched prevalently in the NE-SE area. The highest levels of Au and Cu at Vulcano occur E-SE from the craters, following the prevailing wind direction.

Concentration and reference interval of trace elements in human hair from students living in Palermo, Sicily (Italy)

Trace element contents in specimens of hair collected from 137 children aged 11-13 years old, living in Palermo (Sicily, Italy) were determined by ICP-MS. This work reports analytical data for the following 19 elements: Al, As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sr, U, V and Zn. The most abundant chemical elements were zinc and copper (Zn > Cu), with concentrations exceeding 10 μg/g (Zn = 189.2 μg/g; Cu = 22.9 μg/g). Other elements with concentrations greater than 1 μg/g were, in order of abundance, Al>Sr>Ba>Pb. The remaining elements were all below 1 μg/g. The average elemental concentrations in hair were statistically compared by Kolmogorov-Smirnovs test taking childrens gender into account. Al, Ba, Cr, Li, Rb, Sb, Sr, V and Zn were statistically different according to gender, with significance p < 0.001. This study thus confirms the need for hair analysis to differentiate female data from those of males. IUPAC coverage intervals and coverage uncertainties for trace elements in the analysed hair samples are also reported.

Occurrence of platinum, palladium and gold in pine needles of Pinus pinea L. from the city of Palermo (Italy)

Abstract Preliminary data on the presence of Pt, Pd and Au in airborne particulate matter from the urban area of Palermo (Sicily, Italy) are presented. They were obtained by analysing 40 samples of pine needles (Pinus pinea L.) collected in and around the city. Observed concentrations range from 1 to 102 μg/kg for Pt, 1 to 45 μg/kg for Pd and 22 to 776 μg/kg for Au. Platinum and Pd concentrations in pine needles are up to two orders of magnitude higher than their crustal abundances. They exhibit a high statistical correlation (R2=0.74) which suggests a common origin. Precious metal concentrations measured within the city centre are much higher than those occurring outside the town. The distribution patterns of Pt and Pd in the study area are compared to the distributions of Au and Pb. Gold is enriched at the same sites where Pt and Pd are enriched, while Pb shows some discrepancies. The most probable local source of all of these elements is traffic. Average Pt and Pd emissions in the city area are estimated to be about 136 and 273 g/a, respectively. This study supports the use of pine needles as biomonitors of PGE in the environment.

Possible markers of traffic-related emissions

Looking for robust indicators of motor vehicle emissions it has been found that brake wear and linings are significant contributors of Cu, Mo and Sb to air particulate matter. These trace elements, whose mutual ratios in airborne particulate matter resulted quite different from those in crustal material, appear to be available fingerprinting tools to identify the contribution of on-road vehicles to traffic-derived particulate matter. In this study, the results of analytical determinations of Cu, Mo and Sb on PM10, PM2.5, vegetation and brake dust samples, together with gas (CO, NOx) concentrations, are discussed. Highly significant correlations among Cu, Sb and Mo were observed in particulate matter from Palermo and between Cu–Sb and Cu–Mo at Catania. Further significant positive correlations have been found in pine needles from Palermo, Gela and in platanus leaves from Catania.

Trace elements in scalp hair of children chronically exposed to volcanic activity (Mt. Etna, Italy).

The aim of this survey was to use scalp hair as a biomonitor to evaluate the environmental exposure to metals and metalloids of schoolchildren living around the Mt. Etna area, and to verify whether the degree of human exposure to trace elements is subject to changes in local environmental factors. Twenty trace elements were determined in 376 samples of scalp hair from schoolboys (11-13 years old) of both genders, living in ten towns located around the volcanic area of Mt. Etna (Sicily). The results were compared with those (215 samples) from children living in areas of Sicily characterized by a different geological setting (reference site). As, U and V showed much higher concentrations at the volcanic site whereas Sr was particularly more abundant at the reference site. Linear Discriminant Analysis (LDA) indicated an Etna factor, made up of V, U and Mn, and a second factor, concerning the reference site, characterized by Ni and Sr, and to a lesser extent by Mo and Cd. Significant differences in element concentrations were also observed among three different sectors of Mt. Etna area. Young people living in the Mt. Etna area are naturally exposed to enhanced intakes of some metals (V, U, Mn) and non-metals (e.g., As) than individuals of the same age residing in other areas of Sicily, characterized by different lithologies and not influenced by volcanic activity. The petrographic nature of local rocks and the dispersion of the volcanic plume explain the differences, with ingestion of water and local food as the most probable exposure pathways.

The effects of anthropogenic particulate emissions on roadway dust and Nerium oleander leaves in Messina (Sicily, Italy)

Complementary studies on the inorganic chemical composition of Nerium oleander leaves collected in the town of Messina (Sicily, Italy) and seven grain-size fractions of local roadway dust have been carried out. Data and maps are presented to show that the particulate matter present in the air of Messina contains trace elements significantly in excess with respect to the average continental earth crust. The anomalies follow the outline of the urban area, the highest concentrations of trace elements being observed where traffic density is highest. Chemical and isotopic analyses of both road dust and Nerium oleander leaves indicate that Pb contamination still characterizes roads with heavy traffic. In addition to Pb, other metals such as Pt, Pd, Sb, Au, Br, Zn, Cu, Mo, and Cd are significantly enriched in roadway dust, indicating their common anthropogenic origin, especially from traffic. SEM/EDS study of some roadway dust particles has shown the presence of gypsum probably of secondary origin, mixed particles formed by coagulation or gas-to-particle conversion, and porous spherical particles apparently emanating from combustion processes.

Metals and metalloids in hair samples of children living near the abandoned mine sites of Sulcis-Inglesiente (Sardinia, Italy)

The Sulcis-Iglesiente district (SW Sardinia, Italy) is one of the oldest and most important polymetallic mining areas in Italy. Large outcrops of sulfide and oxide ores, as well as the products of the long-lasting mining activity, are present throughout the district releasing significant quantities of metals and metalloids into the surrounding environment. Here are reported concentrations of 21 elements determined in scalp hair samples from children (aged 11-13 years) living in different geochemical environments of southwestern Sardinia: Iglesias, hosting several abandoned mines, and the island of Sant׳Antioco, not affected by significant base metal mineralization events. Trace element determinations were performed by ICP-MS. Statistically significant differences (p<0.01) in elemental concentration levels between the two study sites were found. Hair of children from Iglesias exhibited higher concentration values for Ag, Ba, Cd, Cr, Ni, Pb, Rb, Sb, U, V, and Zn. Rubidium, V and U resulted more abundant at Sant׳Antioco. Hair samples from Iglesias showed gender-related differences for a larger number of elements (Ag, Ba, Cd, Co, Cu, Ni, Sr, U and Zn) than at Sant׳Antioco, where only U was significantly different. The above elemental concentrations in females were always higher than in male donors. Robust Principal Component Analysis operated on log-transformed elemental concentrations showed components indicative of a) sulfides ore minerals (PC1) reflecting the influence of the diffuse mineralization covering the entire study area, b) the presence of some bioavailable As sources (PC2) as As-rich pyrite and Fe-containing sphalerite and c) other sources of metals overlapping the diffuse mineralizations, as carbonate rocks and coal deposits (PC3). The results provided evidence of a potential risk of adverse effects on the health of the exposed population, with children living at Iglesias being greatly exposed to several metals and metalloids originated in mining tailings, enriched soils, waters and food.

δ13C variations in tree rings as an indication of severe changes in the urban air quality

Abstract Annual growth rings sampled from three free-standing trees (Platanus hybrida sp.), grew in the metropolitan area of Palermo (Italy) and covering a 118 years time span (1880–1998), have been studied for their 13C/12C carbon isotope ratios. It has been found that the 13C/12C tree ring record, during the study time interval, decreased of −3.6‰, from −26.4‰ in 1880 to −30‰ in 1998. Such a progressive depletion has been attributed to the addition of anthropogenic 13C depleted carbon dioxide to the local atmosphere. The observed 13C/12C decrease has been used to infer some possible pathways of atmospheric CO2 change in the study urban area.

Gender as a key factor in trace metal and metalloid content of human scalp hair. A multi-site study

This multi-site study discusses the content of metals and metalloids (MM) in scalp hair of children, living in different environmental contexts, with the purpose of verifying if hair level of some MM is distinctively gender-specific. A total of 943 hair samples (537 females and 406 males) from adolescents were analyzed for their content of Al, As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sr, U, V and Zn. Elemental quantification was performed by ICP-MS. The obtained data identified different metal distributions in adolescent girls which exhibited significantly higher hair concentrations of some trace metals, especially Sr, Zn and Ni, than boys. On the base of the median value, hair of female donors contained 3.8 times more Sr (6.6μg/g) than males (1.7μg/g). Highest concentrations of Zn in females were observed in samples from the mining area of Sardinia (587μg/g). Nickel showed significant differences resulting 2.5-fold higher in female hair. Regardless of the residence site, these elements resulted always significantly different (at p<0.01) between female and male indicating that gender is a confounding factor that has to be more extensively considered for a correct interpretation of metal profiles in human hair.

Coverage intervals for trace elements in human scalp hair are site specific.

Coverage intervals for trace elements in human scalp hair commonly provide the basis for interpreting laboratory results and also in comparative decision-making processes regarding exposure risk assessment. This short communication documents, by some examples, that those computed for human hair are to be considered site specific, as they reflect local environmental conditions; also each geographic area has a typical profile of hair elemental composition of its inhabitants. Therefore, the levels of trace elements in hair are not strictly comparable between different areas of the world. This issue is particularly relevant when identification of anomalous environmental exposures are requested or even in detecting physiological disorders.