Major and trace elements in Boletus aereus and Clitopilus prunulus growing on volcanic and sedimentary soils of Sicily (Italy).

The aim of this study was to determine and compare the content of 28 elements (Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Se, Sr, Tl, U, V and Zn) in fruiting bodies of Boletus aereus Bull. and Clitopilus prunulus P. Kumm collected from eleven unpolluted sites of Sicily (Italy) and, also to relate the abundance of chemical elements in soil with their concentration in mushrooms. Median concentrations of the most abundant elements in Boletus aereus ranged from 31,290 µg/g (K) to 107 µg/g (Zn) in caps and from 24,009 µg/g (K) to 57 µg/g (Zn) in stalks with the following abundance order: K > Na > Ca > Mg > Fe > Al > Rb > Zn. The same elements, in the whole fruiting body of Clitopilus prunulus samples, varied in the range 54,073-92 µg/g following the abundance order: K > Na > Mg > Ca > Fe > Al > Rb > Zn. Metal contents in Boletus aereus and in the whole fruiting body of Clitopilus prunulus, collected from the same sampling sites, showed statistically significant differences for most elements. In particular, Clitopilus prunulus contained around two to four times more Co, Cr, Fe, Mg, Mo, Pb, U and V than caps and stalks of Boletus aereus species which, in turn, was from two to four times more enriched in Cu, Se and Tl. Thus, the elemental content of Boletus aereus and Clitopilus prunulus appeared to be species-dependent. The distribution of chemical elements in Boletus aereus was not uniform throughout the whole fruiting body as most elements were significantly bioconcentrated in caps. Furthermore, the fruit bodies of Boletus aereus from the volcanic soil differed both in major and minor elements concentrations from those collected from sedimentary soils. Cadmium and lead concentrations were below the threshold limits for wild mushrooms proposed by EU Directives (2008 and 2015). The elemental content was not significantly influenced by soil pH.

Lead isotopic fingerprint in human scalp hair: The case study of Iglesias mining district (Sardinia, Italy).

The Sulcis-Iglesiente district (SW Sardinia, Italy) has been, until recently, one of the most important Italian polymetallic mining areas for the extraction of lead. Epidemiological studies conducted over several decades have indicated this site at high risk of environmental crisis with possible adverse effects on the public health. In the present paper we discuss Pb isotope signatures in human scalp hair and road dust collected from the Sulcis-Iglesiente area in order to trace the exposure of populations to potential Pb sources. A total of 23 determinations (20 on hair samples and 3 on road dust samples) of lead isotope ratios (206Pb/207Pb and 208Pb/206Pb) were carried out. The obtained results were integrate with literature data regarding the total content of Pb in hair samples from the same study area. Hair from children living in Sant'Antioco exhibited lead isotope ratios in the ranges 1.152-1.165 for 206Pb/207Pb and 2.101-2.108 for 208Pb/206Pb, while hair samples from Iglesias resulted less radiogenic: 206Pb/207Pb~1.147-1.154 and 208Pb/206Pb~2.106-2.118. These values pointed to a multi-source mixing between the less radiogenic sources, corresponding to the Pb ore deposits, and the more radiogenic sources identified in local background.

Perturbation vectors to evaluate air quality using lichens and bromeliads: a Brazilian case study.

Samples of one lichen species, Parmotrema crinitum, and one bromeliad species, Tillandsia usneoides, were collected in the state of Rio de Janeiro, Brazil, at four sites differently affected by anthropogenic pollution. The concentrations of aluminum, cadmium, copper, iron, lanthanum, lead, sulfur, titanium, zinc, and zirconium were determined by inductively coupled plasma-atomic emission spectroscopy. The environmental diagnosis was established by examining compositional changes via perturbation vectors, an underused family of methods designed to circumvent the problem of closure in any compositional dataset. The perturbation vectors between the reference site and the other three sites were similar for both species, although body concentration levels were different. At each site, perturbation vectors between lichens and bromeliads were approximately the same, whatever the local pollution level. It should thus be possible to combine these organisms, though physiologically different, for air quality surveys, after making all results comparable with appropriate correction. The use of perturbation vectors seems particularly suitable for assessing pollution level by biomonitoring, and for many frequently met situations in environmental geochemistry, where elemental ratios are more relevant than absolute concentrations.

Penalized linear discriminant analysis and Discrete AdaBoost to distinguish human hair metal profiles: The case of adolescents residing near Mt. Etna.

The research focus of the present paper was twofold. First, we tried to document that human intake of trace elements is influenced by geological factors of the place of residence. Second, we showed that the elemental composition of human hair is a useful screening tool for assessing people's exposure to potentially toxic substances. For this purpose, we used samples of human hair from adolescents and applied two robust statistical approaches. Samples from two distinct geological and environmental sites were collected: the first one was characterized by the presence of the active volcano Mt. Etna (ETNA group) and the second one lithologically made up of sedimentary rocks (SIC group). Chemical data were statistically processed by Penalized Linear Discriminant Analysis (pLDA) and Discrete AdaBoost (DAB). The separation between the two groups turned out well, with few overlaps accounting for less than 5%. The chemical variables that better distinguished ETNA group from SIC group were As, Cd, Co, Li, Mo, Rb, Sr, U and V. Both pLDA and DAB allowed us to characterize the elements most closely related to the volcanic contribution (As, U and V) and those (Cd, Co, Li, Mo, Rb and Sr) prevalently influenced by the geology of the area where SIC samples were collected. We conclude that the geological characteristics of the area of residence constitute a key factor in influencing the potential exposure to trace elements. Hair analysis coupled with robust statistical methods can be effectively used as a screening procedure to identify areas at great environmental risk.

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.

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.

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.

Trace elements in scalp hair of children living in differing environmental contexts in Sicily (Italy).

We present here data about trace elements in human scalp hair samples to test whether they are valuable to reflect environmental exposure and contamination by trace elements. The study compares contents of trace elements in scalp hair from a total of 336 children, aged 11-13 years old, living in various geographical areas of Sicily (southern Italy) characterized by differing environmental conditions. Nineteen elements (Al, As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sr, U, V and Zn) were determined by inductively coupled plasma mass spectrometry (ICP-MS). Coverage intervals (CI) formulated by the elemental composition of hair samples from the Palermo subjects were compared with the median content of hair from children living in the other study areas. Statistical analysis showed that Al, Ba, Sr and Zn concentrations differed significantly between gender, higher concentrations being observed in girls' hair. Children living close to the volcanic area had higher concentrations of As, Cr, Mn, Ni, Rb, Sb, U, V and Zn. Those living in an area with several old quarries had higher levels of Al, As, Pb, Rb and U. The hair of children living near the Pace del Mela industrial area contained higher levels of As, Ba, Mn, Pb, Rb, Sr and U. Linear discriminant analysis (LDA) between Palermo and the other sites allowed to better assess which variables contribute towards differentiating the groups. Our observations suggest that human hair can be used to monitor exposure to several metals, provided that sampling and analytical procedures, together with statistical treatment of data, are carried out according to standardized protocols.

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-Smirnov's test taking children's 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.

Case study: inorganic pollutants associated with particulate matter from an area near a petrochemical plant.

The area of Gela (Sicily, Italy) contains one of the largest petroleum refineries in Europe and also has several oil fields both on land and offshore. This paper discusses how the oil refinery and traffic-related air pollution affect the chemical composition of airborne particulate matter over the town of Gela, using pine needles and urban road dust as the means of survey. Forty-one samples of pine needles from Pinus halepensis (Mill.) and two composite samples of roadway dust, each subdivided into six size fractions, were analyzed for major and trace elements. Information on the natural or anthropogenic origin of the observed heavy metals was deduced from factor analysis and element distribution maps. Factor analysis was applied to a data set of 20 element concentrations in pine needles and identified three main sources of metals: soil, vehicle traffic, and industrial emissions. The petrochemical plant appears to be associated with raised levels of As, Mo, Ni, S, Se, V, and Zn. Similarly, enhanced Cu, Pb, Pt, Pd, Sb, and partly Zn concentrations are closely associated with traffic. High correlations between Ni and V, As and Se, and Pb and Sb were observed. Element distribution maps, showing a decrease in heavy metal contents immediately farther inland, confirm that local sources play a considerable role in heavy metal pollution. Morphological alterations and accumulation of phenols were observed in sections of Pinus halepensis needles collected from sites with high traffic density and industrial emissions.

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.

Migration processes of radon towards the earth surface : Implications for the prediction of seismic and volcanic events

222Rn has been indicated as possible precursor of earthquakes and volcanic eruptions. Scientific literature reports many examples of radon anomalies observed before and after seismic events. However, due to its short half-life, radon activities clearly fall with distance. The immediate consequence for Earth Science is the physical impossibility of 222Rn to migrate over long distances without being sutained by upward motion of a gas carrier. Correct understanding of transport phenomena thus becomes of especial importance. The general aspects of radon migration processes are discussed.(AU)

Environmental gamma radiation measurements on the island of Pantelleria.

The population exposure to those living on the island of Pantelleria, Italy, was estimated by measuring the natural gamma background. Gamma spectra of natural rocks and measurements of absorbed dose in air were taken. A correlation was found between the mean gamma exposure rate and the mean values of natural radionuclide concentrations in the investigated rocks.