0000000000135875
AUTHOR
Gaetano Dongarra
Speciation of Sb in airborne particulate matter, vehicle brake linings, and brake pad wear residues
Insights into the speciation of Sb in samples of brake linings, brake pad wear residues, road dust, and atmospheric particulate matter PM10 and PM2.5 were obtained combining several well established and advanced characterization techniques, such as scanning electron microscopy e energy dispersive spectrometry (SEM-EDS), inductively coupled plasma mass spectrometry (ICP-MS) and synchrotron radiation X-ray absorption spectroscopy (SR-XAS). The advantage of SR-XAS is that samples do not undergo any chemical treatment prior to measurements, thus excluding possible alterations. These analyses revealed that the samples of wheel rims dust, road dust, and atmospheric particulate matter are composed…
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 re…
Dust, Metals and Metalloids in the Environment: From Air to Hair .
Billions tons of particulate matter, made up of inorganic and organic compounds, are released every year into the atmosphere, from both anthropogenic and natural sources. The latter, which include geogenic material from erosion, agriculture, sea spray and volcanic activity, account for about 97% of the total mass of particles. The contribution of anthropogenic sources, about 3%, is more pronounced in industrialised and also in urban areas, where vehicular traffic is one of the most important sources. When examining the health impact, in addition to mass level and size, two other main characteristics of particulate matter need to be considered: its nature and chemical composition. These para…
Chemical and isotopic characterization of the gases of Mount Etna (Italy)
Abstract In the period 1990–1995, 43 samples of dissolved gases in groundwaters (wells, springs and drainage galleries) and 64 samples of free gases (fumaroles, bubbling and soil gases) from the Mount Etna area were collected and analysed. Isotopic analyses were also carried out of both the carbon of the CO 2 in free gases and dissolved inorganic carbon (DIC) in the waters. The chemical composition of the gases depends on the relative abundances of three interacting components. These are gases of (1) atmospheric origin enriched in O 2 and N 2 , present almost exclusively in dissolved gases, (2) deep origin enriched in CO 2 , prevalent in the majority of cases, and (3) more superficial origi…
Trace elements in the thermal groundwaters of Vulcano Island (Sicily)
The chemical concentrations of many trace elements that have never before been examined in Vulcano Island groundwaters are reported. Chemical data indicate that rock composition is not the only factor determining the metal content in the aqueous system. The observed concentrations depend mainly on: (1) the chemical composition of the host rocks; (2) the chemical–physical conditions of the weathering solution (temperature, acidity, redox conditions); (3) input of magmatic gases; (4) adsorption of metal ions on oxide particles, formation of soluble complexes and/or precipitation of solid phases. Chloride complexes in solution are of minimal significance for all elements with the exception of …
Metals distribution in the organic and inorganic fractions of soil: A case study on soils from Sicily
The content of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, has been determined in the organic and inorganic fraction of eight soil samples from Sicily. A modified type-Tessier sequential extraction procedure has been used to recognize metals in five different fractions categorised as follows: (a) exchangeable metals, (b) metals bound to carbonates, (c) metals bound to iron and manganese oxides, (d) metals bound to organic matter, and (e) metals in residual fraction. The mineralogical composition of soils samples was characterized by X-ray diffraction. Humic substances were extracted by means of an alkaline extraction procedure. It has been found that both the mineralogical composition and the di…
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 analysed 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, hai…
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 tra…
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 distri…
Lichens Used as Monitors of Atmospheric Pollution Around Agadir (Southwestern Morocco)—A Case Study Predating Lead-Free Gasoline
More than 30 epiphytic lichens, collected in Agadir (Morroco) and along a 150-km transect from the Atlantic Ocean eastward, were analyzed for their metal content and lead isotopic composition. This dataset was used to evaluate atmospheric metal contamination and the impact of the city on the surrounding area. The concentrations of Cu, Pb, and Zn (average ± 1 SD) were 20.9 ± 15.2 μg g−1, 13.8 ± 9.0 μg g−1, and 56.6 ± 26.6 μg g−1, respectively, with the highest values observed in lichens collected within the urban area. The 206Pb/207Pb and 208Pb/207Pb ratios in the lichens varied from 1.146 to 1.186 and from 2.423 to 2.460, respectively. Alkyllead-gasoline sold in Morocco by the major petrol …
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 s…
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 dist…
Mass levels, crustal component and trace elements in PM10 in Palermo, Italy.
Abstract Results concerning the levels and elemental compositions of daily PM 10 samples collected at four air quality monitoring sites in Palermo (Italy) are presented. The highest mean value of PM 10 concentrations (46 μg m −3 , with a peak value of 158 μg m −3 ) was recorded at the Di Blasi urban station, and the lowest at Boccadifalco station (25 μg m −3 ), considered as a sub-urban background station. Seventeen elements (Al, As, Ba, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb, Sb, Sr, U, V, Zn) were measured by ICP-MS. Al and Fe showed the highest concentrations, indicating the significant contribution of soil and resuspended mineral particles to atmospheric PM 10 . Ba, Cr, Cu, Mn, Mo, Ni, Pb, …
Anthropogenic Perturbations to the Atmospheric Molybdenum Cycle
Molybdenum (Mo) is a key cofactor in enzymes used for nitrogen (N) fixation and nitrate reduction, and the low availability of Mo can constrain N inputs, affecting ecosystem productivity. Natural atmospheric Mo aerosolization and deposition from sources such as desert dust, sea‐salt spray, and volcanoes can affect ecosystem function across long timescales, but anthropogenic activities such as combustion, motor vehicles, and agricultural dust have accelerated the natural Mo cycle. Here we combined a synthesis of global atmospheric concentration observations and modeling to identify and estimate anthropogenic sources of atmospheric Mo. To project the impact of atmospheric Mo on terrestrial ec…
Trace elements in scalp hair of children chronically exposed to volcanic activity (Mt. Etna, Italy)
Abstract 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 concentrat…
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 Vulc…
Metal distribution in road dust samples collected in an urban area close to a petrochemical plant at Gela, Sicily
Eight samples of road dust were collected from three different localities (industrial, urban, peripheral) of the town of Gela (Italy) to characterize their chemical composition and to assess (a) the influence of the petrochemical plant and the urban traffic on the trace element content in different grain-size fractions of street dust and (b) the solid-phase speciation of the analysed metal using sequential extraction. The samples were sieved into six particle size ranges: 500–250, 250–125, 125–63, 63–40, 40–20 and <20 μm and then analysed for 15 trace elements by ICP-MS. Sequential extraction of metals was performed on each subsample. A principal component analysis was also carried out to d…
Trace elements in scalp hair samples from patients with relapsing-remitting multiple sclerosis
Background Epidemiological studies have suggested a possible role of trace elements (TE) in the etiology of several neurological diseases including Multiple Sclerosis (MS). Hair analysis provides an easy tool to quantify TE in human subjects, including patients with neurodegenerative diseases. Objective To compare TE levels in scalp hair from patients with MS and healthy controls from the same geographic area (Sicily). Methods ICP-MS was used to determine the concentrations of 21 elements (Ag, Al, As, Ba, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sr, U, V and Zn) in scalp hair of 48 patients with relapsing–remitting Multiple Sclerosis compared with 51 healthy controls. Results MS …
Isotope composition of rain water, well water and fumarole steam on the island of Vulcano, and their implications for volcanic surveillance
Abstract Water samples from eight wells in the Vulcano Porto area and fumarole steam from the crater of Vulcano (Southern Italy) were collected at monthly intervals over a two-year period from February 1987 to January 1989. Samples of bulk precipitation were also collected in three points at Vulcano Porto and Vulcano Piano (island of Vulcano) and Castroreale (Tyrrhenian coast of Sicily), again at monthly intervals. The weighted mean isotopic composition of rain water on Vulcano is δ D =−32‰ , and δ D 18 O =−6.4‰ . Results for well waters tend to support the existence of at least two water bodies: one of purely meteoric water and the other of brackish thermal water. An intermediate water bod…
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 PM(10), PM(2.5), vegetation and brake dust samples, together with gas (CO, NOx) concentrations, are discussed. Highly significant correlations among Cu, Sb and Mo were observed in parti…
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). Chemica…
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.
Metals and metalloids in hair samples of children living near the abandoned mine sites of Sulcis-Inglesiente (Sardinia, Italy)
International audience; 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 ev…
Study on ambient concentrations of PM10, PM10-2.5, PM2.5 and gaseous pollutants. Trace elements and chemical speciation of atmospheric particulates
Abstract This study provides the first comprehensive report on mass concentrations of particulate matter of various sizes, inorganic and organic gas concentrations monitored at three sampling sites in the city of Palermo (Sicily, Italy). It also provides information on the water-soluble species and trace elements. A total of 2054 PM10 (1333) and PM2.5 (721) daily measurements were collected from November 2006 to February 2008. The highest mass concentrations were observed at the urban stations, average values being about two times higher than those at the suburban (control) site. Time variations in PM10 and also PM10–2.5 were observed at the urban stations, the highest concentrations being …
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 10microg/g (Zn = 189.2microg/g; Cu= 22.9microg/g). Other elements with concentrations greater than 1microg/g were, in order of abundance, Al > Sr > Ba > Pb. The remaining elements were all below 1microg/g. The average elemental concentrations in hair were statistically compared by Kolmogorov–Smirnov’s t…
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 …
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 …
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.
Degassing of trace volatile metals during the 2001 eruption of Etna
This paper provides new data on sulfur, halogens, and minor and trace metal contents in airborne particulate matter from the Mt. Etna volcanic plume. Aerosol samples were collected by conventional filtration techniques before and during the summer 2001 eruption, in order to investigate relations between plume chemistry and volcano dynamics. Data analysis reveals that abundances of trace metals in the plume result from mixing of erosive and volatile components. The former is responsible for the contents of rare earth elements (REE), Ca, Ba, Sr, Ti, Sc, Y, Hf and Th; the latter contributes significantly to the abundance of Cs, Rb, Na and K, probably transported in the plume as metal halides, …
Geochemical characteristics of waters in mineralised area of Peloritani Mountains (Sicily, Italy)
Abstract This paper presents the results of a study on the geochemistry of waters circulating in the mineralised area of the south-eastern sector of Mt. Peloritani (north-eastern Sicily, Italy), aimed at basic understanding of the geochemical processes influencing their chemical composition. Chemico-physical parameters and data on 26 major and minor chemical elements are reported for 103 water samples. Water chemistry is mainly dominated by dissolution of carbonates and hydrolysis of aluminosilicate minerals. Total dissolved salts (TDS) range from 80 to 1398 mg/L. All the waters exhibit E H characteristic of an oxygenated environment. Excluding two samples, which show very high H + activity…
Hydrogeochemistry and Water Balance in the Coastal Wetland Area of “Biviere di Gela,” Sicily, Italy
In the study area physical and chemical factors control the composition of surface and groundwaters, which in turn determine the water quality of the "Biviere di Gela" lake. These factors combine to create diverse water types which change their compositional character spatially as rainfall infiltrates the soil zone, moves down a topographically defined flow path, and interacts with bedrock minerals. Low-salinity waters, which represent the initial stage of underground circulation, start dissolving calcium carbonate from the local rocks. The progressive increase in salinity, characterized by substantially higher Ca, SO4, Na and Cl concentrations, suggests that dissolution of CaSO4 and NaCl i…
Sicilian bottled natural waters: Major and trace inorganic components
Sixteen bottled waters of various Sicilian brands, 11 natural mineral waters and five normal drinking waters, were analyzed for major and trace inorganic components by ion chromatography (IC) and inductively coupled plasma-mass spectrometry (ICP-MS), respectively. The bottled waters represent a variety of water types with significantly different compositions in terms of salinity, major components and trace elements. Chemically, they range from Ca–HCO3 and Ca–SO4 to Na–HCO3 types. Total dissolved solids ranges from 54 to 433 mg/L, total hardness from 25 to 238 mg/L CaCO3, and measured Na content from 5.7 to 57 mg/L. According to total dissolved ions, all the bottled waters were classified as…
Inorganic geochemistry of roadway dust from the metropolitan area of Palermo, Italy
Inorganic matter from roadway dust collected in the urban area of Palermo, Italy, was analysed to identify the chemical elements introduced into the environment as a result of human activities. Metals of environmental concern exhibit very high enrichment factors, which in some cases exceed 100. Metal size distribution indicates that Pd, Pt, Au, Sb, Zn, S, Ni, V, Mo and Cr substantially accumulate in the finest particles, whereas Pb, Br, As, Cu, Ag and Ba are almost independent of the size fraction. SEM/EDS analyses revealed that some individual particles contain clusters of foreign particles (<10 μm) made up of Fe-Ni, Cr-Ni or Fe alone, typical of the abrasion of stainless steel. Others are…
Perturbation vectors to evaluate air quality using lichens and bromeliads: a Brazilian case study.
10 pages; International audience; 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 s…