Gian Maria Beone

Determination of heavy metals in soils and sediments by microwave-assisted digestion and inductively coupled plasma optical emission spectrometry analysis

The determination of the total content and the leachable aliquot by aqua regia dissolution of eight heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) in soils and sediments was developed by microwave digestion technique combined with inductively coupled plasma atomic emission spectrometry. A complete digestion of soils and sediments was achieved by using an acid mixture of HF–HCl–HNO3 (1:3:1); the microwave-irradiated closed vessel system used for the determination of aqua regia leachable quota, proved to be a viable alternative to the traditional reflux system. The experimental study was conducted using five BCR standard reference materials (CRM 141R ‘Calcareous Loam Soil’, CRM 142 ‘Light Sandy Soil’, CRM 143 ‘Sewage Sludge Amended Soil’, CRM 277 ‘Estuarine Sediment’ and CRM 320 ‘River Sediment’) in two laboratories with different microwave ovens and ICP-OES. Calculated recovery, repeatability, and reproducibility confirm the good performance of the procedures adopted. A Nested Design statistical analysis was carried out for both procedures and showed that the major source of variability in the analysis was due to ICP-OES measurements rather than microwave-assisted dissolution.

Characterization of mercury species in soils by HPLC–ICP-MS and measurement of fraction removed by diffusive gradient in thin films

The properties and behaviour of Hg depend on both the oxidation state and the chemical form: the bioavailability, toxicity, persistence and accumulation of mercury in the food web are strongly influenced by chemical speciation. The present work aims to determine the chemical forms of mercury present in soil and to evaluate the fraction of mercury in soil solution available to plants. In order to do this, we analyzed eight samples of contaminated soils with Hg concentrations ranging from 1.31 to 21.7 mg kg(-1), collected from different depths (0-10 and 40-50 cm) close to an abandoned industrial site in Val Basento (southern Italy). Two innovative analytical techniques were used: HPLC-ICP-MS and diffusive gradient in thin films (DGT). The analytical procedure was validated using ERM 580-certified sediment and spiked samples in the case of HPLC-ICP-MS, and by a performance test in the case of DGT. In all samples, the only species found in soil and soil solution was MeHg(+) and Hg(2+). In soil, the MeHg(+)/Hg(tot) ratio ranged from 0.05% to 0.82%; total mercury in soil solution was less than 0.01% of total mercury in soil. The percentage of MeHg(+) in soil solution varied considerably (from 0% to 50%), with a maximum concentration of 0.02 mg L(-1). The root available concentration evaluated by DGT is comparable to the total mercury content of the soil solution measured by HPLC-ICP-MS. The DGT results suggest that all mercury in solution is available for uptake in DGT, and that mercury is supplied from soil to solution. However, for all samples the soluble and root available (DGT-labile) fractions of mercury are generally very low with respect to the total mercury concentration. This study confirmed that both HPLC-ICP-MS and DGT techniques are suitable tools for the estimation of Hg root availability and in assessing the risk from contaminated soils.

Comparison of different analytical procedures in the determination of trace elements in lichens.

A BCR standard reference material of lichen (CRM 482) was used to validate an analytical procedure consisting of a microwave oven digestion associated with ICP-OES, ICP-MS and GFAAS techniques for the analysis of trace elements (Al, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in biomonitor samples. Two different acid mixtures were used: (a) 7 ml of HNO3, 1 ml of H2O2; (b) 7 ml of HNO3, 1 ml of H2O2 and 200 microl of HF; all digestions were carried out using 100-250 mg samples brought to a final volume of 50 ml. The validation of the procedure was carried out by two laboratories in terms of accuracy and precision; the former was estimated as percentage recovery by comparing experimental data with certificate values; the latter evaluated according to ISO standard 5725. Real lichen samples were analysed too with the procedures above described. In certified CRM 482 and real lichen samples the procedure with HF showed higher recovery values for Al, Ti, V, Ba and Fe than the procedure without HF. For all the other elements the two procedures gave comparable results both in terms of accuracy and precision. The recovery obtained with HF procedure for all the elements was generally better than 90-103%.

Determination of rare earth elements in tomato plants by inductively coupled plasma mass spectrometry techniques

In recent years identification of the geographical origin of food has grown more important as consumers have become interested in knowing the provenance of the food that they purchase and eat. Certification schemes and labels have thus been developed to protect consumers and genuine producers from the improper use of popular brand names or renowned geographical origins. As the tomato is one of the major components of what is considered to be the healthy Mediterranean diet, it is important to be able to determine the geographical origin of tomatoes and tomato-based products such as tomato sauce. The aim of this work is to develop an analytical method to determine rare earth elements (RRE) for the control of the geographic origin of tomatoes. The content of REE in tomato plant samples collected from an agricultural area in Piacenza, Italy, was determined, using four different digestion procedures with and without HF. Microwave dissolution with HNO3 + H2O2 proved to be the most suitable digestion procedure. Inductively coupled plasma quadrupole mass spectrometry (ICPQMS) and inductively coupled plasma sector field plasma mass spectrometry (ICPSFMS) instruments, both coupled with a desolvation system, were used to determine the REE in tomato plants in two different laboratories. A matched calibration curve method was used for the quantification of the analytes. The detection limits (MDLs) of the method ranged from 0.03 ng g(-1) for Ho, Tm, and Lu to 2 ng g(-1) for La and Ce. The precision, in terms of relative standard deviation on six replicates, was good, with values ranging, on average, from 6.0% for LREE (light rare earth elements) to 16.5% for HREE (heavy rare earth elements). These detection limits allowed the determination of the very low concentrations of REE present in tomato berries. For the concentrations of REE in tomato plants, the following trend was observed: roots > leaves > stems > berries.

Metal contamination of home garden soils and cultivated vegetables in the province of Brescia, Italy: Implications for human exposure.

BACKGROUND For the past century, ferroalloy industries in Brescia province, Italy produced particulate emissions enriched in manganese (Mn), lead (Pb), zinc (Zn), copper (Cu), cadmium (Cd), chromium (Cr), iron (Fe), and aluminum (Al). This study assessed metal concentrations in soil and vegetables of regions with varying ferroalloy industrial activity levels. METHODS Home gardens (n=63) were selected in three regions of varying ferroalloy plant activity durations in Brescia province. Total soil metal concentration and extractability were measured by X-Ray Fluorescence (XRF), aqua regia extraction, and modified Community Bureau of Reference (BCR) sequential extraction. Unwashed and washed spinach and turnips cultivated in the same gardens were analyzed for metal concentrations by flame atomic absorption spectrometry. RESULTS Median soil Al, Cd, Fe, Mn, Pb, and Zn concentrations were significantly higher in home gardens near ferroalloy plants compared to reference home gardens. The BCR method yielded the most mobile soil fraction (the sum of extractable metals in Fractions 1 and 2) and all metal concentrations were higher in ferroalloy plant areas. Unwashed spinach showed higher metal concentrations compared to washed spinach. However, some metals in washed spinach were higher in the reference area likely due to history of agricultural product use. Over 60% of spinach samples exceeded the 2- to 4-fold Commission of European Communities and Codex Alimentarius Commission maximum Pb concentrations, and 10% of the same spinach samples exceeded 2- to 3-fold maximum Cd concentrations set by both organizations. Turnip metal concentrations were below maximum standard reference values. CONCLUSIONS Prolonged industrial emissions increase median metal concentrations and most soluble fractions (BCR F1+F2) in home garden soils near ferroalloy plants. Areas near ferroalloy plant sites had spinach Cd and Pb metal concentrations several-fold above maximum standard references. We recommend thorough washing of vegetables to minimize metal exposure.

Iodine and selenium carry over in milk and cheese in dairy cows: effect of diet supplementation and milk yield.

Iodine and selenium are essential trace elements involved in the regulation of thyroid metabolism and antioxidant status. Two experiments were undertaken on lactating cows to determine the milk concentrations of iodine and selenium, carry over (CO) in milk, the fraction in curdle portion and how milk yield affects the milk iodine and selenium concentrations and CO. Sources of elements were potassium iodide and sodium selenite. In Experiment 1, 12 cows were randomly allotted to three diet groups in a completely randomized design: control group (CTR) - total mixed ration (TMR) containing 1.71 and 0.08 mg/kg dry matter (DM); Group 1 (T1) - TMR plus 23.8 and 2.2 mg; Group 2 (T2) - TMR plus 45.5 and 4.3 mg, respectively, for iodine and selenium. In Experiment 2, 30 cows were allotted to three groups according to milk yield: high (H), average (A) and low (L). Within each group, cows were randomly assigned two levels of iodine and selenium: Level 1: TMR containing 1.55 and 0.15 mg/kg DM; Level 2: TMR plus 47.2 mg and 8.0 mg, respectively, iodine and selenium. In both experiments, individual milk samples were collected and analyzed for iodine and selenium contents. In Experiment 1, Grana Padano cheese was obtained at lab scale and the iodine and selenium fractions in the curd were measured. In Experiment 1, the iodine intake increased (P < 0.001) the concentration and total excretion in milk. The CO increased (P < 0.05) from 16 (CTR) to 27 (T1) and 26% (T2); the sampling time was significant (P < 0.05) with no interaction with treatments. Concentration of selenium in milk was increased (P < 0.05) by treatment and CO decreased (P < 0.01) from 26 (CTR) to 12 (T1) and 9% (T2). The iodine showed a mild enrichment factor in the curdle (about 1.7-fold), whereas selenium enriched five- to sevenfold. In Experiment 2, the level of iodine supplementation affected (P < 0.05) the concentration and total excretion in milk. No effects on milk iodine concentration were related to milk yield or milk yield × treatment interaction; however, the iodine excretion in milk was major (P < 0.05) in higher yielding groups. The iodine CO was affected (P < 0.05) by the milk yield in supplemented groups. The selenium milk concentration and excretion were affected (P < 0.01) by the milk yield, whereas the CO was affected (P < 0.05) by the milk yield and selenium supplementation. Results highlight the possibility of fortification with iodine in milk and selenium in cheese through animal feeding.

Levels of PCDD/Fs and trace elements in superficial soils of Pavia Province (Italy)

Trace elements and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in soils from rural and light-industrialized sites (n = 168) of Province of Pavia (Northern Italy). Most of the trace element values fit in typical ranges of concentrations in soils and are similar to the ones reported for rural sites in Italy or sites with no direct anthropogenic impact. Total concentrations of 2,3,7,8 chlorine substituted PCDD/Fs in superficial soils ranged between 24.4 and 1287 pg g(-1) dw (0.5-28.9 pg WHO98-TEQ g(-1) dw). The North Eastern part of the Province presented significantly higher levels (p < 0.001) than the rest of the Province for As, Cd, Hg, Pb, Zn and PCDD/Fs. While the existence of a defined heavy metal polluting source for this specific site has been suggested, in the case of PCDD/Fs, profiles were not linked to any specific emission source fingerprint. In the whole extension of Pavia Province, OCDD/F dominated the 2,3,7,8 chlorine substituted congener soil pattern, followed by the 1,2,3,4,6,7,8 hepta-CDD/F congener. Principal Component Analysis (PCA) showed that this profile could not be associated to any described PCDD/F emission source fingerprint and was relatively similar to the baseline deposition of sites with no direct impact of PCDD/F emission sources independently of land use.

Biomonitoring study of an estuarine coastal ecosystem, the Sacca di Goro lagoon, using Ruditapes philippinarum (Mollusca: Bivalvia)

Coastal lagoons are constantly subjected to releases of chemical pollutants, and so organisms may be exposed to such toxicants. This study investigated through a multivariate approach the physiological status of bivalve Ruditapes philippinarum, farmed in Sacca di Goro lagoon. Biomarkers at different levels of biological organization (catalase, superoxide dismutase, genotoxicity, reburrowing behavior) were evaluated at three sites exposed to different environmental conditions. A seasonal trend was observed, and micronucleus frequency was significantly lowest at the relatively pristine reference site. Enzymatic activity toward oxyradicals be quite efficient since variations in responsiveness were not consistent. However, behavioral impairment was observed in reburrowing rates. Sediment concentrations showed low PAH levels and high natural levels of trace metals Cr and Ni. DistLM statistical analysis revealed a non-significant relationship between selected biomarkers and xenobiotics. Therefore other potentially toxic compounds in admixture at low doses may be involved in driving differing spatial distribution of physiological impairment.

Gamma-spectrometric measurement of radioactivity in agricultural soils of the Lombardia region, northern Italy

This work is part of a wider monitoring project of the agricultural soils in Lombardia, which aims to build a database of topsoil properties and the potentially toxic elements, organic pollutants and gamma emitting radionuclides that the topsoils contain. A total of 156 agricultural soils were sampled according to the LUCAS (Land Use/Cover Area frame statistical Survey) standard procedure. The aim was to provide a baseline to document the conditions present at the time of sampling. The results of the project concerning soil radioactivity are presented here. The aim was to assess the content of (238)U, (232)Th, (137)Cs and (40)K by measuring soil samples by gamma spectrometry. (238)U, (232)Th and (40)K activities range 24-231, 20-70, and 242-1434 Bq kg(-1) respectively. The geographic distribution of (238)U reflects the geophysical framework of the Lombardia region: the soils with high content of uranium are distributed for the most part in the South Alpine belt, where the presence of magmatic rocks is widespread. These soils show an higher activity of (238)U than of (232)Th. The (238)U activities become lower than (232)Th when soils are located in the plain, originating from basic sedimentary rocks. (137)Cs activity ranges 0.4-86.8 kBq m(-2). The lowest activity of (137)Cs is in the plain, whereas the highest is in the North on soils kept as lawn or pasture. The (137)Cs activity of some samples suggests the presence of accumulation processes that lead to (137)Cs enriched soils. This is the first survey of gamma emitting radionuclides in Lombardia that is based on the LUCAS standard sampling. The results from this monitoring campaign are important for the human radiation exposure and provide the zero point, which will be useful for assessing future effects due to external factors such as human activities.

Quantification of Cr(VI) in soil samples from a contaminated area in northern Italy by isotope dilution mass spectrometry.

The aims of the work were to detect and quantify hexavalent chromium in 14 soil samples from an area in Lombardia (northern Italy) contaminated by two polluted water plumes. Cr(VI) was extracted from the solid samples by applying focused microwaves in an alkaline medium after Cr(III) complexation with EDTA. Cr(VI) was reduced to Cr(III) when previously reported extraction conditions for the analysis of certified reference materials were used, and Cr(VI) could not be reliably quantified in the soil samples. The influence of organic matter and iron contents in the samples on the reduction of Cr(VI) was subsequently studied using a new set of soil samples with different iron and organic matter concentrations. Isotope dilution mass spectrometry (IDMS) measured two different enriched stable isotopes of Cr (54 and 53) to evaluate the reduction extent of hexavalent chromium during the analytical procedure. The extraction conditions were optimized to obtain the lowest amount of Cr(VI) reduction and quantify Cr(VI) in the polluted soil samples from Lombardia.