Anna Pino

Baseline Trace Metals in Seagrass, Algae, and Mollusks in a Southern Tyrrhenian Ecosystem (Linosa Island, Sicily)

Trace elements were analyzed in organisms collected at five sampling stations along coastal areas of Linosa Island, Sicily (southern Tyrrhenian Sea, Italy). Concentrations of Cd, Cr, Cu, Pb, and Zn were measured in Posidonia oceanica L. Delile tissues, the two brown algae Padina pavonica (L.) Thivy and Cystoseira sp., and the two gastropod mollusks Monodonta turbinata Born and Patella caerulea L. Seawater samples were also collected at each site to assess soluble metal concentrations and to gain relevant information on their bioaccumulation ability. Data were processed by multivariate techniques, such as principal component analysis (PCA) and linear discriminant analysis on PCA factors. The scoreplots obtained showed that the pollutant distribution is more significantly correlated with species than with sites. For seaweeds, P. oceanica was associated with higher Cd, Cu, and Zn levels; Padina species had higher Cr concentrations, and Cystoseira had higher Pb levels. For mollusks, Monodonta species had high concentrations of Cu and Cr and Patella species were associated with Cd. Some general metal bioaccumulation patterns are described but no one sampling site was more contaminated than the others. The hypothesis of Linosa island serving as a reference ecosystem for baseline trace metal levels in southern Tyrrhenian areas is indeed supported by the statistical comparison among other southern Tyrrhenian ecosystems performed with Kruskall Wallis and Mann-Whitney tests. For P. oceanica leaves, P. pavonica, M. turbinata, and P. caerulea, this study confirms their usefulness as possible cosmopolitan biomonitors of trace metals in marine Mediterranean areas.

Metal changes in CSF and peripheral compartments of parkinsonian patients

BACKGROUND Involvement of metals in the risk of developing Parkinsons disease (PD) has been suggested. In the present study, concentration of metals in cerebrospinal fluid (CSF), blood, serum, urine and hair of 91 PD patients and 18 controls were compared. METHODS Blood and hair were microwave digested, while CSF, serum and urine were water-diluted. Elements quantification was achieved by Inductively Coupled Plasma Atomic Emission Spectrometry and Sector Field Inductively Coupled Plasma Mass Spectrometry. RESULTS Some metal imbalances in PD were observed: i), in CSF, lower Fe and Si; ii), in blood, higher Ca, Cu, Fe, Mg and Zn; iii), in serum, lower Al and Cu; iv), in urine, lower Al and Mn, higher Ca and Fe; and v), in hair, lower Fe. The ROC analysis suggested that blood Ca, Fe, Mg and Zn were the best discriminators between PD and controls. In addition, hair Ca and Mg were at least 1.5 times higher in females than in males of patients and controls. A decrement with age of patients in hair and urine Ca and, with less extent, in urine Si was observed. Magnesium concentration in CSF decreased with the duration and severity of the disease. Elements were not influenced by the type of antiparkinsonian therapy. CONCLUSIONS Variation in elements with the disease do not exclude their involvement in the neurodegeneration of PD.

Lichen Usnea barbata as biomonitor of airborne elements deposition in the Province of Tierra del Fuego (southern Patagonia, Argentina).

Lichen Usnea barbata was tested as a possible biomonitor of atmospheric deposition in a supposedly pristine environment Tierra del Fuego (Argentina). Lichen samples were collected in 2005 and again in 2006 in 71 sites covering almost the entire region. The aim of the study was to evaluate the bioaccumulation of 26 elements in order to define the background levels in the region. The quantification was carried out by the sector field inductively coupled plasma mass spectrometry. No relevant temporal accumulation patterns between 2005 and 2006 sampling campaigns were observed. Then, the results were submitted to multivariate statistical analysis (cluster and principal component analyses). Cluster analysis produced a dendrogram where the 71 sites were divided into four clusters at (Dlink/Dmax)100<30. The areas and the elements were correlated according to the element concentrations by principal component analysis. Four significant components that accounted for 67% were obtained. Cluster 1 was mainly composed of sites of Ushuaia-Road 3 (E area) and it was characterized by high levels of Cd, Co, Ni, Pb, Sb, and W in lichens. The present study has revealed the good capacity of U. barbata to reflect the baseline levels of elements in the environment at a regional scale level. The presence of certain level of elements in lichens agrees with the hypothesis that Tierra del Fuego is not a relatively pristine environment as occasionally supposed. However, when comparing our results with other countries, Tierra del Fuego lichens have a very low content of the measured elements.

Simple, fast, and low-contamination microwave-assisted digestion procedures for the determination of chemical elements in biological and environmental matrices by sector field ICP-MS

A simple and convenient method for the digestion of animal tissues, lichens, and plants for 33 metals measured by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) was described. Microwave-assisted acid digestions were performed at atmospheric pressure by means of a multi-samples rotor designed for processing a large number of samples at once in screw-capped disposable polystyrene liners. The digested samples were filled up to final volume directly in the polystyrene liners ready for elemental quantification. Seven certified reference materials, namely BCR 184 (bovine muscle), BCR 186 (pig kidney), DORM-2 (dogfish muscle), BCR 422 (cod muscle), BCR 62 (olive leaves), BCR 100 (beech leaves), and BCR 482 (lichen) were analysed to verify the accuracy of the method. The linearity range, limit of quantification, precision, and recovery by addition of non-certified elements were also assessed. All elements, with the exception of Hg in BCR 184 and As in BCR 186, were above the quantification limit and blank concentrations, and good agreement existed between found and target values in bovine muscle, pig kidney, and cod muscle. Significant deviations were observed for Al, Co, Cr, Mn, and Ni in dogfish muscle and for Ca, Cr, Fe, and Hg in lichens and plants. The proposed digestion procedure offers a low contamination risk, simplicity, speed, low cost, and applicability in routine analysis, and the SF-ICP-MS method allowed metals from a fraction of ng g−1 to hundreds of µg g−1 to be quantified in one analytical run.

Italian network for human biomonitoring of metals: preliminary results from two regions

The Italian program for human biomonitoring (HBM) of chemical elements, PROgram for Biomonitoring of the Exposure (PROBE), started in 2008 with the aim to provide the knowledge about risk assessment of the Italian population following the environmental exposure to metals. The project is implemented through a HBM campaign for the production of data on 19 metals in the blood and serum of subjects living in different Italian Regions. The metals studied are: antimony, beryllium, cadmium, chromium, cobalt, iridium, lead, manganese, mercury, molybdenum, nickel, palladium, platinum, rhodium, thallium, tin, tungsten, uranium and vanadium. The first phase of the project has included the development and validation of laboratory protocols for the collection of fluids and quantification of metals. The second phase provides the HBM data expressed as the reference values (RVs) for the Italian population, i.e., as the level of metals in the general population not occupationally exposed. In this paper, the experimental protocols used for the maintenance of high standards of analysis and the RVs for metals in serum of inhabitants of two Italian Regions (Calabria and Umbria) are described.

Iridium, platinum and rhodium baseline concentration in lichens from Tierra del Fuego (South Patagonia, Argentina)

Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, <0.010-1.011 ng g⁻¹; Pt, 0.016-2.734 ng g⁻¹; and Rh, 0.063-1.298 ng g⁻¹. Data on 7 areas were similar suggesting that no specific source, for example traffic or anthropogenic activity, influenced directly the metal concentrations in Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.

Human biomonitoring for metals in Italian urban adolescents: data from Latium Region.

As a part of the activities of the first Italian human biomonitoring survey (PROBE - PROgramme for Biomonitoring general population Exposure), a reference population of adolescents, aged 13-15 years, was examined for their exposure to metals. The study included 252 adolescents living in urban areas, representative of Latium Region (Italy) and blood specimens were analyzed for metals (As, Be, Cd, Co, Cr, Hg, Ir, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Sb, Sn, Tl, U, V and W) by sector field inductively coupled plasma mass spectrometry. The results obtained will improve the knowledge about the body burden in adolescents and are tentative reference values for Italian young people as a basis for risk evaluation deriving from urban/environmental exposure to metals.

Serum elements and oxidative status in clinically isolated syndromes Imbalance and predictivity

Background: Metals are suspected of being involved in the pathogenesis of various neurologic diseases. We previously found a complex imbalance in serum chemical elements and oxidative status in patients with clinically definite multiple sclerosis (CDMS). Objective: To understand whether this imbalance affects people with clinically isolated syndrome (CIS) and, if so, whether it predicts conversion to CDMS. Methods: We studied 22 chemical elements and the oxidative status in 49 patients with CIS, 49 patients with CDMS, and 49 healthy donors (HD). Univariate and multivariate approaches were used to identify profiles for each group. A logistic regression analysis was used to identify the predictive potential of baseline data (elements, oxidative status, and MRI findings) for conversion to CDMS over 36 months. Results: Several elements and oxidative status values differed significantly among the 3 groups. Discriminant analysis revealed a major contribution of Ca, Fe, Sn, Zn, serum antioxidant capacity, and serum oxidative status, which resulted in distinct profiles (the prediction of group membership was 96% [cross-validated 92%] for HD, 92% [cross-validated 92%] for CDMS, and 90% [cross-validated 86%] for CIS). A weighted combination of element concentrations and oxidative status values, adjusting for all other predictors, would predict a reduction in the risk of conversion to CDMS within 3 years (odds ratio 0.37; 95% confidence interval 0.18–0.76; p = 0.007), thereby proving more effective than MRI at baseline. Conclusions: The peculiar imbalance in serum elements and oxidative status that characterizes patients with CIS and may predict conversion to CDMS warrants studies on larger sample sizes.

3D-Modelling and Prediction by Whim Descriptors. Part 7. Physico-Chemical Properties of Haloaromatics: Comparison Between Whim and Topological Descriptors

Abstract Quantitative Structure-Activity Relationships (QSAR) studies are powerful tools to rationalize complex systems where physico-chemical properties and biological activities of compounds of environmental and toxicological interest are involved. In these fields, due to costs, time, and difficulties in obtaining experimental measures, one of the main objectives is to fill the need for general predictive models. The challenge is to describe and represent, on a quantitative basis, all the molecular structural features in order to use them as descriptors in quantitative structure-activity models. In this study, two different sets of molecular indices have been employed for modelling: Topological Indices (TIs) and Weighted Holistic Invariant Molecular (WHIM) descriptors. In particular, the recently proposed WHIM indices, containing complete 3D information on molecular size, shape, symmetry and atom distribution, have already been successfully used in modelling physico-chemical properties and biological ac...

Heavy metals in powder-based cosmetics quantified by ICP-MS: an approach for estimating measurement uncertainty

A method based on microwave digestion and high resolution mass spectrometry was developed for the determination of Cd, Co, Cr, Ni and Pb in powder cosmetic samples. The procedure was validated in-house at the native concentration found in the cosmetic and at three fortification levels. Measurement uncertainties were calculated using data generated from repeatability, recovery and calibration linearity studies. The mean repeatability estimates were ≤11% for Cd, Co, Ni and Pb and ≤25% for Cr. The average recoveries ranged between 70% (Cr) and 112% (Pb). The expanded uncertainties (k = 2) of the method were between 34% (Cd) and 63% (Cr) at the native concentration and from 14% (Cd and Pb) to 34% (Cr) at the highest fortification level. The results accompanied by their uncertainty statements in the powder cosmetic were as follows (in mg kg−1): Cd, 0.026 ± 0.009; Co, 1.61 ± 0.60; Cr, 3.00 ± 1.88; Ni, 6.87 ± 2.53; Pb, 0.25 ± 0.09.