Daniela Mattei

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.

Health risk evaluation associated to Planktothrix rubescens: An integrated approach to design tailored monitoring programs for human exposure to cyanotoxins

Increasing concern for human health related to cyanotoxin exposure imposes the identification of pattern and level of exposure; however, current monitoring programs, based on cyanobacteria cell counts, could be inadequate. An integrated approach has been applied to a small lake in Italy, affected by Planktothrix rubescens blooms, to provide a scientific basis for appropriate monitoring program design. The cyanobacterium dynamic, the lake physicochemical and trophic status, expressed as nutrients concentration and recycling rates due to bacterial activity, the identification/quantification of toxic genotype and cyanotoxin concentration have been studied. Our results indicate that low levels of nutrients are not a marker for low risk of P. rubescens proliferation and confirm that cyanobacterial density solely is not a reliable parameter to assess human exposure. The ratio between toxic/non-toxic cells, and toxin concentrations, which can be better explained by toxic population dynamic, are much more diagnostic, although varying with time and environmental conditions. The toxic fraction within P. rubescens population is generally high (30-100%) and increases with water depth. The ratio toxic/non-toxic cells is lowest during the bloom, suggesting a competitive advantage for non-toxic cells. Therefore, when P. rubescens is the dominant species, it is important to analyze samples below the thermocline, and quantitatively estimate toxic genotype abundance. In addition, the identification of cyanotoxin content and congeners profile, with different toxic potential, are crucial for risk assessment.

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.

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.

ELISA and LC-MS/MS methods for determining cyanobacterial toxins in blue-green algae food supplements

The use of natural products as a diet supplement is increasing worldwide but sometimes is not followed by adequate sanitary controls and analyses. Twenty samples of pills and capsules of lyophilised cyanobacteria (blue-green algae), commercialised in Italy as dietary supplements, were found positive at the Vibrio fischeri bioassay. Further analyses with ELISA and LC-MS/MS methods revealed the presence of four microcystin (MC) analogues, MC-LR, -YR, -LA, -RR and two demethylated forms of MC-RR. The highest total microcystin content was 4.5 and 1.4 µg g−1 in pills and capsules, respectively. The ELISA measurements, compared to the LC-MS/MS analyses, showed significantly lower concentrations of microcystins in pills, this confirming a possible ELISA underestimate of mixed microcystins, due to different sensitivities for some toxic analogues.

A Study on Metals Content in Patients with Colorectal Polyps

Data on metals involvement in colorectal polyps are scarce and fragmentary. The aim of this study was to examine whether the level of metals could be associated with risk of colorectal polyp development. The concentration of 15 chemical elements (Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg Mg, Mn, Pb, Se, Sr, and Zn) in 17 colorectal biopsies of healthy individuals, in 15 polypotic and corresponding nonpolypotic biopsies taken from the same individual, was evaluated. Concentration in polyps of metals such as Al, Ca, Mg, Mn, Pb, Sr, and Zn was unchanged both in unpaired and paired samples; elements such as Ba, Cd, and Hg were significantly lower and Fe was significantly higher both in individual and paired tissues. Cobalt, Cr, and Cu were significantly different only between polyps and the adjacent normal tissue area; Se showed a significant accumulation comparing polyps versus healthy tissues. The difference found in some elements between polyps and a control tissue provides an indication about the role of essential and nonessential elements in the early stage (polyps) in the colon carcinogenic process and encourages further studies to confirm the involvement of such elements in neoplastic processes.

Sub-Chronic Oral Exposure to Iridium (III) Chloride Hydrate in Female Wistar Rats: Distribution and Excretion of the Metal

Iridium tissue distribution and excretion in female Wistar rats following oral exposure to iridium (III) chloride hydrate in drinking water (from 1 to 1000 ng/ml) in a sub-chronic oral study were determined. Samples of urine, feces, blood and organs (kidneys, liver, lung, spleen and brain) were collected at the end of exposure. The most prominent fractions of iridium were retained in kidney and spleen; smaller amounts were found in lungs, liver and brain. Iridium brain levels were lower than those observed in other tissues but this finding can support the hypothesis of iridium capability to cross the blood brain barrier. The iridium kidney levels rose significantly with the administered dose. At the highest dose, important amounts of the metal were found in serum, urine and feces. Iridium was predominantly excreted via feces with a significant linear correlation with the ingested dose, which is likely due to low intestinal absorption of the metal. However, at the higher doses iridium was also eliminated through urine. These findings may be useful to help in the understanding of the adverse health effects, particularly on the immune system, of iridium dispersed in the environment as well as in identifying appropriate biological indices of iridium exposure.

Risk Management of Ostreopsis spp. Blooms Along Italian Coasts

ABSTRACT SCARDALA, S., DI GIROLAMO, I., FATTORUSSO, E., FUNARI, E., GRAMACCIONI, L., BERTOLOTTO, R., ICARDI, G., MATTEI, D., POLETTI, R and TESTAI, E., 2011. Risk Management of Ostreopsis spp. Blooms Along Italian Coasts. In: Micallef, A. (ed.), MCRR3-2010 Conference Proceedings, Journal of Coastal Research, Special Issue, No. 61, pp. 435–439. Grosseto, Tuscany, Italy, ISSN 0749-0208 In the last years Ostreopsis spp. blooms have been reported in several Italian coastal stretches, showing a clear trend towards their extension. In 2005, during summer, an O.ovata bloom occurring in the coastal area in front of Genoa was tentatively associated with some human effects. Symptoms like rhinorrea, cough, fever, conjunctivitis, bronchoconstriction with mild dyspnea, and wheezes were observed in people exposed to marine aerosols, possibly containing algal fragments and/or its toxin. With less severe symptoms, similar episodes have been sporadically recorded in other coastal areas. Up to these events, the institutional monitoring activities were focused only on the surveillance of planktonic microalgae whereas benthonic ones, such as Ostreopsis spp. were ignored. To fill this gap, in 2006 a group of experts was appointed by the Italian Ministry of Health with the task to elaborate specific guidelines to manage the possible riskassociated to Ostreopsis spp. blooms. After their formal endorsement, the guidelines were published in the official site of the Ministry and implemented by local structures. The guidelines identify surveillance activities to be carried out, subdividing them into the routine, alert and alarm phases. These guidelines are currently under revision in order to update the scientific background and refine the approach on the basis of the two-year application experience.

Composition of essential and non-essential elements in tissues and body fluids of healthy subjects and patients with colorectal polyps.

This study was devoted to the quantification of 21 metals (Al, Ba, Ca, Cd, Co, Cr, Cs, Cu, Fe, Hg, Li, Mg, Mn, Mo, Ni, Pb, Se, Sn, Sr, V and Zn) in the colorectal tissue of 52 healthy subjects, 31 patients with polyps and 21 post-operated patients, and in blood, serum and urine of all subjects. Tissues of healthy subjects had a content of metals similar to those of post-operated patients and to normal tissues adjacent to the polyp. The polyps had concentrations of Al, Ba, Ca, Cd, Co, Cr, Cu, Hg, Mo, Ni, Sr and V significantly lower and of Fe and Se significantly higher respect to normal tissues. Polypotic patients had higher serum Cr, Cu and Pb and lower urinary Mo levels than healthy subjects, whereas blood showed no difference. Results highlighted metal-specific differences both at tissue and systemic level probably caused by the early stage of colorectal cancer.

Harmful algal blooms: new methods of control and management

The general increase in eutrophication of waters and the changes in global climatic conditions have caused over the last 30 years the spread of algal blooms in seas all over the world. The paper describes the different aspects of this problem, the known classes of marine algal toxins and their effects on human activities, and the problem of ballast waters. New strategies of remote sensing control, informative medical net projects and methods of managing and avoiding the related health consequences are also discussed.