Rossana Rando

Statistical study of the influence of fungicide treatments (mancozeb, zoxamide and copper oxychloride) on heavy metal concentrations in Sicilian red wine

The aim was to assess the influence of mancozeb, zoxamide and copper oxychloride fungicide treatments on Mn, Zn, Cu, Cd and Pb concentrations in Sicilian red wines, grapes, marcs and grape stalks. The experimentation was carried out over two crop years: 2003 and 2004. Trace metals analysis was performed by derivative stripping chronopotentiometry, which allowed detection of concentrations lower than 1 ng g−1. The data obtained gave evidence that the levels of Mn and Zn in wines from plots treated with zoxamide–mancozeb were about threefold higher than those observed in the control. Wines treated with Cu oxychloride had a significant increase in Cu(II) concentrations with respect to the control; in particular, samples from 2004 showed a 50% increase in Cu levels. Furthermore, as shown in a previous paper, the fungicides treatments studied led to a moderate increase in Pb(II) and Cd(II) levels in treated samples with respect to the control. Wines from 2004 had higher Cu and Pb amounts than wines from 2003; but the concentrations of all the other metals were similar. Statistical analysis of the data by linear discriminant analysis (LDA) and the Kruskal–Wallis test confirmed that both zoxamide–mancozeb treatments and copper oxychloride treatments exerted a significant influence on Mn(II), Zn(II) Cu(II), Pb(II) and Cd(II) concentrations in wines, grapes, marcs and grape stalks samples from both the studied vintages.

Study of quantitative and qualitative variations in essential oils of Sicilian oregano biotypes

Essential oil (EO) was extracted using hydrodistillation from samples of Origanum vulgare subspecies hirtum (Link) Ietswaart, gathered from the wild in various parts of Sicily, Italy; GC-FID and GC-MS analyses were subsequently performed. The aim of the study was to analyze the relationship between essential oil yields and the geographical distribution of oregano wild populations based on variations in environmental factors as collection sites. Moreover, the purpose was to group Origanum vulgare subspecies hirtum biotypes according to the chemical composition of the EO. The seven principal components in the EO was thymol (24.0–54.4%), γ-terpinene (9.8–30.5%), ρ-cymene (5.2–18.7%), α-terpinene (2.7–5.7%), carvacrol (0.3–8.3%), terpinen-4-ol (0.5–9.4%) and trans-sabinene hydrate (0.0–12.8%). All the biotypes analyzed were identified as thymol-chemotype. Statistical analysis shows that essential oil yields are mostly affected by weather/climate and topographic characteristics of the collection sites.

Statistical analysis of heavy metals in Cerastoderma edule glaucum and Venerupis aurea laeta from Ganzirri Lake, Messina (Italy).

Our study was carried out on two species of clams, Venerupis aurea laeta and Cerastoderma edule glaucum, from Ganzirri Lake considered as “environmental biomarkers” for their changes in physiology, morphology or distribution under the influence of substances in the environment. The aim of the present study was to conduct a statistical analysis on Venerupis and Cerastoderma to investigate the difference between the two autochthonous clams according to the presence of metals, and to link metal concentrations to the reproductive cycle of clam during 2009–2010. Metal analysis was carried out with inductively coupled plasma mass spectrometry (ICP-MS). Accuracy and precision were assessed by analyzing the certified standard matrix: mussel tissue NIST SRM 2976. The multivariate analysis was made using the SPSS 13.0 software package for Windows (SPSS Inc., Chicago, IL). In this study, the concentrations of some metals found in clam tissues showed seasonal cycles with higher values in summer than in winter. The significances of metal concentrations differences between Venerupis and Cerastoderma samples were estimated with Mann–Whitney U-test. The concentrations of Ag, As, Cd, Mn, Se and Zn show a significant p-level that suggests a difference between the two group samples. Statistical analysis showed that the link of metal concentrations to the reproductive cycles of Venerupis and Cerastoderma was not evident.

Levels of Cd (II), Mn (II), Pb (II), Cu (II), and Zn (II) in Common Buzzard (Buteo buteo) from Sicily (Italy) by Derivative Stripping Potentiometry

The purpose of this study was to determine the concentrations of heavy metals (Cd, Pb, Cu, Mn, and Zn) in different organs (liver, kidney, muscle, lung, skin, and feathers) of buzzards (Buteo buteo), utilized as a “biological indicator” for environmental contamination, from different areas of Sicily and to investigate the relationships between birds sex, age, and weight and metal levels in these samples. All samples of common buzzards were collected at the “Recovery Center of Wild Fauna” of Palermo, through the Zooprophilactic Institute. Potentiometric stripping analysis (PSA) was used to determine the content of Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II) in bird tissues. For toxic metals, the highest levels of Pb were in liver and those of Cd in lung; Zn levels were higher than Cu and Mn in all tissues analyzed. The concentrations in liver, lung, kidney, and muscle could be considered as an indicative of chronic exposure to metals while the presence of metals in skin could be consequential to storing and elimination processes. The found concentrations of metals in the studied matrices required a highly sensitive method for their determination and a simple sample preparation procedure, and the proposed method was well suited for this purpose.

Gas chromatography-tandem mass spectrometry multi-residual analysis of contaminants in Italian honey samples

ABSTRACT Contaminants belonging to various classes, including polychlorobiphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), pyrethroid insecticides (PYRs), fungicides (Fs), herbicides (Hs), synergists (SYNs) and insect growth regulators (IGRs) were analysed simultaneously in honey samples using a new simultaneous, easy and rapid method based on a liquid–liquid extraction with a mixture of n-hexane and ethyl acetate. It allowed recoveries in the range 80–137%, with limits of detection (LODs) between 0.10 and 5.21 ng g–1, showing a good sensitivity and accuracy. All the analysed Italian honeys showed the presence of residues of OPPs; PAHs were in 46.8% of the samples and PCBs were always below the LODs; 53.2% of the samples were contaminated by OCPs, PYRs, SYNs and IGRs. In addition, 46.8% of the samples exceeded the maximum residue limits (MRLs) established by the European Community in honey for chlorfenvinphos (cis + trans), TPP, γ-HCH, tebuconazole, coumaphos and τ-fluvalinate (cis + trans). GRAPHICAL ABSTRACT

4.22 – Sample Preparation for the Determination of Metals in Food Samples

The main aspects of sample preparation for the determination of metals in food samples are here described. The need for a correct sampling and sample pretreatment, the choice of high purity reagents, and the control of possible sources of contamination are taken into account. Sample digestion techniques are treated: dry ashing, open wet digestion, closed wet digestion, microwave assisted digestion, and UV photolysis digestion. Metal extraction by ultrasonic assistance and direct analysis of solid (or slurry) sampling are considered too. Several examples of sample preparation for the determination of metals in different foods, regarding all the highlighted techniques, are reported and compared.

Determination of Alkyl Esters Content in PDO Extra Virgin Olive Oils from Sicily

The quality parameter of alkyl esters of fatty acids was checked in a variety of Italian olive oil samples. In particular, 34 samples of extra virgin olive oils (EVOOs) from South Italy (Sicilian orchards), produced in the years 2014-2015, have been subjected to the analytical protocol dictated by the European Union for the determination of alkyl esters, as an indicator of oil’s quality. All the samples analyzed resulted to be well below the limit set by EU Directive. Besides recently produced EVOOs, a set of very aged oils, produced in the years 1996–2000, were analyzed as well. The main finding was that alkyl esters increased in correspondence with deterioration processes.

Functional properties and fatty acids profile of different beans varieties

Abstract Dried seeds of four varieties of Phaseolus vulgaris, three of Vigna unguiculata ssp. unguiculata and two of Vigna angularis grown and marketed in Italy, Mexico, India, Japan, Ghana and Ivory Coast were analysed for fatty acids content. In oils from seeds of P. vulgaris, the main fatty acids were linolenic (34.7–41.5%) and linoleic (30.7–40.3%), followed by palmitic (10.7–16.8%). The first three aforementioned fatty acids in the lipid fraction of V. unguiculata varieties were 28.4, 28.7 and 26.2%, respectively; while in V. angularis varieties, main fatty acids were linoleic (36.4–39.1%) and palmitic (26.9–33.3%), followed by linolenic (17.9–22.2%). Statistical analyses indicate that botanical species play a rule in bean fatty acids distribution, while the same was not verified for geographical origin. Furthermore, the atherogenic index (AI) and the thrombogenic index (TI) were investigated for health and nutritional information. The results showed that these wide spread legumes have functional features to human health.

Classification of Sicilian Olive Oils According to Heavy Metal and Selenium Levels using Canonical Discriminant Analysis (CDA)

Publisher Summary The presence of metals in vegetable oils depends on many factors: they might originate from the soil, fertilizers, and presence of industry or highways near the plantations, and be incorporated in the oil. The metals may also be introduced during the production process or by contamination from the metal processing equipment and thus be suspended in the oil. Taking into account the metabolic role of some metals and the large use of olive oils, it is of great concern to evaluate the presence of Cd (II), Cu (II), Pb (II), Zn (II) and Se (IV) in olive oils produced in Sicily in two different crop years (2000 and 2001). Stripping chronopotentiometry was used as a rapid, sensitive, and reproducible method to determine metal trace levels in acid extracts of olive oils. Recently the classification of olive oils based on the chemical composition has become an important challenge for researchers; in this regard it has been shown that the concentration of an inorganic element such as selenium is characteristic of the cultivar. This chapter aims (1) to summarize results from previous studies reporting the concentrations of some heavy metals and selenium in Sicilian virgin olive oils from three different varieties; (2) to use a statistical tool as canonical discriminant analysis (CDA) to classify virgin olive oils from different cultivars according to their heavy metal and selenium content.