Giuseppa Di Bella

Gas chromatographic–tandem mass spectrometric identification of phenolic compounds in Sicilian olive oils

Phenolic compounds in Sicilian olive oils were analyzed by GC–MS and GC–MS/MS after extraction with methanol:water 80:20 and derivatization with bis(trimethylsilyl)trifluoracetamide and trimethylchlorosilane (BSTFA:TMCS 99:1). Numerous compounds were detected and 23 were identified. Tyrosol, hydroxytyrosol and the decarbomethoxy ligstroside and oleuropein aglycons in the dialdehydic forms were the most abundant compounds. 4-(Acetoxyethyl)-1-hydroxybenzene, 3,4-dihydroxyphenylacetaldehyde, syringaldehyde and the cis form of ferulic acid were identified: these compounds were not found in olive oils before. The presence of the dialdehydic form of elenolic acid (without carbomethoxy group) linked to 3-methoxy-4-hydroxyphenylethanol was hypothesized. There were quantitative differences in oils from the varieties Nocellara del Belice, Santagatese and Cerasuola; these differences could depend on the olive varieties and ripeness.

Trace elements in Thunnus thynnus from Mediterranean Sea and benefit–risk assessment for consumers

Trace elemental levels were determined by inductively coupled plasma-mass spectrometry in muscle, eggs and sperm of 23 Thunnus thynnus fishes collected from May to August 2013 in the Mediterranean Sea. Zn, Mn, Fe, Cu, Cr, Ni and Se content was compared with Recommended Daily Allowances. Cd, Hg and Pb concentrations were below the maximum limits fixed by the European Legislation. Tuna food safety was evaluated considering Tolerable Weekly Intake (TWI) or Provisional Tolerable Weekly Intake for As, Hg, Cd and Pb. Only BMDL01 data for As and Pb were calculated as established by the Joint FAO/WHO Expert Committed on Food Additives. The daily consumption of fresh tuna ensures a good intake of these elements. None of the tested samples surpassed the European maximum limits. Cd, Hg and Pb remained within safety margins, while As is slightly higher than the provisional TWI.

Statistical characterisation of heavy metal contents in Paracentrotus lividus from Mediterranean Sea

This work focuses on the estimation of Hg, As, Cr, Ni, Cu, V, Cd and Pb by inductively coupled plasma mass spectrometry in 135 adult specimens of Paracentrotus lividus collected in different coastal areas of Sicily (Gela, Punta Secca, Ragusa (RG), Siracusa, Priolo, Catania, Messina, Milazzo, Brolo and Filicudi), in order to monitor the Mediterranean marine ecosystem by use of sea urchin as bioindicator. Moreover, the paper deals with the statistical classification of the tested samples according to the sampling area based on metal concentrations. The descriptive statistics findings were obtained and, a starting multivariate matrix was built. Data-sets were subjected to Kruskal–Wallis test to verify the significance of differences in metal concentrations, and then a factor analysis with principal components extraction was performed to try to differentiate urchin samples collected in different areas. The results showed that P. lividus is a suitable organism to be used as bioindicator.

High performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry for sensitive determination of bioactive amines in donkey milk

In the present study we report on the optimization and validation of a sensitive high performance liquid chromatography atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS) method for the determination of 8 bioactive amines (histamine, tyramine, tryptamine, 2-phenylethylamine, cadaverine, putrescine, spermidine and spermine) in donkey milk samples. The method involves donkey milk pre-treatment to remove proteins and pre-column dansylation of the amines. HPLC in reversed phase mode has been used for bioactive amines separation and the operating condition of the APCI-MS system proved to be powerful and very efficient for peak assignment. The separation was accomplished in a short time with an excellent resolution for all the amine peaks. Quantification was carried out by monitoring the characteristic [M+H](+) ion of each amine derivative. The method sensitivity, linearity and repeatability were assayed with satisfactory results. The detection limits of the analysed amines ranged from 0.5 microg L(-1) to 15 microg L(-1); the highest LOD was for spermine. Also remarkably good recovery values were obtained; at the lowest spiking level (1 microg L(-1)) the percent mean recoveries ranged from 77.7 to 109.7. Furthermore, as the investigations relate to a complex matrix as donkey milk, suitable studies on matrix effect were performed. Finally, the developed and validated method was applied to analyse 13 donkey milk samples. Among the identified bioactive amines, putrescine, spermine and spermidine proved to be the main amines in donkey milk. Their concentration levels in the present study were lower than the values determined in mature human, cow and sow milk.

Heavy metals content by ICP-OES in Sarda sarda, Sardinella aurita and Lepidopus caudatus from the Strait of Messina (Sicily, Italy)

In this study copper, nickel, lead, cadmium, arsenic, chromium and vanadium content was measured in the muscles and gills of 24 fishes (Sarda sarda, Sardinella aurita and Lepidopus caudatus) caught in the Strait of Messina, by inductively coupled plasma-optical emission spectroscopy with microwave digestion techniques. In general, it was found that arsenic was higher than other analytes in all fish species, particularly its content was much higher in S. aurita than in the other two exemplary species. Lead and cadmium were always detected with values below the legal limits (CE no. 1881/2006 and subsequent modification CE no. 629/2008).

Chemometric analysis of minerals and trace elements in Sicilian wines from two different grape cultivars

Abstract Chemometric analysis are used for food authenticity evaluation, correlating botanical and geographical origins with food chemical composition. This research was carried out in order to prove that it is possible linked red wines to Nero d’Avola and Syrah cultivars of Vitis vinifera according to their mineral content, while the values of the physical and chemical parameters do not affect relevantly this discrimination. The levels of mineral elements were determined by ICP-OES and ICP-MS. Samples from cv Nero d’Avola had the highest content of Zn, Cr, Ni, As and Cd, whereas the highest mineral concentration in cv Syrah samples was represented by K, Mg, Cu, and Sb. The research highlights that it is possible linked red wines to Nero d’Avola and Syrah cultivars of V. vinifera according to their mineral contents, adding knowledge to the determination studies of the wine botanical origin.

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.

Pesticide Residues in Uruguayan Lemon Oils

Abstract Organophosphorus and organochlorine residues were studied on 31 samples of Uruguayan lemon oils corresponding to the 1995 season from North and South areas of fruit production in the country. Organochlorine pesticides were absent in all die samples analyzed. The average level of contamination for the organophosphorus pesticides (Chlorpyrifos and Methidathion) was 0.80 ppm and 15.05 ppm for die samples corresponding to the North and South areas, respectively. The results were compared with those obtained in 1993 in lemon oils from the same areas of production.

Contamination of Citrus Essential Oils: The Presence of Phosphorated Plasticizers

Abstract Organophosphorus insecticides are common pollutants of the citrus oils. Unknown phosphorated compounds, different from organophosphorus pesticides, were detected during GC analyses of citrus oils; the chromatographic profile was similar to a triarylphosphate mixture. Standard mixtures of triarylphosphates were analyzed and mass spectra were obtained; the results showed that the contamination was due to triphenylphosphate and tritolylphosphate isomers essentially. The contaminants were found to probably originate from contact of the oils with plastic materials from which they leached on oil storage.

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