Multielement and chemometric analysis for the traceability of the Pachino Protected Geographical Indication (PGI) cherry tomatoes.

To prevent PGI (Protected Geographical Indication) cherry tomato of Pachino (Sicily, Italy) from frauds, an alternative method, which includes chemometric treatments, was proposed. The content of 32 inorganic elements (macro-micronutrients and lanthanides) present in 16 PGI and 24 not PGI cherry tomato samples cv Naomy, and in 16 PGI and 8 not PGI soil samples, was determined by Inductively Coupled Plasma - Mass Spectrometer (ICP-MS). To identify the elements able to differentiate PGI and not PGI cherry tomato samples, Principal Components Analysis (PCA) and Canonical discriminant analysis (CDA) were performed. The first two principal components (PC1-PC2) explain a total variance of 71,41% between PGI and not PGI group, whereas CDA showed Zn, Cd, Mn and Ca as inorganic markers able to correctly classify the 100% of samples. Furthermore, with a translocation factor (K), evaluated in soil/plant chain, the comparison of absorption trends for PGI and not PGI samples was realized.

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.