Identification of aroma compounds of Vitis vinifera L. flowers by SPME GC-MS analysis

Using a gas chromatographic method (GC-MSanalysis), it was possible to determine the volatile constituent of an odorous flower from Vitis vinifera varieties growing in Sicily. More than 50 compounds were identified and the technique allowed us to determine that sesquiterpenes, as well as monoterpenes such as limonene and cymene, were the principal components. The odour-profiles allowed us to distinguish between variety groups or even single varieties.

YREE determination in seawater. Standardization and validation of a new method based on preconcentration techniques

The most interesting attraction of using rare-earth elements and yttrium (YREE) to address geochemical and marine chemical problems consists of their chemical coherence as group of trace elements. These characters allow YREE compositions of rocks and minerals to be extensively used in studies of provenance, petrogenesis and chemical evolution of the geological materials (1). Similarly, YREE compositions in the hydrosphere were used in studies of coagulation, particle-solution reactions and oceanic circulation of water masses (2-4). Unfortunately, very low concentrations of YREE (ng l-1 or sub-ng l-1) associated to high ionic strength of seawater always represented the main difficulty to analyse dissolved YREE in marine environment. The first geochemical investigations of YREE contents in seawater were carried out using neutron activation and isotope dilution mass spectrometry that were almost entirely replaced by inductively coupled plasma supplemented by mass spectrometry (ICP-MS) in recent years. This technique offers many advantages including simultaneous analysis of all the elements of series and their quantitative determination with detection limits of the order of ng l-1 if associated to preconcentration techniques (5). To perform ultra-trace YREE analyses in seawater, we developed a preconcentration method based on CHELEX-100 iminodiacetate resin followed by ICP-MS determination (Ref). In this study the YREE behaviour was quantitatively investigated during interactions with ion chelating resin and estimation of composed measurement uncertainty associated to measurements was evaluated with a rigorous metrological approach based on method validation and quality control of YREE data. These goals were achieved using synthetic seawater where YREE had concentrations as occurring in natural seawater samples. Under these conditions good recovery were obtained along the YREE series, ranging from 75%-85% and 90%-100% for heavy REE and Y and light REE, respectively. Composed measurement uncertainty was expressed in terms of precision, recovery uncertainties, reference material uncertainty and instrumental calibration uncertainty. The obtained results were critically discussed on the basis of the different contributions and confirm the quadrupole ICP-MS technique as highly sensitive to determine very low YREE concentrations. REFERENCES 1. S. R. Taylor, S.M. McLennan, The Continental Crust: its Composition and Evolution. Blackwell Scientific Publications, Oxford, 1985). 2. G.J. Piepgras, G.J. Wasserburg, Science 217 (1982) 207. 3. J. Zhang, Y. Nozaki, Geochim. Cosmochim. Acta 60 (1996) 4631. 4. R.H. Byrne, E. Sholkovitz, In: Gschneidner, J.K.A., Eyring, (Eds.), Handbook on the Physics and Chemistry of Rare Earths. Elsevier, New York, (1996) 498-593. 5. P. M\uf6ller, P. Dulski P., J. Luck, Spectrochim. Acta, 47B, 1379

Analysis of geochemical tracers in different systems soil-Citrus limon (L.) Osbeck

Today is increasing the attention of consumers for the origin of food and high reputation of products with a distinct geographical identity. Food traceability is an important issue in food safety and quality control, with impacts on food security, its quantity and overall availability. The knowledge of a chemistry relationship between the soil and the agricultural products is an important tool for the quality assessment of food. Citrus Limon is the most important fruit tree crop in the world and the detection of potential fraud could improve by using tools linking the chemistry composition of this production to its typical growing area. This study use rare earth elements (REEs) as geochemical tracers. The REEs are a set of 14 elements, from lanthanum to lutetium that can be divided in light rare earth elements (LREEs), from La to Gd and heavy rare earth elements (HREEs), from Tb to Lu. The REEs have recognized as very useful tracers due to their generally coherent and predictable behavior. The aim of the research is to observe whether the fruits of various cultivars of citrus cultivated on the same soil and their products (fruit and juice) reproduce the same distribution of REEs. Taking into account of our previous works carried out on grapevine – soil system [1, 2], we applied the same technique to evaluate and trace the REEs distribution in soil– Citrus Limon fruits system. Ten different varieties of Lemon fruits (Citrus limon Osbeck (L.)) were sampled. Lemon plant were grafted onto an unique rootstock (Citrus × aurantium L.), grown on volcanic soil in two experimental farms, located at the "Acireale" region (latitude 37 ° 37'23 N, longitude 15° 09'51.00 E and 205 m a.s.l., in Sicily, Italy) and “Portici” region (latitude 40 ° 81' 55 N, longitude 14° 34'75.00 E and 75 m a.s.l., in Campania, Italy). The varieties selected were: Akragas, Erice, Selinunte, Segesta, Continella, Femminello Siracusano, Femminello Dosaco, Kamarina, Sfusato, Ovale di Sorrento, Interdonato. A sample of 2 kg of fruit was collected at technological ripeness from each plant of three for every cultivar. As well as, three soil samples (about 2 kg) in the field corresponding to lemon sampling were collected and to reduce any surface contamination from a depth of 10–30 cm. The REEs amount, the HREEs/LREEs relations and their distribution in the fruit and citrus juice with respect to the own soil were determined and calculated. Results obtained were treated with statistical methods. The intriguing results obtained with a geochemical approach are the first on the soil–Citrus Limon fruits system

Quick assessment of the economic value of olive mill waste water

Background: Olive biophenols are emerging as a valued class of natural products finding practical application in the food, pharmaceutical, beverage, cosmetic and nutraceutical industries due to their powerful biological activity which includes antioxidant and antimicrobial properties. Olive mill waste water (OMWW), a by-product in olive oil manufacturing, is rich in biophenols such as hydroxytyrosol and tyrosol. The amount of biophenols depends on the cultivar, the geographical area of cultivation, and the seasonal conditions. The goal of this study was to develop a straightforward method to assess the economic value of OMWW via quantification of hydroxytyrosol and tyrosol. Results: The amount of hydroxytyrosol and tyrosol phenolic compounds in the OMWW from four different cultivars grown in four different regions of Sicily was analyzed using liquid-liquid and solid-liquid analytical protocols developed ad hoc. Results showed significant differences amongst the different cultivars and their geographical origin. In all samples, the concentration of hydroxytyrosol was generally from 2 to 10 times higher than that of tyrosol. In general, the liquid-liquid extraction protocol gave higher amounts of extracted biophenols. The cultivar Cerasuola had the highest amount of both hydroxytyrosol and tyrosol. The cultivar Nocellara Etnea had the lowest content of both biophenols. Conclusions: A quick method to assess the economic value of olive mill waste water via quantification of hydroxytyrosol and tyrosol in olive phenolic enriched extracts is now available

Preliminary studies of geochemical tools to traceability of Sicilian honey

Today is increasing the attention of consumers for the origin of food and high reputation of products with a distinct geographical identity. Food traceability is an important issue in food safety and quality control, with impacts on food security, its quantity and overall availability. Furthermore, the possibility of tracing the origin of foodstuff is assuming an increasingly important role at the legislative level, as a tool that may allow to prove on product authenticity and to control adulteration So, establish systems to trace food or feed products through specified stages of production, processing and distribution play a key role also to ensure food safety. For these reason, in the last years, a various of analytical techniques have been tested to found ways to establish the geographical origin of different kinds of food and many works reported that the combination of different analytical methods associated a multifactorial analysis of the data seems to be the most promising system to establish univocal traceability systems. Despite, the honey is a well appreciated natural product in the world and the detection of potential fraud could be favored through tools linking the chemistry composition of this production to producing area. A relatively small number of investigations regarding traceability of honey can be found in the scientific literature. Therefore, in these contest the development of fingerprinting techniques based on the determination of the specific markers of provenance analyzed whit chemometric approach represents an interesting area of research. Recent works have been demonstrated the potentiality of the study of the distribution patterns of rare earth as a promising analytical method for traceability of food products due coherent and predictable chemical behaviour of these compounds. Also, have been demonstrated that their distribution in soil keeps unaltered in plants growing on that soil and eventually in agricultural products obtained from those plants and through the normalization of the REEs distribution, it is possible to appreciate their relative enrichments in soil-plant- agro food products The aim of the research is to observe if the REEs normalizated pattern of honey is kept unaltered respect the soils of production to establish a correlation between geographic area and honey product. In this first study the REE approach, give very intriguing results in the geographical traceability of honey samples. The results have been supported by statistical treatment. A larger study is in progress to optimize the analytical methodology and to extend the research to a major number of sample for a better geographical characterization

ATR-FTIR chemical screening for adulterants and sugar characterisation in honeys

The search for improvements in honey analysis is an important topic due to the relevance that adulterations and variations of sugar composition have in this food. Attenuated Total Reflectance Fourier Transform InfraRed spectroscopy (ATR-FTIR) is a reliable and fast analytical instrumentation for analysis of liquids, semi-solids and solids, which is currently used in food chemistry for qualitative and quantitative investigations. This work is aimed to build a fast analytical method, using ATR-FTIR and Partial Least Square (PLS) chemometric tool, to quantitative determination of glucose, fructose and sucrose present in honeys. We analyzed 25 honeys from Trentino and Sicily and a significant spectral range from the whole ATR-FTIR spectra were selected. Then a PLS multivariate calibration model was built by using mixtures of glucose, fructose and sucrose at various concentration. Samples for cross-validation were selected, thereby allowing quantitative evaluation of glucose, fructose and sucrose in all samples. Furthermore, a representative number of honeys were mixed with common adulterant syrups to simulate adulteration procedures and to verify the reliability of the ATR-FTIR technique in recognizing them. Preliminary results revealed not only the quantitative reliability of ATR-FTIR spectroscopy in the evaluation of sugars in honeys, but also its ability in recognizing honey adulteration

Accumulation of rare earth elements in common vine leaves is achieved through extraction from soil and transport in the xylem sap

Rare Earth Elements play a critical role in current clean technologies but face scarcity and environmental challenges in their extraction. Using semi-natural controlled experiments, we tested the ability of V. vinifera L. to accumulate Rare Earth Elements naturally present in the soil. We demonstrate that V. vinifera L. passively transports all Rare Earth Elements from soil to leaves via Xylem-sap mirroring soil conditions. Since this process starts from the fifth month of V. vinifera L. growth without damaging the crops, we. estimate that it is possible to recover 900 milligrams of Rare Earth Elements per hectares from vineyard without harvesting the whole plant. We propose the direct extraction of Rare Earth Elements from leaves overcoming unstainable biomass burning yielding environmental and economic benefits.The pathway for the accumulation of rare earth elements in Vitis vinifera L. leaves is extraction from vineyard soils and subsequent transport in the xylem sap, suggests a semi-natural controlled experiment

New chemiometric technique applied to traceability of Sicilian honey of Sulla (Hedysarum coronarium L.)

The consumers have an increasing interest about food traceability with respect to safety, quality and typicality issues. Food traceability is an important issue in food safety and quality control, with impacts on food security, its quantity and overall availability. Furthermore, the possibility of tracing the origin of foodstuff is assuming an increasingly important role at the legislative level, as a tool that may allow to prove on product authenticity and to control adulteration. So, establish systems to trace food products through specified stages of production, processing and distribution play a key role also to ensure food safety. In the last years, several of analytical techniques have been tested to found ways to establish the geographical origin of different kinds of food and many works reported that the combination of different analytical methods associated a multifactorial analysis of the data seems to be the most promising system to establish univocal traceability systems. The honey is a natural food well appreciated in the world and the detection of potential fraud could be favored through tools linking the chemistry composition of this production to producing area. A small number of investigations regarding traceability of honey can be found in the scientific literature. Therefore, in these contest the development of fingerprinting techniques based on the determination of the specific markers of provenance analyzed whit chemometric approach represents an interesting area of research. Recent works have been demonstrated the potentiality of the study of the distribution patterns of rare earth as a promising analytical method for traceability of food products due coherent and predictable chemical behavior of these compounds. Also, have been demonstrated that their distribution in soil keeps unaltered in plants growing on that soil and eventually in agricultural products obtained from those plants and through the normalization of the REEs distribution, it is possible to appreciate their relative enrichments in soil-plant- agro food products The aim of the research was to observe if the REEs normalizated pattern of honey of Sulla (Hedysarum coronarium L.) was kept unaltered respect the soils of production to establish a correlation between geographic area and honey product. For this study, different production areas of Sulla in Sicily were considered. The production fields explored by the bees within 2 km of the hives were taken into consideration, the soil and the flowering plants were sampled. Flowers and leaves were analyzed from the plant. In the hive, pollen and honey were taken in three different days during the flowering period of the Sulla. Of same areas were sampled to the same methods in different periods where other monofloral honeys were product, these samples were used for a control. In this study the REE approach, give very intriguing results in the geographical traceability of honey samples and are the first. The results have been supported by statistical treatment

Do Grapholita funebrana Infestation Rely on Specific Plum Fruit Features?

The effective control of the plum fruit moth, Grapholita funebrana (Lepidoptera: Tortricidae) still represents a difficult challenge for organic plum farming. Little information is available on the susceptibility of plum cultivars to this moth pest. We investigated the roles of several fruit parameters (i.e., shape, volume, hardness, fruit colour, and physiochemical properties) on the susceptibility of four different plum cultivars (Angeleno, Friar, President and Stanley) to G. funebrana attack. Field data demonstrated the importance of some fruit parameters (i.e., elongation index, sugar degree, titratable acidity, cover colour percentage) on susceptibility to G. funebrana infestation. Under laboratory conditions, colour and shape had a significant role in determining the time spent on false fruits, i.e., female moths preferred yellow and rounded fruits over elongated red or green fruits. Angeleno (yellow and rounded fruits) and Stanley (green and elongated fruits) were the most and least susceptible cultivars, respectively. Overall, this study adds useful knowledge about plum cultivar susceptibility to G. funebrana. Information reported here may be useful to improve integrated pest management strategies both in conventional and organic orchards because the use of less susceptible cultivars may reduce insecticidal treatments, limiting the development of resistance in target insects and the harmful side effects on beneficial species

Environmental impact of Mt. Etna’s degassing: volcanogenic trace elements bioaccumulation in two endemic plant species (Senecio aethnensis and Rumex aethnensis)

A biomonitoring survey, above tree line level, using two endemic species (Senecio aethnensis and Rumex aethnensis) was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic atmospheric emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (1500- 3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analyzed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind sector, confirming that the eastern flank of Mt. Etna is the most impacted by volcanic emissions. Leaves collected along two radial transects from the active vents on the eastern flank, highlight that the levels of metals decrease one or two orders of magnitude with increasing distance from the source. This variability is higher for volatile elements (As, Bi, Cd, Cs, Pb, Sb, Tl) than for more refractory elements (Al, Ba, Sc, Si, Sr, Th, U). The two different species of plants do not show significant differences in the bioaccumulation of most of the analyzed elements, except for lanthanides, which are systematically enriched in Rumex leaves. The high concentrations of many toxic elements in the leaves allow us to consider these plants as highly tolerant species to the volcanic emissions, and suitable for biomonitoring researches in the Mt. Etna area