Simultaneous determinations of zirconium, hafnium, yttrium and lanthanides in seawater according to a co-precipitation technique onto iron-hydroxide

Very low concentrations (pg mL 1 or sub-pg mL 1 level) along with the high salinity are the main problems in determining trace metal contents in seawater. This problem is mainly considered for investigations of naturally occurring YLOID (Y and Lanthanides) and Zr and Hf in order to provide precise and accurate results. The inductively coupled plasma mass spectrometry (ICP-MS), both in high and low resolution, offers many advantages including simultaneous analyses of all elements and their quantitative determination with detection limits of the order of pg mL 1. However in the analysis of YLOID in seawater, a better determination needs an efficient combination of ICP-MS measurement with a preconcentration technique. To perform an ultra-trace analysis in seawater, we have validated an analytical procedure involving an improved modified co-precipitation on iron hydroxides to ensure the simultaneous quantitative recovery of YLOID, Zr and Hf contents with measurement by a quadrupole ICP-MS. The validity of the method was assessed through a series of co-precipitation experiments and estimation of several quality control parameters for method validation, namely working range and its linearity, detection limit, quantification limit, precision and spike recoveries, and the methodological blank choice, are introduced, evaluated and discussed. Analysis of NASS-6, is the first report on the latest seawater reference material for YLOID, hafnium and zirconium

Distribution of YLOID in soil-grapevine system (Vitis vinifera L.) as tool for geographical characterization of agro-food products. A two years case study on different grafting combinations

The knowledge of a chemistry relationship between the soil and the agricultural products is an important tool for the quality assessment of food. We studied YLOID (Y, La and lanthanoids), recognized as very useful tracers due their coherent and predictable behavior, to trace and evaluate their distribution from soil to the grape in Vitis vinifera L. Because much of the world’s viticulture is based on grafting, and rootstocks have proved affect vine growth, yield, fruit and wine quality, we carried out experimental trials to analyse the YLOID distribution of two different red cultivars, grafted onto six different rootstocks, on the same soil. The YLOID amounts, the relationship Heavy vs Light YLOID and the pattern of YLOID were calculated. The results showed that the different grafting combinations were not able to induce significant differences in YLOID uptake from the soil maintaining the same fingerprint (with the exception of Eu)

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

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.

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

Distribution of REEs in soil-citrus limon system(L.) Osbeck

The consumers have an increasing interest about food traceability with respect to safety, quality and typicality issues. 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 behaviour. 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. Sampling of soil and of fruits was carried out in the CREA experimental farm located in Acireale (CT, Sicily) where are present several Citrus Limon cultivars cultivated in Sicily. 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. The intriguing results obtained with a geochemical approach are the first on the soil–Citrus Limon fruits system

Geochemical behaviour of rare earths in Vitis vinifera grafted onto different rootstocks and growing on several soils

The geochemical behaviour of lanthanides and yttrium(Rare Earth Elements, REEs) has been investigatedmainly in geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. This behaviour is assessed according to features recorded in sequences of REE concentrations along the REE series normalised with respect to a reference material. In this study, the geochemical behaviour of REE was investigated in different parts of Vitis vinifera specimens grown off-soil, on soils of different nature and grafted onto several rootstocks in order to evaluate effects induced by these changes. The results indicated that roots are the plant organs where REEs are preferentially concentrated, in particular elements from Sm to Ho (middle REE, MREE) whereas Eu enrichments occur in aerial parts. The geochemical behaviour of REE suggests that MREE enrichments in roots are due to preferential MREE interactions with biological membranes or to surface complexation with newly formed phosphates. Eu-positive anomalies suggest that Eu3+ can form stable organic complexes in place of Ca2+ in several biological processes in xylem fluids. The possibility that Eu mobility in these fluids can be enhanced by its reductive speciation as Eu2+ cannot be ruled out. The assessment of the geochemical behaviour of REE according to the theory of the Tetrad Effect carried out confirms that REEs coming fromsoil are scavenged onto root tissues or mineral surfaceswhereas their behaviour in aerial parts of V. vinifera is driven by dissolved complexation

SUSTAINABLE PRODUCTION OF FENNEL AND DILL BY INTERCROPPING

Intercropping is claimed to be one of the most significant cropping techniques in sustainable agriculture, and much research and many reviews attribute to its utilization a number of environmental benefits, from promoting land biodiversity to diversifying agricultural outcome. In this sense, intercropping is thought to be a useful means of minimizing the risks of agricultural production in many environments, including those typical of under-developed or marginal areas. In order to validate this hypothesis in a representative area of the semiarid Mediterranean environment, we evaluated the possibility of growing dill and fennel, both belonging to the family Apiaceae, in temporary intercropping. Our trial was performed in Sicily in 2000–01 and 2001–02; in the first year, fennel and dill were cultivated in a mixture using a substitution scheme, whereas in 2001–02 we evaluated the bio-agronomical and chemical features of fennel alone. The biological efficiency of the intercropping system was evaluated by using the Land Equivalent Ratio and the Competitive Ratio, and an estimate of the interaction effects of both crops was performed by analyzing the major vegetative and yield traits of plants, along with the chemical profile of volatiles of the fruits. Both in grain yield and in biomass yield, the most efficient cropping system was the intercropping ratio with a higher proportion of fennel, in which the competitive ratio values calculated for dill reached 1.90 for grain and 2.59 for biomass. Our results also indicate that the presence of dill exerted a clear stabilizing effect on fennel seed yield of the following year: whereas no difference in fennel seed yield was detected from one year to the following on the previously intercropped plots, in the repeated pure stand a 50% yield reduction was recorded. In the trial environment, the technique showed a good potential to improve the efficiency of resource utilization; further long-term experiments will be necessary in order to demonstrate the application of such a technique to other medicinal and aromatic plant mixtures

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