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

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

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

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

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