A. Gonzálvez

A review of non-chromatographic methods for speciation analysis.

This manuscript overviews relevant scientific literature concerning speciation of trace elements by using non-chromatographic methods. The main principles of the different strategies proposed in the published works and their advantages and drawbacks are discussed in order to provide to the readers an appropriate picture of the state-of the-art of fast and cheap methodologies available to obtain information about the presence of different chemical forms of trace elements in environmental, clinical and food samples. A selection of the methods proposed for the speciation of the different elements studied was also provided together with their main features.

Searching the Most Appropriate Sample Pretreatment for the Elemental Analysis of Wines by Inductively Coupled Plasma-Based Techniques

Different sample preparation methods were evaluated for the simultaneous multielement analysis of wine samples by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Microwave-assisted digestion in closed vessel, thermal digestion in open reactor, and direct sample dilution were considered for the determination of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Y, Mo, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, and Bi in 12 samples of red wine from Valencia and Utiel-Requena protected designation of origin. ICP-MS allows the determination of 17 elements in most of the samples, and using ICP-OES, a maximum of 15 elements were determined. On comparing the sample pretreatment methodology, it can be concluded that the three assayed procedures provide comparable results for the concentration of Li, Na, Mg, Al, K, Ca, Mn, Fe, Zn, and Sr by ICP-OES. Furthermore, ICP-MS data found for Cu, Pb, and Ba were comparable. Digestion treatment provides comparable values using both total decomposition in open system and microwave-assisted treatment for Cu by ICP-OES and for Cr, Ni, and Zn by ICP-MS. Open vessel total digestion provides excess values for Cr, Mn, Fe, and Zn by ICP-OES and defect values for Se. However, direct measurement of diluted wine samples provided uncomparable results with the digestion treatment for Mn, Cu, Pb, Zn, Ba, and Bi by ICP-OES and for Mg, Cr, Fe, Ni, and Zn by ICP-MS. Therefore, it can be concluded that microwave-assisted digestion is the pretreatment procedure of choice for elemental analysis of wine by ICP-based techniques.

Elemental composition of seasoning products.

The elemental composition of seasoning products, like spices garlic and onion, has been reviewed paying special attention to methods proposed in the literature to determine specific elements or as much as possible components of these products which are widespread used in food preservation or food flavouring and can contribute to the intake of both, essential and toxic elements. Sample treatment and metal speciation aspects have been critically revised concerning onion, garlic and pepper (the most commonly studied products).

The ways to the trace level analysis in infrared spectroscopy

The future of infrared (IR) spectroscopy as an analytical technique is assured due to its versatility and its numerous advantages; such as the possibility to obtain molecular specific information for virtually any sample in any state with no treatment or minimal sample preparation. However, spectroscopists are not satisfied with relegating IR spectroscopy just to major and minor component analysis and have been looking at analysis at the trace level too. This review is the recognition of the brilliant research performed during the past two decades and the advances achieved in this area, which have made possible the analysis of contaminants at parts per billion (ppb) levels by IR in different matrices; such as water and soils.

Inductively coupled plasma optical emission spectroscopy determination of trace element composition of argan oil.

A methodology based on inductively coupled plasma optical emission spectroscopy (ICP-OES) after microwave assisted acid digestion has been developed to determine the trace element content of Moroccan argan oil. Limit of detection values equal or lower than few mg/kg were obtained for all elements under study. To assure the accuracy of the whole procedure, recovery studies were carried out on argan oil samples spiked at different concentration levels from 10 to 200 µg/L. Quantitative average recovery values were obtained for all elements evaluated, demonstrating the suitability of this methodology for the determination of trace elements in argan oil samples. Aluminum, calcium, chromium, iron, potassium, lithium, magnesium, sodium, vanadium and zinc were quantitatively determined in Moroccan argan oils being found that their concentration is different of that found in other edible oils thus offering a way for authentication and for the evaluation of possible adulterations.

Headspace-liquid phase microextraction for attenuated total reflection infrared determination of volatile organic compounds at trace levels.

A combination of headspace (HS) sampling and liquid phase microextraction (LPME) has been successfully developed to solve sensitivity problems in attenuated total reflection (ATR) infrared determination of volatile organic compounds (VOCs). The HS sampling facilitates the selective extraction of the target volatile analytes from the sample matrix, while the liquid phase microextraction allows their preconcentration prior to infrared analysis. The direct determination of extracted analytes in the acceptor solvent provides high preconcentration factors of the order of 200 with a reduced consumption of organic solvents and a minimum generation of wastes, being thus the developed methodology a green alternative method. The qualitative and quantitative capability of the proposed approach has been evaluated on the basis of two different examples: (i) screening of benzene, toluene and xylene (BTX) compounds in soil samples and (ii) quantitative determination of toluene in cosmetic nail products.

Determination at low ppm levels of dithiocarbamate residues in foodstuff by vapour phase-liquid phase microextraction-infrared spectroscopy.

A methodology based on the vapour phase (VP) generation of carbon disulphide from non-volatile dithiocarbamate compounds has been developed for determination of pesticide residues in foodstuff at low ppm levels. The method involves a selective reaction combined with liquid phase microextraction (LPME) and transmission infrared measurements. The use of a home made transmission cell improved the detection limits (LOD) compared to the use of attenuated total reflectance measurements by a factor of approximately 80. Using the most appropriate experimental conditions for the CS(2) generation and LPME preconcentration, the precision of the methodology, expressed as the relative standard deviation (RSD), was of the order of 3.1% and the absolute LOD was 0.3 μg dithiocarbamate, which corresponds to 60-120 μg kg(-1), for a sample mass ranging from 2.5 to 5 g. The usefulness of the methodology has been evidenced by the determination of mancozeb residues in strawberries, lettuce and corn samples at concentrations between 1 and 5 mg kg(-1), where the VP-LPME IR provided results comparable with those obtained by a head space gas chromatography mass spectrometry reference procedure.

Trace elemental composition of curry by inductively coupled plasma optical emission spectrometry (ICP-OES)

A methodology based on inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave-assisted acid digestion was developed to determine the content of traces elements in curry samples from the Spanish market. The methodology was validated in terms of accuracy by the analysis of citrus and tomato leaf reference materials achieving comparable results with the certified values. The trace metal content of curry samples was compared with data available from previously published reports concerning Indian samples, especially in terms of heavy metal composition, in order to guarantee the quality of the commercially available spices in the European countries. Values found for the analysis of arsenic, lead and cadmium were significantly lower than the maximum limit allowed by European Union statutory limits for heavy metals and lower than those obtained for Indian curry leaves reported by Indian research teams by using neutron activation and γ-ray analysis.

Chapter 3 – Mineral Profile

The identification of foods with protected designation of origin (PDO) has been a long-standing issue. Its detection provides valuable information to regulatory commissions (government and industries) which can regulate precise quality control procedures for their products. Authentication of food covers many different aspects, including characterization, mislabelling and misinformation regarding origin, and adulteration, which is defined as the process to reduce the quality or nature of a given substance by adding a foreign or an inferior substance and removing a vital element. Numerous methods have been developed as fingerprinting methodologies for PDO products. The analytical techniques critically evaluated in this chapter include atomic absorption spectroscopy, atomic emission spectrometry and inductively coupled plasma techniques. These techniques, in combination with chemometric methods, allow accurate discrimination of samples of different geographical origins and with different characteristics related to their mineral composition. These techniques have been applied to many different food products such as wines, rice, cheese, vegetables, fruits, drinks, meat products and fish, and in all these cases, the presence of trace and oligo elements at different concentration levels was of great value in verifying the geographical origin and the manufacturing processes involved.

Hydrodistillation–liquid-phase microextraction for infrared analysis of food

A combination of hydrodistillation (HD) and liquid-phase microextraction (LPME) has been successfully developed to improve sensitivity and selectivity in attenuated total reflection (ATR) infrared determination of semivolatile organic compounds from high water content plant and food matrices contributing to solve extraction efficiency drawbacks. The HD sampling facilitates the extraction of the semivolatile analytes from the sample matrix compared to headspace sampling, while the liquid-phase microextraction using a water immiscible solvent allows analyte preconcentration prior to ATR analysis. Experimental conditions regarding temperature and time of extraction, water effect and number of consecutive extractions have been deeply studied. The qualitative and quantitative capability of the developed methodology has been evaluated through the identification of the main semivolatile substances in plant and food matrices like spices and citrus peels and the effect of different drying treatments on the volatile composition of rosemary samples was studied through the quantification of camphor and eucalyptol.