Trace elements determination in red and white wines using total-reflection X-ray fluorescence

Several wines produced in different regions from south of Brazil and available in markets in Rio de Janeiro were analyzed for their contents of elements such as: P, S, Cl, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Rb and Sr. Multi-element analysis was possible with simple sample preparation and subsequent analysis by total-reflection X-ray fluorescence using synchrotron radiation. The measurement was carried at the X-ray fluorescence beamline in the Synchrotron Light Source Laboratory in Campinas, Brazil. The levels of the various elements obtained were lower in the Brazilian wines than the values generally found in the literature. The present study indicates the capability of multi-element analysis for determining the contents of various elements present in wines coming from Brazil vineyards by using a simple, sensitive and precise method.     

Optimized determination of calcium in grape juice,wines, and other alcoholic beverages by atomic absorption spectrometry

This paper describes a study of the different methods of sample preparation for the determination of calcium in grape juice, wines, and other alcoholic beverages by flame atomic absorption spectrometry; results are also reported for the practical application of these methods to the analysis of commercial samples produced in Spain. The methods tested included dealcoholization, dry mineralization, and wet mineralization with heating by using different acids and/or mixtures of acids. The sensitivity, detection limit, accuracy, precision, and selectiviy of each method were established. Such research is necessary because of the better analytical indexes obtained after acid digestion of the sample, as recommended by the European Union, which advocates the direct method. In addition, although high-temperature mineralization with an HNO3-HCIO4 mixture gave the best analytical results, mineralization with nitric acid at 80 degrees C for 15 min gave the most satisfactory results in all cases, including those for wines with high levels of sugar and beverages with high alcoholic content. The results for table wines subjected to the latter treatment had an accuracy of 98.70-99.90%, a relative standard deviation of 2.46%, a detection limit of 19.0 microg/L, and a determination limit of 31.7 microg/L. The method was found to be sufficiently sensitive and selective. It was applied to the determination of Ca in grape juice, different types of wines, and beverages with high alcoholic content, all of which are produced and widely consumed in Spain. The values obtained for Ca were 90.00 +/- 20.40 mg/L in the grape juices, 82.30 +/- 23.80 mg/L in the white wines, 85.00 +/- 30.25 mg/L in the sweet wines, 84.92 +/- 23.11 mg/L in the red wines, 85.75 +/- 27.65 mg/L in the rosé wines, 9.51 +/- 6.65 mg/L in the brandies, 11.53 +/- 6.55 mg/L in the gin, 7.3 +/- 6.32 mg/L in the pacharán, and 8.41 +/- 4.85 mg/L in the anisettes. The method is therefore useful for routine analysis in the quality control of these beverages.     

Analysis of organic sulfur compounds in wine aroma

Sulfur-containing compounds in wines have been extensively studied because of their effect on wine aroma. The aim of this paper was to give an overview on the analytical methods developed to determine them in wines with special emphasis on gas chromatographic methods, as well as the results obtained. In addition, the problems occurring in application of the common extraction procedures, such as liquid-liquid extraction, static and dynamic headspace and solid-phase microextraction, are presented and discussed.     

ICP-MS multi-element analysis of wine samples - a comparative study of the methodologies used in two laboratories

A comparison of the performance of the methodologies used in two distinct laboratories (Lab A and Lab B) for multi-element analysis in different wines was carried out. ICP-MS apparatus (quadrupole mass analyzers) of different brands as well as different wine pre-treatments were used. At Lab A, a pre-treatment by UV-irradiation was performed. At Lab B, a micro-concentric nebulizer was used for direct analysis of the wine. Twenty-six elements (Li, V, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Pb) were measured in common at the two labs in three different wine samples (red and white Bordeaux table wines and Port wine) and the results were compared. The two methodologies provided similar LODs and similar precisions, with RSDs of 0.5-5%, for most of the elements. The recovery percentages were 85-120% at Lab A for the three wines, and 78-119% at Lab B for the Bordeaux wines, validating the accuracy of the methods used. Comparable results were obtained at both labs for ten elements (Li, V, Co, Ni, Cu, Zn, Rb, Sr, Ba, and Pb) in the three selected wines; the differences were lower than 10% in most cases. For REEs, the differences observed were slightly higher, but still in the acceptable range due to the sub-ppb levels involved. The results obtained for As and Ga were not comparable, due to methodological influence. A comparison through linear least-squares adjustment indicated that the results obtained by the two labs were linearly correlated (correlation coefficient =0.997) but statistically different as the slope was slightly, but significantly different from one, for a confidence level of 95% (the intercept was statistically identical to zero in any case). In the future, strictly more identical results can be achieved by using a reference wine sample.     

Semiautomatic flow-injection method for determination of volatile acidity in wines.

A flow-injection (FI) method based on analytical pervaporation was assessed for its routine use in the determination of volatile acidity in winery laboratories. The new method was compared with both the official method and the Mathieu method, which is most often used in Spanish wineries, by testing 30 different wines, including young and aged, and sweet and dry wines from Montilla-Moriles appellation d'origine. The robustness of the new method was established, and then all 3 methods were studied in terms of range of linearity and regression of the calibration curve, repeatability, reproducibility, sensitivity, detection and quantitation limits (LOD and LOQ, respectively), and time of analysis. The FI method surpassed the Mathieu method in reproducibility and both the Mathieu and official methods in LOD and LOQ and sensitivity; it also required less personnel involvement and shorter analysis time. The statistical criteria established by the Office International de la Vigne et du Vin were applied to the data and the results obtained indicated that the differences between the analytical parameters of the 3 methods are not significant and can be applied indistinctly. The correlation of the methods was studied by taking them 2 by 2, and the corresponding equations, coefficients, and deviations confirmed the statistical results. Thus, the new method can be used in winery laboratories with clear advantages over its 2 counterparts (the routine and official methods).     

High reliability atomic absorption spectrometry of major and minor elements in biological materials

Summary Reliable analytical information is of fundamental importance for decisions of far-reaching impact in many regulatory, medical and scientific areas and disciplines. It is however at times elusive. Although the technique of atomic absorption spectrometry (AAS) as become widely established in analytical laboratories throughout the world for the determination of inorganic elements, only few AAS-based methods have reached official status and even fewer have attained reference method status. Research is underway to delineate impacts of a number of parameters on method performance to lead to protocols for standard and reference flame AAS (FAAS) methods for the reliable measurement of major and minor levels of elements of nutritional and toxicological pertinence in clinical and biological materials. Factors investigated include preparation of standards, calibration techniques, sampling and sample decomposition, solution preparation, instrumental parameters, and measurement protocols. Examples of some pronounced effects of sample decomposition and calibration techniques are presented as well as indications of the excellent performance of well-applied AAS procedures determined by use of standard reference materials and comparison with other techniques of analysis. Reference will be made to the determination of the major and minor nutrient elements Na, K, Mg, Ca, Mn, Fe, Cu and Zn in plant biological reference materials.Formerly at Plant Research Centre, Agriculture Canada, Ottawa, Ontario K1A OC6, CanadaContribution No. 1030 from Plant Research Centre     

Comparative Evaluation of Red Wine from Various European Regions Using Mass Spectrometry Tools

The goal of this work was to assess differences in the composition of red wine produced in Poland, Hungary, Moldova, and Bulgaria, related to their geographical origin. Inductively coupled plasma–mass spectrometry results obtained for 23 elements were submitted to principal component analysis, indicating the association of Li, Co, Se, Cu, Sr with Moldovan products; Hungarian and Moldovan wines were characterized by V, As, Al, Fe variables, whereas Be was distinctive for Hungarian products. Polish wines were grouped with Cd and Pb and Bulgarian with Tl, Ba, Rb, and Mo; U and Mn were found as characteristic variables for wines from Bulgaria and Moldova. According with current legislation, the investigated wines were not contaminated with heavy metals and might be even considered a good source of essential elements (Cu, Mn, Fe, Zn, Cr, and Co). Gas chromatography–high-resolution time-of-flight mass spectrometry was used as a complementary analytical tool, targeting nonvolatile organic compounds amenable for silylation. Statistical data analysis revealed that geographical factors strongly affected the metabolic profiles. Specifically, 15 compounds presenting higher abundances in Bulgarian as compared to Polish wines were found, including monosaccharides, polyols, organic acids, sugar acids, and the amino acid proline. The highest fold change was obtained for ribose (37.9), followed by proline (12.2) and inositol (5.68), suggesting that these compounds might be especially useful for discrimination purposes. The obtained results encourage for further studies aimed at the discrimination of wine produced over the entire Central-East European region based on metal/metalloid profiling and on the evaluation of specific metabolites.     

Problems of calibration in trace, in situ-micro and surface analysis

Summary A systematic survey will be given on different strategies of calibration in dependence on given analytical and statistical conditions, particularly on several procedures of least squares regression (ordinary, orthogonal, unweighted and weighted LSR), of robust regression, addition methods and multicomponent calibration. In this connection calibration by means of latent variables (principal component regression PCR, partial least squares PLS) will be dealt with. The special conditions in the case of microanalysis and surface analysis will be considered under practical analytical as well as chemometrical aspects. Problems of homogeneity, representativness of samples and sample regions will be treated.     

Optimization of TXRF measurements by variable incident angles

Variable incident angles in TXRF instrumentation open up new possibilities in the field of analytical quality assurance of TXRF measurements as well as the possibility of optimizing the measurement angle with respect to the sample carrier. Measurements on the same sample with different incident angles allow a check to be made on the behavior of the internal standard and the elements under investigation within the sample, which makes quantification more reliable, even for difficult samples. This is demonstrated on the example of standard reference material NIST 1633a comparing the relative fluorescence intensities of the elements K, Ti and Fe obtained from a sample prepared from a suspension and a digestion of the SRM material, respectively. Furthermore, it will be shown how the measurement conditions for different sample carrier materials such as quartz and acrylic glass can be optimized by measuring angular-dependent signal and background intensities.     

Fluorimetry compared to spectrophotometry for uranium evaluation in liquid waste

Uranium concentration levels in surface waters are of great importance because uranium presents both chemical and radiological hazard to the environment. The subject of this article is to establish that spectrophotometric method for uranium evaluation in effluents collected from liquid waste treatment generated during fabrication of nuclear fuel elements could be replaced by the optical fluorimetric technique. Both methods are briefly described. The comparison of the two methods was carried out with regard to international standards and national regulations offering from a statistical point of view a useful approach to compare two analytical measurement techniques. This methodology can be applied to any other measurement procedures. A discussion about the compliance of the fluorimetric analytical method with the mandatory discharge level of uranium concentration in surface waters is also presented.     

Determination of heavy metals and rare earth elements in environmental samples by ICP-MS after solid phase preconcentration with chelating resin fibers and anion exchanger filters.

A solid phase collection/concentration method using anion exchanger filters and a small syringe packed with chelating resin fibers is adopted as a preconcentration tool for trace elements and a separation tool for matrices in aqueous samples prior to the measurement by inductively coupled plasma-mass spectrometry (ICP-MS). The effects of fiber volume, sample volume, eluent volume, and sample flow rate on metal recoveries were investigated in detail to obtain optimum pretreatment conditions. Several heavy metals (HMs) such as, V, Mn, Co, Ni, Cu, Zn, Ga, Cd, Pb, Th and U, as well as 14 rare earth elements (REEs) in sample solutions at pH 6 were quantitatively collected on the solid phase. These adsorbed elements were completely recovered by eluting with 2 ml of 1.0 M nitric acid. At pH 6, more than 99% of alkali and alkaline earth metals in sample solutions were eliminated. The proposed method was evaluated by analyzing two standard reference materials (SRM): peach leaves (NIST 1547) and pond sediment (NIES No. 2). The solid samples were decomposed by microwave-heating and pressurizing acid digestion technique, and then treated by the proposed syringe-type pretreatment method, followed by the ICP-MS measurement. The analytical results for HMs in the SRMs obtained by the present method agreed well with the certified values.     

Tannin Content in Vitis Species Red Wines Quantified Using Three Analytical Methods

Tannin content in red wines is positively correlated with astringency perception and wine grade; however, tannin quantification is one of the main challenges. In this study, tannin content was quantified using three analytical methods in commercial red wines from Vitis vinifera and interspecific cold-hardy hybrids including Marquette, Frontenac, and Petite pearl cultivars. Protein (PP) and methylcellulose precipitation (MCP) methods were compared to a HPLC-DAD method, which is based on the interaction between tannins and a hydrophobic surface (RPC). Frontenac wines were the poorest in tannins and Cabernet sauvignon wines were the richest regardless of the method used. In cold-hardy red wines, the tannin content was higher in Marquette with high alcohol content, which suggested that the tannins were extracted from seeds rather than skins. The high limit of quantification of the PP method and the presence of anthocyanin di-glucosides in cold-hardy wines were parameters suggesting that protein and methylcellulose precipitation methods were neither suitable nor reliable for the quantification of tannins in cold-hardy red wines. The tannin content quantified by RPC was positively correlated to tannin quantified by MCP, suggesting that the RPC method would be relevant for the quantification of tannins in red wines.     

The use of multiple correspondence analysis for the evaluation of inter-laboratory comparisons

Participation in inter-laboratory comparisons (ILC) is one of the recommended means of external quality control according to ISO/IEC 17025:2005. Providers of ILC or proficiency test (PT) schemes collect, besides the measurement results on the test samples, information on the sample treatment and measurement procedure. The objective of this paper is to evaluate in a non-traditional way, using numerical and non-numerical data provided by the participants in IMEP-20 (trace elements in tuna fish), the additional information concerning the applied analytical methods and the accreditation/nomination status. Arsenic was taken as an example. The basic statistical procedure for the evaluation of questionnaire information was the multiple correspondence analysis (MCA). Univariate clustering techniques were applied for the categorization of the numerical data (measurement values). The methodology of the evaluation of supplementary non-numeric information used in this paper might serve (a) to providers of ILC (PT) schemes to modify/improve their questionnaires and (b) to give laboratories better guidance in the methods used for the determination of various analytes in different matrices. This paper is meant serve as a guide for the possible interpretation of the questionnaires accompanying ILC schemas. Presented at the 3rd International Conference on Metrology, November 2006, Tel Aviv, Israel     

Characterization of the geographical origin of Italian red wines based on traditional and nuclear magnetic resonance spectrometric determinations

Chemical characterization of Italian red wines from different geographical locations in the Apulia, region of southern Italy, have been performed by means of chromatographic, analyses routine analyses (density, alcohol content, acidity, dry extract and ash content), inductively coupled plasma-atomic emission spectrometric measurements and nuclear magnetic resonance (¹H NMR) spectrometric determinations. Multivariate statistical methods were applied separately to the analytical and NMR data. The results showed that Apulian red wines are divided in three groups according to their geographical origin.     

New method for determination of (E)-resveratrol in wine based on microextraction using packed sorbent and ultra-performance liquid chromatography

An ultra-fast and improved analytical methodology based on microextraction by packed sorbent (MEPS) combined with ultra-performance LC (UPLC) was developed and validated for determination of (E)-resveratrol in wines. Important factors affecting the performance of MEPS such as the type of sorbent material (C2, C8, C18, SIL, and M1), number of extraction cycles, and sample volume were studied. The optimal conditions of MEPS extraction were obtained using C8 sorbent and small sample volumes (50-250 μL) in one extraction cycle (extract-discard) and in a short time period (about 3 min for the entire sample preparation step). (E)-Resveratrol was eluted by 1×250 μL of the mixture containing 95% methanol and 5% water, and the separation was carried out on a high-strength silica HSS T3 analytical column (100 mm × 2.1 mm, 1.8 μm particle size) using a binary mobile phase composed of aqueous 0.1% formic acid (eluent A) and methanol (eluent B) in the gradient elution mode (10 min of total analysis). The method was fully validated in terms of linearity, detection (LOD) and quantification (LOQ) limits, extraction yield, accuracy, and inter/intra-day precision, using a Madeira wine sample (ET) spiked with (E)-resveratrol at concentration levels ranging from 5 to 60 μg/mL. Validation experiments revealed very good recovery rate of 95±5.8% RSD, good linearity with r(2) values >0.999 within the established concentration range, excellent repeatability (0.52%), and reproducibility (1.67%) values (expressed as RSD), thus demonstrating the robustness and accuracy of the MEPS(C8) /UPLC-photodiode array (PDA) method. The LOD of the method was 0.21 μg/mL, whereas the LOQ was 0.68 μg/mL. The validated methodology was applied to 30 commercial wines (24 red wines and six white wines) from different grape varieties, vintages, and regions. On the basis of the analytical validation, the MEPS(C8)/UPLC-PDA methodology shows to be an improved, sensitive, and ultra-fast approach for determination of (E)-resveratrol in wines with high resolving power within 6 min.     

Assessment of reproducibility and uncertainty of food microbiology methods: statistical approach of a multi-site laboratory

The validation of food microbiology methods and assessment of measurement uncertainty are required for laboratories operating EN ISO/IEC 17025 accreditation systems. This paper aims to describes the statistical approach adopted by a multi-site laboratory to satisfy these requirements and to routinely check the performance of the methods. A validation protocol was performed, reflecting a great variability of experimental conditions, represented by the period of time during which determinations were made, the different laboratories concerned, the large number of technicians involved, the differences in the level of contamination of the matrix analyzed and the operating conditions (equipment, reagents, culture media, environmental conditions, etc.). Despite the very high variability of the experimental conditions, the values of repeatability and reproducibility obtained for the methods were lower than those stated in the respective regulations. In addition, the top-down approach adopted in this study is to be considered effective overtime and allows to randomize all variable factors, including the effects of sensitivity and specificity, in order to simulate the conditions of real reproducibility. A specific Excel spreadsheet was also developed for the routine expression of analytical results. This spreadsheet represents a very useful tool for operators to calculate and routinely check the results, as well as to assess the uncertainty of measurement. This particular quality assessment system is enabling the multi-site laboratory to implement the accuracy, reliability and comparability of the analytical results and to ensure the analytical control of data output.     

Activation analysis of alkaline rocks. A comparison between destructive and non-destructive methods

The United States Geological Survey reference sample AGV-1 andesite, and three alkaline rocks from the apatite mine of Jacupiranga, Brasil, were analyzed by thermal neutron activation analysis using destructive and non-destructive methods, and high resolution Ge(Li) gamma-ray detectors. One of the rocks, a carbonatite, was also analyzed by instrumental activation analysis with epithermal neutrons. A greater number of elements can be determined using the radiochemical separation, but the precision and accuracy attained by INAA and RNAA were of the same order for most of the elements analyzed. Epithermal activation was more advantageous for tantalum, terbium and holmium. Comparison of the analytical results for USGS reference sample (AGV-1) with the data published by others gave good agreement. Statistical tests used for comparison of the results of destructive and non-destructive methods, as well as other results are presented.     

电感耦合等离子体原子发射光谱（ICP-AES）法测定铁矿石中钒

建立了电感耦合等离子体原子发射光谱(ICP-AES)法测定铁矿石中钒含量的分析方法。采用盐酸、硝酸、氢氟酸、高氯酸分解试样,不溶物残渣碱熔融回收,稀盐酸溶解盐类的方式对样品进行分解。对仪器的主要工作参数和分析谱线进行了选择,讨论了基体和共存元素的干扰,以及溶解酸和熔剂等条件实验,确立了最佳分析条件。按实验方法对铁矿石标准样品和试样中钒量进行测定,测定值与标准值或其它方法的认定值基本一致,相对标准偏差RSD<6.5%。     

Validation of two analytical methods for the determination of ochratoxin A by reversed-phased high-performance liquid chromatography coupled to fluorescence detection in musts and sweet wines from Andalusia

Some Spanish sweet wines are made from raisins, grapes dried by direct exposure to the sun after picking. This drying process can encourage ochratoxin A (OTA) formation. OTA is a mycotoxin formed by several fungi. It has been linked to nephropathy in humans, and may have a long half-life in humans. The aim of this study is to develop and to apply two procedures for the analysis of OTA in grape musts (during the raisining process) and sweet wines, respectively. Reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to fluorescence detection (FLD) was employed in both analytical methods. In grape must, the method involves the direct injection of the sample in a HPLC-FLD system without any kind of prior clean-up procedure. The complexity of the sweet wine samples requires a solid-phase extraction (SPE) clean-up on a C18 column which enables the OTA to be isolated from the matrix. The methods used were statistically validated. The validation also included the comparison of the slopes of the curve obtained with standards and the regression curves obtained by the addition of a standard. Two different studies of standard additions were conducted. One method was validated without sample preparation and it was applied to must samples. The other method was validated with SPE extraction and it was applied to sweet wine samples. Recovery was always better than 89.69%. The limit of detection (S/N = 3) and limit of quantification (S/N = 10) were established at 0.22 and 0.77 μg l⁻¹, respectively. In general, the analytical data obtained provided good results at the sub-μg l⁻¹ concentration level.     

Spectroscopic interferences in Fourier transform infrared wine analysis

Fourier transform infrared (FTIR) spectrometry has brought many advantages to wine analysis, such as fast analysis and good precision and accuracy for a great number of parameters. This technology has to be cautiously applied, therefore the need for analytical validation. Recovery results of several current wine control parameters using a FTIR wine analyser were determined. Good results were obtained for ethanol (addition of ethanol), total acid (addition of tartaric acid), total sugars in sweet wines (addition of glucose) and sulfate (addition of sulfuric acid). On the contrary, worse results were obtained for total acid (addition of acetic and sulfuric acids), volatile acid (addition of acetic acid) and total sugars in dry wines (addition of glucose). These findings can be explained by spectroscopic interferences that were also a subject of analysis in this work. In fact, ethanol, organic acids and other compounds, present in high concentrations in wine, can produce major interferences in the analysis for compounds such as volatile acid and sugars in dry wines, when their strong infrared absorption bands do not differ significantly from other abundant compounds.