The Influence of the Soil Profile on the Formation of the Elemental Image of Grapes and Wine of the Cabernet Sauvignon Variety.

The features for assessing the authenticity of wines by region of origin are studied, based on the relationship between the mineral composition of the wine, the grapes, and the soil profile (0 to 160 cm) from the place of growth of Cabernet Sauvignon grapes. Soil, grape, and wine samples were taken from the territories of six vineyards in the Anapa district of Krasnodar Territory, Russia. Using the methods of ICP-OES, thermal, and X-ray phase analysis, the soils were differentiated into three groups, differing in mineralogical and mineral compositions. The soil samples of the first group contained up to 31% quartz, the second group up to 25% quartz and 19% mixed calcite, and the third group up to 32% calcite and 15% quartz. The formation of the elemental image of the grapes was studied, taking into account the total content and mobile forms of metals in the soil. The territorial proximity of the vineyards did not affect the extraction of elements from the soil into the grape berry, and the migration of metals for each territory was selective. According to the values of the biological absorption coefficient, the degree of transition of metals from the soil to a berry was estimated. For K, Ti, Zn, Rb, Cu, and Fe in all berries, the coefficient was higher than 1.00, which means that the berry extracts contained not only mobile-form, but also difficult-to-dissolve metal compounds. The migration of macro-components from the soil to the berry was low, and amounted to 6-7% for Ca, 0.8-3.0% for Na, and 25-70% for Mg of the concentration of their mobile forms. For all territories, the maximum correlation between metal concentrations in grapes and soil was observed for samples from a depth of 0-40 cm. The discriminant model based on concentrations of Rb, Al, K, Sr, Co, Na, Pb, Ca, and Ni showed the formation of clusters in the territories of vineyard cultivation. The developed model allow the problems of identifying wines by region to be solved with high accuracy, using their elemental image.

Possibilities and Limitations of ICP-Spectrometric Determination of the Total Content of Tin, Its Inorganic and Organic Speciations in Waters with Different Salinity Levels-Part 1: Determination of the Total Tin Content.

This paper considers the features of determining the total tin content in waters with different salinity. Direct ICP-spectrometric analysis of sea waters with a salinity of more than 6‱ significantly reduced the analytical signal of tin by 70% (ICP-MS) and 30% (ICP-OES). The matrix effect of macrocomponents was eliminated by generating hydrides using 0.50 M sodium borohydride and 0.10 M hydrochloric acid. The effect of transition metals on the formation of tin hydrides was eliminated by applying L-cysteine at a concentration of 0.75 g/L. The total analyte concentrations, considering the content of organotin compounds, were determined after microwave digestion of sample with oxidizing mixtures based on nitric acid. The generation of hydrides with the ICP-spectrometric determination of tin leveled the influence of the sea water matrix and reduced its detection limit from 0.50 up to 0.05 µg/L for all digestion schemes. The developed analysis scheme made it possible to determine the total content of inorganic and organic forms of tin in sea waters. The total content of tin was determined in the waters of the Azov and Black seas at the levels of 0.17 and 0.24 µg/L, respectively.

Possibilities and Limitations of ICP-Spectrometric Determination of the Total Content of Tin and Its Inorganic and Organic Speciations in Waters with Different Salinity Levels-Part 2: Separate Determination of Inorganic and Organic Speciations of Tin.

In this study, determination of the inorganic and organic forms of tin in waters of different salinities is considered. The possibility of the separation of speciations of tin using liquid-liquid extraction (LLE); precipitation with fluorides, iodides, ammonia, and iron (III) chloride; and sorption of organotin compounds (OTCs) was studied. The LLE and analyte precipitation methods proved to be ineffective. Inorganic and organic forms of tin were separated by the sorption of OTCs using silica gel sorbent Diapak C18. Under optimized conditions, a technique for the separate determination of the forms of tin in natural waters was developed. The technique combines hydride generation and microwave mineralization of solutions followed by ICP spectrometry. The inorganic forms of tin were determined after their solid-phase separation from organotin compounds. The lower limits of analyte quantification were 0.03 µg/L (ICP-MS) and 0.05 µg/L (ICP-OES), which provide separate determinations of inorganic and organic forms of tin in waters with different salinities. The content of OTCs in water was determined by subtracting the inorganic concentration from the total concentration of tin. The technique will allow a comprehensive assessment of the toxicological impact of tin speciations on the aquatic ecosystem.

Can Rare Earth Elements Be Considered as Markers of the Varietal and Geographical Origin of Wines?

The possibility of establishing the varietal and territorial affiliation of wines by the content of rare earth elements (REE) in them was studied. ICP-OES and ICP-MS with subsequent chemometric processing of the results were applied to determine the elemental image of soils containing negligible REE amounts, grapes grown on these soils, and wine materials of Cabernet Sauvignon, Merlot, and Moldova varieties produced from these grapes. To stabilize and clarify wine materials, the traditional processing of wine materials with various types of bentonite clays (BT) was used, which turned out to be a source of REE in the wine material. Discriminant analysis revealed that the processed wine materials were homogeneous within one denomination and that those of different denominations were heterogeneous with respect to the content of REE. It was found that REE in wine materials were transferred from BT during the processing, and thus they can poorly characterize the geographical origin and varietal affiliation of wines. Analysis of these wine materials according to the intrinsic concentrations of macro- and microelements showed that they formed clusters according to their varietal affiliation. In terms of their influence on the varietal image of wine materials, REE are significantly inferior to macro- and microelements, but they enhance their influence to a certain extent when used together.

A Novel Method for the Background Signal Correction in SP-ICP-MS Analysis of the Sizes of Titanium Dioxide Nanoparticles in Cosmetic Samples.

We discuss the features involved in determining the titanium dioxide nanoparticle (TiO2NP) sizes in cosmetic samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) in the millisecond-time resolution mode, and methods for considering the background signal. In the SP-ICP-MS determination of TiO2NPs in cosmetics, the background signal was recorded in each dwell time interval due to the signal of the Ti dissolved form in deionized water, and the background signal of the cosmetic matrix was compensated by dilution. A correction procedure for the frequency and intensity of the background signal is proposed, which differs from the known procedures due to its correction by the standard deviation above the background signal. Background signals were removed from the sample signal distribution using the deionized water signal distribution. Data processing was carried out using Microsoft Office Excel and SPCal software. The distributions of NP signals in cosmetic product samples were studied in the dwell time range of 4-20 ms. The limit of detection of the NP size (LODsize) with the proposed background signal correction procedure was 71 nm. For the studied samples, the LODsize did not depend on the threshold of the background signal and was determined by the sensitivity of the mass spectrometer.

Simultaneous Dispersive Liquid-Liquid Microextraction and Determination of Different Polycyclic Aromatic Hydrocarbons in Surface Water.

Polycyclic aromatic hydrocarbons (PAHs) are a class of persistent organic pollutants of water, and their determination at trace levels in the aquatic ecosystems is essential. In this work, an ultrasound-assisted dispersive liquid-liquid microextraction (DLLME) procedure was suggested utilizing a binary dispersive agent for recovery of different molecular weight polycyclic aromatic hydrocarbons (PAHs) from waters. The detection was carried out by gas chromatography-mass spectrometry (GC-MS) as well as high-performance liquid chromatography with fluorescence and diode-array detection (HPLC-FD/PDA). The method was optimized for the extraction of analytes with respect to the mixture composition, ratios of components, ultrasonication time and centrifugation parameters. The analytical schemes for PAHs extraction from water samples using different ratios of extraction and dispersive solvents are reported. The mixture consisting of chloroform and methanol was applied for the extraction of PAHs containing two or three fused aromatic rings; the mixture of chloroform and acetonitrile is suitable for PAHs containing more than four aromatic rings. The mixture of chloroform:acetone + acetonitrile was applied in the universal scheme and allowed for the simultaneous extraction of 20 PAHs with different structures. The developed sample preparation schemes were combined with GC-MS and HPLC-FD/PDA, which allowed us to determine the analytes at low concentrations (from 0.0002 µg/L) with the recoveries exceeding 80% and relative standard deviations of about 8%. The developed methods for the determination of 20 PAHs were applied to the analysis of water samples from the Karasun Lake (Krasnodar), Azov Sea (Temryuk) and Black Sea (Sochi).

Authentication of selected white wines by geographical origin using ICP spectrometric and chemometric analysis.

An important aspect of assessing the authenticity of wines is its geographical origin. The aim of the work is to authenticate by geographical origin according to the data of the ICP-spectrometric and chemometric analysis of elemental "images" of wines produced from white grape varieties Chardonnay, Riesling and Muscat grown in four regions of the Krasnodar Territory, Russia. The difference in the contents of Al, Ba, Ca and Rb in wines was found depending on the variety, and Al, Ba, Rb, Fe, Li, Sr - depending on the region of grape growth. Different models of the experimental data processing were used for attribution of the produced varieties of wine to the area of the grape's growth. The criterion for the quality of the constructed models was the accuracy of the attribution of a wine variety to the area of the grape's growth (%). Analysis of the elemental analysis data of 153 wine samples showed that in terms of attribution accuracy, automated neural networks (100 %) are preferred among machine learning methods, followed by support vector machines (98.69 %) and general discriminant analysis (94.77 %). The applied mathematical models enabled the revealing of the cluster structure of the analyzed wine varieties and their attribution to the area of a grape growth with high accuracy. Sr, Li and Fe concentrations in wines were found as the dominating predictors in the constructed models for definition of the geographical origin of wines. The combination of ICP-spectrometric analysis data with the capabilities of statistical modeling of machine learning methods focused on large-dimensional data made it possible to successfully solve small-dimensional problems of the definition of the geographical origin of wines by their elemental composition and variety.

Multidimensional analysis of the interaction of volatile compounds and amino acids in the formation of sensory properties of natural wine.

The content of free amino acids and aroma compounds present in wine and dependent on the grape variety, conditions of its growing and technology of production form its consumer properties. In this paper, the structure of interactions of amino acids and volatile organic compounds in 150 samples of natural dry red and white wines produced in the Krasnodar region, Russia, (2010-2013) was studied. The aim of this work was to comparatively evaluate the contribution of volatile compounds and amino acids to the sensory properties of wines by using regression, canonical, covariance, factor analyses, as well as principal component analysis. The list of volatile compounds, i.e., acetaldehyde, ethyl acetate, methanol, the total content of higher alcohols, acetic acid, and furfural, and such amino acids as arginine, proline, threonine was selected based on their influence on sensory properties of wines. The concentrations of volatile compounds and amino acids in wines were determined by gas chromatography and capillary electrophoresis, respectively. Sensory evaluation was conducted by experts with professional experience in wine tasting. Application of statistical methods allowed to establish intra- and inter-group correlations among amino acids and volatile compounds as well as between the groups of these compounds, which determined sensory properties of wines. More than 80% of the variability of the sensory assessment of wines is determined by the degree of relationship between the selected amino acids and volatile compounds; the contribution of amino acids to this indicator is 4.5-fold higher. The results obtained can be used to predict the sensory assessment of red and white wines based on the levels of volatile compounds and amino acids.

Data on the influence of clarification and stabilization with bentonite clays on the elemental composition of red wines determining their varietal affiliation.

The research data on the effect of bentonite clays (BT) in the process of clarification and stabilization on the elemental composition determining the varietal affiliation of wines are analyzed in the article. The initial objects were three untreated wine samples produced from Cabernet Sauvignon, Merlot and Moldova grape varieties in the Krasnodar Territory. Clarification and stabilization of untreated wine samples was carried out with 32 samples of BT of various degrees of dispersion and trademarks. The concentrations of metals, i.e., macro- and microelements, in bentonite clays, untreated and treated wine samples were determined by ICP-OES and ICP-MS methods. The results of the influence of stabilization and clarification of various wines with 32 BT on their elemental composition based on the concentrations of 16 micro- and macroelements isolated chemometrically from 39 elements are shown in the article. The elemental composition of the initial wine varieties as well as wine samples obtained after their clarification and stabilization (32 samples per each variety) was established based on the results of three parallel measurements. The aim of the study was to assess the contribution of macro- and microelements to the formation of the elemental image of wines determining their varietal affiliation. Using discriminant analysis and principal component analysis, the presence of cluster structures in treated and untreated wine samples was established in accordance with their varieties with respect to the concentrations of isolated macro- and microelements. The role of microelements was shown to be higher than that of macroelements in the formation of varietal image of wines. The combination of the most informative macro- and microelements in determining the cluster structure of wine samples increases the possibilities of assessing the intravarietal similarity and intervarietal differences of wines.

The method of establishing the authenticity and quality of Hypericum perforatum L. and Salvia officinalis L.

The paper presents methods for the criteria for quality control, authenticity and stability of preparations and raw materials based on Hypericum perforatum L. and Salvia officinalis L. Various methods of extracting the most valuable components that make up the studied plants, as well as methods for their chromatographic determination, were proposed, metrological characteristics were obtained.•The criteria for quality control and stability of drugs and raw materials were substantiated•The ratio of rutin to hyperforin determines the quality of Hypericum perforatum L.•The ratio of carnosic acid to carnosol characterizes Salvia officinalis L.

Data on the sensory evaluation of the dry red and white wines quality obtained by traditional technologies from European and hybrid grape varieties in the Krasnodar Territory, Russia.

The analysis of data on the sensory evaluation of the quality of wines obtained using traditional technologies in the Krasnodar Territory, Russia, was carried out using the statistical ranking criteria - the Spearman and Kendall correlation coefficients, as well as the positional analysis - Cronbach's alpha. Data on the sensory evaluation of 60 samples of natural dry red and white wines are presented, among which 20 are white wines, 40 are red wines produced in 2010-2015. Eleven specialists aged between 32 and 66 years (the average age was 50 years; 4 females and 7 males) participated in the sensory evaluation procedure. All participants are considered experts in the field of wine, work in the wine industry and have professional experience in the field of sensory analysis. The results of the consistency study of expert evaluations, the reliability of the general score scale, as well as the analysis of the loyalty of experts in the wine quality assessment are presented in the article. The reliability of the proposed loyalty scale is shown, i.e., the scale of the sum of scores given by each expert in the evaluation of the quality of wines. The database on the sensory evaluation of the quality of wines, obtained for all wine samples using positional analysis, makes it possible to assess the contribution of each of the 60 wine samples to their ranking by mean scores. The data may be of interest to scientists and oenologists for the wine quality assessment.

A novel photochemical vapor generator for ICP-MS determination of As, Bi, Hg, Sb, Se and Te.

A scheme of determination of As, Bi, Hg, Sb, Se and Te with photochemical generation of their volatile derivatives and inductively coupled plasma mass spectrometry (ICP-MS) detection was developed. The volatile compounds were produced using a novel photochemical reactor with direct contact of a sample with an ultraviolet (UV) lamp. Essential experimental parameters such as the concentrations of the reagents and the flow rates of the carrier gas and the sample were optimized. For each element, individual optimum values of these parameters were obtained. The detection limits in the optimal single element modes for As, Bi, Hg, Sb, Se and Te were 0.5, 13, 0.6, 0.3, 0.4 and 0.7 ng L-1 respectively. Compromise conditions were determined for simultaneous multielement analysis. The increase of the detection limit for each element in the multielement mode was experimentally estimated. The applicability of the proposed scheme was demonstrated by analysis of certified reference samples of water and fish muscle. Acceptable accuracy of determination of As, Se, Sb, Te and Hg in samples of local lake water was proved by spike recovery test. Possible matrix effects were screened using Placket-Berman design and further examined in detail.