КОМПЬЮТЕРНЫЙ АНАЛИЗ ЭКСПЕРТНОЙ ОЦЕНКИ ОРГАНОЛЕПТИЧЕСКОГО ПОКАЗАТЕЛЯ КАЧЕСТВА ВИН

The objects of the current research were the samples of grape wines, wine materials, sparkling wines and wine beverages of the Kuban origin. A group of experts with the specialized education and years of experience in the wine industry conducted a working tasting of these drinks on a 100-point scale in "North-Caucasian Zonal Research Institute of Horticulture and Viticulture" (Krasnodar). It was shown that in the absence of agreement among the experts the results of the current examination would not reflect the actual status of the objects of investigation. This paper explored the possibility of computer data analysis when assessing the unanimity of experts and ranking the samples of wine products. Calculations were performed with the STATISTICA software package using "Descriptive statistics", "Reliability and positional analysis, Friedman rank analysis of variance" and "Cluster analysis" (hierarchical classification procedure) modules through which the consensus of experts and the scope of their applicability in assessing the quality of test samples were evaluated. By using Friedman rank analysis of variance a consensus of experts was calculated, the method of reliability and positional analysis allowed determining the contribution of each expert in the evaluation of the reliability of wine tasting, the advantages of Cronbach's alpha statistics in evaluating the consensus of tasters was shown, and by method of hierarchical classification and multidimensional scaling the full ranking of samples of wine products was performed.Keywords: grape wine, organoleptic analysis, computer analysis of the consensus of experts.DOI: http://dx.doi.org/10.15826/analitika.2017.21.2.010A.A. Khalaphyan1, Z.А. Temerdashev1, T.I. Guguchkina2, Yu.Th. Yakuba21Kuban state university, ul. Stavropol, 149, Krasnodar, 350040, Russian Federation,2The North Caucasian zonary scientific research institute of Horticulture and Viticulture, ul 40-letiia Pobedy, 39, Krasnodar, 350901, Russian FederationОбъектами исследования были образцы виноградных вин, виноматериалов, игристых вин и винных напитков кубанских производителей. Группой специалистов, имеющих профильное образование и многолетний опыт работы в винодельческой отрасли, была проведена рабочая дегустация этих напитков по 100-балльной системе в «Северо-Кавказском зональном научно-исследовательском институте садоводства и виноградарства» (г. Краснодар). Показано, что при отсутствии согласия среди экспертов результаты экспертизы не будут отражать действительное состояние объектов исследования. В работе исследуются возможности компьютерного анализа данных при оценке единодушия экспертов и ранжировании образцов винодельческой продукции. Вычисления проведены в среде пакета STATISTICA с использованием модулей «Описательные статистики», «Надежность и позиционный анализ», «Ранговый дисперсионный анализ Фридмана» и «Кластерный анализ» (процедура иерархическая классификация), посредством которых осуществлена оценка единодушия экспертов и области их применимости при оценке качества испытуемых образцов. Посредством рангового дисперсионного анализа Фридмана  оценено единодушие экспертов; методом надежность и позиционный анализ определен вклад каждого эксперта в оценку надежности дегустации вин, показаны преимущества статистики альфа Кронбаха при оценке единодушия дегустаторов; методом иерархической классификации и многомерного шкалирования проведено ранжирование образцов винной продукции.Ключевые слова: виноградные вина, дегустационные оценки, компьютерный анализ единодушия экспертов DOI: http://dx.doi.org/10.15826/analitika.2017.21.2.01

ГРАФИЧЕСКИЙ ОБРАЗ ВЫСОКОКАЧЕСТВЕННЫХ ВИН

The objects of the research were samples of high quality wines of various types produced by the enterprises of the Krasnodar Territory, the Rostov Region and foreign producers of different grape varieties. The method of automatic titration of acids in wines was applied by coulometric generation of the base with the recording of the results of potentiometric indication on the computer. The influence of the grape variety and the duration of aging of table wine on the appearance of the titration curves was carried out using 77 technical grades and clones of grapes (44 red grapes and 33 white grapes) from the Anapsko-Tamanskaya zone of the Krasnodar Territory from 2001 to 2016. Grapes of the studied varieties were processed under the micro nodulation conditions according to two schemes. Dry table red wines were obtained by fermentation on the mash. Dry table white wines were produced using the high quality low-oxidized wines. The experimental studies confirming the individuality of the titration curves and the absorption spectra of wine samples for specific brands have been carried out. The principal possibility was shown of using the coordinates of the titration curve of a wine sample for establishing a relationship with the grape variety and the authenticity of the production of wines with the protected geographical indication and appellation of origin. To confirm the authenticity of the wine products, it was suggested to compare the data matrix with the coordinates describing the average titration curve of a specific wine product obtained by the manufacturer with a similar matrix obtained by the controlling party under the reproducibility conditions. When the appearance of the titration curves of red wines obtained from different grape varieties was identical, it was suggested to additionally apply a matrix of data describing the absorption spectrum in the visible region.Key words: organic acids, authenticity of wines, potentiometric titration curves, spectral characteristicsDOI: http://dx.doi.org/10.15826/analitika.2018.22.3.003(Russian)O.N. Shelud`ko1,2, N.K. Strizhov2, T.I. Guguchkina1, T.V. Guzik2 1Northern-Caucasian Federal Scientific Center for Horticulture, Viticulture, Winemaking. Russian Federation,  350901, Krasnodar,40th Anniversary of the Victory st., 392Kuban State Technological University,  Russian Federation, 350072, Krasnodar, Moscow st.,2Объектами исследований были образцы высококачественных вин различных типов, выработанных предприятиями Краснодарского края, Ростовской области и зарубежными производителями из разных сортов винограда. Применяли метод автоматического титрования кислот в винах путем кулонометрической генерации основания с записью результатов потенциометрической индикации на компьютере. Оценку влияния сорта винограда и продолжительности хранения столового сухого вина на вид кривых титрования проводили на 77 технических сортах и клонах винограда (44 красных и 33 белых), районированных в Анапско-Таманской зоне Краснодарского Края в период с 2001 по 2016 гг. Виноград изучаемых сортов перерабатывали в условиях микровиноделия по двум схемам. Столовые красные сухие вина получали брожением на мезге. Столовые белые сухие вина получали по технологии высококачественных малоокисленных вин. Проведены экспериментальные исследования, подтверждающие индивидуальность кривой потенциометрического титрования и спектров поглощения проб вина конкретного наименования. Показана принципиальная возможность по координатам кривой титрования пробы вина устанавливать связь с сортом винограда и подлинностью производства вин с защищенными географическими указанием и наименованием места происхождения. Для подтверждения подлинности винодельческой продукции предложено сравнивать матрицу данных с координатами, описывающими среднюю кривую титрования конкретной винодельческой продукции, полученную производителем, с аналогичной матрицей, полученной контролирующей стороной, в условиях воспроизводимости. При близости вида кривых титрования проб вин, полученных из красных сортов винограда, предложено дополнительно прилагать матрицу данных, описывающих спектр поглощения в видимой области.Ключевые слова: органические кислоты, подлинность вин, кривые потенциометрического титрования, спектральные характеристикиDOI: http://dx.doi.org/10.15826/analitika.2018.22.3.00

Graphic image of high quality wines

The objects of the research were samples of high quality wines of various types produced by the enterprises of the Krasnodar Territory, the Rostov Region and foreign producers of different grape varieties. The method of automatic titration of acids in wines was applied by coulometric generation of the base with the recording of the results of potentiometric indication on the computer. The influence of the grape variety and the duration of aging of table wine on the appearance of the titration curves was carried out using 77 technical grades and clones of grapes (44 red grapes and 33 white grapes) from the Anapsko-Tamanskaya zone of the Krasnodar Territory from 2001 to 2016. Grapes of the studied varieties were processed under the micro nodulation conditions according to two schemes. Dry table red wines were obtained by fermentation on the mash. Dry table white wines were produced using the high quality low-oxidized wines. The experimental studies confirming the individuality of the titration curves and the absorption spectra of wine samples for specific brands have been carried out. The principal possibility was shown of using the coordinates of the titration curve of a wine sample for establishing a relationship with the grape variety and the authenticity of the production of wines with the protected geographical indication and appellation of origin. To confirm the authenticity of the wine products, it was suggested to compare the data matrix with the coordinates describing the average titration curve of a specific wine product obtained by the manufacturer with a similar matrix obtained by the controlling party under the reproducibility conditions. When the appearance of the titration curves of red wines obtained from different grape varieties was identical, it was suggested to additionally apply a matrix of data describing the absorption spectrum in the visible region.Объектами исследований были образцы высококачественных вин различных типов, выработанных предприятиями Краснодарского края, Ростовской области и зарубежными производителями из разных сортов винограда. Применяли метод автоматического титрования кислот в винах путем кулонометрической генерации основания с записью результатов потенциометрической индикации на компьютере. Оценку влияния сорта винограда и продолжительности хранения столового сухого вина на вид кривых титрования проводили на 77 технических сортах и клонах винограда (44 красных и 33 белых), районированных в Анапско-Таманской зоне Краснодарского Края в период с 2001 по 2016 гг. Виноград изучаемых сортов перерабатывали в условиях микровиноделия по двум схемам. Столовые красные сухие вина получали брожением на мезге. Столовые белые сухие вина получали по технологии высококачественных малоокисленных вин. Проведены экспериментальные исследования, подтверждающие индивидуальность кривой потенциометрического титрования и спектров поглощения проб вина конкретного наименования. Показана принципиальная возможность по координатам кривой титрования пробы вина устанавливать связь с сортом винограда и подлинностью производства вин с защищенными географическими указанием и наименованием места происхождения. Для подтверждения подлинности винодельческой продукции предложено сравнивать матрицу данных с координатами, описывающими среднюю кривую титрования конкретной винодельческой продукции, полученную производителем, с аналогичной матрицей, полученной контролирующей стороной, в условиях воспроизводимости. При близости вида кривых титрования проб вин, полученных из красных сортов винограда, предложено дополнительно прилагать матрицу данных, описывающих спектр поглощения в видимой области

Colour and quality peculiarities of induced red variety of anchellote grape for manufacturing qualitative wine materials

It is established that the introduced Anchellotte grape variety corresponds to the requirements of GOST 32030-2013 by organoleptic and physicochemical parameters. The qualitative indicators of wort and wine material from Anchellotte variety are determined in comparison with the control Saperavi variety. Tasting assessment confirmed the viability of the Anchellotte grape variety as a raw material for the production of quality red wines

New approach for wine authenticity screening by a cumulative

New methodological approach for rapid control of wine authenticity without sample preparation, based on the quantitative NMR spectroscopy (qNMR) of the protium 1H and deuterium 2H nucleus is suggested. The content of dominant (e.g. water, ethanol) and some minor (e.g. glycerol, organic acids) components of wine are determined from qNMR 1H spectra for authentication of molecular composition. The sum of all exchanging hydrogen atoms of wine's components provide the 1H signal with a chemical shift of 4.8 ppm. Accounting for their content from 1H spectrum allows us calculate the 2H isotopic content in wine water from integral intensity of corresponding signal in the 2H qNMR spectrum using an internal or external standard with a known content of the 2H isotope. The possible addition of water can be found from comparison of this value with values of surface and/or ground waters from corresponding viticulture areas. This approach was used for white and red wines from the Black Sea region (Krasnodar area & Crimea peninsula). The 2H contents in investigated wines range from 157 to 165 ppm. The maximum 2H isotope content in surface waters does not exceed 148 ppm. A qNMR measurement of wine according to the proposed approach takes some minutes, that significantly exceeds the laboriousness of methods based on IRMS/SIRA (e.g. δ13C, δ18O). The error of qNMR measurements is less than 2.0%. The qNMR screening of deuterium (2H) in ethanol can be used for detection of possible wine chaptalization. This approach is similar to the known SNIF-NMR method. The positive difference with this method is the use of minimal quantity of enriched 2H standard and measurement of integral intensities of all signals instead of heights. It allows to reduce measurements' time as well as to measure the 2H content of all fragments of ethanol molecules – CH3−, CH2−, OH-groups. The publication has been prepared with the support of the “RUDN University Program 5–100”

Сompute analysis of the expert evaluation of the organoleptic indexes of quality of wines

The objects of the current research were the samples of grape wines, wine materials, sparkling wines and wine beverages of the Kuban origin. A group of experts with the specialized education and years of experience in the wine industry conducted a working tasting of these drinks on a 100-point scale in “North-Caucasian Zonal Research Institute of Horticulture and Viticulture” (Krasnodar). It was shown that in the absence of agreement among the experts the results of the current examination would not reflect the actual status of the objects of investigation. This paper explored the possibility of computer data analysis when assessing the unanimity of experts and ranking the samples of wine products. Calculations were performed with the STATISTICA software package using “Descriptive statistics”, “Reliability and positional analysis, Friedman rank analysis of variance” and “Cluster analysis” (hierarchical classification procedure) modules through which the consensus of experts and the scope of their applicability in assessing the quality of test samples were evaluated. By using Friedman rank analysis of variance a consensus of experts was calculated, the method of reliability and positional analysis allowed determining the contribution of each expert in the evaluation of the reliability of wine tasting, the advantages of Cronbach’s alpha statistics in evaluating the consensus of tasters was shown, and by method of hierarchical classification and multidimensional scaling the full ranking of samples of wine products was performed.Объектами исследования были образцы виноградных вин, виноматериалов, игристых вин и винных напитков кубанских производителей. Группой специалистов, имеющих профильное образование и многолетний опыт работы в винодельческой отрасли, была проведена рабочая дегустация этих напитков по 100-балльной системе в «Северо-Кавказском зональном научно-исследовательском институте садоводства и виноградарства» (г. Краснодар). Показано, что при отсутствии согласия среди экспертов результаты экспертизы не будут отражать действительное состояние объектов исследования. В работе исследуются возможности компьютерного анализа данных при оценке единодушия экспертов и ранжировании образцов винодельческой продукции. Вычисления проведены в среде пакета STATISTICA с использованием модулей «Описательные статистики», «Надежность и позиционный анализ», «Ранговый дисперсионный анализ Фридмана» и «Кластерный анализ» (процедура иерархическая классификация), посредством которых осуществлена оценка единодушия экспертов и области их применимости при оценке качества испытуемых образцов. Посредством рангового дисперсионного анализа Фридмана оценено единодушие экспертов; методом надежность и позиционный анализ определен вклад каждого эксперта в оценку надежности дегустации вин, показаны преимущества статистики альфа Кронбаха при оценке единодушия дегустаторов; методом иерархической классификации и многомерного шкалирования проведено ранжирование образцов винной продукции

Mass-spectrometric study on

The present study continues the 2015–2016 research project on biological characteristics of stable isotopes fractionation in grapes taking into account the agro-climatic growth conditions of this representative of the C3-pathway of photosynthesis group of plants in different geographical Black Sea regions. The first parts of the project were presented at the 39th and 40th Congresses of OIV in Bento Gonçalves (Brazil) and Sofia (Bulgaria). The scientific data on compositions of 13C/12C carbon and 18O/16O oxygen stable isotopes in carbohydrates, organic acids, and intracellular water were obtained for grapes of 2015–2016 growing seasons in the four areas of the Crimean peninsula as well as in several areas of the Don Basin and the Western Caspian region. This report presents the results of the 2017 season study of 13C/12C carbon and 18O/16O oxygen stable isotopes in carbohydrates and intracellular water of 12 red and white grape varieties (Aligote, Rkatsiteli, Sauvignon Zeleny, Chardonnay, Cabernet Sauvignon, Sauvignon Blanc, Merlot, Risling, Pinot Noir, Cabernet Franc, Sira, Krasnostop) as well as in ethanol of wines made from corresponding grapes from the Crimean Peninsula and South-West Coast of the Greater Caucasus. To measure the ratio of carbon isotopes 13C/12C in grape (must) carbohydrates and wine ethanol the Flash-Combustion technique (FC-IRMS/SIRA) has been used, while the method of isotopic equilibration (EQ-IRMS/SIRA) has been used for the measurement of 18O/16O oxygen isotopes ratio in the intracellular water of grapes (must) and in the water fraction of wine. The GC-Combustion technique (GC-IRMS/SIRA) has been used for the first time to measure the carbon isotopes 13C/12C distribution in ethanol of studied wines. It has been found that the δ13CVPDB values for carbohydrates of red and white grape varieties as a result of biological fractionation of carbon isotopes in the agro-climatic conditions of plant growth (2017 season) for the studied geographical areas formed the following quantitative ranges: from − 26.72 to − 23.35‰ (the Crimean Peninsula) and from − 25.92 to − 23.87‰ (South-West Coast of the Greater Caucasus). The δ13CVPDB values for wine ethanol are in the following ranges: from − 28.15 to − 24.47‰ (the Crimean Peninsula) and from − 27.29 to − 25.78‰ (South-West Coast of the Greater Caucasus). The δ18OVSMOW values in intracellular water of grapes of the 2017 season range from − 1.24 to 2.17‰ (the Crimean Peninsula) and from 1.08 to 4.09‰ (South-West Coast of the Greater Caucasus). The results of this study show, in comparison with the results of studies of the 2015 and 2016 seasons, a decrease in the δ13CVPDB values for carbohydrates of grapes and ethanol of wine, which is explained by the changed climatic conditions of grapes growing in the vegetation period of 2017

New approach for wine authenticity screening by a cumulative 1H and 2H qNMR

New methodological approach for rapid control of wine authenticity without sample preparation, based on the quantitative NMR spectroscopy (qNMR) of the protium 1H and deuterium 2H nucleus is suggested. The content of dominant (e.g. water, ethanol) and some minor (e.g. glycerol, organic acids) components of wine are determined from qNMR 1H spectra for authentication of molecular composition. The sum of all exchanging hydrogen atoms of wine's components provide the 1H signal with a chemical shift of 4.8 ppm. Accounting for their content from 1H spectrum allows us calculate the 2H isotopic content in wine water from integral intensity of corresponding signal in the 2H qNMR spectrum using an internal or external standard with a known content of the 2H isotope. The possible addition of water can be found from comparison of this value with values of surface and/or ground waters from corresponding viticulture areas. This approach was used for white and red wines from the Black Sea region (Krasnodar area & Crimea peninsula). The 2H contents in investigated wines range from 157 to 165 ppm. The maximum 2H isotope content in surface waters does not exceed 148 ppm. A qNMR measurement of wine according to the proposed approach takes some minutes, that significantly exceeds the laboriousness of methods based on IRMS/SIRA (e.g. δ13C, δ18O). The error of qNMR measurements is less than 2.0%. The qNMR screening of deuterium (2H) in ethanol can be used for detection of possible wine chaptalization. This approach is similar to the known SNIF-NMR method. The positive difference with this method is the use of minimal quantity of enriched 2H standard and measurement of integral intensities of all signals instead of heights. It allows to reduce measurements' time as well as to measure the 2H content of all fragments of ethanol molecules – CH3−, CH2−, OH-groups. The publication has been prepared with the support of the “RUDN University Program 5–100”

Mass-spectrometric study on13C/12C carbon and18O/16O oxygenstable isotopes distributions in grapes and wines from the BlackSea regions

The present study continues the 2015–2016 research project on biological characteristics of stableisotopes fractionation in grapes taking into account the agro-climatic growth conditions of this representativeof the C3-pathway of photosynthesis group of plants in different geographical Black Sea regions. The firstparts of the project were presented at the 39th and 40th Congresses of OIV in Bento Gonc ̧alves (Brazil) andSofia (Bulgaria). The scientific data on compositions of13C/12C carbon and18O/16O oxygen stable isotopes incarbohydrates, organic acids, and intracellular water were obtained for grapes of 2015–2016 growing seasonsin the four areas of the Crimean peninsula as well as in several areas of the Don Basin and the Western Caspianregion. This report presents the results of the 2017 season study of13C/12C carbon and18O/16O oxygen stableisotopes in carbohydrates and intracellular water of 12 red and white grape varieties (Aligote, Rkatsiteli,Sauvignon Zeleny, Chardonnay, Cabernet Sauvignon, Sauvignon Blanc, Merlot, Risling, Pinot Noir, CabernetFranc, Sira, Krasnostop) as well as in ethanol of wines made from corresponding grapes from the CrimeanPeninsula and South-West Coast of the Greater Caucasus. To measure the ratio of carbon isotopes13C/12Cin grape (must) carbohydrates and wine ethanol the Flash-Combustion technique (FC-IRMS/SIRA) has beenused, while the method of isotopic equilibration (EQ-IRMS/SIRA) has been used for the measurement of18O/16O oxygen isotopes ratio in the intracellular water of grapes (must) and in the water fraction of wine. TheGC-Combustion technique (GC-IRMS/SIRA) has been used for the first time to measure the carbon isotopes13C/12C distribution in ethanol of studied wines. It has been found that theδ13CVPDBvalues for carbohydratesof red and white grape varieties as a result of biological fractionation of carbon isotopes in the agro-climaticconditions of plant growth (2017 season) for the studied geographical areas formed the following quantitativeranges: from−26.72 to−23.35‰ (the Crimean Peninsula) and from−25.92 to−23.87‰ (South-West Coastof the Greater Caucasus). Theδ13CVPDBvalues for wine ethanol are in the following ranges: from−28.15to−24.47‰ (the Crimean Peninsula) and from−27.29 to−25.78‰ (South-West Coast of the GreaterCaucasus). Theδ18OVSMOWvalues in intracellular water of grapes of the 2017 season range from−1.24to 2.17‰ (the Crimean Peninsula) and from 1.08 to 4.09‰ (South-West Coast of the Greater Caucasus). Theresults of this study show, in comparison with the results of studies of the 2015 and 2016 seasons, a decreasein theδ13CVPDBvalues for carbohydrates of grapes and ethanol of wine, which is explained by the changedclimatic conditions of grapes growing in the vegetation period of 201