rmjournalЭталоны. Стандартные образцыMeasurement Standards. Reference Materials2687-0886D. I. Mendeleyev Institute for Metrology10.20915/2077-1177-2023-19-3-129-144rmjournal-408Research ArticleСовременные методы анализа веществ и материаловModern methods of analysis of substances and materialsМетодика измерений отношения изотопов углерода в ванилине методом CM–CRDS с расширенной неопределенностью менее 0,1 %The CM–CRDS Method for Measuring the Carbon Isotope Ratio in Vanillin With an Expanded Uncertainty of Less Than 0.1 %https://orcid.org/0000-0002-3408-5116ЧубченкоЯ. К.ChubchenkoI. K.

Чубченко Ян Константинович – к анд. тех. наук, старший научный сотрудник научно-исследовательского отдела госэталонов в области физико-химических измерений

190005, г. Санкт-Петербург, Московский пр., д. 19 

Ian K. Chubchenko –  Cand. Sci. (Eng.), Senior Researcher of the Research Department of State Standards in the Field of Physical and Chemical Measurements

19 Moskovskiy ave., St. Petersburg, 190005

ycc@b10.vniim.ruФГУП «Всероссийский научно-исследовательский институт метрологии им. Д. И. Менделеева»РоссияD. I. Mendeleyev Institute for MetrologyRussian Federation202320072023193129144Copyright © Чубченко Я.К., 20232023Чубченко Я.К.Chubchenko I.K.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.rmjournal.ru/jour/article/view/408

Изотопный анализ является эффективным методом осуществления контроля качества и выявления фальсифицированной пищевой продукции. Традиционно применяемым в области изотопного анализа пищевой продукции и регламентированным в соответствующих нормативных документах методом является метод изотопной масс-спектрометрии с элементным анализатором (далее – E A-IRMS). В настоящий момент наибольший интерес в рамках изотопного анализа пищевой продукции представляет стремительно развивающийся и обладающий рядом достоинств метод измерений отношения изотопов углерода –  метод спектроскопии внутрирезонаторного затухания с модулем сжигания (далее – C M–CRDS). Однако исследований метрологических характеристик метода CM–CRDS в рамках анализа изотопного состава ванилина не проводилось. Цель данного исследования состояла в разработке методики измерений отношения изотопов углерода в ванилине методом CM–CRDS с расширенной неопределенностью (при k = 2) менее 0,1 ‰.

Разработка методики измерений проводилась в рамках подготовки к международным ключевым сличениям CCQM-K167 «Измерение отношения изотопов углерода в ванилине», организованным международной рабочей группой по измерениям отношения изотопов Консультативного Комитета по Количеству Вещества Международного Бюро Мер и Весов, проходившим с 2019 по 2022 гг. Экспериментальная часть исследований проводилась на эталонной установке, входящей в состав Государственного первичного эталона единиц молярной доли, массовой доли и массовой концентрации компонентов в газовых и газоконденсатных средах ГЭТ 154-2019.

Расширенная неопределенность (при k = 2) данной методики измерений отношения изотопов углерода в ванилине методом CM–CRDS составляет менее 0,1 ‰. Для достижения поставленной цели решены следующие задачи: определены факторы, формирующие бюджет неопределенности измерений, часть из которых устранена или минимизирована путем разработки порядка подготовки оборудования и проб, порядка выполнения и контроля точности измерений, порядка обработки результатов измерений.

Результаты международных сличений СCQM-K167 подтвердили возможность измерений отношения изотопов углерода в ванилине методом CM–CRDS по разработанной методике с расширенной неопределенностью (при k = 2) 0,09 ‰, что соответствует наилучшим измерениям, выполняемым методом EA-IRMS.

Достигнутый результат обладает практической значимостью, потому что подтверждает возможность применения метода CM–CRDS для осуществления контроля качества и выявления фальсифицированного ванилина. Дальнейшие исследования будут направлены на разработку методик измерений отношения изотопов углерода методом CM–CRDS в других веществах и материалах, анализируемых в пищевой промышленности, в том числе, для контроля качества и подтверждения безопасности соковой продукции по ТР ТС 023/2011 и алкогольной продукции по ТР ЕАЭС 047/2018.

Isotopic analysis is an efficient method for quality control and detection of counterfeit food products. The method of elemental analysis isotope ratio mass spectrometry (hereinafter referred to as EA-IRMS) is traditionally used in the field of isotopic analysis of food products and is regulated in the relevant regulatory documents. The method of combustion module-cavity ring-down spectroscopy (hereinafter referred to as CM–CRDS) is a rapidly developing method for measuring the carbon isotope ratio with a number of advantages; currently, this method is of most interest for the isotope analysis of food products. However, studies of the metrological characteristics of the CM–CRDS method as part of the analysis of the isotopic composition of vanillin have not been carried out. The purpose of the research was to develop a procedure for measuring the carbon isotope ratio in vanillin by the CM–CRDS method with an expanded uncertainty (at k = 2) of less than 0.1 ‰.

The development of the measurement procedure was carried out in preparation for the international key comparison CCQM-K167 «Carbon isotope delta measurements of vanillin» (2019–2022) organized by the international Working Group on Isotope Ratios of the Consultative Committee for Amount of Substance of the International Bureau of Weights and Measures. The experimental part of the research was carried out on a reference installation, which is part of the State primary standard of units of molar part, mass part and mass concentration of components in gas and gas condensate environs GET 154-2019.

The expanded uncertainty (at k = 2) of this procedure for measuring the carbon isotope ratio in vanillin by the CM–CRDS method is less than 0.1 ‰. The following tasks were solved to achieve the set goal: the factors that form the measurement uncertainty budget were identified, some of which were eliminated or minimized by developing a procedure for preparing equipment and samples, a procedure for performing and controlling the measurement accuracy, and a procedure for processing measurement results.

The results of international comparisons CCQM-K167 confirmed the possibility of measuring the carbon isotope ratio in vanillin by the CM–CRDS method using the developed procedure with an expanded uncertainty (at k = 2) of 0.09 ‰, which corresponds to the best measurements performed by the EA-IRMS method.

The achieved result is of practical importance, because it confirms the possibility of applying the CM–CRDS method for quality control and detection of counterfeit vanillin.

Further research will be aimed at developing procedures for measuring the carbon isotope ratio using the CM–CRDS method in other substances and materials analyzed in the food industry, including for quality control and safety confirmation of juice products according to TR CU023/2011 and alcoholic products according to TR EAEU047/2018.

метрологиястабильные изотопыизотопная масс-спектрометрияизотопная инфракрасная спектроскопияCRDSCM–CRDSEA-IRMSванилин13C/12Cδ13Cотношение изотоповметодика измеренийmetrologystable isotopesisotope ratio mass spectrometryisotope ratio infrared spectroscopyisotopic reference materialsCRDSCM–CRDSEA-IRMSvanillin13C/12Cδ13Cisotope ratiomeasurement procedureВсе измерения проводились с использованием оборудования научно-исследовательского отдела государственных эталонов в области физико-химических измерений № 242 ФГУП «ВНИИМ им. Д. И. Менделеева». Автор благодарит сотрудников и руководителя отдела № 242, канд. техн. наук Анну Викторовну Колобову.All measurements were carried out using the equipment of the Research Department of State Standards in the Field of Physical and Chemical Measurements No. 242, D. I. Mendeleyev Institute for Metrology. The author expresses his gratitude to the workers and Anna V. Kolobova, Cand. Sci. 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The authors declare that there are no conflicts of interest present.