МЕТОДИКА ОПРЕДЕЛЕНИЯ ИЗОТОПНЫХ ОТНОШЕНИЙ Cu И Zn МЕТОДОМ МК ИСП-МС С ИСПОЛЬЗОВАНИЕМ СМОЛЫ AG MP-1

The isotopic composition of copper is of great interest for researchers in various fields of science, geochemistry and hydrology in particular, wherein the consideration is being given to the variations in the isotopic composition of the Earth's crust, extraterrestrial matter, and water basins, as well as to the origin and transfer of matter. Zn isotopes appear to be promising for identifying the sources and pathways of the environmental pollution. The aim of this study involves the refinement and validation of the zinc and copper isotopic ratio determination methodology covering the whole process from sample digestion to MC ICP-MS measurements. For this reason, as well as to assess the suitability of the methodology for the analysis of environmental samples, Zn and Cu isotopic analysis of the BHVO-2, BCR-2 and AGV2 USGS certified reference materials has been performed. The method for determination of Cu and Zn stable isotope ratios by multi-collector inductively coupled plasma mass spectrometry in environmental samples is developed. The application of the AG MP1 resin with optimized layer parameters (resin bed height 3.5 cm, diameter 1 cm) provides the highpurity Cu and Zn fractions. The method is characterized by high throughput and adequate analytical figures of merit when using the standardsample bracketing technique for mass bias correction. The procedural blanks related to chemical dissolution and ion exchange procedures are lower than 1 and 3 ng for Cu and Zn, respectively, assuring no blank effect on the isotopic composition of samples. The accuracy and precision obtained for Cu and Zn isotope measurements in the BHVO2, BCR2 and AGV2 geological certified reference materials demonstrate good agreement with the reference values published. © 2022 Institute of the Earth's Crust. All rights reserved.ААААА181180530900458; Ministry of Education and Science of the Russian Federation, Minobrnauka: 075-15-2021-680; Russian Science Foundation, RSF: 18-77-10024The work of Okuneva T.G. is supported by the Russian Science Foundation (project 18-77-10024), the rest authors are supported by the state assignment of the IGG UB RAS ААААА181180530900458. Isotopic analyses are performed at the "Geoanalitik" Shared Research Facilities of the IGG UB RAS. The reequipment and comprehensive development of the "Geoanalitik" Shared Research Facilities of the IGG UB RAS is financially supported by the grant of the Ministry of Science and Higher Education of the Russian Federation (Agreement 075-15-2021-680).authors are supported by the state assignment of the IGG UB RAS ААААА 猃?猃猃稃爃眃甃爃笃爃爃瘃?稁 Isotopic analyses are performed at the 㘀Geoanalitik ? Shared Research Facilities of the IGG UB RAS. The reequipment and comprehensive development of the 㘀Geoanalitik 㘀 Shared Research Facilities of the IGG UB RAS is 퀀inancially supported by the grant of the Ministry of Science and Higher Education of the Russian Federation (Agreement 075-15-2021-680).FUNDING: The work of Okuneva T.G. is supported by the Russian Science Foundation (project 18-77-10024), the res

THE METHOD FOR Cu AND Zn ISOTOPE RATIO DETERMINATION BY MC ICP-MS USING THE AG MP-1 RESIN

The isotopic composition of copper is of great interest for researchers in various fields of science, geochemistry and hydrology in particular, wherein the consideration is being given to the variations in the isotopic composition of the Earth’s crust, extraterrestrial matter, and water basins, as well as to the origin and transfer of matter. Zn isotopes appear to be promising for identifying the sources and pathways of the environmental pollution. The aim of this study involves the refinement and validation of the zinc and copper isotopic ratio determination methodology covering the whole process from sample digestion to MC ICP-MS measurements. For this reason, as well as to assess the suitability of the methodology for the analysis of environmental samples, Zn and Cu isotopic analysis of the BHVO-2, BCR-2 and AGV-2 USGS certified reference materials has been performed. The method for determination of Cu and Zn stable isotope ratios by multi-collector inductively coupled plasma mass spectrometry in environmental samples is developed. The application of the AG MP-1 resin with optimized layer parameters (resin bed height 3.5 cm, diameter 1 cm) provides the high-purity Cu and Zn fractions. The method is characterized by high throughput and adequate analytical figures of merit when using the standard-sample bracketing technique for mass bias correction. The procedural blanks related to chemical dissolution and ion exchange procedures are lower than 1 and 3 ng for Cu and Zn, respectively, assuring no blank effect on the isotopic composition of samples. The accuracy and precision obtained for Cu and Zn isotope measurements in the BHVO-2, BCR-2 and AGV-2 geological certified reference materials demonstrate good agreement with the reference values published

ИЗУЧЕНИЕ ПРОЦЕССА СООСАЖДЕНИЯ МЫШЬЯКА И СУРЬМЫ ПРИ ОТДЕЛЕНИИ МАКРОКОЛИЧЕСТВ ЖЕЛЕЗА, ХРОМА В ВИДЕ Na3FeF6, Na3CrF6

Theoretical and experimental studies were carried out for the first time in order to determine the mechanism of co-precipitation of arsenic and antimony during their separation from the macro-quantities of iron and chromium in the form of Na3FeF6 and Na3CrF6 sediments. It was found that the application of Dubinin-Radushkevich adsorption isotherm gives the most accurate description of the process. The average free energy of adsorption for As and Sb is 9.6 and 9.7 kJ/mol respectively. Co-precipitation of analytes in the micropores of precipitates occurred as a result of the chemical (ion-exchange) reaction. The possibility of inhibiting this process by introducing a different amount of complexing agent (hydrofluoric acid) was studied. The addition of HF led to the formation of more coarse crystalline precipitates with lower specific surface area and porosity. For the accurate ICP-AES determination of analytes (As, Sb) the molar ratio of precipitating agent / complexing agent (NaF / HF) ≈ 1 should be strictly observed. According to the developed procedure, state standard samples of steels and nickel-based precision alloys were prepared for ICP-AES determination of As and Sb contents. The difference between the found and certified content of analytes did not exceed the permitted deviations given in the corresponding Russian state standards. The ICP-AES method of simultaneous determination of As and Sb contents after their preliminary separation from the main components is recommended for the analysis of materials with high content of Fe and Cr.Keywords: sorption, co-precipitation, determination of arsenic and antimony, inductively coupled plasma atomic emission spectroscopy (ICP-AES), adsorption isotherms, fluorides, matrix componentsDOI: http://dx.doi.org/10.15826/analitika.2017.21.3.001 A.V. Maiorova1, S.Yu. Melchakov1,2, T.G. Okuneva2 , K.A. Vorontsova1, M.A. Mashkovtsev21Institute of Metallurgy of Ural Branch of Russian Academy of Sciences,101 Amundsena st., Yekaterinburg, 620016, Russian Federation2Ural Federal University, 19 Mira st., Yekaterinburg, 620002, Russian FederationВпервые проведены теоретические и экспериментальные исследования с целью определения механизма соосаждения мышьяка и сурьмы при отделении от макроколичеств железа, хрома в виде Na3FeF6, Na3CrF6. Установлено, что использование изотермы адсорбции Дубинина-Радушкевича приводит к наиболее точному описанию процесса. Средняя свободная энергия адсорбции для As и Sb принимает значения 9.6 и 9.7 кДж/моль соответственно. Соосаждение в микропорах осадков происходит в результате химической (ионообменной) реакции. Изучена возможность ингибирования процесса с помощью введения разного количества комплексообразующего агента – фтороводородной кислоты. Ее использование приводит к получению более крупнокристаллических осадков с меньшей удельной поверхностью и пористостью. Для точного ИСП-АЭС определения аналитов необходимо строгое соблюдение мольного соотношения осадитель/комплексообразующий агент (NaF/HF) ≈ 1. По разработанной процедуре к ИСП-АЭС определению содержания As и Sb были подготовлены ГСО состава стали и сплавов прецизионного типа на никелевой основе. Разница между найденным и аттестованным их содержанием не превышает нормативов, приведенных в соответствующих ГОСТах.  ИСП-АЭС методика одновременного определения содержания As и Sb с предварительным отделением основных компонентов рекомендована для анализа материалов с высоким содержанием Fe и Cr.Ключевые слова: адсорбция, соосаждение, определение мышьяка и сурьмы, атомно-эмиссионная спектрометрия с индуктивно связанной плазмой (ИСП-АЭС), изотермы адсорбции, фториды, матричные компонентыDOI: http://dx.doi.org/10.15826/analitika.2017.21.3.00

OPTIMIZATION OF CONDITIONS OF SEPARATION OF CHROMIUM AND IRON FOR ICP-AES DETERMINATION OF ARSENIC AND ANTIMONY IN STEELS

For the first time is given a new approach to solve the problem of separation of trace analytes (As, Sb) from matrix elements (Fe, Cr) forming steels. Matrix elements provide an interfering effect on the results of arsenic and antimony determination employing the ICPAES analysis. It is found that required deposition conditions of macroamounts (Fe, Cr) should meet the molar ratio NaF/HF close to 1 in aim to inhibit analytes coprecipitation.Работа выполнена при финансовой поддержке РФФИ (грант № 16-33-00317)

Определение фоновых изотопных отношений биодоступного стронция для рудника бронзового века новотемирский

To assess the mobility and provenance of ancient populations, it is necessary to compare their 87Sr/86Sr isotopic ratios with the local bioavailable strontium baseline (background), characteristic of each specific location or potential provenance region of an individual or artifact. Its definition requires a comprehensive approach to the analysis of heterogeneous samples («proxies») characterizing the ecosystem of the archaeological site under study, the identification of the most suitable proxies, as well as the unification and standardization of the sampling and analytic protocols. A pilot study is presented devoted the definition of the local range of bioavailable strontium by the example of the Novotemirskiy Bronze Age mine (Southern Urals). 87Sr/86Sr isotope ratios were determined in surface and underground water, bedrock (serpentinite), clay from the mine wall, and steppe polecat’s bone, as well as in grass and a bivalve shell from the lake. The lowest range of strontium isotope ratios relative to each other is characteristic of surface and groundwater, shell and grass, which allows them to be used to determine the combined baseline of bioavailable strontium. Multi-proxy (surface and underground water, grass and a bivalve shell) local bioavailable strontium baseline for the Novotemirskiy ancient mine (Southern Urals) is 0,7096 ± 0,0003 (2σ, n = 5). © 2021 Russian Academy of Sciences, Institute of Archaeology. All rights reserved.Работа выполнена при финансовой поддержке РНФ, проект No 20-18-00402 «Миграции человеческих коллективов и индивидуальная мобильность в рамках мультидисциплинарного анализа археологической информации (бронзовый век Южного Урала)», в ЮУрГУ (НИУ) (Д. В. Киселева – геохимическая интерпретация, П. С. Анкушева – археологическая документация и аналитика; Т. Г. Окунева, А. В. Касьянова – измерения проб и стандартных образцов; Е. С. Шагалов, М. Н. Анкушев – отбор проб и геологическая характеристика)

DETERMINATION OF GOLD IN ORES AND ROCKS BY ETAAS AFTER ITS EXTRACTION BY BRILLIANT GREEN

The aim of this work is to study the possibility of gold microconcentration in organic phase for its subsequent determination by ETAAS. The calibration curves obtained in this work indicate the possibilities of using proposed method for the extraction and concentration of gold from ores and rocks.Работа выполнена в ЦКП «Геоаналитик» в рамках темы № АААА-А18-118053090045-8 государственного задания ИГГ УрО РАН

ENVIRONMENTAL GEOCHEMISTRY OF HEAVY METALS AND METALLOIDS IN THE WATER-SOLUBLE SOIL FRACTION (ORENBURG REGION)

The study is devoted to the investigation of distribution of heavy metals and metalloids (HMM) in the water-soluble soil fraction of soil samples collected over the territory of the Orenburg Region. HMM are analyzed by ICP-MS, and their environmental-geochemical indices are calculated and discussed.Работа выполнена в ЦКП УрО РАН «Геоаналитик» в рамках темы № 123011800012-9 государственного задания ИГГ УрО РАН

87Sr/86Sr ISOTOPE RATIOS IN THE RIVER WATERS OF THE SOUTHERN URALS

87Sr/86Sr isotopic ratios are widely used to identify strontium sources and study strontium behaviour in (bio)geochemical cycles. 87Sr/86Sr in surface waters can reflect the average composition of bioavailable (i.e. available for further absorption by plants and animals) strontium in the catchment specific area. Based on those 87Sr/86Sr ratios, the regional maps of the bioavailable strontium distribution (strontium isoscapes) can be compiled. A complex block structure characterizes the Ural mountain system. Individual parts (blocks) are composed of rocks of various ages, genesis and geochemical characteristics, which can radically change at a distance of several tens of kilometres. Such variability would be reflected in strontium isotopic ratios, thus making it possible to determine the local isotopic signatures of bioavailable strontium. This work aimed to study 87Sr/86Sr in the water in the rivers of the Southern Urals. We determined the contents and isotopic ratios of strontium in river water samples collected from the territories of the Orenburg and Chelyabinsk regions and the Republic of Bashkortostan in 2019-2020. For the first time in the surface water of the rivers in the Southern Urals (Ural, Belaya, Tobol, Karagaily-Ayat, Sim, and others), the 87Sr/86Sr isotopic ratios have been determined, and their variations have been analyzed. 87Sr/86Sr values vary in the range 0.70666-0.71063 (average 0.70908) for the rivers of the Urals basin, 0.70749-0.71058 (average 0.70924) for the Kama-Volga basin, 0.70946-0.71176 (average 0.71071) for the Tobol basin. Such features of the strontium isotopic composition may be due to the influence of underlying rocks of the catchment area drained by river water. The data obtained can be used to identify the sources of strontium input into the water system during hydrological and environmental studies; to confirm the authenticity of food products of plant and animal origin; to carry out comparisons in the studies of the migration of ancient people and animals, as well as to determine the raw material areas for the production of vegetable and woollen textiles and wooden products in antiquity. © 2022 Institute of the Earth's Crust. All rights reserved.Russian Foundation for Basic Research, РФФИ: 20-09-00194; Ministry of Education and Science of the Russian Federation, Minobrnauka: 075-15-2021-680The study is supported by the Russian Foundation for Basic Research (project 20-09-00194) and performed within the state task of the IGG UB RAS АААА-А18-118053090045-8 at the "Geoanalitik" shared research facilities of the IGG UB RAS. The re-equipment and comprehensive development of the "Geoanalitik" shared research facilities of the IGG UB RAS is financially supported by the grant of the Ministry of Science and Higher Education of the Russian Federation (Agreement 075-15-2021-680).FUNDING: The study is supported by the Russian Foundation for Basic Research (project 20-09-00194) and performedwithin the state task of the IGG UB RAS АААА-А 猃稁猃猃稃爃眃甃爃? 爃爃瘃省稀 at the 㘀Geoana?itik 㘀 shared research faci?ities of the IGG UB RAS. The re-equipment and comprehensive deve?opment of the 㘀Geoana?itik 㘀 shared research faci?ities of the IGG UB RAS is 퀀inancia??y supported by the grant of the Ministry of Science and Higher Education of the Russian Federation (Agreement 075-15-2021-680)

THE ANALYSIS OF ELEMENTAL AND 87Sr/86Sr ISOTOPIC COMPOSITON FOR THE AUTHENTICATION AND DETERMINATION OF THE GEOGRAPHICAL ORIGIN OF RUSSIAN WINES

The study is devoted to the development of the analytical methodology for elemental and Sr isotopic composition by Q-ICP-MS and MC-ICP-MS of wines in order to their further authentication and determination of the geographical origin by the example of Russian wines.Работа выполнена в ЦКП УрО РАН «Геоаналитик» в рамках темы № 123011800012-9 государственного задания ИГГ УрО РАН

МЕТОДИКА ОПРЕДЕЛЕНИЯ ИЗОТОПНЫХ ОТНОШЕНИЙ Cu И Zn МЕТОДОМ МК ИСП-МС С ИСПОЛЬЗОВАНИЕМ СМОЛЫ AG MP-1

The isotopic composition of copper is of great interest for researchers in various fields of science, geochemistry and hydrology in particular, wherein the consideration is being given to the variations in the isotopic composition of the Earth’s crust, extraterrestrial matter, and water basins, as well as to the origin and transfer of matter. Zn isotopes appear to be promising for identifying the sources and pathways of the environmental pollution. The aim of this study involves the refinement and validation of the zinc and copper isotopic ratio determination methodology covering the whole process from sample digestion to MC ICP-MS measurements. For this reason, as well as to assess the suitability of the methodology for the analysis of environmental samples, Zn and Cu isotopic analysis of the BHVO-2, BCR-2 and AGV-2 USGS certified reference materials has been performed. The method for determination of Cu and Zn stable isotope ratios by multi-collector inductively coupled plasma mass spectrometry in environmental samples is developed. The application of the AG MP-1 resin with optimized layer parameters (resin bed height 3.5 cm, diameter 1 cm) provides the high-purity Cu and Zn fractions. The method is characterized by high throughput and adequate analytical figures of merit when using the standard-sample bracketing technique for mass bias correction. The procedural blanks related to chemical dissolution and ion exchange procedures are lower than 1 and 3 ng for Cu and Zn, respectively, assuring no blank effect on the isotopic composition of samples. The accuracy and precision obtained for Cu and Zn isotope measurements in the BHVO-2, BCR-2 and AGV-2 geological certified reference materials demonstrate good agreement with the reference values published.Изотопный состав меди представляет большой интерес для исследователей в различных областях науки, в частности в геохимии и гидрологии, где рассматриваются вариации изотопного состава земной коры и внеземного вещества, водных бассейнов, а также вопросы происхождения и процессы переноса вещества. Изотопы Zn перспективны для определения источников и путей загрязнения окружающей среды. Целью данного исследования является уточнение и валидация методики измерения изотопных соотношений цинка и меди, охватывающей весь процесс – от разложения образца до измерений методом МК ИСП-МС. Для оценки пригодности методики анализа образцов окружающей среды был проведен изотопный анализ Zn и Cu в стандартных образцах BHVO-2, BCR-2 и AGV-2, сертифицированных Геологический службой США. Разработан метод определения отношений стабильных изотопов Cu и Zn с помощью мультиколлекторной масс-спектрометрии с индуктивно связанной плазмой в экологических пробах. Применение смолы AG MP-1 с оптимизированными параметрами слоя (высота слоя смолы 3.5 см, диаметр 1 см) обеспечивает получение фракций Cu и Zn высокой чистоты. Метод отличается высокой производительностью и удовлетворительными метрологическими характеристиками при использовании брекетинга для коррекции дискриминации ионов по массе. Процедурные бланки (холостые пробы), относящиеся к процедурам химического растворения и хроматографии, составляют менее 1 нг для Cu и 3 нг для Zn, что гарантирует отсутствие значимого влияния холостой (контрольной) пробы на изотопный состав образцов. Точность и прецизионность, полученные при измерениях изотопов Cu и Zn в сертифицированных геологических стандартных материалах BHVO-2, BCR-2 и AGV-2, демонстрируют хорошее согласие с опубликованными сертифицированными значениями