IСP-MS ANALYSIS OF HONEY AND BEE PRODUCTS

The microelement composition and isotopic ratios (87Sr/86Sr) of bee tissues and apicultural products from the Perm Krai, Republic of Bashkortostan, and Krasnodar Krai have been investigated. The obtained statistical data allowed the meads to be classified

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

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

Temperature Evolution of Sodium Nitrite Structure in a Restricted Geometry

The NaNO$_{2}$ nanocomposite ferroelectric material in porous glass was studied by neutron diffraction. For the first time the details of the crystal structure including positions and anisotropic thermal parameters were determined for the solid material, embedded in a porous matrix, in ferro- and paraelectric phases. It is demonstrated that in the ferroelectric phase the structure is consistent with bulk data but above transition temperature the giant growth of amplitudes of thermal vibrations is observed, resulting in the formation of a "premelted state". Such a conclusion is in a good agreement with the results of dielectric measurements published earlier.Comment: 4 pages, 4 figure

АТОПИЧЕСКИЙ ДЕРМАТИТ У ДЕТЕЙ: НАЛИЧИЕ СПЕЦИФИЧЕСКИХ АНТИТЕЛ К СУПЕРАНТИГЕНАМ STAPHYLOCOCCUS AUREUS И ЕГО АНТИБИОТИКОРЕЗИСТЕНТНОСТЬ

Background. Staphylococcus aureus function in atopic dermatitis (AD) children skin is double-handed: an infectious trigger and an allergen. The aim of the study was to evaluate the frequency of S. aureus enterotoxins the IgE in children with infected AD skin and to compare the IgE levels with antibiotic resistance of S. aureus. Methods: specific IgE to S. aureus enterotoxins A and B (ImmunoCap, Phadia AB, Sweden) were detected in the serum of 90 children infected with AD. The IgE levels were compared with the resistance to antibiotics (McNemar test and 95% confidential intervals of related frequencies). Results: specific IgE > 0,35 kUA/l to S. aureus enterotoxin A were found with a frequency of 0,29; to enterotoxin B — 0,36; to at least one of them — 0,43. The number of children with IgE > 0,35 kUA/l and S. aureus resistant to antibiotics was about 1/3 of the number of children with IgE < 0,35 kUA/l and S. aureus sensitive to antibiotics (р < 0,001). S. aureus in children with IgE > 0,35 kUA/l remained sensitive to oxacillin. Conclusion. In children infected with AD S. aureus enterotoxins A or/and B are revealed in 25–50% of cases. Specific IgE levels to S. aureus enterotoxins are similar in antibiotic resistant and antibiotic sensitive S. aureus skin swabs — about 30%. The IgE level to enterotoxins of S. aureus and its antibiotic resistance don't seem to be conditioned by each other.Актуальность. Наличие атопии создает условия для функционирования Staphylococcus aureus не только в качестве триггера инфекционного процесса, но и в качестве аллергена. Цель работы — оценить частоту выявления специфических IgE к энтеротоксинам S. aureus кожи детей с атопическим дерматитом (АтД), осложненным вторичным инфицированием кожи, и сопоставить наличие IgE с антибиотикорезистентностью S. aureus. Пациенты и методы. Обследовано 90 детей с АтД, осложненным вторичным инфицированием кожи. Специфические IgE-антитела к энтеротоксинам А и В  S. aureus определяли иммунохемилюминесцентным методом (ImmunoCap, Phadia AB, Швеция). Оценивали взаимосвязь наличия IgE к энтеротоксинам S. aureus с его антибиотикорезистентностью (критерий МакНемара, 95% доверительные интервалы относительных частот). Результаты. Специфические IgE к энтеротоксину А обнаружены с частотой 0,29, к энтеротоксину В — 0,36, хотя бы к одному из них — 0,43. Количество детей с наличием специфических IgE и устойчивыми к антибиотикам штаммами S. aureus составляло 1/3 количества детей с отсутствием IgE и чувствительными штаммами S. aureus (р < 0,001). Заключение. У детей с АтД, осложненным вторичной инфекцией, энтеротоксины А и/или В S. aureus обнаруживаются в 25–50% наблюдений. Частота выявления IgE к энтеротоксинам S. aureus одинакова у штаммов с различной антибиотикорезистентностью и составляет 30%. Взаимной опосредованности антибиотикорезистентности S. aureus и выработки специфических IgE-антител к его энтеротоксинам не выявлено

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)

INFORMATIVE CAPACITY OF THE SARGAT CULTURE’S DISTURBED BURIALS: KURGAN NOVOPOKROVKA 16 IN THE MIDDLE IRTYSH RIVER BASIN 1

The article deals with a complex study of the materials obtained during archaeological excavation of the kurgan Novopokrovka 16 in the middle Irtysh river basin (Omsk region). The site, which is attributed to the Sargat culture (5th century BC – second half of the 3rd centuryAD), was located farmost on the right bank of the river Irtysh, nearby the group of “Princely kurgans”. Despite almost total disturbance by robbers and agricultural activity, common scholars’ efforts demonstrate high informative capacity of the multidisciplinary approach, while modern level of undertaken research is not just being declared but enables to reconstruct seemingly lost information. The kurgan erection stages and mound structure features have been decoded using the results of a geophysical survey and soil morphology data. The paleoanthropological study of the incomplete skeletal remains does not support multiple or inlet interment inside the central grave, and provides sexing and aging of the buried individuals as well as some paleopathological observations. Apart from species examination, archaeozoological data testify that a warm period from spring to early autumn was the season of animal slaughter. Characteristics of mortuary rituals and direction of intercultural contacts of the ancient forest-steppe groups have been completed by new details based on the results of strontium isotope analyses (dental enamel of humans and animals) and evidence non-local origin of the individual buried under the excavated kurgan, what is different from local origin of horses butchered for funereal feasts. The proposed hypothesis supports previously suggested archaeological, paleoanthropological and paleogenetic facts on the origin of the forest-steppe population, indicating an involvement of various population groups with notable external components. Based on the archaeological materials, the kurgan under study might be dated back to mid-4th – 3rd centuries BC. © 2023 The Author(s).Ministry of Education and Science of the Russian Federation, Minobrnauka: 075-15-2021-680The article was prepared in the framework of the state orders No. 121102500121-8, 123011800012-9, 1021061810416-7, АААА-А19-119013090163-2, RFBR grant No. 21-59-23003. Sr isotopic analyses were obtained in the Geoanalitik shared research facilities of the IGG UB RAS, whose re-equipment and comprehensive development is supported by a grant of the Ministry of Science and Higher Education of the Russian Federation (Agreement No. 075-15-2021-680)

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

Study of arsenic and antimony co-precipitation process during the separation from the macro quantities of iron and chromium in the form of Na3FeF6 and 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.Впервые 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.All measurements were carried out with scientific instruments included in the “Ural-M” Collective Equipment Center. The study was supported by the State program of IMET UB RAS № 0396-2015-0087 (research of precision nickel-based alloys) with RFBR financial support (grant № 16-33-00317) (research of steels)