zldmЗаводская лаборатория. Диагностика материаловIndustrial laboratory. Diagnostics of materials1028-68612588-0187ООО «Издательство «ТЕСТ-ЗЛ»10.26896/1028-6861-2023-89-4-5-15zldm-1903Research ArticleАНАЛИЗ ВЕЩЕСТВАSUBSTANCES ANALYSISПрименение микроволновых систем MARS-5 и UltraWAVE для разложения силикатных пород с последующим МС-ИСП анализомApplication of MARS-5 and UltraWAVE microwave systems to the digestion of silicate rocks followed by ICP-MS analysisНиколаеваИ. В.NikolaevaI. V.

Ирина Викторовна Николаева

630090, г. Новосибирск, просп. Коптюга, д. 3

Irina V. Nikolaeva

 3, prosp. Koptuga, Novosibirsk, 630090

inikol@igm.nsc.ruПалесскийС. В.PalesskiyS. V.

Станислав Владиславович Палесский

Stanislav V. Palesskiy

Институт геологии и минералогии им. В. С. Соболева СО РАНРоссияSobolev Institute of Geology and Mineralogy, Siberian Branch by the Russian Academy of SciencesRussian Federation202319042023894515Copyright © Николаева И.В., Палесский С.В., 20232023Николаева И.В., Палесский С.В.Nikolaeva I.V., Palesskiy S.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.zldm.ru/jour/article/view/1903

Проведено сравнение эффективности двух микроволновых систем — камерной MARS-5 и реакторной UltraWAVE — для разложения силикатных пород с последующим определением 32 элементов (Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Ta, Cs, Ba, 14 РЗЭ, Hf, Ta, Th, U) методом масс-спектрометрии с индуктивно-связанной плазмой (МС-ИСП). Отработка методик разложения и подтверждение правильности полученных результатов выполнены с использованием международных стандартных образцов — базальтов BHVO-2 и BCR-2, серпентинита UB-N и перидотита JP-1. Микроволновое разложение включало двухстадийную обработку проб смесью концентрированных кислот HF, HNO3, HCl в MARS-5 (T = 190 °C, P = 20 бар) и UltraWAVE (T = 240 °C, P = 80 бар) с отгонкой избытка фторида в виде SiF4 между стадиями микроволнового разложения. Определение концентраций аналитов в полученных растворах выполнено с использованием масс-спектрометра высокого разрешения ELEMENT в низком и среднем разрешении по внешней градуировке с учетом кислотного состава растворов и внутренним стандартом (In). Пределы обнаружения аналитов после кислотного разложения в MARS-5 и UltraWAVE сравнимы и позволяют определить все заданные элементы, кроме Ta в JP-1. Использование разработанной методики пробоподготовки в MARS-5 обеспечивает полноту разложения BHVO-2, BCR-2, UB-N с последующим МС-ИСП определением 32 заданных элементов в полученных растворах без дополнительных стадий концентрирования. Погрешность определения составляет 2 – 9 % для BHVO-2, BCR-2 и 3 – 12 % для UB-N с увеличением до 16 – 25 % (Nb, Ta) в связи с приближением к пределу обнаружения. Более эффективное микроволновое разложение в UltraWAVE по сравнению с MARS-5 доказано на примере полного разложения образца JP-1 с переведением в раствор всех элементов, включая Cr.

Two microwave systems MARS-5 and UltraWAVE are compared in the efficiency with regard to the digestion of silicate rocks with subsequent determination of 32 elements (Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Ta, Cs, Ba, 14 REE, Hf, Ta, Th, U) by inductively coupled plasma mass spectrometry (ICP-MS). The development of digestion methods and validation of the obtained results has been carried out using international reference materials — basalts BHVO-2 and BCR-2, serpentinite UB-N and peridotite JP-1. Microwave digestion included a two-stage treatment of samples with a mixture of concentrated acids HF, HNO3, HCl in MARS-5 (T = 190°C, P = 20 bar) and UltraWAVE (T = 240°C, P = 80 bar) with distillation of excess fluorides in the form of SiF4 between microwave digestion stages. The determination of concentrations in the obtained solutions was carried out on a high-resolution mass spectrometer ELEMENT in low and medium resolution according to external calibration with the internal standard (In), taking into account the acid composition of the analyzed solutions. The detection limits of the analytes after acid digestion in MARS-5 and UltraWAVE are comparable and provide the determination of all specified elements, except for Ta in JP-1. The use of the developed sample preparation procedure in MARS-5 ensures complete decomposition of BHVO-2, BCR-2, UB-N followed by ICP-MS determination of 32 specified elements in the obtained solutions without additional preconcentration steps. The relative standard deviations for the determined elements are 2 – 9% for the reference materials BHVO-2, BCR-2, 3 – 12% for UB-N with an increase to 16 – 25% (Nb, Ta) due to the approach to the detection limit. The more efficient microwave digestion in UltraWAVE compared to MARS-5 was proved by the complete decomposition of JP-1 with the transfer of all the elements, including Cr, to the solution.

масс-спектрометрия с индуктивно-связанной плазмоймикроволновое кислотное разложениестандартные образцымикроволновые системы MARS-5 и UltraWAVE.inductively coupled plasma–mass-spectrometry (ICP-MS)microwave acid digestionreference materialsmicrowave systems MARS-5 and UltraWAVEReferencesPinto F., Escalfoni R., Saint’Pierre T. Sample preperation for determination of rare earth elements in geological samples by ICP-MS: a critical review / Anal. Lett. 2012. Vol. 45. N 12. P. 1537 – 1556. DOI: 10.1080/00032719.2012.677778Pinto F., Escalfoni R., Saint’Pierre T. Sample preperation for determination of rare earth elements in geological samples by ICP-MS: a critical review / Anal. Lett. 2012. Vol. 45. N 12. P. 1537 – 1556. DOI: 10.1080/00032719.2012.677778Balaram V., Subramanyam K. S. V. Sample preparation for geochemical analysis: Strategies and significance / Adv. Sample Prep. 2022. Vol. 1. 100010. DOI: 10.1016/j.sampre.2022.100010Balaram V., Subramanyam K. S. V. Sample preparation for geochemical analysis: Strategies and significance / Adv. Sample Prep. 2022. Vol. 1. 100010. DOI: 10.1016/j.sampre.2022.100010Cotta A., Enzweiler J. Classical and New Procedures of Whole Rock Dissolution for Trace Element Determination by ICP-MS / Geostand. Geoanal. Res. 2012. Vol. 36. N 1. P. 27 – 50. DOI: 10.1111/j.1751-908X.2011.00115.xCotta A., Enzweiler J. Classical and New Procedures of Whole Rock Dissolution for Trace Element Determination by ICP-MS / Geostand. Geoanal. Res. 2012. Vol. 36. N 1. P. 27 – 50. DOI: 10.1111/j.1751-908X.2011.00115.xNavarro M., Andrade S., Ulbrich H., et al. The direct determination of rare earth elements in basaltic and related rocks using ICP-MS: Testing the efficiency of microwave oven sample decomposition procedures / Geostand. Geoanal. Res. 2008.Vol. 32. N 2. P. 167 – 180. DOI: 10.1111/j.1751-908X.2008Navarro M., Andrade S., Ulbrich H., et al. The direct determination of rare earth elements in basaltic and related rocks using ICP-MS: Testing the efficiency of microwave oven sample decomposition procedures / Geostand. Geoanal. Res. 2008.Vol. 32. N 2. P. 167 – 180. DOI: 10.1111/j.1751-908X.2008Zhang W., Yang F., Zhang C., Wang W. An Experimental Method for Effectively Digesting Geological Samples / J. Geosci. Environ. Prot. 2019. Vol. 7. P. 83 – 89. DOI: 10.4236/gep.2019.76007Zhang W., Yang F., Zhang C., Wang W. An Experimental Method for Effectively Digesting Geological Samples / J. Geosci. Environ. Prot. 2019. Vol. 7. P. 83 – 89. DOI: 10.4236/gep.2019.76007Bychkova Y. V., Sinitsyn M. Yu., Petrenko D. B., et al. Methodical features of multielement analysis of rocks by inductively coupled plasma mass spectrometry / Vestn. Mosk. Univ. Ser. 4. Geol. 2016. N 6. P. 56 – 63 [in Russian]. DOI: 10.33623/0579-9406-2016-6-56-63Bychkova Y. V., Sinitsyn M. Yu., Petrenko D. B., et al. Methodical features of multielement analysis of rocks by inductively coupled plasma mass spectrometry / Vestn. Mosk. Univ. Ser. 4. Geol. 2016. N 6. P. 56 – 63 [in Russian]. DOI: 10.33623/0579-9406-2016-6-56-63Magaldi T., Navarro M., Enzweiler J. Assessment of Dissolution of Silicate Rock Reference Materials with Ammonium Bifluoride and Nitric Acid in a Microwave Oven / Geostand. Geoanal. Res. 2019. Vol. 43. N 1. P. 189 – 208. DOI: 10.1111/ggr.12242Magaldi T., Navarro M., Enzweiler J. Assessment of Dissolution of Silicate Rock Reference Materials with Ammonium Bifluoride and Nitric Acid in a Microwave Oven / Geostand. Geoanal. Res. 2019. Vol. 43. N 1. P. 189 – 208. DOI: 10.1111/ggr.12242Roy P., Balaram V., Kumar A., et al. New REE and trace element data on two kimberlitic reference materials by ICP-MS / Geostand. Geoanal. Res. 2007. Vol. 31. N 3. P. 261 – 273. DOI: 10.1111/j.1751-908X.2007.00836.xRoy P., Balaram V., Kumar A., et al. New REE and trace element data on two kimberlitic reference materials by ICP-MS / Geostand. Geoanal. Res. 2007. Vol. 31. N 3. P. 261 – 273. DOI: 10.1111/j.1751-908X.2007.00836.xNna-Mvondo D., Martin-Redondo M., Martinez-Frias J. New application of microwave digestion-inductively coupled plasma-mass spectrometry for multi-element analysis in komatiites / Anal. Chim. Acta. 2008. Vol. 628. N 2. P. 133 – 142.DOI: 10.1016/j.aca.2008.09.008Nna-Mvondo D., Martin-Redondo M., Martinez-Frias J. New application of microwave digestion-inductively coupled plasma-mass spectrometry for multi-element analysis in komatiites / Anal. Chim. Acta. 2008. Vol. 628. N 2. P. 133 – 142.DOI: 10.1016/j.aca.2008.09.008Kubrakova I. V., Toropchenova E. S. Microwave sample preparation for geochemical and ecological studies / J. Anal. Chem. 2013. Vol. 68. N 6. P. 467 – 476. DOI: 10.1134/S1061934813060099Kubrakova I. V., Toropchenova E. S. Microwave sample preparation for geochemical and ecological studies / J. Anal. Chem. 2013. Vol. 68. N 6. P. 467 – 476. DOI: 10.1134/S1061934813060099Totland M., Jarvis I., Jarvis K. An assessment of dissolution techniques for the analysis of geological samples by plasma spectrometry / Chem. Geol. 1992. Vol. 95. N 1 – 2. P. 35 – 62. DOI: 10.1016/0009-2541(92)90042-4Totland M., Jarvis I., Jarvis K. An assessment of dissolution techniques for the analysis of geological samples by plasma spectrometry / Chem. Geol. 1992. Vol. 95. N 1 – 2. P. 35 – 62. DOI: 10.1016/0009-2541(92)90042-4Yu Z., Robinson P., McGoldrick P. An evaluation of methods for the chemical decomposition of geological materials for trace element determination using ICP-MS / Geostand. Newsl. 2001. Vol. 25. N 2 – 3. P. 199 – 217. DOI: 10.1111/j.1751-908X.2001.tb00596.xYu Z., Robinson P., McGoldrick P. An evaluation of methods for the chemical decomposition of geological materials for trace element determination using ICP-MS / Geostand. Newsl. 2001. Vol. 25. N 2 – 3. P. 199 – 217. DOI: 10.1111/j.1751-908X.2001.tb00596.xFedyunina N., Seregina I., Bolshov M., et al. Investigation of the efficiency of the sample pretreatment stage for the determination of the Rare Earth Elements in rock samples by inductively coupled plasma mass spectrometry technique / Anal. Chim. Acta. 2012. Vol. 713. P. 97 – 102. DOI: 10.1016/j.aca.2011.11.035Fedyunina N., Seregina I., Bolshov M., et al. Investigation of the efficiency of the sample pretreatment stage for the determination of the Rare Earth Elements in rock samples by inductively coupled plasma mass spectrometry technique / Anal. Chim. Acta. 2012. Vol. 713. P. 97 – 102. DOI: 10.1016/j.aca.2011.11.035Gupta J. G., Bertrand N. B. Direct ICP-MS determination of trace and ultratrace elements in geological materials after decomposition in a microwave oven. I. Quantitation of Y, Th, U and the lanthanides / Talanta. 1995. Vol. 42. N 11. P. 1595 –1607. DOI: 10.1016/0039-9140(95)01612-0Gupta J. G., Bertrand N. B. Direct ICP-MS determination of trace and ultratrace elements in geological materials after decomposition in a microwave oven. I. Quantitation of Y, Th, U and the lanthanides / Talanta. 1995. Vol. 42. N 11. P. 1595 –1607. DOI: 10.1016/0039-9140(95)01612-0Yasnygina T. A., Markova M. E., Rasskazov S. V., Pakhomova N. N. Determination of Rare-Earth Elements Y, Zr, Nb, Hf, Ta, Th in Reference Specimens from DB Series Using Inductuvely Coupled Plasma Mass-Spectromentry (ICP-MS) / Zavod. Lab. Diagn. Mater. 2015. Vol. 81. N 2. P. 10 – 20 [in Russian].Yasnygina T. A., Markova M. E., Rasskazov S. V., Pakhomova N. N. Determination of Rare-Earth Elements Y, Zr, Nb, Hf, Ta, Th in Reference Specimens from DB Series Using Inductuvely Coupled Plasma Mass-Spectromentry (ICP-MS) / Zavod. Lab. Diagn. Mater. 2015. Vol. 81. N 2. P. 10 – 20 [in Russian].Kravchenko A. A., Nikolaeva I. V., Palessky S. V. Microwave acid digestion of mafic and ultramafic rocks in ICP-MS determination of the rare earth elements / Zavod. Lab. Diagn. Mater. 2020. Vol. 86. N 10. P. 10 – 17 [in Russian]. DOI: 10.26896/1028-6861-2020-86-10-10-17Kravchenko A. A., Nikolaeva I. V., Palessky S. V. Microwave acid digestion of mafic and ultramafic rocks in ICP-MS determination of the rare earth elements / Zavod. Lab. Diagn. Mater. 2020. Vol. 86. N 10. P. 10 – 17 [in Russian]. DOI: 10.26896/1028-6861-2020-86-10-10-17UltraWAVE: the Game Changer in Microwave Sample Preparation. https://www. milestonesrl.com/products/microwave-digestion/ultrawave (accessed November 18, 2022).UltraWAVE: the Game Changer in Microwave Sample Preparation. https://www. milestonesrl.com/products/microwave-digestion/ultrawave (accessed November 18, 2022).Michel T. Breaking the Sample Preparation Bottleneck With a New Approach to Microwave Digestion / Am. Lab. 2010. Vol. 42. N 11. P. 32 – 35.Michel T. Breaking the Sample Preparation Bottleneck With a New Approach to Microwave Digestion / Am. Lab. 2010. Vol. 42. N 11. P. 32 – 35.Karasinski J., Bulska E., Wojciechowski M., et al. On-line separation of strontium from a matrix and determination of the 87Sr/86Sr ratio by Ion Chromatography/Multicollector-ICPMS / J. Anal. At. Spectrom. 2016. Vol. 31. N 7. P. 1459 – 1463.DOI: 10.1039/C6JA00109BKarasinski J., Bulska E., Wojciechowski M., et al. On-line separation of strontium from a matrix and determination of the 87Sr/86Sr ratio by Ion Chromatography/Multicollector-ICPMS / J. Anal. At. Spectrom. 2016. Vol. 31. N 7. P. 1459 – 1463.DOI: 10.1039/C6JA00109BKarasinski J., Bulska E., Wojciechowski M., et al. High precision direct analysis of magnesium isotope ratio by ion chromatography/multicollector-ICPMS using wet and dry plasma conditions / Talanta. 2017. Vol. 165. P. 64 – 68.DOI: 10.1016/j.talanta. 2016. 12.033Karasinski J., Bulska E., Wojciechowski M., et al. High precision direct analysis of magnesium isotope ratio by ion chromatography/multicollector-ICPMS using wet and dry plasma conditions / Talanta. 2017. Vol. 165. P. 64 – 68.DOI: 10.1016/j.talanta. 2016. 12.033Pontér S., Pallavicini N., Engström E., et al. Chromium isotope ratio measurements in environmental matrices by MC-ICP-MS / J. Anal. At. Spectrom. 2016. V. 31. P. 1464 – 1471. DOI: 10.1039/c6ja00145aPontér S., Pallavicini N., Engström E., et al. Chromium isotope ratio measurements in environmental matrices by MC-ICP-MS / J. Anal. At. Spectrom. 2016. V. 31. P. 1464 – 1471. DOI: 10.1039/c6ja00145aCruz-Hernández Y., Ruiz-García M., Villalobos M., et al. Fractionation and mobility of thallium in areas impacted by mining-metallurgical activities: Identification of a water-soluble Tl(I) fraction / Environ. Pollut. 2018. Vol. 237. P. 154 –165. DOI: 10.1016/j.envpol.2018.02.031Cruz-Hernández Y., Ruiz-García M., Villalobos M., et al. Fractionation and mobility of thallium in areas impacted by mining-metallurgical activities: Identification of a water-soluble Tl(I) fraction / Environ. Pollut. 2018. Vol. 237. P. 154 –165. DOI: 10.1016/j.envpol.2018.02.031Shafiee N. S., Achmad Bahar A. M., Ali Khan M. M. Potential of Rare Earth Elements (REEs) in Gua Musang Granites, Gua Musang, Kelantan / IOP Conference Series: Earth and Environmental Science. 2020. Vol. 549. N 1. P. 012027. DOI: 10.1088/1755-1315/549/1/012027Shafiee N. S., Achmad Bahar A. M., Ali Khan M. M. Potential of Rare Earth Elements (REEs) in Gua Musang Granites, Gua Musang, Kelantan / IOP Conference Series: Earth and Environmental Science. 2020. Vol. 549. N 1. P. 012027. DOI: 10.1088/1755-1315/549/1/012027Jochum K., Weis U., Schwager B., et al. Reference Values Following ISO Guidelines for Frequently Requested Rock Reference Materials / Geostand. Geoanal. Res. 2016. Vol. 40. N 3. P. 333 – 350. DOI: 10.1111/j.1751-908X.2015.00392.xJochum K., Weis U., Schwager B., et al. Reference Values Following ISO Guidelines for Frequently Requested Rock Reference Materials / Geostand. Geoanal. Res. 2016. Vol. 40. N 3. P. 333 – 350. DOI: 10.1111/j.1751-908X.2015.00392.xGodard M., Awaji S., Hansen H., et al. Geochemistry of a long in-situ section of intrusive slow-spread oceanic lithosphere: Results from IODP Site U1309 (Atlantis Massif, 30 degrees N Mid-Atlantic-Ridge) / Earth Planet. Sci. Lett. 2009. Vol. 279. N 1 – 2. P. 110 – 122. DOI: 10.1016/j.epsl.2008.12.034Godard M., Awaji S., Hansen H., et al. Geochemistry of a long in-situ section of intrusive slow-spread oceanic lithosphere: Results from IODP Site U1309 (Atlantis Massif, 30 degrees N Mid-Atlantic-Ridge) / Earth Planet. Sci. Lett. 2009. Vol. 279. N 1 – 2. P. 110 – 122. DOI: 10.1016/j.epsl.2008.12.034Makishima A., Nakamura E. Determination of major, minor and trace elements in silicate samples by ICP-QMS and ICPSFMS applying isotope dilution-internal standardisation (ID-IS) and multi-stage internal standardisation / Geostand. Geoanal. Res. 2006. Vol. 30. N 3. P. 245 – 271.DOI: 10.1111/j.1751-908X.2006.tb01066.xMakishima A., Nakamura E. Determination of major, minor and trace elements in silicate samples by ICP-QMS and ICPSFMS applying isotope dilution-internal standardisation (ID-IS) and multi-stage internal standardisation / Geostand. Geoanal. Res. 2006. Vol. 30. N 3. P. 245 – 271.DOI: 10.1111/j.1751-908X.2006.tb01066.xMakishima A., Nakamura E., Nakano T. Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 levels in geological materials by direct nebulisation of sample HF solution into FL-ICP-MS / Geostand. Newslett. 1999. Vol. 23. N 1. P. 7 – 20. DOI: 10.1111/j.1751-908X.1999.tb00555.xMakishima A., Nakamura E., Nakano T. Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 levels in geological materials by direct nebulisation of sample HF solution into FL-ICP-MS / Geostand. Newslett. 1999. Vol. 23. N 1. P. 7 – 20. DOI: 10.1111/j.1751-908X.1999.tb00555.xDebret B., Albers E., Walter B., et al. Shallow forearc mantle dynamics and geochemistry: New insights from IODP Expedition 366 / Lithos. 2019. Vol. 326. P. 230 – 245.DOI: 10.1016/j.lithos.2018.10.038Debret B., Albers E., Walter B., et al. Shallow forearc mantle dynamics and geochemistry: New insights from IODP Expedition 366 / Lithos. 2019. Vol. 326. P. 230 – 245.DOI: 10.1016/j.lithos.2018.10.038Rospabe M., Benoit M., Candaudap F. Determination of Trace Element Mass Fractions in Ultramafic Rocks by HRICPMS: A Combined Approach Using a Direct Digestion/Dilution Method and Preconcentration by Coprecipitation / Geostand. Geoanal. Res. 2018. Vol. 42. N 1. P. 115 – 129. DOI: 10.1111/ggr.12181Rospabe M., Benoit M., Candaudap F. Determination of Trace Element Mass Fractions in Ultramafic Rocks by HRICPMS: A Combined Approach Using a Direct Digestion/Dilution Method and Preconcentration by Coprecipitation / Geostand. Geoanal. Res. 2018. Vol. 42. N 1. P. 115 – 129. DOI: 10.1111/ggr.12181

The authors declare that there are no conflicts of interest present.