{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:10:20Z","timestamp":1760145020092,"version":"build-2065373602"},"reference-count":46,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2024,6,6]],"date-time":"2024-06-06T00:00:00Z","timestamp":1717632000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Natural Science Foundation, China","award":["42103009","2021YFC2901902","300102272502","300102272504"],"award-info":[{"award-number":["42103009","2021YFC2901902","300102272502","300102272504"]}]},{"name":"National Key Research and Development Project, China","award":["42103009","2021YFC2901902","300102272502","300102272504"],"award-info":[{"award-number":["42103009","2021YFC2901902","300102272502","300102272504"]}]},{"name":"Open Fund of Xi\u2019an Key Laboratory for Mineralization and Efficient Utilization of Critical Metals, Chang\u2019an University","award":["42103009","2021YFC2901902","300102272502","300102272504"],"award-info":[{"award-number":["42103009","2021YFC2901902","300102272502","300102272504"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Tourmaline, a boron-bearing mineral, has been extensively applied as a geothermometer, provenance indicator, and fluid-composition recorder in geological studies. In this paper, the decomposition capability of an HF-HNO3\u2013mannitol mixture for a tourmaline sample was investigated in detail for the first time, and a wet acid digestion method based on the boron\u2013mannitol complex for accurate boron determination in tourmaline by inductively coupled plasma mass spectrometry (ICP-MS) was proposed. With a digestion temperature of 140 \u00b0C, tourmaline samples of 25 mg (\u00b10.5 mg) can be completely decomposed by a ternary mixture, which consisted of 0.6 mL of HF, 0.6 mL of HNO3, and 0.7 mL of 2% mannitol (wt.), via a continuous heating treatment of 36 h. Following gentle evaporation at 100 \u00b0C, the sample residues were re-dissolved using 2 mL of 40% HNO3 solution (wt.) and diluted to about 2.0 \u00d7 105-fold by a two-step method using 2% HNO3 solution (wt.). The boron contents in a batch of parallel tourmaline samples were then determined by ICP-MS, and results showed that the boron concentration levels were in a range of 3.20\u20133.44% with determination RSDs less than 4.0% (n = 5). It was found that the boron concentrations obtained at the mass of 10B were comparable with results from the measurements at the mass of 11B. This revealed that the usage of 2% mannitol with a quantity as high as 0.7 mL in this developed approach did not exhibit significant effect on the quantification accuracy of boron at the mass of 11B. It was also found that the processes including fluoride-forming prevention and fluoride decomposition deteriorated the boron-reserving efficiency of mannitol for tourmaline, causing the averaged boron contents to vary from 2.25% to 3.57% (n = 5). Furthermore, the stability of the boron\u2013mannitol complex under 185 \u00b0C by applying the laboratory high pressure-closed digestion method was evaluated, which showed that there existed a 60.36% loss of boron compared to that under 140 \u00b0C by using this proposed approach. For this ternary mixture, the tourmaline decomposing efficiency was found to be weakened prominently using 100 \u00b0C as the digestion temperature, and tourmaline powders can be observed even after 72 h of continuous heating with B contents within 1.09\u20131.23% (n = 5). To assess the accuracy of this developed method, the boron recovery of anhydrous lithium tetraborate was studied. It was found that the boron recoveries were within 96.59\u2013102.12% (RSD &lt; 1%, n = 5), demonstrating the accuracy and reliability of this proposed method, which exhibits advantages of high B preserving efficiency, and giving concentration information of both B and trace elements simultaneously. By applying such a boron\u2013mannitol complex-based wet acid digestion method, the chemical composition of boron and trace elements in three tourmaline samples from different pegmatites were quantified, which provided valuable information to distinguish regional deposits and the associated evolution stages.<\/jats:p>","DOI":"10.3390\/molecules29112701","type":"journal-article","created":{"date-parts":[[2024,6,6]],"date-time":"2024-06-06T08:45:37Z","timestamp":1717663537000},"page":"2701","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Accurate Boron Determination in Tourmaline by Inductively Coupled Plasma Mass Spectrometry: An Insight into the Boron\u2013Mannitol Complex-Based Wet Acid Digestion Method"],"prefix":"10.3390","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1533-3329","authenticated-orcid":false,"given":"Xijuan","family":"Tan","sequence":"first","affiliation":[{"name":"Laboratory of Mineralization and Dynamics, College of Earth Sciences and Land Resources, Chang\u2019an University, 126 Yanta Road, Xi\u2019an 710054, China"},{"name":"Xi\u2019an Key Laboratory for Mineralization and Efficient Utilization of Critical Metals, Xi\u2019an 710054, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1228-7574","authenticated-orcid":false,"given":"Yonggang","family":"Feng","sequence":"additional","affiliation":[{"name":"Laboratory of Mineralization and Dynamics, College of Earth Sciences and Land Resources, Chang\u2019an University, 126 Yanta Road, Xi\u2019an 710054, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ruili","family":"Zhou","sequence":"additional","affiliation":[{"name":"Laboratory of Mineralization and Dynamics, College of Earth Sciences and Land Resources, Chang\u2019an University, 126 Yanta Road, Xi\u2019an 710054, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Denghong","family":"Wang","sequence":"additional","affiliation":[{"name":"Chinese Academy of Geological Sciences, Beijing 100037, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ting","family":"Liang","sequence":"additional","affiliation":[{"name":"Laboratory of Mineralization and Dynamics, College of Earth Sciences and Land Resources, Chang\u2019an University, 126 Yanta Road, Xi\u2019an 710054, China"},{"name":"Xi\u2019an Key Laboratory for Mineralization and Efficient Utilization of Critical Metals, Xi\u2019an 710054, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yan","family":"Wang","sequence":"additional","affiliation":[{"name":"Xi\u2019an Key Laboratory for Mineralization and Efficient Utilization of Critical Metals, Xi\u2019an 710054, China"},{"name":"Chinese Academy of Geological Sciences, Beijing 100037, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,6,6]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"680","DOI":"10.2138\/am.2006.1959","article-title":"Synthetic Ag-rich tourmaline: Structure and chemistry","volume":"91","author":"London","year":"2006","journal-title":"Am. Mineral."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"298","DOI":"10.2138\/am-2018-6289","article-title":"Tourmaline crystal chemistry","volume":"103","author":"Bosi","year":"2018","journal-title":"Am. Mineral."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1054","DOI":"10.2138\/am.2007.2370","article-title":"Crystal chemical relationships in the tourmaline group: Structural constraints on chemical variability","volume":"92","author":"Ferdinando","year":"2007","journal-title":"Am. Mineral."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"895","DOI":"10.2138\/am.2011.3636","article-title":"Nomenclature of the tourmaline-group minerals","volume":"96","author":"Henry","year":"2011","journal-title":"Am. Mineral."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"301","DOI":"10.2113\/gselements.7.5.301","article-title":"Tourmaline: A geologic DVD","volume":"7","author":"Dutrow","year":"2011","journal-title":"Elements"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"126071","DOI":"10.1016\/j.chemer.2023.126071","article-title":"Chemical and boron isotope composition of tourmaline from Koktokay pegmatite, Altay Orogenic Belt, Northwest China: Implications for metallogenic mechanism and prospecting indicator for rare-metal pegmatites","volume":"84","author":"Zheng","year":"2024","journal-title":"Geochemistry"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"552","DOI":"10.2138\/am-2022-8357","article-title":"Tourmaline and zircon trace the nature and timing of magmatic-hydrothermal episodes in granite-related Sn mineralization: Insights from the Libata Sn ore field","volume":"108","author":"Vincent","year":"2023","journal-title":"Am. Mineral."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"153","DOI":"10.3749\/canmin.49.1.153","article-title":"Preliminary experimental data on trace-element partitioning between tourmaline and silicate melt","volume":"49","year":"2011","journal-title":"Can. Mineral."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"117","DOI":"10.3749\/canmin.49.1.117","article-title":"Experimental synthesis and stability of tourmaline: A historical overview","volume":"49","author":"London","year":"2011","journal-title":"Can. Mineral."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1","DOI":"10.3749\/canmin.49.1.1","article-title":"Tourmaline: An ideal indicator of its host environment","volume":"49","author":"Henry","year":"2011","journal-title":"Can. Mineral."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"327","DOI":"10.2113\/gselements.7.5.327","article-title":"Tourmaline as a petrologic forensic mineral: A unique recorder of its geologic past","volume":"7","author":"Henry","year":"2011","journal-title":"Elements"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"132","DOI":"10.1080\/00357529.2016.1113464","article-title":"Reading pegmatites\u2014Part 2: What tourmaline says","volume":"91","author":"London","year":"2016","journal-title":"Rock. Mineral."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"321","DOI":"10.2113\/gselements.7.5.321","article-title":"Tourmaline as a recorder of ore-forming Processes","volume":"7","author":"Slack","year":"2011","journal-title":"Elements"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"105683","DOI":"10.1016\/j.oregeorev.2023.105683","article-title":"In-situ elemental and boron isotopic variations of tourmaline from the Koktokay pegmatitic rare-metal deposit, China: Insights into external contamination and the source of the granitic pegmatite","volume":"162","author":"Bai","year":"2023","journal-title":"Ore Geol. Rev."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"73","DOI":"10.1016\/j.chemgeo.2013.02.025","article-title":"Trace element systematics of tourmaline in pegmatitic and hydrothermal systems from the Variscan Schwarzwald (Germany): The importance of major element composition, sector zoning, and fluid or melt composition","volume":"344","author":"Marks","year":"2013","journal-title":"Chem. Geol."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"428","DOI":"10.18654\/1000-0569\/2022.02.08","article-title":"Geochemistry of tourmaline from granitic pegmatites in East Qinling and its implications for mineralization","volume":"38","author":"Feng","year":"2022","journal-title":"Acta Petrol. Sin."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"105894","DOI":"10.1016\/j.oregeorev.2024.105894","article-title":"Tourmaline geochemical and boron isotopic compositions of the Bailongshan rare-metal pegmatite deposit: Implications for magmatic-hydrothermal evolution of the West Kunlun Orogen (NW China)","volume":"166","author":"Zhang","year":"2024","journal-title":"Ore Geol. Rev."},{"key":"ref_18","first-page":"709","article-title":"Boron isotope geochemistry: An overview","volume":"33","author":"Palmer","year":"1996","journal-title":"Rev. Mineral. Geochem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"431","DOI":"10.1080\/08120099.2013.813585","article-title":"Boron isotope variations and its geochemical application in nature","volume":"60","author":"Xiao","year":"2013","journal-title":"Aust. J. Earth Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1007\/s00410-007-0228-2","article-title":"Tourmaline breakdown in a pelitic system: Implications for boron cycling through subduction zones","volume":"155","author":"Ota","year":"2008","journal-title":"Contrib. Mineral. Petrol."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"465","DOI":"10.1127\/ejm\/2018\/0030-2732","article-title":"Tetrahedral substitutions in tourmaline: A review","volume":"30","author":"Ertl","year":"2018","journal-title":"Eur. J. Mineral."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"495","DOI":"10.2113\/gsecongeo.90.3.495","article-title":"Chemical variation and significance of tourmaline from Southwest England","volume":"90","author":"London","year":"1995","journal-title":"Econ. Geol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1007\/s00410-003-0548-9","article-title":"Boron metasomatism and behaviour of rare earth elements during formation of tourmaline rocks in the eastern Arunta Inlier, central Australia","volume":"147","author":"Raith","year":"2004","journal-title":"Contrib. Mineral. Petrol."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Deer, W.A., Howie, R.A., and Zussman, J. (2013). An Introduction to the Rock-Forming Minerals, The Mineralogical Society.","DOI":"10.1180\/DHZ"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"345","DOI":"10.1016\/S1350-4487(01)00183-4","article-title":"Boron determination in tourmaline by neutron induced radiography","volume":"34","author":"Qureshi","year":"2001","journal-title":"Radiat. Meas."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"255","DOI":"10.2298\/JSC0502255J","article-title":"The spectrophotometric determination of boron in tourmalines","volume":"70","year":"2005","journal-title":"J. Serb. Chem. Soc."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"959","DOI":"10.1039\/an9851000959","article-title":"Determination of boron at trace levels in rocks by inductively coupled plasma spectrometry","volume":"110","author":"Walsh","year":"1985","journal-title":"Analyst"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"84","DOI":"10.1007\/s002160051603","article-title":"Application of sodium carbonate-zinc oxide decomposition mixture on ICP-AES determination of boron in tourmaline","volume":"367","author":"Lihareva","year":"2000","journal-title":"Fresenius J. Anal. Chem."},{"key":"ref_29","first-page":"87","article-title":"Sample Digestion Methods","volume":"Volume 15","author":"Holland","year":"2014","journal-title":"Treatise on Geochemistry"},{"key":"ref_30","first-page":"193","article-title":"Wet Digestion Methods","volume":"41","author":"Matusiewicz","year":"2003","journal-title":"Compr. Anal. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/S0022-1139(00)85269-0","article-title":"Isolation of flourine by Moissan: Setting the scene","volume":"33","author":"Banks","year":"1986","journal-title":"J. Fluorine Chem."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Makishima, A. (2016). Thermal Ionization Mass Spectrometry (TIMS): Silicate Digestion, Separation, and Measurement, Wiley-VCH Verlag GmbH & Co. KGaA.","DOI":"10.1002\/9783527696413"},{"key":"ref_33","first-page":"5","article-title":"An introduction to boron: History, sources, uses, and chemistry","volume":"102","author":"Woods","year":"1994","journal-title":"Environ. Health Persp."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"91","DOI":"10.2183\/pjab.66.91","article-title":"Formation of boron-mannitol complex in the hydrofluoric acid solution and a possibility of the use of acids in the separation of boron from the natural rock samples","volume":"66","author":"Ishikawa","year":"1990","journal-title":"Proc. Japan Acad. Ser. B"},{"key":"ref_35","first-page":"89","article-title":"Determination of B2O3 in tourmaline by inductively coupled plasma-optical emission spectrometry (ICP-OES)","volume":"7","author":"Chen","year":"2017","journal-title":"Chin. J. Inorg. Anal. Chem."},{"key":"ref_36","first-page":"150","article-title":"A table of polyatomic interferences in ICP-MS","volume":"19","author":"May","year":"1998","journal-title":"Atom. Spectrosc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"846","DOI":"10.1039\/C7JA00400A","article-title":"Precise and accurate boron and lithium isotopic determinations for small sample-size geological materials by MC-ICP-MS","volume":"33","author":"Liu","year":"2018","journal-title":"J. Anal. At. Spectrom."},{"key":"ref_38","doi-asserted-by":"crossref","unstructured":"Tan, X.J., Zhou, R.L., Feng, Y.G., and Liang, T. (2023). In-depth method investigation for determination of boron in silicate samples using an improved boron\u2013mannitol complex digestion method by inductively coupled plasma mass spectrometry. Molecules, 28.","DOI":"10.3390\/molecules28010441"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"918","DOI":"10.1127\/ejm\/2019\/0031-2864","article-title":"Thermal decomposition kinetics of Fe-rich tourmaline","volume":"31","author":"Liu","year":"2019","journal-title":"Eur. J. Mineral."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"1295","DOI":"10.1134\/S1061934820100147","article-title":"General high-pressure closed acidic decomposition method of rock samples for trace element determination using inductively coupled plasma mass spectrometry","volume":"75","author":"Tan","year":"2020","journal-title":"J. Anal. Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"229","DOI":"10.2113\/gscanmin.45.2.229","article-title":"Tourmaline: Structural formula calculations","volume":"45","author":"Clark","year":"2007","journal-title":"Can. Mineral."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"955","DOI":"10.1039\/ja9951000955","article-title":"Determination of boron using mannitol-assisted electrothermal vaporization for sample introduction in inductively coupled plasma mass spectrometry","volume":"10","author":"Wei","year":"1995","journal-title":"J. Anal. At. Spectrom."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1343","DOI":"10.1135\/cccc19761343","article-title":"Volumetric determination of boron in natural borosilicates","volume":"41","author":"Povondra","year":"1976","journal-title":"Collect. Czech. Chem. Commun."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1131","DOI":"10.1007\/s10876-015-0948-9","article-title":"Structure of aqueous lithium tetraborate solution","volume":"27","author":"Zhou","year":"2016","journal-title":"J. Clust. Sci."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"100342","DOI":"10.1016\/j.cdc.2020.100342","article-title":"First, in situ generated mannitol-boron or sorbitol-boron chelate complex as a novel, recyclable catalyst for the highly efficient synthesis of bis (indolyl) methanes, tris (indolyl) methanes and diindolyl (carbazolyl) methanes","volume":"25","author":"Lavanya","year":"2020","journal-title":"Chem. Data Collec."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"2612","DOI":"10.1021\/ac00222a017","article-title":"Suppression of boron volatilization from a hydrofluoric acid solution using a boron-mannitol complex","volume":"62","author":"Ishikawa","year":"1990","journal-title":"Anal. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/11\/2701\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T14:54:45Z","timestamp":1760108085000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/11\/2701"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,6,6]]},"references-count":46,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2024,6]]}},"alternative-id":["molecules29112701"],"URL":"https:\/\/doi.org\/10.3390\/molecules29112701","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2024,6,6]]}}}