Sample digestion is a critical stage in the process of chemical analysis of geological materials by ICP-MS. We present a new HF/HNO 3 procedure to dissolve silicate rock samples using a high pressure asher system. The formation of insoluble AlF 3 was the major obstacle in achieving full recoveries. This was overcome by setting an appropriate digestion temperature and adding Mg to the samples before digestion. Sodium peroxide sintering was also investigated and the inclusion of a heating step to the alkaline sinter solution improved the recoveries of thirteen elements other than the lanthanides. The results of these procedures were compared with data sets generated by common acid decomposition techniques. Forty-one trace elements were determined using an ICP-QMS equipped with a collision cell. Under optimum conditions of gas flow and kinetic energy discrimination, polyatomic interferences were eliminated or attenuated. The measurement bias obtained for eight reference materials (BCR-2, BHVO-2, BIR-1, BRP-1, OU-6, GSP-2, GSR-1 and RGM-1) and intermediate precision (RSD) were generally better than ±5%. The expanded measurement uncertainties estimated for two certified reference materials were mostly between 7 and 15%. New data sets for the reference materials are provided, including constituents with previously unavailable values and also for the USGS candidate reference material G-3. © 2011 The Authors. Geostandards and Geoanalytical Research © 2011 International Association of Geoanalysts.3612750Amarasiriwardena, D., Krushevska, A., Argentine, M., Barnes, R.M., Vapor-phase acid digestion of micro samples of biological-material in a high-temperature, high pressure asher for inductively-coupled plasma-atomic emission-spectrometry (1994) The Analyst, 119, pp. 1017-1021Awaji, S., Nakamura, K., Nozaki, T., Kato, Y., A simple method for precise determination of 23 trace elements in granitic rocks by ICP-MS after lithium tetraborate fusion (2006) Resource Geology, 56, pp. 471-478Balaram, V., Ramesh, S.L., Anjaiah, K.V., Comparative study of the sample decomposition procedures in the determination of trace and rare earth elements in anorthosites and related rocks by ICP-MS (1995) Fresenius' Journal of Analytical Chemistry, 353, pp. 176-182Bandura, D.R., Baranov, V.I., Tanner, S.D., Reaction chemistry and collisional processes in multipole devices for resolving isobaric interferences in ICP-MS (2001) Fresenius' Journal of Analytical Chemistry, 370, pp. 454-470Bayon, G., Barrat, J.A., Etoubleau, J., Benoit, M., Bollinger, C., Revillon, S., Determination of rare earth elements, Sc, Y, Zr, Ba, Hf and Th in geological samples by ICP-MS after Tm addition and alkaline fusion (2009) Geostandards and Geoanalytical Research, 33, pp. 51-62Catterick, T., Fairman, B., Harrington, C., Structured approach to achieving high accuracy measurements with isotope dilution inductively coupled plasma mass spectrometry (1998) Journal of Analytical Atomic Spectrometry, 13, pp. 1009-1013Chao, T., Sanzolone, R.F., Decomposition techniques (1992) Journal of Geochemical Exploration, 44, pp. 65-106Cotta, A.J.B., Enzweiler, J., Certificate of analysis of the reference material BRP-1 (Basalt Ribeirão Preto) (2008) Geostandards and Geoanalytical Research, 32, pp. 231-235Cotta, A.J.B., Enzweiler, J., Quantification of major and trace elements in water samples by ICP-MS and collision cell to attenuate Ar and Cl-based polyatomic ions (2009) Journal of Analytical Atomic Spectrometry, 24, pp. 1406-1413Cotta, A.J.B., Enzweiler, J., Wilson, S.A., Pérez, C.A., Nardy, A.J.R., Larizzatti, J.H., Homogeneity of the geochemical reference material BRP-1 (Paraná Basin Basalt) and assessment of minimum mass (2007) Geostandards and Geoanalytical Research, 31, pp. 379-393Cremer, M., Schlocker, J., Lithium borate decomposition of rocks, minerals, and ores (1976) American Mineralogist, 61, pp. 318-321Dexter, M.A., Reid, H.J., Sharp, B.L., The effect of ion energy on reactivity and species selectivity in hexapole collision/reaction cell ICP-MS (2002) Journal of Analytical Atomic Spectrometry, 17, pp. 676-681Du, Z., Houk, R.S., Attenuation of metal oxide ions in inductively coupled plasma-mass spectrometry with hydrogen in a hexapole collision cell (2000) Journal of Analytical Atomic Spectrometry, 15, pp. 383-388Duan, D., Hangting, C., Xianjin, Z., Determination of rare and rare earth elements in soils and sediments by ICP-MS using Ti(OH) 4-Fe(OH) 3 co-precipitation preconcentration (2002) Journal of Analytical Atomic Spectrometry, 17, pp. 410-413Dulski, P., Interferences of oxide, hydroxide and chloride analyte species in the determination of rare earth elements in geological samples by inductively coupled plasma-mass spectrometry (1994) Fresenius' Journal of Analytical Chemistry, 350, pp. 194-203Dulski, P., Reference materials for geochemical studies: New analytical data by ICP-MS and critical discussion of reference values (2001) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 25, pp. 87-125Eggins, S.M., Woodhead, J.D., Kinsley, L.P.J., Mortimer, G.E., Sylvester, P., McCulloch, M.T., Hergt, J.M., Handler, M.R., A simple method for the precise determination of >40 trace elements in geological samples by ICP-MS using enriched isotope internal standardization (1997) Chemical Geology, 134, pp. 311-326Eiden, G., Barinaga, C.J., Koppenaal, D.W., Selective removal of plasma matrix ions in plasma source mass spectrometry (1996) Journal of Analytical Atomic Spectrometry, 11, pp. 317-322Epov, V.N., Larivière, D., Epova, E.N., Evans, R.D., Polyatomic interferences produced by macroelements during direct multi-elemental ICP-MS hydrochemical analysis (2004) Geostandards and Geoanalytical Research, 28, pp. 213-224Feldman, C., Behavior of trace refractory minerals in the lithium metaborate fusion-acid dissolution procedure (1983) Analytical Chemistry, 55, pp. 2451-2453Feldmann, I., Jakubowski, N., Stuewer, D., Application of a hexapole collision and reaction cell in ICP-MS Part I: Instrumental aspects and operational optimization (1999) Fresenius' Journal of Analytical Chemistry, 365, pp. 415-421Hu, Z., Gao, S., Liu, Y., Hu, S., Zhao, L., Lia, Y., Wang, Q., NH 4F assisted high pressure digestion of geological samples for multi-element analysis by ICP-MS (2010) Journal of Analytical and Atomic Spectrometry, 25, pp. 408-413(1992) Terms and definitions used in connection with reference materials, p. 8. , ISO Guide 30 (2nd edition). International Organization for Standardization (Geneva)Jain, J.C., Neal, C.R., Hanchar, J.M., Problems associated with the determination of rare earth elements of a "gem" quality zircon by inductively coupled plasma-mass spectrometry (2001) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 25, pp. 229-237Jarvis, K.E., A critical evaluation of two sample preparation techniques for low-level determination of some geologically compatible elements by ICP-MS (1990) Chemical Geology, 83, pp. 89-103Jochum, K.P., Nohl, U., Herwig, K., Lammel, E., Stoll, B., Hofmann, A.W., GeoReM: A new geochemical database for reference materials and isotopic standards (2005) Geostandards and Geoanalytical Research, 29, pp. 333-338Kane, J., Report of the International Association of Geoanalysts on the certification of Penrhyn Slate, OU-6 (2004) Geostandards and Geoanalytical Research, 28, pp. 53-80Kato, Y., Ohta, I., Tsunematsu, T., Watanabe, Y., Isozaki, Y., Maruyama, S., Imai, N., Rare earth element variations in mid-Archean banded iron formations: Implications for the chemistry of ocean and continent and plate tectonics (1998) Geochimica et Cosmochimica Acta, 62, pp. 3475-3497Kleinhanns, I.C., Kreissig, K., Kamber, B.S., Meisel, T., Nagler, T.F., Kramers, J.D., Combined chemical separation of Lu, Hf, Sm, Nd, and REEs from a single rock digest: Precise and accurate isotope determinations of Lu-Hf and Sm-Nd using multicollector-ICP-MS (2002) Analytical Chemistry, 74, pp. 67-73Leonhard, P., Pepelnik, R., Prange, A., Yamada, N., Yamada, T., Analysis of diluted sea-water at the ngl -1 level using an ICP-MS with an octopole reaction cell (2002) Journal of Analytical Atomic Spectrometry, 22, pp. 189-196Liang, Q., Jing, H., Grégoire, D.C., Determination of trace elements in granites by inductively coupled plasma-mass spectrometry (2000) Talanta, 51, pp. 507-513Liu, Y.S., Zong, K., Kelemen, P.B., Gao, S., Geochemistry and magmatic history of eclogites and ultramafic rocks from the Chinese continental scientific drill hole: Subduction and ultrahigh-pressure metamorphism of lower crustal cumulates (2008) Chemical Geology, 247, pp. 133-153Longerich, H.P., Jenner, G.A., Fryer, B.J., Jackson, S.E., Inductively coupled plasma mass spectrometric analysis of geological samples: Case studies (1990) Chemical Geology, 83, pp. 105-118Madinabeitia, S.G., Lorda, M.E.S., Ibarguchi, J.I.G., Simultaneous determination of major to ultratrace elements in geological samples by fusion-dissolution and inductively coupled plasma-mass spectrometry techniques (2008) Analytica Chimica Acta, 625, pp. 117-130Makishima, A., Nakamura, E., Determination of total sulfur at microgram per gram levels in geological materials by oxidation of sulfur into sulfate with in situ generation of bromine using isotope dilution high resolution ICP-MS (2001) Analytical Chemistry, 73, pp. 2547-2553Makishima, A., Nakamura, E., Determination of major, minor and trace elements in silicate samples by ICP-QMS and ICP-SFMS applying isotope dilution-internal standardisation (ID-IS) and multi-stage internal standardisation (2006) Geostandards and Geoanalytical Research, 30, pp. 245-271Makishima, A., Kobayashi, K., Nakamura, E., Determination of chromium, nickel, copper and zinc in milligram samples of geological materials using isotope dilution high resolution inductively coupled plasma-mass spectrometry (2002) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 26, pp. 41-51McCurdy, E., Woods, G., The application of collision/reaction cell inductively coupled plasma-mass spectrometry to multi-element analysis in variable sample matrices, using He as a non-reactive cell gas (2004) Journal of Analytical Atomic Spectrometry, 19, pp. 607-615McGinnis, C.E., Jain, J.C., Neal, C.R., Characterisation of memory effects and development of an effective wash protocol for the measurement of petrogenetically critical trace elements in geological samples by ICP-MS (1997) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 21, pp. 289-305Meisel, T., Moser, J., Fellner, N., Wegscheider, W., Schoenberg, R., Simplified method for the determination of Ru, Pd, Re, Os, Ir and Pt in chromitites and other geological materials by isotope dilution ICP-MS and acid digestion (2001) The Analyst, 126, pp. 322-328Meisel, T., Schöner, N., Paliulionyte, V., Kahr, E., Determination of rare earth elements, Y, Th, Zr, Hf, Nb and Ta in geological reference materials G-2, G-3, SCo-1 and WGB-1 by sodium peroxide sintering and inductively coupled plasma-mass spectrometry (2002) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 26, pp. 53-61Mori, L., Gómez-Tuena, A., Cai, Y., Goldstein, S.L., Effects of prolonged flat subduction on the Miocene magmatic record of the central Trans-Mexican Volcanic Belt (2007) Chemical Geology, 244, pp. 452-473Muller, M., Heumann, K.G., Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum-group elements (Pt, Pd, Ru, Ir) in environmental samples (2000) Fresenius' Journal of Analytical Chemistry, 368, pp. 109-115Münker, C., Nb/Ta fractionation in a Cambrian arc/back arc system, New Zealand, source constraints and application of refined ICP-MS techniques (1998) Chemical Geology, 144, pp. 23-45Nakamura, K., Chang, Q., Precise determination of ultra-low (sub-ngg -1) level rare earth elements in ultramafic rocks by quadrupole ICP-MS (2007) Geostandards and Geoanalytical Research, 31, pp. 185-197Navarro, M.S., Andrade, S., Ulbrich, H., Gomes, C.B., Girardi, V.A.V., The direct determination of rare earth elements in basaltic and related rocks using ICP-MS: Testing the efficiency of microwave oven sample decomposition procedures (2008) Geostandards and Geoanalytical Research, 32, pp. 167-180Nelms, S.M., (2005) Inductively coupled plasma-mass spectrometry handbook, p. 485. , Blackwell Publishing (Oxford, UK)Niemelä, M., Perämäki, P., Kola, H., Piispanen, J., Determination of arsenic, iron and selenium in moss samples using hexapole collision cell, inductively coupled plasma-mass spectrometry (2003) Analytica Chimica Acta, 493, pp. 3-12(2004), p. 52. , NORDTEST Handbook for calculation of measurement uncertainty in environmental laboratories (2nd edition), Tekniikantie, Finland, (accessed at)Olive, V., Ellam, R.M., Wilson, L., A protocol for the determination of the rare earth elements at picomole level in rocks by ICP-MS: Results on geological reference materials USGS PCC-1 and DTS-1. Geostandards Newsletter (2001) The Journal of Geostandards and Geoanalysis, 25, pp. 219-228Paliulionyte, V., Meisel, T., Ramminger, P., Kettisch, P., High Pressure Asher digestion and an isotope dilution-ICP-MS method for the determination of platinum-group element concentrations in chromitite reference materials CHR-Bkg, GAN Pt-1 and HHH (2006) Geostandards and Geoanalytical Research, 30, pp. 87-96Panteeva, S.V., Gladkochoub, D.P., Donskaya, T.V., Markova, V.V., Sandimirova, G.P., Determination of 24 trace elements in felsic rocks by inductively coupled plasma-mass spectrometry after lithium metaborate fusion (2003) Spectrochimica Acta Part B, 58, pp. 341-350Petrelli, M., Perugini, D., Poli, G., Peccerillo, A., Graphite electrode lithium tetraborate fusion for trace element determination in bulk geological samples by laser ablation ICP-MS (2007) Microchimica Acta, 158, pp. 275-282Pretorius, W., Weis, D., Williams, G., Hanano, D., Kieffer, B., Scoates, J., Complete trace elemental characterisation of granitoid (USGS G-2, GSP-2) reference materials by high resolution inductively coupled plasma-mass spectrometry (2006) Geostandards and Geoanalytical Research, 30, pp. 39-54Raczek, I., Stoll, B., Hofmann, A.W., Jochum, K.P., High-precision trace element data for the USGS reference materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, DTS-1, DTS-2, GSP-1 and GSP-2 by ID-TIMS and MIC-SSMS (2001) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 25, pp. 77-86Raut, N.M., Huang, L.S., Aggarwal, S.K., Lin, K.C., Determination of lanthanides in rock samples by inductively coupled plasma-mass spectrometry using thorium as oxide and hydroxide correction standard (2003) Spectrochimica Acta Part B, 58, pp. 809-822Raut, N.M., Huang, L.S., Lin, K.C., Aggarwal, S.K., Uncertainty propagation through correction methodology for the determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry (2005) Analytica Chimica Acta, 530, pp. 91-103Regnery, J., Stoll, B., Jochum, K.P., High-resolution LA-ICP-MS for accurate determination of low abundances of K, Sc and other trace elements in geological samples (2010) Geostandards and Geoanalytical Research, 34, pp. 19-38Révillon, S., Hureau-Mazaudier, D., Improvements in digestion protocols for trace element and isotope determinations in stream and lake sediment reference materials (JSd-1, JSd-2, JSd-3, JLk-1 and LKSD-1) (2009) Geostandards and Geoanalytical Research, 33, pp. 397-413Robinson, P., Higgins, N.C., Jenner, G.A., Determination of rare-earth elements, yttrium and scandium in rocks by an ion exchange X-ray fluorescence technique (1986) Chemical Geology, 55, pp. 121-137Robinson, P., Townsend, A.T., Yu, Z., Münker, C., Determination of scandium, yttrium and rare earth elements in rocks by high resolution inductively coupled plasma-mass spectrometry (1999) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 23, pp. 31-46Roy, P., Balaram, V., Bhattacharaya, A., Nasipuri, P., Satyanarayanan, M., Estimation of Ti, Zr, Nb, Hf, Ta, Th and U in beach placers and ferrodiorites by inductively coupled plasma-mass spectrometry using lithium metaborate fusion digestion technique (2007) Current Science, 93, pp. 1122-1126SenGupta, J.G., Bertrand, N.B., Direct ICP-MS determination of trace and ultratrace elements in geological materials after decomposition in a microwave oven. 2. Quantitation of Ba, Cs, Ca, Hf, In, Mo, Nb, Pb, Rb, Sn, Sr, Ta and Tl (1995) Talanta, 42, pp. 1947-1957Stoll, B., Jochum, K.P., Herwig, K., Amini, M., Flanz, M., Kreuzburg, B., Kuzmin, D., Enzweiler, J., An automated iridium-strip heater for LA-ICP-MS bulk analysis of geological samples (2008) Geostandards and Geoanalytical Research, 32, pp. 5-26Takei, H., Yokoyama, T., Makishima, A., Nakamura, E., Formation and suppression of AlF 3 during HF digestion of rock samples in Teflon bombs for precise trace element analyses by ICP-MS and ID-TIMS (2001) Proceedings of the Japan Academy, Series B, 77, pp. 13-17Tan, S.H., Horlick, G., Background spectral features in inductively coupled plasma/mass spectrometry (1986) Applied Spectroscopy, 40, pp. 445-460Tanner, S.D., Baranov, V.I., Bandura, D.R., Reaction cells and collision cells for ICP-MS: A tutorial review (2002) Spectrochimica Acta Part B, 57, pp. 1361-1452Totland, M., Jarvis, I., Jarvis, K.E., An assessment of dissolution techniques for the analysis of geological samples by plasma spectrometry (1992) Chemical Geology, 95, pp. 35-62Totland, M., Jarvis, I., Jarvis, K.E., Microwave digestion and alkali fusion procedures for the determination of the platinum-group elements and gold in geological materials by ICP-MS (1995) Chemical Geology, 124, pp. 21-36Turner, P., Merren, T., Speakman, J., Haines, C., Interface studies in the ICP-mass spectrometer (1997) Plasma Source Mass Spectrometry: Developments and Applications, pp. 28-34. , Holland, G., Tanner, S.D. (eds), The Royal Society of Chemistry (Cambridge)(2008), p. 90. , VIM International vocabulary of metrology - Basic and general concepts and associated terms (VIM). (3rd edition), JCGM 200:2008Willbold, M., Jochum, K.P., Multi-element isotope dilution sector field ICP-MS: A precise technique for the analysis of geological materials and its application to geological reference materials (2005) Geostandards and Geoanalytical Research, 29, pp. 63-82Wu, S., Zhao, Y.H., Feng, X.B., Wittmeier, A., Application of inductively coupled plasma-mass spectrometry for total metal determination in silicon-containing solid samples using the microwave-assisted nitric acid-hydrofluoric acid-hydrogen peroxide-boric acid digestion system (1996) Journal of Analytical Atomic Spectrometry, 11, pp. 287-296Yamada, N., Takahashi, J., Sakata, K., The effects of cell-gas impurities and kinetic energy discrimination in an octopole collision cell ICP-MS under non-thermalized conditions (2002) Journal of Analytical Atomic Spectrometry, 17, pp. 1213-1222Yang, L., Lam, J.W.H., Sturgeon, R.E., McLaren, J.W., Decomposition of marine sediments for quantitative recovery of chromium and inductively coupled plasma mass spectrometric analysis (1998) Journal of Analytical Atomic Spectrometry, 13, pp. 1245-1248Yokoyama, T., Makishima, A., Nakamura, E., Evaluation of the coprecipitation of incompatible trace elements with fluoride during silicate rock dissolution by acid digestion (1999) Chemical Geology, 157, pp. 175-187Yu, Z., Robinson, P., Townsend, A.T., Münker, C., Crawford, A.J., Determination of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ngg -1 levels in geological reference materials by magnetic sector ICP-MS after HF/HClO 4 high pressure digestion (2000) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 24, pp. 39-50Yu, Z., Robinson, P., McGoldrick, P., An evaluation of methods for the chemical decomposition of geological materials for trace element determination using ICP-MS (2001) Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 25, pp. 199-217Zheng, J.P., Sun, M., Griffin, W.L., Zhou, M.F., Zhao, G.C., Robinson, P., Tang, H.Y., Zhang, Z.H., Age and geochemistry of contrasting peridotite types in Dabie UHP belt, eastern China: Petrogenetic and geodynamic implications (2008) Chemical Geology, 247, pp. 282-304