Supplementary Material 1 Analytical Methods / ICP-MS Analyses

Supplementary Material 1 – Analytical methods / ICP-MS analyses

Trace element concentrations (Li, Cd, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Cs, Ba, Rare Earth Elements (REE), Hf, Ta, Pb, Th, U and W) were determined on-shore using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) on 228 samples in seven geochemistry laboratories.

A first set of samples was analyzed at the University Montpellier 2 (France) on a quadrupole VG-PQ2 ICP-MS (23 samples) and on a ThermoFinnigan Element2 High Resolution ICP-MS (12 samples) following the procedure described in Ionov et al. (1992) and in Godard et al. (2000). The method involves dissolution of 100 mg aliquots in a HF/HClO4 mixture and dilution by a factor ranging from 1000 to 4000 depending on the concentration of the elements. In and Bi were used as internal standards during ICP-MS measurements. Elemental concentrations were determined by external calibration using multi-element standard solutions (Merck) except for Nb and Ta. To avoid memory effects due to the introduction of concentrated Nb-Ta solutions in the instrument, Nb and Ta concentrations were determined by using, respectively, Zr and Hf as internal standards. This technique is an adaptation to ICP-MS analysis of the method described by Jochum et al. (1990) for the determination of Nb by spark-source mass spectrometry.

A second set of 25 samples was analyzed at the University of Jena (Germany) on a Thermo Fisher Scientific X-Series II quadrupole ICP-MS for all elements except Ti and Zr, which were determined on a Spectroflame (Spectro) Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). The method involves dissolution of 100 mg aliquots in a HF/HClO4/HNO3/HCl mixture and dilution by a factor of 1250 and 2500 for, respectively, ICP-OES and ICP-MS measurements. Ru and Re were used as internal standards.

A third set of 69 samples was analyzed on an Agilent 7500c ICP-MS at the University of Tokyo (Japan). They were prepared following the procedure detailed in Kato et al (2005): 50 mg aliquots were dissolved in a HF/HNO3/HClO4 and the final product was diluted to 1:2000 by mass. A subset of 4 samples were duplicated using the alkali fusion procedure detailed in Awaji et al (2006). A 4:1 mixture of flux (400 mg) and powdered rock sample (100 mg), stirred with a few drops of LiBr solution, was fused; the resulting glass bead was dissolved in a HF/HNO3/HClO4 mixture; the solution was diluted to 1:1000 by mass. Concentrations were the same within the analytical errors using both digestion procedures, except for Zr and Hf in the most differentiated rock samples: Zr and Hf concentrations were higher in duplicates digested using alkali fusion. These elements concentrate in highly refractory microphases, such a zircon or xenotime, which were dissolved better using the alkali fusion procedure.

A fourth set of 24 samples was analyzed using a Thermo Finnigan NEPTUNE double focusing high-resolution multicollector ICP-MS at the University of Bergen (Norway). Prior to the analyses, 100 mg sample powder were dissolved in a HNO3/HF/HClO4 mixture and then diluted by a factor of ~2000 for REE and ~7000 for trace elements. In was used as an internal standard during ICP-MS measurements. REE concentrations were determined by external calibration using Analytika (CZ 9088, MIX 008), while Diabase W2 (USGS) was used for U, Th, Sr, Zr, Hf, Rb and Ba. Standard addition procedure was used for calibration.

A fifth set of 25 samples was analyzed on a Sciex Elan model 250 ICP-MS at Washington State University (USA) following the method described in Knaack et al (1994). The procedure for sample preparation involves mixing 2g of mineral powder with an equal amount of lithium tetraborate flux. The mixture is fused and the fusion bead is ground; 250 mg of this powder is dissolved using HF/HNO3/HClO4 than diluted by a factor of 240. In, Re, and Ru are used as internal standards.

Trace element analyses at the Max-Planck-Institute for Chemistry in Mainz (Germany) were measured in-situ by LA-ICP-MS after making glasses of 23 of the shipboard powders following the technique described in Stoll et al. (2008). The glasses were analyzed in two sessions on a ThermoFinnigan Element2 sector-field ICP-MS, combined with a New Wave UP-193 ablation laser, using a 100 µm spot diameter, and energy density of 7 J/cm2 and helium as ablation medium. Further operating conditions were 80 scans per analysis (of which the first 20 served to monitor the background and possible memory effects), and a wash-out time of 45 s between analyses. All measured masses were ratioed to 43Ca, which served as reference mass. NIST-612 and basaltic glass KL2-G were used as internal standards, using the compiled values reported by Jochum et al. (2006). BIR-1 and the fused powder of BHVO-2 were used as external standards. The reported data are the weighted means of 3 to 6 spot analyses.

The final 25 samples were analyzed on a Thermo Electron X7 ICP-MS at the Pierre Sue CEA-CNRS Laboratory (France) following the method described in Mariet et al (submitted). Prior to the analyses, 50 mg sample powder were dissolved in a HNO3/HF/HClO4 mixture and then diluted by a factor of 500 for V, Cs, La, Ce, Pr and Nd and of 50 for the other trace elements. Ge, In, Tm and Bi were used as internal standards during ICP-MS measurements. REE concentrations were determined by external calibration using e reference solution from SPEX (Ref 1640).

We used two certified reference materials, serpentinite UB-N and basalt BIR-1, (i) to identify interlaboratory and method biases for trace element analyses and, (ii) the accuracy of the analyses. In addition to UB-N and BIR-1, we used internal standards to test the reproducibility and repeatability of trace element analyses. The internal standards are four samples from Hole U1309D we considered as representative of the dominant lithologies at this borehole: SR1, an olivine gabbro, SR2, a gabbro, SR3, an oxide gabbro and SR4, an orthopyroxene-bearing gabbro. Reproducibility of these references samples is generally better than 5% for the analyzed elements at concentrations > 1 ppm; it is better than 10% for concentrations > 0.5 ppm; it is within 10-20% and 20-40% for concentrations of 0.01-0.5 ppm and less than 0.01 ppm respectively. The individual results for UB-N, BIR-1 and the internal rock standards from the seven laboratories are listed in Table A1.

References:

Awaji, S., Nakamura, K., Nozaki, T. and Kato, Y., 2006. A simple method for precise determination of 23 trace elements in granitic rocks by ICP-MS after lithium tetraborate fusion. Resource Geology, 56: 449-456.

Godard, M., Jousselin, D. and Bodinier, J.-L., 2000. Relationships between geochemistry and structure beneath a palaeo-spreading centre: A study of the mantle section in the Oman Ophiolite. Earth Planet. Sci. Lett., 180: 133-148.

Govindaraju, K., 1994. 1994 compilation of working values and sample description for 383 geostandards. Geostandards Newsletter, 18(Sp. Issue): 1-158.

Ionov, D.A., Savoyant, L. and Dupuy, C., 1992. Application of the ICP-MS technique to trace element analysis of peridotites and their minerals. Geostand. Newslett., 16: 311-315.

Jochum, K.P., Seufert, H.M. and Thirwall, M.F., 1990. High-sensitivityNb analysis by spark-source mass spectrometry (SSMS) and calibration of XRF Nb and Zr. Chem. Geol., 81: 1-16.

Jochum, K.P., Stoll, B., Herwig, K., Willbold, M., Hofmann, A.W., Amini, M., Aarburg, S., Abouchami, W., Hellebrand, E., Mocek, B., Raczek, I., Stracke, A., Alard, O., Bouman, C., Becker, S., Ducking, M., Bratz, H., Klemd, R., de Bruin, D., Canil, D., Cornell, D., de Hoog, C.J., Dalpe, C., Danyushevsky, L., Eisenhauer, A., Premo, W.R., Sun, W.D.D., Tiepolo, M., Vannucci, R., Vennemann, T., Wayne, D. and Woodhead, J.D., 2006. MPI-DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios. Geochemistry Geophysics Geosystems, 7: Q02008, doi:10.1029/2005GC001060.

Kato, Y., Fujinaga, K. and Suzuki, K., 2005. Major and trace element geochemistry and Os isotopic composition of metalliferous umbers from the late Cretaceous Japanese accretionary complex. Geochem. Geophys. Geosyst., 6: Q07004, doi:10.1029/2005GC000920.

Knaack, C., Cornelius, S.B. and Hooper, P.R., 1994. Trace Element Analyses of Rocks and Minerals by ICP-MS (available at

Mariet, C., Belhadj, O., Leroy, S., Carrot, F. and Métrich, F., submitted. Relevance of NH4F in acid digestion before ICPMS analysis. Talanta

Stoll, B., Jochum, K.P., Herwig, K., Amini, M., Flanz, M., Kreuzburg, B., Kuzmin, D., Willbold, M. and Enzweiler, J., 2008. An automated iridium-strip heater for LA-ICP-MS bulk analysis of geological samples. Geostandards and Geoanalytical Research 32(1): 5-26.

Table A1 (1/6):Values obtained during this study for international rock standards,basalt BIR-1and serpentinite UBN and for in-house rock standards chosen amongst Site U1309 samples: SR1, an olivine gabbro, SR2, a gabbro, SR3, an oxide gabbro and SR4, an orthopyroxene-bearing gabbro. Concentrations are in ppm.

Sample / UB-N
Source / Lab. A (1) / Lab. B / Lab. C / Lab. D / Lab. E / Lab. F / Lab. A (2) / Average / Precision (%) / Pref'd values / Accuracy (%)
n analyses / 8 / 3 / 1 / 3 / 2 / 3 / 4
ppm
Li / 26.4 / 25.2 / 32.0 / 26.8 / n.a. / 27.4 / 26.8 / 27 / 8.6 / 27 / 1.6
Cd / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / 0.049 / 0.049
Sc / 13.0 / 12.1 / 14.9 / 11.4 / 15.0 / n.d. / 12.8 / 13 / 11.2 / 13 / 1.7
Ti / 588.6 / 529.0 / n.d. / 581.0 / n.a. / 543.4 / n.a. / 560 / 5.1 / 659 / -14.9
V / n.a. / 60.3 / 60.8 / n.a. / n.a. / n.a. / 69.1 / 63 / 7.8 / 75 / -15.5
Cr / n.a. / 2421.0 / n.a. / n.a. / n.a. / n.a. / n.a. / 2421 / 2300 / 5.3
Co / 100.1 / 96.9 / 120.2 / 99.1 / n.a. / 92.5 / 104.8 / 102 / 9.5 / 100 / 2.3
Ni / 2007.9 / 1916.9 / n.d. / 2001.8 / n.a. / 1834.5 / 1950.4 / 1942 / 3.7 / 2000 / -2.9
Cu / 25.8 / 26.9 / 32.1 / 23.0 / n.a. / n.d. / 26.0 / 27 / 12.4 / 28 / -4.4
Zn / n.a. / 82.0 / 86.7 / n.a. / n.a. / n.a. / n.a. / 84 / 4.0 / 85 / -0.7
Rb / 3.30 / 3.32 / 3.76 / 3.27 / 3.40 / 3.04 / 3.16 / 3.32 / 6.9 / 3.50 / -5.1
Sr / 7.70 / 7.20 / 9.39 / 7.00 / 8.45 / 7.19 / 7.25 / 7.7 / 11.3 / 7.66 / 1.0
Y / 2.50 / 2.68 / 2.71 / 2.38 / 2.74 / 2.26 / 2.50 / 2.5 / 7.1 / 2.5 / 1.5
Zr / 3.98 / 3.98 / 4.48 / n.a. / 3.79 / 3.33 / 3.22 / 3.80 / 12.3 / 3.58 / 6.1
Nb / 0.06 / 0.06 / n.d. / n.a. / 0.06 / b.q.l. / 0.07 / 0.06 / 8.1 / 0.05 / 25.3
Cs / 11.91 / 10.16 / 13.95 / 9.94 / 11.34 / 9.81 / 11.05 / 11.17 / 13.0 / 10 / 11.7
Ba / 28.33 / 26.78 / 29.32 / 25.70 / 23.99 / 28.01 / 25.51 / 26.81 / 7.0 / 27 / -0.7
La / 0.32 / 0.31 / 0.38 / 0.29 / 0.32 / 0.35 / 0.22 / 0.31 / 15.7 / 0.35 / -10.3
Ce / 0.83 / 0.79 / 0.91 / 0.79 / 0.83 / 0.85 / 0.78 / 0.83 / 5.5 / 0.83 / -0.5
Pr / 0.12 / 0.12 / 0.14 / 0.12 / 0.13 / 0.12 / 0.11 / 0.12 / 7.1 / 0.12 / 1.3
Nd / 0.64 / 0.60 / 0.70 / 0.54 / 0.64 / 0.63 / 0.60 / 0.62 / 8.0 / 0.6 / 3.7
Sm / 0.22 / 0.21 / 0.27 / 0.18 / 0.21 / 0.22 / 0.20 / 0.22 / 12.9 / 0.2 / 7.9
Eu / 0.08 / 0.08 / 0.10 / 0.07 / 0.09 / 0.08 / 0.08 / 0.08 / 11.1 / 0.08 / 3.0
Gd / 0.34 / 0.30 / 0.36 / 0.30 / 0.35 / 0.33 / 0.33 / 0.33 / 7.0 / 0.311 / 6.4
Tb / 0.06 / 0.06 / 0.06 / 0.06 / 0.07 / 0.06 / 0.06 / 0.06 / 7.0 / 0.06 / 3.5
Dy / 0.47 / 0.42 / 0.45 / 0.38 / 0.49 / 0.42 / 0.43 / 0.44 / 8.5 / 0.41 / 6.7
Ho / 0.10 / 0.09 / 0.10 / 0.09 / 0.11 / 0.09 / 0.09 / 0.10 / 7.5 / 0.10 / 0.5
Er / 0.31 / 0.27 / 0.34 / 0.24 / 0.31 / 0.28 / 0.28 / 0.29 / 11.3 / 0.28 / 3.2
Tm / 0.05 / 0.04 / 0.05 / n.a. / 0.05 / 0.04 / 0.04 / 0.04 / 7.1 / 0.045 / -1.3
Yb / 0.31 / 0.29 / 0.36 / 0.24 / 0.31 / 0.29 / 0.27 / 0.30 / 12.1 / 0.293 / 1.2
Lu / 0.05 / 0.05 / 0.05 / 0.05 / 0.05 / 0.04 / 0.05 / 0.049 / 8.0 / 0.05 / -1.5
Hf / 0.13 / 0.11 / 0.18 / n.a. / 0.14 / n.d. / 0.12 / 0.14 / 18.2 / 0.13 / 4.1
Ta / 0.02 / 0.03 / 0.03 / n.a. / 0.02 / b.q.l. / 0.02 / 0.024 / 22.9 / 0.020 / 18.4
Pb / 13.74 / n.d. / n.d. / n.d. / 12.56 / 13.58 / 11.39 / 12.8 / 8.5 / 13 / 0.1
Th / 0.07 / 0.12 / 0.09 / n.a. / 0.07 / b.q.l. / 0.06 / 0.084 / 30.4 / 0.071 / 17.7
U / 0.06 / 0.05 / 0.07 / n.a. / 0.05 / 0.06 / 0.05 / 0.057 / 15.1 / 0.060 / -4.4
W / n.a. / n.a. / n.a. / n.a. / 19.1 / n.a. / 25.7 / 22 / 20.9 / 20 / 11.9

Abbreviations: Pref’d values: Preferred values for UBN and BIR-1 after Govindaraju (1994); n = number of analyses; n.a.: not analyzed; b.d.l.: below detection limit; b.q.l.: below quantification limit; n.d.: not determined; Precision (%) : 100 x Standard Deviation / Average; Accuracy (%) : 100 x (Average – Pref’d values)/ Average; Lab. A: Geosciences Montpellier (University Montpellier 2, France) – analyses carried out on (1) a quadrupole VG-PQ2 ICP-MS and (2) a ThermoFinnigan Element2 High Resolution ICP-MS; Lab. B: Department of Geosystem Engineering (University of Tokyo, Japan); Lab. C : University of Bergen (Norway); Lab. D: Pierre Sue CEA-CNRS Laboratory (France); Lab. E : Washington State University (USA); Lab. F: University of Jena (Germany); Lab. G: Max-Planck-Institute for Chemistry (Mainz, Germany).

Table A1 (2/6)

Sample / BIR-1
Source / Lab. A (1) / Lab. B / Lab. G / Lab. D / Lab. F / Lab. A (2) / Average / Precision (%) / Pref'd values / Accuracy (%)
n analyses / 7 / 2 / 6 / 1 / 3 / 3
ppm
Li / 3.1 / 3.1 / 2.9 / 3.0 / 3.2 / 3.0 / 3.0 / 3.0 / 3 / -10.6
Cd / n.a. / n.a. / n.a. / n.a. / n.a. / 0.117 / 0.117 / 0.114
Sc / 44 / 44 / 41 / 42 / 35 / 44 / 41.7 / 8.7 / 44 / -5.2
Ti / 5251 / 5717 / 5800 / n.a. / 5531 / n.a. / 5575 / 4.4 / 5755 / -3.1
V / n.a. / 332 / n.a. / n.a. / n.a. / 350 / 341 / 3.7 / 313 / 8.9
Cr / n.a. / 425 / n.a. / n.a. / n.a. / n.a. / 425 / - / 382 / 11.3
Co / 51 / 54 / 51 / 53 / 51 / 55 / 52 / 3.5 / 51 / 2.0
Ni / 183 / 182 / 174 / 174 / 158 / 183 / 176 / 5.6 / 166 / 5.8
Cu / 120 / 110 / 116 / 125 / 114 / 125 / 118.1 / 5.2 / 126 / -6.2
Zn / n.a. / 76.7 / n.a. / n.a. / n.a. / n.a. / 76.7 / - / 71 / 8.1
Rb / 0.19 / n.d. / 0.19 / 0.19 / 0.22 / 0.18 / 0.20 / 7.6 / 0.25 / -21.7
Sr / 105 / 110 / 112 / 111 / 109 / 108 / 109.1 / 2.2 / 108 / 1.0
Y / 15.9 / 16.8 / 13.9 / 15.1 / 14.09 / 16.61 / 15.4 / 8.1 / 16 / -3.7
Zr / 15.55 / 16.04 / 13.23 / n.a. / 15.55 / 16.46 / 15.37 / 8.2 / 15.5 / -0.9
Nb / 0.57 / 0.57 / 0.53 / n.a. / n.d. / 0.60 / 0.57 / 5.6 / 0.6 / -5.2
Cs / 0.006 / 0.009 / 0.007 / b.q.l. / n.d. / 0.01 / 0.007 / 23.8 / 0.007 / -4.3
Ba / 6.57 / 6.57 / 6.37 / 6.99 / 6.98 / 5.99 / 6.58 / 5.8 / 7 / -6.0
La / 0.61 / 0.62 / 0.57 / 0.55 / 0.61 / 0.54 / 0.58 / 5.6 / 0.62 / -5.8
Ce / 1.92 / 1.95 / 1.84 / 1.85 / 1.91 / 1.78 / 1.88 / 3.3 / 1.95 / -3.8
Pr / 0.37 / 0.38 / 0.35 / 0.35 / 0.37 / 0.34 / 0.36 / 4.0 / 0.38 / -4.8
Nd / 2.44 / 2.42 / 2.28 / 2.24 / 2.51 / 2.30 / 2.37 / 4.5 / 2.5 / -5.4
Sm / 1.09 / 1.14 / 1.05 / 1.01 / 1.13 / 1.00 / 1.07 / 5.6 / 1.1 / -2.7
Eu / 0.53 / 0.54 / 0.51 / 0.48 / 0.53 / 0.49 / 0.51 / 4.6 / 0.54 / -5.0
Gd / 1.91 / 1.86 / 1.71 / 1.72 / 1.92 / 1.85 / 1.83 / 5.0 / 1.85 / -1.1
Tb / 0.36 / 0.37 / 0.32 / 0.32 / 0.36 / 0.34 / 0.35 / 6.0 / 0.36 / -3.6
Dy / 2.75 / 2.74 / 2.40 / 2.43 / 2.57 / 2.55 / 2.57 / 5.8 / 2.5 / 2.9
Ho / 0.60 / 0.61 / 0.52 / 0.55 / 0.57 / 0.55 / 0.57 / 6.0 / 0.57 / -0.5
Er / 1.78 / 1.65 / 1.58 / 1.54 / 1.71 / 1.63 / 1.65 / 5.4 / 1.7 / -3.0
Tm / 0.26 / 0.26 / 0.23 / n.a. / 0.24 / 0.24 / 0.25 / 5.9 / 0.26 / -4.9
Yb / 1.68 / 1.77 / 1.58 / 1.53 / 1.66 / 1.52 / 1.62 / 6.0 / 1.65 / -1.6
Lu / 0.28 / 0.26 / 0.23 / 0.24 / 0.25 / 0.25 / 0.25 / 6.7 / 0.26 / -3.5
Hf / 0.58 / 0.55 / 0.52 / n.a. / 0.60 / 0.64 / 0.58 / 7.9 / 0.6 / -3.4
Ta / 0.040 / 0.044 / 0.035 / n.a. / b.q.l. / 0.045 / 0.041 / 11.4 / 0.04 / 2.8
Pb / 3.0 / n.d. / 4.0 / 3.7 / 3.0 / 2.8 / 3.31 / 14.9 / 3 / 10.3
Th / 0.032 / 0.031 / 0.028 / n.a. / b.q.l. / n.d. / 0.031 / 6.8 / 0.03 / 1.7
U / 0.011 / 0.011 / 0.016 / n.a. / 0.015 / 0.009 / 0.013 / 23.2 / 0.01 / 25.1
W / n.a. / n.a. / n.a. / n.a. / n.a. / 0.06 / 0.06 / - / 0.07 / -

Table A1 (3/6)

Sample / SR1
Source / Lab. A (1) / Lab. B / Lab. C / Lab. G / Lab. D / Lab. E / Lab. F / Average / Precision (%)
n analyses / 2 / 3 / 1 / 3 / 1 / 1 / 2
ppm
Li / 2.5 / 3.1 / 2.9 / 2.5 / 3.0 / n.a. / 2.4 / 2.7 / 10.7
Cd / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / n.a.
Sc / 17.9 / 17.3 / 19.0 / 16.8 / 18.4 / 19.7 / n.d. / 18.2 / 5.8
Ti / 1093 / 1060 / n.d. / 1087 / 1099 / n.a. / 1025 / 1073 / 2.9
V / n.a. / 82.3 / 69.0 / n.a. / n.a. / n.a. / n.a. / 76 / 12.5
Cr / n.a. / 1083.1 / n.a. / n.a. / n.a. / n.a. / n.a. / 1083
Co / 57.2 / 61.1 / 61.2 / 59.4 / 58.0 / n.a. / 56.0 / 58.8 / 3.6
Ni / 383 / 400 / 389 / 397 / 367 / n.a. / 344 / 380 / 5.6
Cu / 81.7 / 155.8 / 103.5 / 111.6 / 76.4 / n.a. / 71.46 / 100.1 / 31.5
Zn / n.a. / 19.9 / 38.2 / n.a. / n.a. / n.a. / n.a. / 29.0 / 44.5
Rb / 0.23 / n.d. / 0.23 / 0.21 / 0.27 / 0.32 / 0.20 / 0.24 / 18.6
Sr / 83.9 / 85.4 / 86.8 / 86.9 / 86.7 / 86.7 / 83.3 / 85.7 / 1.8
Y / 4.93 / 5.06 / 4.84 / 4.36 / 5.18 / 5.02 / 4.27 / 4.81 / 7.4
Zr / 9.47 / 7.69 / 9.55 / 7.56 / n.a. / 8.45 / 8.15 / 8.48 / 10.1
Nb / 0.199 / 0.165 / 0.211 / 0.153 / n.a. / 0.169 / n.d. / 0.18 / 13.7
Cs / 0.009 / 0.010 / 0.012 / 0.006 / b.q.l. / 0.010 / n.d. / 0.009 / 25.7
Ba / 1.857 / 2.006 / 2.296 / 1.667 / 2.770 / 2.208 / 1.951 / 2.11 / 17.1
La / 0.241 / 0.224 / 0.385 / 0.204 / 0.280 / 0.245 / 0.213 / 0.26 / 24.3
Ce / 0.782 / 0.762 / 0.878 / 0.756 / 0.910 / 0.807 / 0.750 / 0.81 / 7.9
Pr / 0.158 / 0.152 / 0.211 / 0.147 / 0.200 / 0.161 / 0.149 / 0.17 / 15.5
Nd / 0.952 / 0.923 / 1.050 / 0.933 / 1.040 / 0.973 / 0.972 / 0.98 / 5.1
Sm / 0.396 / 0.405 / 0.493 / 0.403 / 0.460 / 0.399 / 0.409 / 0.42 / 8.9
Eu / 0.254 / 0.245 / 0.275 / 0.255 / 0.280 / 0.271 / 0.254 / 0.26 / 5.0
Gd / 0.634 / 0.621 / 0.662 / 0.602 / 0.710 / 0.676 / 0.654 / 0.65 / 5.5
Tb / 0.118 / 0.115 / 0.129 / 0.109 / 0.140 / 0.134 / 0.114 / 0.12 / 9.5
Dy / 0.862 / 0.843 / 0.907 / 0.787 / 0.930 / 0.944 / 0.806 / 0.87 / 7.0
Ho / 0.186 / 0.185 / 0.195 / 0.167 / 0.210 / 0.197 / 0.175 / 0.19 / 7.7
Er / 0.538 / 0.494 / 0.582 / 0.505 / 0.570 / 0.572 / 0.517 / 0.54 / 6.6
Tm / 0.077 / 0.076 / 0.078 / 0.068 / n.a. / 0.080 / 0.072 / 0.08 / 5.8
Yb / 0.493 / 0.501 / 0.557 / 0.508 / 0.530 / 0.485 / 0.482 / 0.51 / 5.3
Lu / 0.080 / 0.074 / 0.080 / 0.071 / 0.090 / 0.078 / 0.072 / 0.08 / 8.4
Hf / 0.244 / 0.227 / 0.297 / 0.225 / n.a. / 0.257 / n.d. / 0.250 / 11.7
Ta / n.a. / 0.039 / 0.046 / 0.027 / n.a. / 0.032 / b.q.l. / 0.036 / 22.6
Pb / 0.032 / b.q.l. / n.d. / 0.038 / n.d. / 0.052 / 0.079 / 0.05 / 41.5
Th / 0.012 / 0.014 / 0.012 / 0.010 / n.a. / 0.018 / b.q.l. / 0.013 / 25.4
U / 0.006 / 0.005 / 0.006 / 0.003 / n.a. / 0.005 / 0.007 / 0.005 / 24.7
W / n.a. / n.a. / n.a. / n.a. / n.a. / 45 / n.a. / 45 / -

Table A1 (4/6)

Sample / SR2
Source / Lab. A (1) / Lab. B / Lab. C / Lab. G / Lab. D / Lab. E / Lab. F / Average / Precision (%)
n analyses / 2 / 3 / 1 / 3 / 1 / 1 / 2
ppm
Li / 0.8 / 1.3 / 1.0 / 1.1 / 0.9 / n.a. / 0.6 / 0.94 / 26.5
Cd / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / -
Sc / 35.7 / 34.5 / 36.2 / 28.2 / 31.0 / 36.8 / 26.6 / 32.7 / 12.6
Ti / 1422 / 1329 / n.d. / 1216 / 1431 / n.a. / 1325 / 1345 / 6.5
V / n.a. / 145 / 131 / n.a. / n.a. / n.a. / n.a. / 138 / 6.8
Cr / n.a. / 313 / n.a. / n.a. / n.a. / n.a. / n.a. / 313 / -
Co / 33.8 / 35.6 / 35.6 / 31.0 / 34.4 / n.a. / 33.41 / 34.0 / 5.0
Ni / 118 / 125 / 117 / 112 / 112 / n.a. / 108 / 115 / 5.2
Cu / 21.5 / 24.1 / 23.8 / 11.4 / 20.0 / n.a. / 19.99 / 20.1 / 23.0
Zn / n.a. / 24.4 / 27.4 / n.a. / n.a. / n.a. / n.a. / 25.9 / 8.0
Rb / 0.12 / n.d. / 0.12 / 0.11 / 0.10 / 0.22 / 0.11 / 0.13 / 32.8
Sr / 95.2 / 98.8 / 99.3 / 109.2 / 99.8 / 99.2 / 96.9 / 99.8 / 4.5
Y / 7.5 / 7.8 / 7.0 / 5.7 / 6.7 / 7.3 / 6.5 / 6.9 / 10.3
Zr / 6.25 / 5.49 / 6.14 / 3.66 / n.a. / 5.42 / 4.37 / 5.2 / 19.5
Nb / 0.085 / 0.099 / 0.102 / 0.071 / n.a. / 0.072 / b.q.l. / 0.09 / 16.7
Cs / 0.002 / b.q.l. / 0.005 / 0.002 / b.q.l. / 0.003 / n.d. / 0.003 / 50.4
Ba / 2.34 / 2.36 / 3.95 / 2.26 / 2.80 / 2.76 / 2.45 / 2.7 / 21.8
La / 0.26 / 0.23 / 0.34 / 0.21 / 0.26 / 0.25 / 0.24 / 0.26 / 15.8
Ce / 0.82 / 0.82 / 0.87 / 0.72 / 0.83 / 0.81 / 0.81 / 0.81 / 5.5
Pr / 0.17 / 0.17 / 0.20 / 0.15 / 0.19 / 0.17 / 0.16 / 0.17 / 10.0
Nd / 1.11 / 1.11 / 1.18 / 0.93 / 1.07 / 1.09 / 1.15 / 1.09 / 7.5
Sm / 0.52 / 0.52 / 0.59 / 0.44 / 0.51 / 0.51 / 0.55 / 0.52 / 8.8
Eu / 0.40 / 0.40 / 0.39 / 0.39 / 0.38 / 0.42 / 0.40 / 0.40 / 3.0
Gd / 0.92 / 0.91 / 0.90 / 0.72 / 0.88 / 0.94 / 0.93 / 0.88 / 8.6
Tb / 0.18 / 0.17 / 0.17 / 0.14 / 0.17 / 0.19 / 0.17 / 0.17 / 8.9
Dy / 1.33 / 1.30 / 1.23 / 1.03 / 1.23 / 1.35 / 1.23 / 1.24 / 8.7
Ho / 0.29 / 0.29 / 0.29 / 0.22 / 0.28 / 0.29 / 0.27 / 0.27 / 9.9
Er / 0.82 / 0.76 / 0.80 / 0.66 / 0.76 / 0.81 / 0.79 / 0.77 / 7.2
Tm / 0.12 / 0.12 / 0.11 / 0.09 / n.a. / 0.11 / 0.111 / 0.11 / 9.6
Yb / 0.75 / 0.77 / 0.79 / 0.62 / 0.70 / 0.70 / 0.736 / 0.72 / 8.1
Lu / 0.12 / 0.11 / 0.11 / 0.09 / 0.11 / 0.11 / 0.109 / 0.11 / 9.7
Hf / 0.21 / 0.20 / 0.24 / 0.15 / n.a. / 0.22 / n.d. / 0.20 / 16.0
Ta / n.a. / 0.026 / n.d. / 0.015 / n.a. / 0.017 / b.q.l. / 0.02 / 31.8
Pb / 0.042 / n.d. / n.d. / 0.069 / n.d. / 0.075 / 0.057 / 0.061 / 23.8
Th / 0.008 / b.q.l. / b.q.l. / 0.004 / n.a. / 0.010 / b.q.l. / 0.007 / 41.5
U / 0.004 / b.q.l. / 0.003 / 0.001 / n.a. / 0.003 / 0.007 / 0.004 / 53.3
W / n.a. / n.a. / n.a. / n.a. / n.a. / 81 / n.a. / 81 / -

Table A1 (5/6)

Sample / SR3
Source / Lab. A (1) / Lab. B / Lab. G / Lab. D / Lab. E / Lab. F / Average / Precision (%)
n analyses / 2 / 3 / 3 / 1 / 1 / 3
ppm
Li / 1.0 / 1.5 / 0.8 / 1.1 / n.a. / 0.84 / 1.06 / 26.3
Cd / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / -
Sc / 52.1 / 53.0 / 50.8 / 55.3 / 55.9 / 42.0 / 51.5 / 9.8
Ti / n.a. / 35135 / n.a. / n.a. / n.a. / 20860 / 27997 / 36.1
V / n.a. / 1293.8 / n.a. / n.a. / n.a. / n.a. / 1293.8 / -
Cr / n.a. / 220.0 / n.a. / n.a. / n.a. / n.a. / 220.0 / -
Co / 90.8 / 100.0 / 80.7 / 92.8 / n.a. / 92.81 / 91.4 / 7.6
Ni / 108 / 114 / 90 / 103 / n.a. / 96 / 102 / 9.1
Cu / 155.5 / 161.6 / 158.9 / 179.7 / n.a. / 148.2 / 160.8 / 7.3
Zn / n.a. / 318.5 / n.a. / n.a. / n.a. / n.a. / 318.5 / -
Rb / 0.18 / n.d. / 0.20 / 0.63 / 0.60 / 0.24 / 0.37 / 61.0
Sr / 59.8 / 67.1 / 68.0 / 67.3 / 66.3 / 63.72 / 65.4 / 4.7
Y / 32.2 / 35.8 / 32.4 / 35.1 / 31.6 / 29.7 / 32.8 / 7.0
Zr / 65.11 / 54.40 / 61.53 / n.a. / 58.78 / 60.79 / 60.1 / 6.5
Nb / 2.48 / 2.28 / 2.49 / n.a. / 2.38 / n.d. / 2.41 / 4.2
Cs / 0.006 / b.q.l. / 0.008 / b.q.l. / 0.023 / n.d. / 0.012 / 74.6
Ba / 4.22 / 4.55 / 4.27 / 4.74 / 6.82 / 4.49 / 5 / 20.3
La / 0.98 / 1.07 / 1.07 / 0.95 / 1.09 / 0.98 / 1.02 / 5.8
Ce / 3.82 / 4.09 / 3.90 / 4.05 / 3.92 / 3.79 / 3.93 / 3.0
Pr / 0.77 / 0.86 / 0.81 / 0.79 / 0.82 / 0.79 / 0.81 / 3.7
Nd / 5.33 / 5.62 / 5.46 / 5.52 / 5.34 / 5.51 / 5.46 / 2.1
Sm / 2.41 / 2.64 / 2.55 / 2.55 / 2.40 / 2.54 / 2.52 / 3.8
Eu / 1.17 / 1.21 / 1.14 / 1.18 / 1.25 / 1.16 / 1.18 / 3.3
Gd / 4.21 / 4.16 / 4.23 / 4.20 / 4.13 / 4.18 / 4.18 / 0.8
Tb / 0.79 / 0.83 / 0.79 / 0.75 / 0.86 / 0.77 / 0.80 / 5.1
Dy / 5.86 / 6.00 / 5.76 / 5.66 / 6.03 / 5.40 / 5.78 / 4.1
Ho / 1.26 / 1.31 / 1.23 / 1.25 / 1.31 / 1.17 / 1.26 / 4.2
Er / 3.58 / 3.57 / 3.72 / 3.50 / 3.69 / 3.49 / 3.59 / 2.7
Tm / 0.53 / 0.55 / 0.53 / n.a. / 0.53 / 0.50 / 0.53 / 3.6
Yb / 3.37 / 3.69 / 3.57 / 3.53 / 3.32 / 3.33 / 3.47 / 4.4
Lu / 0.56 / 0.54 / 0.54 / 0.53 / 0.53 / 0.51 / 0.53 / 3.0
Hf / 2.02 / 1.88 / 2.09 / n.a. / 2.09 / 2.03 / 2.02 / 4.2
Ta / n.a. / 0.213 / 0.325 / n.a. / 0.296 / b.q.l. / 0.28 / 20.8
Pb / 0.199 / n.d. / 0.177 / n.d. / 0.281 / 0.196 / 0.21 / 21.8
Th / 0.038 / 0.038 / 0.039 / n.a. / 0.087 / b.q.l. / 0.051 / 48.4
U / 0.013 / 0.013 / 0.013 / n.a. / 0.022 / 0.02 / 0.016 / 25.2
W / n.a. / n.a. / n.a. / n.a. / 35.0 / n.a. / 35 / -

Table A1 (6/6)

Sample / SR4
Source / Lab. A (1) / Lab. B / Lab. C / Lab. G / Lab. D / Lab. E / Lab. F / Average / Precision (%)
n analyses / 2 / 3 / 1 / 6 / 1 / 1 / 1
ppm
Li / 0.9 / 0.8 / 0.9 / 0.7 / 0.9 / n.a. / 0.32 / 0.8 / 30.3
Cd / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / n.a. / -
Sc / 37.5 / 36.6 / 39.8 / 34.3 / 39.6 / 40.1 / 27.0 / 36.4 / 12.7
Ti / 1274 / 1259 / n.d. / 1330 / 1335 / n.a. / 1316 / 1303 / 2.6
V / n.a. / 156.3 / 142.8 / n.a. / n.a. / n.a. / n.a. / 150 / 6.4
Cr / n.a. / 1279.4 / n.a. / n.a. / n.a. / n.a. / n.a. / 1279 / -
Co / 40.3 / 42.2 / 41.9 / 36.5 / 40.8 / n.a. / 36.41 / 39.7 / 6.6
Ni / 174 / 182 / 176 / 156 / 163 / n.a. / 149 / 166 / 7.7
Cu / 11.0 / 11.8 / 12.8 / 7.8 / 11.7 / n.a. / 8.5 / 10.6 / 18.9
Zn / n.a. / 14.0 / 20.1 / n.a. / n.a. / n.a. / n.a. / 17.0 / 25.1
Rb / 0.06 / n.d. / 0.06 / 0.05 / 0.11 / 0.13 / 0.03 / 0.07 / 54.9
Sr / 81.7 / 83.1 / 86.3 / 87.3 / 83.8 / 85.3 / 77.5 / 83.5 / 3.9
Y / 7.0 / 7.2 / 6.5 / 5.8 / 7.2 / 6.8 / 5.6 / 6.6 / 10.0
Zr / 4.63 / 4.04 / 4.90 / 3.71 / n.a. / 4.24 / 3.21 / 4.1 / 14.9
Nb / 0.12 / 0.13 / 0.14 / 0.11 / n.a. / 0.12 / b.q.l. / 0.12 / 8.1
Cs / 0.003 / b.q.l. / 0.004 / 0.004 / b.q.l. / 0.002 / n.d. / 0.003 / 32.9
Ba / 1.50 / 1.59 / 2.01 / 1.57 / 1.91 / 2.04 / 1.51 / 1.73 / 14.0
La / 0.21 / 0.17 / 0.32 / 0.17 / 0.26 / 0.22 / 0.17 / 0.22 / 25.0
Ce / 0.66 / 0.64 / 0.75 / 0.66 / 0.81 / 0.71 / 0.63 / 0.70 / 9.4
Pr / 0.15 / 0.14 / 0.18 / 0.14 / 0.19 / 0.15 / 0.14 / 0.15 / 14.1
Nd / 0.98 / 0.94 / 1.05 / 0.95 / 1.12 / 0.98 / 0.98 / 1.00 / 6.5
Sm / 0.48 / 0.48 / 0.58 / 0.47 / 0.56 / 0.46 / 0.50 / 0.50 / 9.2
Eu / 0.36 / 0.35 / 0.35 / 0.36 / 0.41 / 0.37 / 0.36 / 0.365 / 5.6
Gd / 0.86 / 0.82 / 0.84 / 0.77 / 0.95 / 0.89 / 0.85 / 0.85 / 6.7
Tb / 0.16 / 0.16 / 0.16 / 0.15 / 0.19 / 0.18 / 0.15 / 0.17 / 9.2
Dy / 1.23 / 1.17 / 1.13 / 1.07 / 1.35 / 1.25 / 1.11 / 1.19 / 8.1
Ho / 0.26 / 0.26 / 0.27 / 0.23 / 0.31 / 0.27 / 0.25 / 0.26 / 9.6
Er / 0.77 / 0.71 / 0.76 / 0.66 / 0.82 / 0.76 / 0.72 / 0.74 / 7.1
Tm / 0.11 / 0.11 / 0.11 / 0.10 / n.a. / 0.11 / 0.10 / 0.10 / 5.2
Yb / 0.69 / 0.69 / 0.74 / 0.63 / 0.77 / 0.64 / 0.67 / 0.69 / 7.4
Lu / 0.11 / 0.10 / 0.10 / 0.09 / 0.12 / 0.10 / 0.10 / 0.10 / 9.5
Hf / 0.18 / 0.17 / 0.23 / 0.15 / n.a. / 0.20 / n.d. / 0.19 / 16.3
Ta / n.a. / 0.077 / 0.060 / 0.059 / n.a. / 0.065 / b.q.l. / 0.07 / 12.5
Pb / 0.073 / 0.087 / n.d. / 0.066 / n.d. / 0.093 / 0.077 / 0.08 / 13.6
Th / 0.004 / b.q.l. / b.q.l. / 0.004 / n.a. / 0.020 / b.q.l. / 0.009 / 100.6
U / 0.003 / b.q.l. / 0.006 / 0.003 / n.a. / 0.007 / 0.01 / 0.005 / 40.3
W / n.a. / n.a. / n.a. / n.a. / n.a. / 109 / n.a. / 109 / -