The laser ablation technique, coupled with the use of quadrupole ICPMS equipment, proved a powerful tool for determination of trace elements in minerals. At the University of São Paulo, the technique was implemented for the study of minerals such as olivines, pyroxenes and biotites. The main problem to be tackled is the availability of proper multi-element reference materials usually prepared synthetically as glasses with various compositions by NIST and fused rock glasses by the Max Planck Institute (MPI) and USGS (basalts, andesite, quartz diorite, komatiites). The best tested ones are the NIST glasses, with good homogeneity and reliable compositional data for over 40 elements. Results are here presented that test additional RM’s. NIST 612 and 610 were used for calibration purposes. The best results were obtained for rock glasses USGS basalts BHVO-2G, BIR- 1G and BCR-2G (better homogeneity and recommended values). Our contribution tests especially the MPI komatiites glasses GOR-128 and GOR-132G, basalts KL-2G and ML-3BG, andesite StHs-6/ 80G and quartz diorite T-1G, discussing homogeneity issues and providing new data. There is a need for additional preparation of reliable reference materials.
Inductively coupled plasma mass spectrometry, hyphenated with laser ablation (LA-ICPMS), represents an important tool for the direct chemical analyses in solid phases. The main advantage is the possibility of determining the composition even in substances with a complex matrix, as usually present in geologic and environmental materials, semi-conductors, and others. The technique has the advantage of high sensitivity, a wide range of linear intensity responses, and requiring little surface preparation, without presenting major problems with contamination issues. The obtained results can be expressed as either elemental or isotopic proportions and the spatial resolution is of the order of 10 to 300 µm and depth resolution is about 60 nm per pulse [
Mass spectrometers can isolate ions with a positive charge effectively by their mass/charge relations. Three types of equipments are available, each one with its own advantages and shortcomings, the quadrupole setting, the time-of-flight performance and the high-resolution sector arrangement.
The quadrupole mass spectrometer setting is the most cost-effective, and hence has become the preferred instrument in many laboratories. The equipment generates voltage intervals and radiofrequencies that can stabilize a definite ion within the quadrupole rods and guide it towards the detector window. Given a predefined setting, ions with a different mass-to-charge ratio will become unstable and be eliminated within the vacuum system. All the desired spectra of ionic masses can be quickly scanned within the quadrupole. Although this analyzer works in a sequential fashion, it can separate efficiently more than 5000 atomic mass units (amu) per second [
Therefore, Q-ICPMS equipments associated with laser ablation can perform very fast multi-element determinations of over 40 elements, with sensitivities of the order of ng∙g−1 in any mineral phase, or of materials hidden within them, such as fluid inclusions, in a time-span that does not exceed 1 or 2 minutes of operation.
These techniques opened up new fields of research in igneous petrology, mineralogy and geochronology, determining the distribution of trace elements in several phases (both solid as well as liquid), and enabling also the calculation of the corresponding partition coefficients between mineral pairs, or mineral phases and melts [
The main drawback of the quadrupole setting associated with LA is the possibility of isotopic fractionation during analysis, a subject widely discussed in the literature [
The implementation of this methodology at our laboratory started with the handling and analytical determinations using NIST materials for calibration, followed by analytical determinations of the USGS synthetic basaltic glasses (BHVO-2G, BIR-1G and BCR-2G) [
The indications given in [
Mean analytical time spent for analyzing up to 44 elements was 120 s (60 s for reading a blank, 60 s for preparing the instrument and reading results from the analyzed sample). Intensities in cps are calculated as concentrations in real time by the Glitter® software (developed by the GEMOC program, Geochemical Evolution and Metallogeny of Continents, Macquarie University, Australia) [
Our results were obtained from the determination of the before-mentioned RM’s (USGS basalt glasses BHVO-2G, BIR-1G and BCR-2G; Max Planck’s komatiites GOR-128 and GOR-132G, basalts KL02G and ML03BG, quartz diorite T-1G, andesite StHs-6/80G). The obtained results were processed with the Glitter® software [
The analyzed elements and their masses (cited in
The sequence for data acquisition is as follows:
Nist-612 (a), Nist-612 (b), sample (1), ···, sample (6), Nist-612 (c), Nist-612 (d), sample (7), ···, sample (14), Nist-612 (e), Nist-612 (f).
Cleaning was performed after each sample analysis for about 2 minutes with He fluxes, a procedure that stabilizes rapidly the background values, more so than an alternative method, such as obtained with the use of Argon gas. Readings from Nist-612 (a, b, c, d, e, f) were used as an internal standard and for drift correction during the entire 1-hour analytical work. The entire procedure lasts about 3 hours, counting also laser and plasma stabilization times at the beginning of the determinations.
Isotopic interferences occurring during analysis, such as the ones due to 28Si17O+, 27Al18O+, 90Zr2+ on 45Sc+; 43Ca16O+ on 59Co+; 44Ca16O+ on 60Ni; 135Ba16O+ on 151Eu, and several others, can however be ignored, since they are usually very limited in dry plasmas, with hydroxyl and oxygen absent. The daily rate of generation of oxide was controlled holding ThO+ formation lower than 1%. The formation of double-charged species, such as Ba2+, was kept to a maximum of 3%, controlling the gas fluxes.
. Instrumental parameters used in analytical routine for determination of trace elements by LA-Q-ICPMS
ICP-MS | Elan-6100DRC | Laser Ablation | Laser New Wave UP-213 | |
---|---|---|---|---|
RF power | 1300 W | Type | Nd:YAG | |
Auxiliary gas flux (Ar) | 1.0 L/min | Wavelength | 213 nm | |
Plasma gas flux (Ar) | 16 L/min | Pulse duration | 5 ns | |
Sample cell | Super cell | Laser repeat rate | 10 Hz | |
Carrier gas flux | Ar = 0.58 L/min, He = 0.60 L/min | |||
Distance to sample | 4 mm | |||
Pt Sampler dimension | 1.1 mm | |||
Pt Skimmer dimension | 0.9 mm | |||
Ionic lens voltage | 5.5 to 8.5 V | |||
Energy density | 65% laser power ~8.60 J/cm2 and 0.2 mJ (spot 65 μm) for pyroxenes, amphiboles | |||
Energy density | 70% laser power ~7 - 10 J/cm2 and 0.2 - 0.3 mJ (raster with spot of 65 μm) Ablation speed 5 μm/s, line of 300 μm for quartz, alkali feldspars |
. Time parameters and signal processing used for determinations of trace elements
ICP-Q-MS | Parameters | ICP-Q-MS | Parameters |
---|---|---|---|
Sweeps/reading | 1 | Number of replicates | 1 |
Readings/replicates | 270 | Settling time | 2 ms |
Scan mode | Peak hopping | MCA channel | 1 |
Detector | Analogic pulse | Units | Cps |
Auto-lens | ON | Mode | Standard (without DRC) |
. Analyzed elements and their isotope masses (time parameters of signal integration, see text)
Element | Mass (u.m.a) | Element | Mass (u.m.a) |
---|---|---|---|
Li | 7 | Sn | 118 |
Be | 9 | Sb | 121 |
Mg | 25 | Cs | 133 |
Si | 29 | Ba | 137 |
P | 31 | La | 139 |
Ca | 42 | Ce | 140 |
Sc | 45 | Pr | 141 |
Ti | 49 | Nd | 143 |
V | 51 | Sm | 147 |
Cr | 52 | Eu | 151 |
Mn | 55 | Gd | 155 |
Co | 59 | Tb | 159 |
Ni | 60 | Dy | 163 |
Cu | 65 | Ho | 165 |
Zn | 66 | Er | 166 |
Ga | 71 | Tm | 169 |
Rb | 85 | Yb | 173 |
Sr | 88 | Lu | 175 |
Y | 89 | Hf | 179 |
Zr | 90 | Ta | 181 |
Nb | 93 | Pb | 208 |
Mo | 95 | Th | 232 |
U | 238 |
Determination of elemental concentrations can be achieved by means of any of the three cited methods:
1) Entirely by external calibration with a solid reference material;
2) External calibration with a solid reference material coupled with internal standardization;
3) Calibration using solutions.
In our laboratory, the second type of calibration was implemented. The external reference material was used simultaneously with an internal standard. This procedure represents a more robust calibration method, since a correction can be applied on the ablation yield of the sample (the mass of removed material) and the external reference material. The methodology is especially adapted for use with the Glitter® software [
The concentration of elements, even though calculated directly with the Glitter® software [
where:
where:
Calculation of this detection limit was defined [
where
Detection limits of about tens of ng∙g−1 are expected for present-day instruments, for a moderate spatial peak resolution between 30 to 40 µm. Higher spatial resolutions (of the order of 10 μm) will present detection limits at the mg∙kg−1 range, lower resolutions (>100 μm) at a sub-ng∙g−1 range.
Detection limits are calculated for each element in each sample directly by the Glitter® software (cf. Equation (3) [
Data obtained during the last 4 years in our laboratory for USGS basaltic glasses BCR-2G, BIR-1G and BHVO- 2G are listed in Tables 5-7. These RM’s were used as quality control standards with 30 to 60 obtained values for each analyzed element. Reference values for LA-ICPMS are quoted in [
Data obtained for the Max Planck Institute basaltic glasses KL-2G and ML-3BG, andesite StHs-6/80G, quartz diorite T-1G and komatiites GOR-128 and GOR-132G are quoted in Tables 8-13 (six to twelve determinations for each material).
Data obtained for materials BHVO-2G, BCR-2G and BIR-1G were calibrated against the synthetic glasses Nist-610 or 612, while the RM from the Max Planck Institute were calibrated exclusively against Nist-612.
The obtained values for the analyzed elements (Tables 5-7) in the basaltic glasses BHVO-2G, BCR-2G and BIR-1G are represented in graphical form in
. Mean detection limits (mg∙kg−1) and standard deviations (sd) obtained in several analytical runs
Isotope | DL | sd | Isotope | DL | sd | Isotope | DL | sd |
---|---|---|---|---|---|---|---|---|
7Li | 0.53 | 0.101 | 88Sr | 0.05 | 0.008 | 159Tb | 0.03 | 0.003 |
9Be | 3.05 | 0.264 | 89Y | 0.04 | 0.007 | 163Dy | 0.12 | 0.011 |
25Mg | 1.40 | 0.267 | 90Zr | 0.07 | 0.014 | 165Ho | 0.03 | 0.004 |
31P | 19.74 | 2.973 | 93Nb | 0.05 | 0.006 | 166Er | 0.09 | 0.015 |
42Ca | 0.03 | 0.011 | 95Mo | 0.38 | 0.053 | 169Tm | 0.03 | 0.002 |
45Sc | 0.60 | 0.079 | 118Sn | 0.70 | 0.081 | 173Yb | 0.17 | 0.034 |
49Ti | 2.09 | 0.182 | 121Sb | 0.13 | 0.018 | 175Lu | 0.03 | 0.005 |
51V | 0,45 | 0.089 | 133Cs | 0.04 | 0.005 | 179Hf | 0.20 | 0.012 |
52Cr | 2.43 | 0.202 | 137Ba | 0.27 | 0.050 | 181Ta | 0.03 | 0.004 |
55Mn | 0.61 | 0.281 | 139La | 0.04 | 0.005 | 208Pb | 0.09 | 0.009 |
59Co | 0.11 | 0.018 | 140Ce | 0.03 | 0.007 | 232Th | 0.03 | 0.001 |
60Ni | 0.52 | 0.085 | 141Pr | 0.03 | 0.004 | 238U | 0.03 | 0.004 |
65Cu | 0.55 | 0.052 | 143Nd | 0.23 | 0.031 | |||
66Zn | 1.43 | 0.313 | 147Sm | 0.19 | 0.031 | |||
71Ga | 0.19 | 0.056 | 151Eu | 0.06 | 0.009 | |||
85Rb | 0.11 | 0.020 | 155Gd | 0.24 | 0.050 |
Relationship between average values and recommended values [11] , determined with the LA-Q-ICPMS technique for the analyzed elements in the BCR-2G, BHVO-2G and BIR-1G basaltic glasses (cf. Tables 5-7)
relation to the preferred mean, taking as mean values the ones quoted in [
Most obtained values for the referred glasses lie within an interval of ±15% of the reference values of the cited elements, as determined by the LA-Q-ICPMS technique in [
. Obtained values in mg∙kg−1 for BCR-2G, compared with values quoted in [11] (LA-ICPMS technique) and preferred values in [14]
Element | Obtained values | Gao et al. [11] | GEOREM [14] | |||||
---|---|---|---|---|---|---|---|---|
Mean | sd | n | Mean | sd | n | Recom** | sd** | |
Li | 9.37 | 0.52 | 33 | 9.9 | 0.7 | 67 | 9 | 1 |
Be | 2.30 | 1.10 | 25 | 2 | 0.1 | 7 | 2.3 | 0.4 |
Mg | 21184 | 1806 | 43 | 20980 | 607 | 94 | 21470 | 1492 |
P | 1334 | 194 | 22 | n.d | 1615 | 44 | ||
Sc | 32.0 | 3.8 | 41 | 32 | 2 | 132 | 33 | 2 |
Ti | 13080 | 1182 | 43 | 13005 | 1081 | 124 | 14100 | 1000 |
V | 421 | 11 | 33 | 425 | 7 | 98 | 425 | 18 |
Cr | 17.0 | 1.3 | 39 | 17 | 2 | 91 | 17 | 2 |
Mn | 1482 | 34 | 40 | 1463 | 23 | 10 | 1550 | 70 |
Co | 37.2 | 1.8 | 39 | 38 | 1 | 118 | 38 | 2 |
Ni | 12.2 | 0.8 | 29 | 12.7 | 0.9 | 126 | 13 | 2 |
Cu | 17.1 | 1.1 | 35 | 18 | 1 | 78 | 21 | 5 |
Zn | 146 | 8 | 38 | 153 | 9 | 14 | 125 | 5 |
Ga | 22.7 | 1.1 | 38 | 24 | 1 | 71 | 23 | 1 |
Rb | 48.5 | 2.3 | 39 | 51 | 3 | 133 | 47 | 0.5 |
Sr | 326 | 12 | 39 | 321 | 6 | 122 | 342 | 4 |
Y | 31.6 | 5.5 | 38 | 31 | 2 | 138 | 35 | 3 |
Zr | 172 | 20 | 32 | 167 | 8 | 127 | 184 | 15 |
Nb | 11.1 | 0.8 | 42 | 10.9 | 0.6 | 133 | 12.5 | 1 |
Mo | 237 | 10 | 42 | n.d | 270 | 30 | ||
Sn | 2.67 | 0.46 | 36 | 2.4 | 0.4 | 14 | 2.6 | 0.4 |
Sb | 0.34 | 0.06 | 25 | 0.51 | 0.87 | 10 | 0.35 | 0.08 |
Cs | 1.18 | 0.07 | 34 | 1.17 | 0.08 | 71 | 1.16 | 0.07 |
Ba | 647 | 21 | 34 | 641 | 14 | 125 | 683 | 7 |
La | 25.1 | 1.4 | 42 | 25 | 1 | 144 | 24.7 | 0.3 |
Ce | 51.5 | 1.8 | 41 | 52 | 2 | 139 | 53.3 | 0.5 |
Pr | 6.37 | 0.36 | 41 | 6.3 | 0.4 | 140 | 6.7 | 0.4 |
Nd | 27.6 | 2.1 | 42 | 27 | 1 | 132 | 28.9 | 0.3 |
Sm | 6.31 | 0.57 | 38 | 6.3 | 0.5 | 115 | 6.59 | 0.07 |
Eu | 1.95 | 0.12 | 37 | 1.91 | 0.09 | 108 | 1.97 | 0.02 |
Gd | 6.32 | 0.81 | 32 | 6.5 | 0.6 | 112 | 6.71 | 0.07 |
Tb | 0.96 | 0.11 | 37 | 0.95 | 0.07 | 115 | 1.02 | 0.08 |
Dy | 5.92 | 0.73 | 37 | 6 | 0.4 | 106 | 6.44 | 0.06 |
Ho | 1.21 | 0.15 | 35 | 1.2 | 0.07 | 104 | 1.27 | 0.08 |
Er | 3.29 | 0.45 | 29 | 3.3 | 0.2 | 94 | 3.7 | 0.04 |
Tm | 0.47 | 0.07 | 33 | 0.46 | 0.04 | 111 | 0.51 | 0.04 |
Yb | 3.38 | 0.28 | 30 | 3.2 | 0.3 | 112 | 3.39 | 0.03 |
Lu | 0.48 | 0.06 | 35 | 0.47 | 0.04 | 109 | 0.503 | 0.005 |
Hf | 4.47 | 0.61 | 36 | 4.5 | 0.4 | 94 | 4.84 | 0.28 |
Ta | 0.62 | 0.08 | 36 | 0.63 | 0.06 | 97 | 0.78 | 0.06 |
Pb | 10.1 | 0.5 | 36 | 10.9 | 0.5 | 104 | 11 | 1 |
Th | 5.66 | 0.38 | 36 | 5.5 | 0.2 | 103 | 5.9 | 0.3 |
U | 1.69 | 0.09 | 35 | 1.7 | 0.08 | 120 | 1.69 | 0.12 |
**Mean values obtained with various techniques (ID-TIMS, MC-LAICPMS, EPMA, LA-ICPMS). n: number of determinations; Recom: recommended values; n.d: not determined.
. Obtained values in mg∙kg−1 for BIR-1G, compared with values quoted in [11] (LA-ICPMS technique) and preferred values in [14]
Element | Obtained values | Gao et al. [11] | GEOREM [14] | ||||||
---|---|---|---|---|---|---|---|---|---|
Mean | sd | n | Mean | sd | n | Recom** | sd** | ||
Li | 3.28 | 0.36 | 38 | 3.6 | 0.4 | 57 | 3 | 0.7 | |
Be | 0.44 | 0.15 | 13 | 0.69 | 0.88 | 9 | 0.1 | ||
Mg | 60101 | 6839 | 38 | 58471 | 1517 | 65 | 56400 | 600 | |
P | 109 | 6 | 21 | n.d | 118 | 13 | |||
Sc | 38.9 | 2.6 | 44 | 41 | 1 | 95 | 43 | 3 | |
Ti | 5786 | 598 | 37 | 5532 | 323 | 97 | 5400 | 200 | |
V | 330 | 11 | 39 | 338 | 6 | 91 | 326 | 32 | |
Cr | 394 | 13 | 40 | 403 | 11 | 85 | 392 | 24 | |
Mn | 1341 | 56 | 44 | 1417 | 30 | 17 | 1472 | 77 | |
Co | 54.2 | 2.0 | 37 | 57 | 1 | 78 | 52 | 5 | |
Ni | 176 | 8 | 40 | 190 | 6 | 85 | 178 | 18 | |
Cu | 124 | 4 | 35 | 132 | 6 | 69 | 119 | 12 | |
Zn | 77.6 | 4.9 | 39 | 86 | 5 | 25 | 78 | 17 | |
Ga | 16.0 | 0.7 | 37 | 17 | 1 | 76 | 15 | 2 | |
Rb | 0.22 | 0.03 | 33 | 0.26 | 0.05 | 68 | 0.197 | 0.007 | |
Sr | 106 | 4 | 41 | 104 | 2 | 102 | 109 | 2 | |
Y | 12.2 | 1.0 | 36 | 13.3 | 0.6 | 99 | 14.3 | 1.4 | |
Zr | 12.0 | 1.2 | 36 | 12.9 | 0.6 | 98 | 14 | 1.2 | |
Nb | 0.51 | 0.05 | 40 | 0.48 | 0.04 | 94 | 0.52 | 0.04 | |
Mo | 0.089 | 0.03 | 23 | n.d | 0.075 | 0.011 | |||
Sn | 1.27 | 0.26 | 41 | 0.84 | 0.23 | 9 | 2.3 | 1.3 | |
Sb | 0.55 | 0.15 | 39 | 0.47 | 0.13 | 12 | 0.56 | 0.09 | |
Cs | 0.011 | 0.004 | 21 | 0.0069 | 0.0020 | 31 | 0.007 | 0.002 | |
Ba | 6.31 | 0.44 | 40 | 6.3 | 0.3 | 99 | 6.5 | 0.07 | |
La | 0.59 | 0.05 | 43 | 0.60 | 0.04 | 91 | 0.609 | 0.02 | |
Ce | 1.92 | 0.12 | 45 | 1.9 | 0.08 | 76 | 1.89 | 0.04 | |
Pr | 0.36 | 0.04 | 46 | 0.36 | 0.02 | 78 | 0.37 | 0.02 | |
Nd | 2.29 | 0.20 | 42 | 2.3 | 0.2 | 73 | 2.37 | 0.03 | |
Sm | 1.06 | 0.11 | 37 | 1.1 | 0.1 | 72 | 1.09 | 0.02 | |
Eu | 0.52 | 0.05 | 39 | 0.51 | 0.04 | 78 | 0.517 | 0.005 | |
Gd | 1.59 | 0.17 | 33 | 1.6 | 0.1 | 76 | 1.85 | 0.02 | |
Tb | 0.31 | 0.04 | 30 | 0.32 | 0.03 | 81 | 0.35 | 0.04 | |
Dy | 2.19 | 0.21 | 32 | 2.3 | 0.2 | 78 | 2.55 | 0.02 | |
Ho | 0.50 | 0.06 | 30 | 0.51 | 0.05 | 86 | 0.56 | 0.03 | |
Er | 1.44 | 0.10 | 26 | 1.5 | 0.1 | 80 | 1.7 | 0.02 | |
Tm | 0.21 | 0.02 | 35 | 0.22 | 0.02 | 69 | 0.24 | 0.03 | |
Yb | 1.46 | 0.17 | 34 | 1.5 | 0.1 | 80 | 1.64 | 0.03 | |
Lu | 0.22 | 0.02 | 27 | 0.23 | 0.02 | 63 | 0.248 | 0.009 | |
Hf | 0.49 | 0.10 | 28 | 0.53 | 0.06 | 71 | 0.57 | 0.03 | |
Ta | 0.03 | 0.01 | 40 | 0.032 | 0.01 | 80 | 0.036 | 0.006 | |
Pb | 3.36 | 0.21 | 31 | 3.6 | 0.2 | 78 | 3.7 | 0.3 | |
Th | 0.03 | 0.01 | 44 | 0.028 | 0.01 | 65 | 0.03 | 0.002 | |
U | 0.02 | 0.01 | 31 | 0.032 | 0.01 | 67 | 0.023 | 0.006 | |
**Mean values obtained with various techniques (ID-TIMS, MC-LAICPMS, EPMA, LA-ICPMS). n: number of determinations; Recom: recommended values; n.d: not determined.
. Obtained values in mg∙kg−1 for BHVO-2G, compared with values quoted in [11] (LA-ICPMS technique) and preferred values in [14]
Element | Obtained values | Gao et al. [11] | GEOREM [14] | ||||||
---|---|---|---|---|---|---|---|---|---|
Mean | sd | n | Mean | sd | n | Recom** | sd** | ||
Li | 4.67 | 0.42 | 65 | 5.0 | 0.4 | 26 | 4.4 | 0.8 | |
Be | 1.24 | 0.36 | 40 | 1.4 | 0.2 | 6 | 1.3 | 0.2 | |
Mg | 45594 | 4910 | 51 | 42682 | 1071 | 25 | 42992 | 121 | |
P | 1281 | 126 | 40 | 1266 | 87 | ||||
Sc | 29.6 | 2.1 | 72 | 31 | 1 | 51 | 33 | 2 | |
Ti | 16165 | 1249 | 39 | 15621 | 453 | 53 | 16300 | 900 | |
V | 319 | 9 | 64 | 329 | 9 | 42 | 308 | 19 | |
Cr | 288 | 9 | 67 | 285 | 14 | 51 | 293 | 12 | |
Mn | 1310 | 58 | 74 | 1345 | 25 | 22 | 1317 | 233 | |
Co | 45.2 | 2.1 | 70 | 47 | 2 | 53 | 44 | 2 | |
Ni | 120 | 7 | 70 | 112 | 9 | 48 | 116 | 7 | |
Cu | 120 | 7 | 72 | 142 | 10 | 52 | 127 | 11 | |
Zn | 114 | 6 | 72 | 107 | 26 | 36 | 102 | 6 | |
Ga | 21.7 | 0.8 | 71 | 21 | 1 | 44 | 22 | 3 | |
Rb | 9.43 | 0.53 | 69 | 10.1 | 0.6 | 49 | 9.2 | 0.04 | |
Sr | 388 | 16 | 72 | 328 | 10 | 53 | 396 | 1 | |
Y | 22.1 | 1.6 | 45 | 23 | 1 | 57 | 26 | 2 | |
Zr | 155 | 11 | 49 | 160 | 8 | 56 | 170 | 7 | |
Nb | 16.9 | 1.2 | 55 | 16.4 | 0.7 | 56 | 18.3 | 0.8 | |
Mo | 4.09 | 0.29 | 62 | n.d | 3.8 | 0.2 | |||
Sn | 2.06 | 0.17 | 58 | 2.6 | 0.6 | 22 | 2.6 | 0.6 | |
Sb | 0.24 | 0.07 | 35 | 0.21 | 0.04 | 10 | 0.3 | 0.13 | |
Cs | 0.10 | 0.01 | 65 | 0.11 | 0.02 | 29 | 0.1 | 0.02 | |
Ba | 129 | 7 | 71 | 128 | 4 | 56 | 131 | 2 | |
La | 15.2 | 0.9 | 63 | 15.6 | 0.6 | 38 | 15.2 | 0.2 | |
Ce | 37.5 | 1.4 | 71 | 37 | 1 | 32 | 37.6 | 0.2 | |
Pr | 5.08 | 0.22 | 68 | 5.0 | 0.3 | 33 | 5.35 | 0.22 | |
Nd | 23.5 | 1.3 | 67 | 24 | 1 | 32 | 24.5 | 0.2 | |
Sm | 5.75 | 0.35 | 59 | 5.8 | 0.5 | 32 | 6.1 | 0.03 | |
Eu | 2.01 | 0.11 | 67 | 2.0 | 0.1 | 28 | 2.07 | 0.01 | |
Gd | 5.50 | 0.34 | 51 | 5.9 | 0.4 | 30 | 6.16 | 0.05 | |
Tb | 0.85 | 0.06 | 40 | 0.86 | 0.06 | 31 | 0.92 | 0.04 | |
Dy | 4.92 | 0.38 | 46 | 4.9 | 0.4 | 33 | 5.28 | 0.05 | |
Ho | 0.91 | 0.07 | 45 | 0.91 | 0.06 | 32 | 0.98 | 0.04 | |
Er | 2.28 | 0.18 | 39 | 2.3 | 0.2 | 28 | 2.56 | 0.02 | |
Tm | 0.29 | 0.04 | 56 | 0.30 | 0.05 | 32 | 0.34 | 0.02 | |
Yb | 1.96 | 0.17 | 41 | 2.0 | 0.2 | 30 | 2.01 | 0.02 | |
Lu | 0.25 | 0.03 | 51 | 0.26 | 0.04 | 29 | 0.279 | 0.003 | |
Hf | 4.02 | 0.31 | 43 | 4.1 | 0.4 | 52 | 4.32 | 0.18 | |
Ta | 0.96 | 0.08 | 54 | 0.94 | 0.07 | 54 | 1.15 | 0.1 | |
Pb | 1.80 | 0.13 | 63 | 1.4 | 0.2 | 43 | 1.7 | 0.2 | |
Th | 1.15 | 0.08 | 53 | 1.18 | 0.09 | 48 | 1.22 | 0.05 | |
U | 0.45 | 0.04 | 56 | 0.44 | 0.03 | 42 | 0.403 | 0.003 | |
**Mean values obtained with various techniques (ID-TIMS, MC-LAICPMS, EPMA, LA-ICPMS). n: number of determinations; Recom: recommended values; n.d: not determined.
. Obtained values in mg∙kg−1 for 12 determinations of basalt glass KL-2G, compared with values quoted in [15]
Elements | Obtained values | Jochum et al. [15] | ||||
---|---|---|---|---|---|---|
Mean | sd | % rsd | Mean | U | % var. | |
Li | 5.35 | 0.48 | 8.9 | 5.10 | 0.50 | 9.8 |
Sc | 29.7 | 1.2 | 4.0 | 31.8 | 0.90 | 2.8 |
Ti | 16079 | 1279 | 8.0 | 15347 | 540 | 3.5 |
V | 294 | 14 | 4.7 | 309 | 38 | 12.3 |
Cr | 283 | 6 | 2.1 | 294 | 27 | 9.2 |
Mn | 1190 | 53 | 4.5 | 1278 | 70 | 5.5 |
Co | 39.4 | 1.1 | 2.7 | 41.2 | 2.3 | 5.6 |
Ni | 101 | 5.0 | 4.9 | 112 | 5 | 4.5 |
Cu | 81.6 | 3.5 | 4.2 | 87.9 | 9.1 | 10.4 |
Zn | 105 | 4 | 3.4 | 110 | 10 | 9.1 |
Ga | 20.1 | 0.5 | 2.5 | 20.0 | 1.2 | 6.0 |
Rb | 8.38 | 0.77 | 9.1 | 8.70 | 0.40 | 4.6 |
Sr | 342 | 11 | 3.0 | 356 | 8 | 2.2 |
Y | 22.2 | 0.5 | 2.4 | 25.4 | 1.1 | 4.3 |
Zr | 129 | 3 | 2.0 | 152 | 5 | 3.3 |
Nb | 14.2 | 0.3 | 1.9 | 15.0 | 0.5 | 3.3 |
Mo | 2.98 | 0.14 | 4.7 | 3.6 | 0.6 | 16.7 |
Sn | 1.51 | 0.12 | 8.3 | 1.54 | 0.29 | 18.8 |
Sb | 0.126 | 0.016 | 12.8 | 0.14 | 0.03 | 21.4 |
Cs | 0.108 | 0.009 | 8.0 | 0.115 | 0.009 | 7.8 |
Ba | 110 | 3 | 2.0 | 123 | 5 | 4.1 |
La | 12.9 | 0.4 | 3.4 | 13.1 | 0.2 | 1.5 |
Ce | 31.3 | 1.7 | 5.5 | 32.4 | 0.7 | 2.2 |
Pr | 4.34 | 0.14 | 3.1 | 4.60 | 0.10 | 2.2 |
Nd | 20.8 | 0.6 | 2.7 | 21.6 | 0.4 | 1.9 |
Sm | 5.30 | 0.20 | 3.8 | 5.54 | 0.09 | 1.6 |
Eu | 1.91 | 0.09 | 4.7 | 1.92 | 0.04 | 2.1 |
Gd | 5.29 | 0.32 | 3.8 | 5.92 | 0.20 | 3.4 |
Tb | 0.79 | 0.04 | 5.0 | 0.890 | 0.031 | 3.5 |
Dy | 4.78 | 0.35 | 6.6 | 5.22 | 0.12 | 2.3 |
Ho | 0.88 | 0.05 | 5.6 | 0.961 | 0.022 | 2.3 |
Er | 2.26 | 0.10 | 4.3 | 2.54 | 0.07 | 2.8 |
Tm | 0.30 | 0.01 | 4.5 | 0.331 | 0.001 | 0.3 |
Yb | 1.95 | 0.12 | 5.9 | 2.10 | 0.05 | 2.4 |
Lu | 0.26 | 0.01 | 4.6 | 0.285 | 0.009 | 3.2 |
Hf | 3.53 | 0.16 | 4.6 | 3.93 | 0.14 | 3.6 |
Ta | 0.88 | 0.05 | 6.2 | 0.961 | 0.022 | 2.3 |
Pb | 1.94 | 0.06 | 2.9 | 2.07 | 0.10 | 4.8 |
Th | 0.94 | 0.04 | 4.3 | 1.02 | 0.03 | 2.9 |
U | 0.53 | 0.08 | 14.5 | 0.548 | 0.016 | 2.9 |
U: Uncertainty at 95% confidence level; % var.: percent of variability calculated.
. Mean obtained value for 12 determinations in mg∙kg−1 for basalt glass ML-3BG, compared with values quoted in [15]
Elements | Obtained values | Jochum et al. [15] | ||||
---|---|---|---|---|---|---|
Mean | sd | % rsd | Mean | U | % var. | |
Li | 4.25 | 0.15 | 3.6 | 4.5 | 0.4 | 8.9 |
Sc | 28.8 | 1.2 | 4.3 | 31.6 | 2.9 | 9.2 |
Ti | 13198 | 836 | 6.3 | 12767 | 1259 | 9.9 |
V | 264 | 6.9 | 2.6 | 268 | 23 | 10.5 |
Cr | 154 | 4 | 2.9 | 179 | 44 | 24.6 |
Mn | 1193 | 42 | 3.5 | 1224 | 108 | 8.9 |
Co | 40.2 | 1.5 | 3.8 | 42.0 | 6.0 | 14.3 |
Ni | 97.2 | 2.5 | 2.6 | 103 | 9 | 8.7 |
Cu | 107 | 3 | 2.5 | 110 | 9 | 8.2 |
Zn | 110 | 5 | 4.5 | 102 | 21 | 20.6 |
Ga | 19.0 | 0.4 | 2.1 | 18.5 | 2.8 | 15.1 |
Rb | 5.68 | 0.25 | 4.3 | 5.82 | 0.6 | 10.3 |
Sr | 308 | 12 | 3.9 | 309 | 12 | 3.9 |
Y | 21.1 | 1.2 | 5.6 | 23.3 | 1.7 | 7.3 |
Zr | 105 | 6 | 5.3 | 117 | 8 | 6.8 |
Nb | 7.99 | 0.34 | 4.2 | 8.43 | 0.38 | 4.5 |
Mo | 15.5 | 0.9 | 5.8 | 16.1 | 3.4 | 21.1 |
Sn | 1.17 | 0.08 | 6.6 | 1.15 | 0.48 | 41.7 |
Sb | 0.123 | 0.015 | 12.2 | 0.11 | 0.04 | 36.4 |
Cs | 0.131 | 0.011 | 8.5 | 0.137 | 0.027 | 19.7 |
Ba | 74.5 | 2.5 | 3.3 | 79.2 | 4.1 | 5.2 |
La | 8.84 | 0.30 | 3.4 | 9.04 | 0.45 | 5.0 |
Ce | 22.5 | 0.8 | 3.4 | 23.2 | 0.9 | 3.9 |
Pr | 3.23 | 0.15 | 4.5 | 3.42 | 0.14 | 4.1 |
Nd | 16.2 | 0.5 | 2.8 | 16.9 | 0.6 | 3.6 |
Sm | 4.58 | 0.18 | 3.9 | 4.74 | 0.24 | 5.1 |
Eu | 1.62 | 0.09 | 5.7 | 1.67 | 0.06 | 3.6 |
Gd | 4.65 | 0.35 | 7.4 | 5.10 | 0.32 | 6.3 |
Tb | 0.72 | 0.03 | 4.9 | 0.783 | 0.057 | 7.3 |
Dy | 4.45 | 0.39 | 8.8 | 4.84 | 0.21 | 4.3 |
Ho | 0.85 | 0.05 | 6.2 | 0.901 | 0.051 | 5.7 |
Er | 2.21 | 0.16 | 7.1 | 2.41 | 0.13 | 5.4 |
Tm | 0.30 | 0.02 | 7.1 | 0.324 | 0.02 | 6.2 |
Yb | 1.97 | 0.10 | 5.2 | 2.06 | 0.12 | 5.8 |
Lu | 0.27 | 0.023 | 8.7 | 0.287 | 0.019 | 6.6 |
Hf | 2.97 | 0.24 | 8.2 | 3.14 | 0.20 | 6.4 |
Ta | 0.52 | 0.04 | 7.0 | 0.552 | 0.033 | 6.0 |
Pb | 1.30 | 0.07 | 5.5 | 1.40 | 0.15 | 10.7 |
Th | 0.51 | 0.03 | 5.0 | 0.55 | 0.03 | 5.5 |
U | 0.41 | 0.020 | 4.9 | 0.448 | 0.055 | 12.3 |
U: Uncertainty at 95% confidence level; % var.: percent of variability calculated.
. Mean obtained values for 10 determinations in mg∙kg−1 for andesite glass StHs6/80G, compared with values quoted in [15]
Elements | Obtained values | Jochum et al. [15] | ||||
---|---|---|---|---|---|---|
Mean | sd | % rsd | Mean | U | % var. | |
Li | 18.0 | 1.11 | 6.2 | 21.7 | 3.8 | 17.5 |
Sc | 10.4 | 0.46 | 4.4 | 11.9 | 1.3 | 10.9 |
Ti | 4887 | 103 | 2.1 | 5591 | 487 | 8.71 |
V | 76.5 | 2.95 | 3.9 | 88.0 | 8.0 | 9.10 |
Cr | 12.1 | 0.53 | 4.4 | 15.5 | 3.4 | 21.9 |
Mn | 528 | 17 | 3.3 | 558 | 31 | 5.56 |
Co | 10.9 | 0.55 | 5.0 | 13.6 | 1.6 | 11.8 |
Ni | 15.7 | 0.57 | 3.6 | 23.4 | 7.1 | 30.3 |
Cu | 29.5 | 1.66 | 5.6 | 42.0 | 13.4 | 31.9 |
Zn | 60.8 | 4.23 | 7.0 | 71.0 | 10.0 | 14.1 |
Ga | 18.0 | 0.72 | 4.0 | 22.0 | 5.10 | 23.2 |
Rb | 24.1 | 0.94 | 3.9 | 31.7 | 4.40 | 13.9 |
Sr | 462 | 17.2 | 3.6 | 477 | 21.0 | 4.42 |
Y | 10.8 | 0.64 | 5.9 | 11.4 | 1.10 | 9.65 |
Zr | 105 | 6.00 | 5.7 | 115 | 10.0 | 8.70 |
Nb | 6.31 | 0.29 | 4.6 | 6.90 | 0.55 | 7.97 |
Mo | 1.42 | 0.10 | 7.3 | 1.80 | 0.80 | 44.4 |
Sn | 1.05 | 0.16 | 15.5 | 1.10 | 0.30 | 27.3 |
Sb | 0.20 | 0.04 | 21.3 | 0.18 | 0.09 | 50.0 |
Cs | 1.29 | 0.03 | 2.3 | 1.75 | 0.23 | 13.1 |
Ba | 277 | 6.28 | 2.3 | 298 | 15.0 | 5.0 |
La | 11.5 | 0.42 | 3.6 | 12.1 | 0.70 | 5.8 |
Ce | 23.8 | 0.74 | 3.1 | 26.3 | 1.20 | 4.6 |
Pr | 2.97 | 0.11 | 3.8 | 3.21 | 0.16 | 5.0 |
Nd | 12.7 | 0.35 | 2.8 | 13.0 | 0.60 | 4.6 |
Sm | 2.59 | 0.13 | 5.2 | 2.79 | 0.12 | 4.3 |
Eu | 0.95 | 0.03 | 2.7 | 0.96 | 0.05 | 4.8 |
Gd | 2.56 | 0.18 | 7.0 | 2.55 | 0.20 | 7.8 |
Tb | 0.33 | 0.02 | 4.8 | 0.37 | 0.02 | 6.3 |
Dy | 2.09 | 0.13 | 6.1 | 2.22 | 0.15 | 6.8 |
Ho | 0.40 | 0.03 | 7.7 | 0.42 | 0.03 | 6.7 |
Er | 1.09 | 0.03 | 3.1 | 1.19 | 0.08 | 6.7 |
Tm | 0.16 | 0.02 | 10.6 | 0.17 | 0.02 | 8.8 |
Yb | 1.10 | 0.05 | 4.6 | 1.14 | 0.08 | 7.0 |
Lu | 0.16 | 0.02 | 9.8 | 0.17 | 0.02 | 10.2 |
Hf | 2.78 | 0.18 | 6.4 | 2.98 | 0.21 | 7.0 |
Ta | 0.39 | 0.01 | 3.9 | 0.42 | 0.04 | 8.5 |
Pb | 10.4 | 0.50 | 4.8 | 10.4 | 1.97 | 18.9 |
Th | 2.18 | 0.08 | 3.5 | 2.30 | 0.21 | 9.1 |
U | 0.91 | 0.04 | 4.5 | 1.02 | 0.11 | 10.8 |
U: Uncertainty at 95% confidence level; % var.: percent of variability calculated.
. Mean obtained values for 6 determinations in mg∙kg−1 for quartz diorite glass T-1G, compared with values quoted in [15]
Elements | Obtained values | Jochum et al. [15] . | ||||
---|---|---|---|---|---|---|
Mean | sd | % rsd | Mean | U | % var. | |
Li | 19.7 | 0.4 | 2.0 | 20.2 | 1.6 | 7.9 |
Sc | 30.12 | 0.37 | 1.2 | 27.1 | 2.4 | 8.9 |
Ti | 5255 | 83 | 1.6 | 4699 | 210 | 4.5 |
V | 167 | 3 | 2.1 | 190 | 16 | 8.4 |
Cr | 15.7 | 0.6 | 3.9 | 20.3 | 1.5 | 7.4 |
Mn | 942 | 15 | 1.6 | 968 | 93 | 9.6 |
Co | 17.0 | 0.3 | 2.0 | 19.1 | 1.8 | 9.4 |
Ni | 8.38 | 0.22 | 2.6 | 10.7 | 2.4 | 22.4 |
Cu | 16.4 | 0.3 | 1.9 | 18.5 | 2.2 | 11.9 |
Zn | 60.3 | 2.2 | 3.6 | 69 | 12 | 17.4 |
Ga | 18.3 | 0.2 | 1.3 | 19.8 | 1.5 | 7.6 |
Rb | 74.7 | 1.6 | 2.1 | 80.5 | 9 | 11.2 |
Sr | 282 | 5 | 1.8 | 283 | 16 | 5.7 |
Y | 28.2 | 0.3 | 1.2 | 24.1 | 1.8 | 7.5 |
Zr | 169 | 2 | 1.3 | 141 | 12 | 8.5 |
Nb | 8.41 | 0.15 | 1.8 | 8.92 | 0.53 | 5.9 |
Mo | 5.60 | 0.19 | 3.3 | 3.6 | 2.5 | 69.4 |
Sn | 1.70 | 0.15 | 8.7 | 1.8 | 0.6 | 33.3 |
Sb | 0.26 | 0.03 | 10.8 | 0.23 | 0.08 | 34.8 |
Cs | 2.59 | 0.08 | 3.1 | 2.58 | 0.39 | 15.1 |
Ba | 385 | 8 | 2.1 | 393 | 23 | 5.9 |
La | 78.0 | 1.6 | 2.0 | 72.1 | 4.7 | 6.5 |
Ce | 121 | 2 | 1.9 | 129 | 6 | 4.7 |
Pr | 12.8 | 0.2 | 1.7 | 12.5 | 0.8 | 6.4 |
Nd | 46.3 | 0.8 | 1.8 | 42 | 2.5 | 6.0 |
Sm | 7.31 | 0.20 | 2.8 | 6.58 | 0.33 | 5.0 |
Eu | 1.22 | 0.05 | 4.0 | 1.20 | 0.07 | 5.8 |
Gd | 8.41 | 0.49 | 5.8 | 5.32 | 0.67 | 12.6 |
Tb | 0.85 | 0.02 | 2.7 | 0.74 | 0.044 | 5.9 |
Dy | 5.24 | 0.15 | 2.9 | 4.49 | 0.30 | 6.7 |
Ho | 1.06 | 0.02 | 2.3 | 0.867 | 0.067 | 7.7 |
Er | 2.98 | 0.13 | 4.4 | 2.51 | 0.15 | 6.0 |
Tm | 0.43 | 0.03 | 8.2 | 0.352 | 0.032 | 9.1 |
Yb | 2.89 | 0.13 | 4.5 | 2.39 | 0.24 | 10.0 |
Lu | 0.44 | 0.01 | 3.2 | 0.353 | 0.035 | 9.9 |
Hf | 4.44 | 0.06 | 1.4 | 3.80 | 0.33 | 8.7 |
Ta | 0.54 | 0.03 | 4.9 | 0.464 | 0.038 | 8.2 |
Pb | 8.29 | 0.22 | 2.7 | 12 | 3.1 | 25.8 |
Th | 36.0 | 0.5 | 1.5 | 31.2 | 2.7 | 8.7 |
U | 1.44 | 0.04 | 3.0 | 1.72 | 0.26 | 15.1 |
U: Uncertainty at 95% confidence level; % var.: percent of variability calculated.
. Mean obtained values for 6 determinations in mg∙kg−1 for komatiite GOR-128G, compared with values quoted in [15]
Elements | Obtained values | Jochum et al. [15] | ||||
---|---|---|---|---|---|---|
Mean | sd | % rsd | Mean | U | % var. | |
Li | 8.33 | 0.44 | 5.3 | 12.2 | 1.5 | 12.3 |
Sc | 35.6 | 1.5 | 4.3 | 32.5 | 1.8 | 5.5 |
Ti | 1865 | 75 | 4.0 | 1811 | 192 | 10.6 |
V | 138 | 4 | 2.6 | 191 | 17 | 8.9 |
Cr | 1868 | 53 | 2.9 | 2364 | 222 | 9.4 |
Mn | 1111 | 14 | 1.2 | 1416 | 232 | 16.4 |
Co | 73.2 | 1.1 | 1.4 | 95.7 | 9.8 | 10.2 |
Ni | 840 | 32 | 3.8 | 1076 | 106 | 9.9 |
Cu | 48.3 | 4.2 | 8.6 | 64.5 | 17.3 | 26.8 |
Zn | 56.2 | 3.6 | 6.5 | 75.0 | 4.6 | 6.1 |
Ga | 7.68 | 0.29 | 3.8 | 9.04 | 1.11 | 12.3 |
Rb | 0.27 | 0.03 | 10.7 | 0.40 | 0.04 | 10.9 |
Sr | 29.2 | 1.3 | 4.3 | 29.5 | 1.9 | 6.4 |
Y | 12.5 | 0.3 | 2.4 | 11.8 | 1.2 | 10.2 |
Zr | 10.5 | 0.4 | 3.8 | 9.8 | 1.1 | 11.2 |
Nb | 0.091 | 0.005 | 5.9 | 0.096 | 0.012 | 12.5 |
Mo | 0.43 | 0.06 | 14.2 | 0.73 | 0.27 | 37.0 |
Sn | 0.35 | 0.05 | 15.4 | 0.23 | 0.10 | 42.7 |
Sb | <0.03 | 0.006 | 0.002 | 33.3 | ||
Cs | 0.16 | 0.02 | 11.6 | 0.24 | 0.05 | 21.9 |
Ba | 0.94 | 0.09 | 10.0 | 1.06 | 0.07 | 6.6 |
La | 0.118 | 0.019 | 15.8 | 0.118 | 0.007 | 5.9 |
Ce | 0.38 | 0.03 | 9.0 | 0.45 | 0.03 | 6.3 |
Pr | 0.091 | 0.015 | 15.9 | 0.098 | 0.005 | 5.1 |
Nd | 0.76 | 0.10 | 13.6 | 0.78 | 0.10 | 12.9 |
Sm | 0.51 | 0.07 | 14.4 | 0.51 | 0.04 | 7.6 |
Eu | 0.25 | 0.04 | 16.9 | 0.26 | 0.02 | 6.1 |
Gd | 1.19 | 0.10 | 8.4 | 1.15 | 0.11 | 9.6 |
Tb | 0.25 | 0.02 | 8.7 | 0.25 | 0.03 | 10.1 |
Dy | 1.96 | 0.13 | 6.7 | 1.97 | 0.18 | 9.1 |
Ho | 0.45 | 0.03 | 7.6 | 0.44 | 0.04 | 9.9 |
Er | 1.49 | 0.08 | 5.3 | 1.40 | 0.14 | 10.0 |
Tm | 0.212 | 0.011 | 5.2 | 0.21 | 0.02 | 8.8 |
Yb | 1.46 | 0.09 | 6.2 | 1.41 | 0.14 | 9.9 |
Lu | 0.22 | 0.03 | 14.3 | 0.20 | 0.02 | 10.3 |
Hf | 0.34 | 0.08 | 24.0 | 0.34 | 0.04 | 10.5 |
Ta | 0.019 | 0.009 | 45.7 | 0.019 | 0.002 | 10.5 |
Pb | 0.21 | 0.04 | 16.8 | 0.33 | 0.06 | 19.3 |
Th | 0.012 | 0.005 | 45.1 | 0.008 | 0.002 | 25.0 |
U | 0.009 | 0.004 | 42.9 | 0.012 | 0.002 | 12.7 |
U: Uncertainty at 95% confidence level; % var.: percent of variability calculated.
. Mean obtained values for 6 determinations in mg∙kg−1 for komatiite glass GOR-132G, compared with values quoted in [15]
Elements | Obtained values | Jochum et al. [15] | ||||
---|---|---|---|---|---|---|
Mean | sd | % rsd | Mean | U | % var. | |
Li | 8.18 | 0.48 | 5.8 | 9.6 | 1.0 | 10.4 |
Sc | 38.9 | 2.87 | 7.4 | 37.2 | 1.6 | 4.3 |
Ti | 2090 | 103 | 4.9 | 1954 | 144 | 7.4 |
V | 185 | 8 | 4.5 | 219 | 25 | 11.4 |
Cr | 2257 | 120 | 5.3 | 2640 | 207 | 7.8 |
Mn | 1056 | 50 | 4.7 | 1138 | 108 | 9.5 |
Co | 84.8 | 4.1 | 4.8 | 94.5 | 10.7 | 11.3 |
Ni | 994 | 43 | 4.4 | 1187 | 58 | 4.9 |
Cu | 169 | 8 | 4.9 | 208 | 20 | 9.6 |
Zn | 54.7 | 2.7 | 4.9 | 79.9 | 16.2 | 20.3 |
Ga | 9.28 | 0.59 | 6.4 | 10.1 | 1.3 | 12.9 |
Rb | 1.59 | 0.13 | 8.2 | 2.1 | 0.22 | 10.5 |
Sr | 14.7 | 0.9 | 6.3 | 15.1 | 1.3 | 8.6 |
Y | 12.6 | 0.9 | 6.8 | 13.0 | 1.0 | 7.7 |
Zr | 9.44 | 0.77 | 8.2 | 9.7 | 0.8 | 8.2 |
Nb | 0.06 | 0.02 | 27.6 | 0.07 | 0.03 | 37.7 |
Mo | 25.0 | 2.0 | 8.0 | 29.9 | 4.0 | 13.4 |
Sn | 0.35 | 0.16 | 46.5 | 0.34 | 0.09 | 26.5 |
Sb | 0.07 | 0.03 | 44.0 | 0.04 | 0.02 | 50.0 |
Cs | 6.26 | 0.14 | 2.2 | 7.12 | 1.23 | 17.3 |
Ba | 0.73 | 0.10 | 13.2 | 0.82 | 0.14 | 17.6 |
La | 0.084 | 0.010 | 12.1 | 0.084 | 0.006 | 7.1 |
Ce | 0.34 | 0.03 | 8.0 | 0.40 | 0.04 | 10.8 |
Pr | 0.082 | 0.006 | 7.0 | 0.087 | 0.006 | 6.9 |
Nd | 0.70 | 0.07 | 9.3 | 0.68 | 0.03 | 5.0 |
Sm | 0.50 | 0.07 | 14.3 | 0.50 | 0.03 | 6.3 |
Eu | 0.27 | 0.02 | 8.6 | 0.25 | 0.02 | 6.3 |
Gd | 1.13 | 0.11 | 10.0 | 1.16 | 0.09 | 7.8 |
Tb | 0.27 | 0.03 | 12.8 | 0.26 | 0.02 | 7.6 |
Dy | 2.08 | 0.14 | 6.9 | 2.16 | 0.14 | 6.5 |
Ho | 0.49 | 0.07 | 14.2 | 0.49 | 0.04 | 7.1 |
Er | 1.56 | 0.14 | 9.1 | 1.53 | 0.10 | 6.5 |
Tm | 0.24 | 0.03 | 11.4 | 0.23 | 0.02 | 7.3 |
Yb | 1.54 | 0.12 | 7.5 | 1.60 | 0.09 | 5.6 |
Lu | 0.23 | 0.02 | 10.3 | 0.24 | 0.02 | 8.0 |
Hf | 0.28 | 0.07 | 24.3 | 0.35 | 0.04 | 10.0 |
Ta | 0.035 | 0.002 | 5.8 | 0.030 | 0.003 | 10.0 |
Pb | 17.1 | 0.80 | 4.7 | 19.5 | 2.8 | 14.4 |
Th | 0.007 | 0.005 | 77.4 | 0.009 | 0.003 | 33.3 |
U | 0.035 | 0.006 | 16.6 | 0.049 | 0.010 | 20.4 |
U: Uncertainty at 95% confidence level; % var.: percent of variability calculated.
Variation diagrams obtained for the REE contents in the BHVO-2G, BCR-2G and BIR-1G basaltic glasses, normalized with C1 chondrite [16] [17]
Figures 3-5 show the variations in obtained and preferred mean values for the Max Planck RM’s (basaltic glasses KL-2G and ML-3BG, andesite StHs6/80G and quartz diorite T-1G, komatiites GOR-128 and GOR- 132G). In these diagrams the observed errors are calculated for our obtained results compared with the preferred values for these materials cited in [
Variations diagrams for REE are presented in Figures 6-8 normalized with respect to the C1 chondrite [
Some obtained values shown in
The obtained values compared with the expected ones for the andesite glass StHs6/80G are somewhat outside the limit of ±15% for the following elements: Li, Cr, Co, Ni, Cu, Ga, Rb, Mo and Cs. Chromium and Ni deficiencies are also observed in T-1G, possibly indicating calibration problems, other than inhomogeneous distribution. The REE variation diagram, presented in
In komatiite GOR-128 (
The obtained values for the several reference materials made available by the USGS and the Max Planck Institute cover a rather wide spectrum of elemental abundances for the over 40 elements determined with the LA-Q- ICPMS technique, the methodology used in this contribution.
Average values obtained in relation to preferred values for several elements in basalt glasses KL-2G and ML-3BG, compared with the mean values cited in [17] , cf. Table 8 and Table 9
Average values obtained in relation to preferred values for several elements in glasses T-1G (quartz diorite) and StHs6/80G (andesite), compared with the mean certified values cited in [17] , cf. Table 10 and Table 11
The used technique provides high quality results, in terms of analytical accuracy, and is also very fast. The samples can be prepared as thin sections, with a thickness of around 40 to 60 microns, or as mineral grains mounted within polished epoxy resins.
Interferences can be kept at minimum levels, a result achieved with the use of dry plasma, thereby diminishing the influence of agents such as present in aqueous acid systems (O2−, OH−, Cl−,
Average values obtained in relation to preferred values for several elements in komatiite glasses GOR-128 and GOR-132G, compared with the mean certified values cited in [17] , cf. Table 12 and Table 13
Variation diagrams obtained for the REE contents in basaltic glasses KL-2G and ML-3BG, from the Max Planck Institute, normalized with the C1 chondrite [16] [17]
The rock glasses prepared by the Max Planck Institute cover an adequate spectrum of elements important for studies in igneous petrology, but the materials seem to present a lack of homogeneity for some elements, depending on the analyzed mass and of the spot used for identification [
The use of internal standards, especially MgO and CaO, is a necessary tool to standardize obtained results with our discussed technique. But many minerals may lack sufficient contents of CaO to be subjected to the LA- Q-ICPMS methodology, a fact that limits the scope of the glasses prepared by NIST, with low to very low MgO contents [
The authors are grateful for the support given by the São Paulo Science Foundation (FAPESP) for the acquisi-
Variation diagrams obtained for the REE contents in basaltic glasses StHs6/80G (andesite) and T-1G (quartz diorite), from the Max Planck Institute, normalized with the C1 chondrite [16] [17]
Variation diagrams obtained for the REE contents for komatiite glasses GOR-128 and GOR- 132G, from the Max Planck Institute, normalized with the C1 chondrite [16] [17]
tion of the spectrometer Q-ICPMS (1999/04824-9) and Laser Ablation System (2004/08856-2) and maintenance and update of the Laboratório de Química e ICP-OES/MS of the Instituto de Geociências, University of São Paulo. This is a contribution of the newly created Geoanalítica-USP Core Facility at the same institute, devoted to mineralogical and petrological studies. Support was also provided by a grant from FAPESP (Nr. 2012/ 06082-6, coordinator, Prof. Excelso Ruberti).
*Corresponding author.