Femtosecond Laser Ablation-ICP-Mass Spectrometry and CHNS Elemental Analyzer Reveal Trace Element Characteristics of Danburite from Mexico, Tanzania, and Vietnam
Abstract
:1. Introduction
2. Materials and Methods
2.1. Sample Material
2.2. Analytical Methods
3. Results
4. Discussion
4.1. Substitution Mechanisms of REEs, Be, and Sr in Danburite Structure
4.2. Substitution Mechanisms Involving OH and Al in the Danburite Lattice
4.3. Constraints on the Geochemical Formation Environment of Danburite
5. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Operating Conditions of NWRFemto200 Laser System | |
Wavelength λ (nm) | 200 |
Fluence (J·cm−2) | 0.51 |
Pulse length (fs) | 150 |
Pulse repetition rate (Hz) | 50 |
Laser energy output (%) | 100 |
Spot size (μm) | 55 |
Line length (µm) | 300 |
Scan speed (μm∙s−1) | 5 |
Warm-up time (s) | 28 |
Dwell time (s) | 60 |
Washout time (s) | 30 |
Operating Conditions of the Element2 Mass Spectrometer | |
RF power (W) | 1055 |
Cooling gas (Ar) flow rate (L·min−1) | 16 |
Auxiliary gas (Ar) flow rate (L∙min−1) | 1.19 |
Additional gas (He) flow rate (L∙min−1) | 0.7 |
Sample gas (Ar) flow rate (L∙min−1) | 0.7 |
Sample time (s) | 0.002 |
Samples per peak | 100 |
Mass window (%) | 10 |
Time per pass (s) | 2 |
Scan mode (Escan/Bscan) | both |
Mass resolution | 300 |
BE-N Altered Basalts (SARM) | H TCD | C TCD | N TCD | S TCD | S IR |
n | 14 | 20 | 17 | 21 | 8 |
Average (µg·g−1) | 2771 ± 534 | 2301 ± 147 | 197 ± 42 | 301 ± 37 | 298 ± 23 |
RSD % | 19 | 6 | 21 | 12 | 8 |
BAM-U110 | |||||
n | 13 | 18 | 18 | 17 | – |
Average (µg·g−1) | 12,258 ± 1758 | 72,340 ± 2640 | 4237 ± 165 | 9114 ± 1082 | – |
RSD % | 14 | 4 | 4 | 12 | – |
JP-1 Peridotite massif (JGS) | |||||
n | 4 | 12 | 14 | 14 | 14 |
Average (µg·g−1) | 3195 ± 170 | 763 ± 82 | 91 ± 23 | 27 ± 14 | 26 ± 7 |
RSD % | 5 | 11 | 26 | 51 | 27 |
Element | Isotope Used | L.O.D. | Charcas, San Luis Potosi, Mexico | Morogoro, Tanzania | Luc Yen, Vietnam | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Mex-1 | Mex-2 | Tanz-1 | Tanz-2 | Viet-1 | Viet-2 | |||||||||||||||
Ø (µg∙g−1) | Ø (µmol∙g−1) | RSD (%) | Ø (µg∙g−1) | Ø (µmol∙g−1) | RSD (%) | Ø (µg∙g−1) | Ø (µmol∙g−1) | RSD (%) | Ø (µg∙g−1) | Ø (µmol∙g−1) | RSD (%) | Ø (µg∙g−1) | Ø (µmol∙g−1) | RSD (%) | Ø (µg∙g−1) | Ø (µmol∙g−1) | RSD (%) | |||
CaO* | – | – | 22.47 | 0.04 | 0.49 | 22.43 | – | 0.71 | 22.63 | 0.04 | 0.60 | 22.48 | 0.04 | 0.57 | 22.32 | 0.03 | 0.51 | 22.40 | 0.03 | 0.37 |
B | 11 | 10 | 86218 | 7975 | 6.67 | 90471 | 8368 | 4.05 | 86280 | 7981 | 1.56 | 87270 | 8072 | 2.69 | 85698 | 7927 | 3.13 | 89138 | 8245 | 3.19 |
SiO2 * | – | – | 48.31 | 0.8 | 0.40 | 48.81 | 0.8 | 0.33 | 48.80 | 0.8 | 0.36 | 48.88 | 0.8 | 0.38 | 48.81 | 0.8 | 0.43 | 48.43 | 0.8 | 0.37 |
La | 139 | 0.01 | 0.15 | 0.0011 | 63.5 | 0.01 | 0.0001 | 124.0 | 675 | 4.9 | 35.3 | 807 | 5.8 | 4.7 | 368 | 2.7 | 42.3 | 400 | 2.9 | 22.0 |
Ce | 140 | 0.01 | 0.20 | 0.0014 | 48.1 | 0.05 | 0.0004 | 10.00 | 827 | 5.9 | 34.7 | 964 | 6.9 | 3.4 | 508 | 3.6 | 36.9 | 525 | 3.8 | 19.6 |
Pr | 141 | 0.03 | <0.03 | – | – | <0.03 | – | – | 51.4 | 0.37 | 35.1 | 59.5 | 0.42 | 4.0 | 37.4 | 0.27 | 35.3 | 36.5 | 0.26 | 17.5 |
Nd | 143 | 0.08 | <0.08 | – | – | <0.08 | – | – | 91.1 | 0.63 | 34.5 | 106 | 0.74 | 4.9 | 80.9 | 0.56 | 32.2 | 72.8 | 0.51 | 16.2 |
Sm | 147 | 0.05 | <0.05 | – | – | <0.05 | – | – | 4.65 | 0.03 | 28.7 | 5.68 | 0.04 | 9.6 | 5.94 | 0.04 | 27.1 | 5.23 | 0.03 | 18.7 |
Eu | 151 | 0.05 | <0.05 | – | – | <0.05 | – | – | 0.28 | 0.002 | 37.7 | 0.31 | 0.002 | 14.1 | 0.34 | 0.002 | 28.5 | 0.41 | 0.003 | 38.2 |
Gd | 157 | 0.04 | <0.04 | – | – | <0.04 | – | – | 2.05 | 0.013 | 28.1 | 2.38 | 0.015 | 10.9 | 2.46 | 0.016 | 37.1 | 2.13 | 0.014 | 28.3 |
Tb | 159 | 0.01 | <0.01 | – | – | <0.01 | – | – | 0.15 | 0.001 | 22.4 | 0.16 | 0.001 | 15.5 | 0.18 | 0.001 | 29.5 | 0.20 | 0.001 | 26.1 |
Dy | 163 | 0.05 | <0.05 | – | – | <0.05 | – | – | 0.58 | 0.004 | 35.7 | 0.68 | 0.004 | 7.80 | 0.85 | 0.005 | 30.5 | 0.92 | 0.006 | 33.7 |
Ho | 165 | 0.01 | <0.01 | – | – | <0.01 | – | – | 0.10 | 0.001 | 35.9 | 0.11 | 0.001 | 11.3 | 0.13 | 0.001 | 40.3 | 0.20 | 0.001 | 31.1 |
Er | 167 | 0.04 | <0.04 | – | – | <0.04 | – | – | 0.25 | 0.001 | 30.0 | 0.28 | 0.002 | 38.6 | 0.46 | 0.003 | 41.0 | 0.61 | 0.004 | 33.3 |
Tm | 169 | 0.02 | <0.02 | – | – | <0.02 | – | – | 0.03 | 0.0002 | 40.5 | 0.04 | 0.0002 | 49.3 | 0.09 | 0.0005 | 31.4 | 0.12 | 0.0007 | 40.1 |
Yb | 173 | 0.04 | <0.04 | – | – | <0.04 | – | – | 0.23 | 0.0013 | 44.4 | 0.26 | 0.0015 | 32.5 | 0.64 | 0.0037 | 42.1 | 0.90 | 0.0052 | 22.4 |
Lu | 175 | 0.02 | <0.02 | – | – | <0.02 | – | – | 0.02 | 0.0001 | 50.3 | 0.03 | 0.0002 | 43.5 | 0.12 | 0.0007 | 23.7 | 0.13 | 0.0007 | 32.2 |
Al | 27 | 10 | 325 | 12.0 | 14.9 | 171 | 6.4 | 40.5 | 84.3 | 3.1 | 36.2 | 101 | 3.7 | 7.58 | 288 | 10.7 | 12.8 | 257 | 9.5 | 6.41 |
As | 69 | 1 | 46.6 | 0.6 | 8.74 | 7.05 | 0.1 | 19.0 | <1 | 0.01 | 56.5 | <1 | 0.01 | 67.8 | 1.13 | 0.02 | 103 | 1.10 | 0.01 | 46.0 |
Ba | 135, 137 | 0.1 | 0.50 | 0.004 | 54.1 | 0.19 | 0.001 | 36.60 | 0.29 | 0.002 | 25.06 | 0.22 | 0.002 | 14.77 | 0.48 | 0.003 | 89.66 | 0.63 | 0.005 | 27.03 |
Be | 9 | 3 | 3.06 | 0.3 | 12.5 | 4.94 | 0.5 | 26.0 | 156 | 17.4 | 32.8 | 178 | 19.8 | 2.42 | 71.7 | 8.0 | 14.09 | 67.0 | 7.4 | 12.2 |
Cr | 53 | 5 | <5 | – | – | <5 | – | – | <5 | – | – | <5 | – | – | 6.44 | 0.12 | 43.8 | <5 | – | – |
Cu | 65 | 1 | 1.56 | 0.02 | 65.3 | <1 | – | – | <1 | – | – | <1 | – | – | 1.10 | 0.02 | 78.2 | 2.00 | 0.03 | 56.4 |
Fe | 57 | 20 | <20 | – | – | <20 | – | – | <20 | – | – | <20 | – | – | <20 | – | – | <20 | – | – |
K | 39 | 7 | <7 | – | – | <7 | – | – | <7 | – | – | <7 | – | – | <7 | – | – | <7 | – | – |
Mg | 25 | 9 | <9 | – | – | <9 | – | – | <9 | – | – | <9 | – | – | <9 | – | – | <9 | – | – |
Mn | 55 | 1 | <1 | – | – | <1 | – | – | <1 | – | – | <1 | – | – | 18.4 | 0.34 | 8.93 | 14.57 | 0.27 | 14.3 |
Na | 23 | 50 | <50 | – | – | <50 | – | – | <50 | – | – | <50 | – | – | <50 | – | – | <50 | – | – |
Ni | 62 | 18 | <18 | – | – | <18 | – | – | <18 | – | – | <18 | – | – | <18 | – | – | <18 | – | – |
Pb | 207, 208, 209 | 0.1 | 0.27 | 0.0013 | 49.2 | 0.23 | 0.0011 | 40.0 | 7.46 | 0.0360 | 33.8 | 8.05 | 0.0389 | 8.94 | 11.1 | 0.0534 | 5.05 | 10.6 | 0.0514 | 5.60 |
Sb | 121, 123 | 1 | 13.0 | 0.1 | 81.9 | 35.8 | 0.3 | 75.6 | <1 | – | – | <1 | – | – | <1 | – | – | <1 | – | – |
Sr | 88 | 0.1 | 767 | 8.8 | 12.09 | 1611 | 14.8 | 40.6 | 387 | 4.4 | 1.44 | 381 | 4.4 | 1.02 | 66.5 | 0.8 | 2.81 | 66.1 | 0.8 | 5.08 |
Th | 232 | 0.01 | <0.01 | – | – | <0.01 | – | – | 0.47 | 0.0020 | 41.3 | 0.66 | 0.0028 | 8.45 | 0.11 | 0.0005 | 51.7 | 0.11 | 0.0005 | 44.6 |
Ti | 49 | 3 | <3 | – | – | <3 | – | – | <3 | – | – | <3 | – | – | <3 | – | – | <3 | – | – |
V | 51 | 0.5 | 0.71 | 0.01 | 36.54 | 0.98 | 0.02 | 19.1 | 0.84 | 0.02 | 10.8 | 0.83 | 0.02 | 11.3 | 0.73 | 0.01 | 33.8 | 0.95 | 0.02 | 22.5 |
Y | 89 | 0.1 | <0.1 | – | – | <0.1 | – | – | 4.21 | 0.05 | 35.1 | 5.23 | 0.1 | 6.19 | 10.6 | 0.1 | 21.2 | 14.1 | 0.2 | 27.9 |
Zn | 67 | 10 | 59.6 | 0.9 | 34.6 | 27.5 | 0.4 | 53.1 | 15.8 | 0.2 | 32.5 | 15.5 | 0.2 | 41.7 | 63.2 | 1.0 | 39.3 | 89.9 | 1.4 | 49.0 |
Sample Location | Unpowdered Samples | Powdered Samples | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
H | eq. H2O+ (wt %) | C | N | S | H | eq. H2O+ (wt %) | C | N | S | |
Mexico | <10 | <0.01 | 200 ± 5 | 50 ± 10 | 13 ± 1 | 31 ± 10 | 0.028 | 130 ± 50 | 230 ± 130 | 25 ± 7 |
Tanzania | <10 | <0.01 | 120 ± 40 | 100 ± 50 | 8 ± 1 | 14 ± 1 | 0.012 | 70 ± 40 | 100 ± 50 | 22 ± 3 |
Vietnam | 300 ± 50 | 0.244 | 5600 ± 20 | 1000 ± 10 | 15 ± 3 | 40 ± 10 | 0.036 | 3000 ± 40 | 520 ± 20 | 19 ± 11 |
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Huong, L.T.-T.; Otter, L.M.; Förster, M.W.; Hauzenberger, C.A.; Krenn, K.; Alard, O.; Macholdt, D.S.; Weis, U.; Stoll, B.; Jochum, K.P. Femtosecond Laser Ablation-ICP-Mass Spectrometry and CHNS Elemental Analyzer Reveal Trace Element Characteristics of Danburite from Mexico, Tanzania, and Vietnam. Minerals 2018, 8, 234. https://doi.org/10.3390/min8060234
Huong LT-T, Otter LM, Förster MW, Hauzenberger CA, Krenn K, Alard O, Macholdt DS, Weis U, Stoll B, Jochum KP. Femtosecond Laser Ablation-ICP-Mass Spectrometry and CHNS Elemental Analyzer Reveal Trace Element Characteristics of Danburite from Mexico, Tanzania, and Vietnam. Minerals. 2018; 8(6):234. https://doi.org/10.3390/min8060234
Chicago/Turabian StyleHuong, Le Thi-Thu, Laura M. Otter, Michael W. Förster, Christoph A. Hauzenberger, Kurt Krenn, Olivier Alard, Dorothea S. Macholdt, Ulrike Weis, Brigitte Stoll, and Klaus Peter Jochum. 2018. "Femtosecond Laser Ablation-ICP-Mass Spectrometry and CHNS Elemental Analyzer Reveal Trace Element Characteristics of Danburite from Mexico, Tanzania, and Vietnam" Minerals 8, no. 6: 234. https://doi.org/10.3390/min8060234