scholarly journals Characterization of Four Copper Materials for Application as Reference Materials for High Precision Copper Isotope Analysis by Laser Ablation Inductively Coupled Plasma Multi-Collector Mass Spectrometry

2021 ◽  
Vol 9 ◽  
Author(s):  
Zhaoping Yang ◽  
Simon Edward Jackson ◽  
Thomas Skulski

Laser ablation inductively coupled plasma multi-collector mass spectrometry (LA-MC-ICP-MS) allows rapid, in situ, highly precise measurements of Cu isotope ratios of native Cu and Cu-bearing minerals. However, the National Institute of Standards and Technology Cu-metal isotope standard NIST SRM976 that is commonly used to calibrate LA-MC-ICP-MS Cu isotope measurements of native Cu is no longer available. We have investigated the suitability of four Cu metal materials, SSC-1, SSC-3 and SSC-4 (cathode Cu metal rods) and CUPD-1 (Cu anode sawings), originally developed by the Canada Centre for Mineral and Energy Technology (CANMET) as certified reference materials for trace element analysis, as Cu isotope reference materials for LA-MC-ICP-MS analysis and solution nebulization (SN) of Cu. The Cu isotopic composition and homogeneity of these four materials were characterised by SN- and LA-MC-ICP-MS, and are reported for the first time. The bulk Cu isotopic compositions, expressed as δ65CuSRM976 in per mil (‰) relative to NIST SRM976 with combined uncertainties (U, k = 2), of SSC-1, SSC-3 and SSC-4, determined utilizing SN-MC-ICP-MS, are identical within analytical uncertainty at 0.03 ± 0.07‰ (n = 29), 0.04 ± 0.04‰ (n = 28), and 0.05 ± 0.08‰ (n = 29), respectively; the composition of CUPD-1 is 2.14 ± 0.08‰ (n = 28). The compositions are 0.01 ± 0.07‰ (n = 29), 0.04 ± 0.06‰ (n = 29), 0.03 ± 0.06‰ (n = 28) and 2.15 ± 0.06‰ (n = 28), respectively, relative to the European Reference Material ERM®-AE633 Cu isotope standard. The Cu isotope homogeneity of the four new reference materials was assessed by determining whether multiple individual in situ Cu isotope measurements made by LA-MC-ICP-MS analysis (43 µm spot size), using each of the other three reference materials as a calibrator, approximate a single normal distribution. We also investigate whether there are statistically significant differences between the mean δ65Cu values of three independent data sets for each of the Cu isotope reference materials using one-way analysis of variance (ANOVA). Normality tests (graphical assessment of normal distribution quantile-quantile plots, and the Shapiro-Wilk, Jarque-Bera and reduced chi-squared statistic tests) show that: 1) the Cu isotope data acquired on SSC-1, SSC-3, SSC-4 and CUPD-1 do not depart significantly from a normal distribution, 2) the scatter of the Cu isotope data is due to analytical uncertainty with 95% confidence, and 3) there are no other significant sources of scatter; e.g. heterogeneity of the reference materials. The results of one-way ANOVA reveal that the mean difference of the δ65Cu value for each of the reference materials SSC-1, SSC-3, SSC-4 and CUPD-1 is statistically not significant at the 0.05 level. The mean δ65CuSRM976 values with combined uncertainties (U, k = 2) of SSC-1, SSC-3, SSC-4 and CUPD-1, determined by LA-MC-ICP-MS using each of the other three reference materials as a calibration standard, are 0.03 ± 0.09‰ (n = 132), 0.05 ± 0.09‰ (n = 154), 0.03 ± 0.09‰ (n = 144) and 2.14 ± 0.10‰ (n = 106), respectively. These values are in agreement with those determined by SN-MC-ICP-MS analysis at the 95% confidence level and have excellent precision (2 s.d. ≤ 0.10‰). These results suggest that SSC-1, SSC-3, SSC-4 and CUPD-1 can be considered isotopically homogeneous at a spatial resolution of 43 μm, and they are suitable reference materials for calibration and quality control of in situ and solution nebulization Cu isotope analyses of Cu.

2020 ◽  
Vol 8 ◽  
Author(s):  
Han Zhao ◽  
Xin-Miao Zhao ◽  
P. J. Le Roux ◽  
Wen Zhang ◽  
Hao Wang ◽  
...  

Clinopyroxene is a major host mineral for lithophile elements in the mantle lithosphere, and therefore, its origin is vital for constraints on mantle evolution and melt generation. In situ Sr isotopic measurement of clinopyroxene has been available since the recent development of laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) in the 2000s. Therefore, there is an increasing demand for natural clinopyroxene reference materials for Sr isotope microanalysis. In this contribution, we present six natural clinopyroxene reference materials from South Africa (JJG1424) and China (YY09-47, YY09-04, YY09-24, YY12-01, and YY12-02) for Sr isotope microanalysis. The Sr content of these clinopyroxenes ranges from 50 to 340 μg g−1, which covers most natural clinopyroxene compositions. Homogeneity of these potential reference materials were investigated and evaluated in detail over a 2-year period using 193-nm nanosecond and 257-nm femtosecond laser systems coupled to either a Neptune or Neptune Plus MC-ICP-MS. Additionally, the major and trace element of these clinopyroxenes were examined by electron probe microanalyzer (EPMA) as well as solution and laser ICP-MS. The in situ87Sr/86Sr values obtained for the six natural clinopyroxene reference materials agree well with data obtained using the thermal ionization mass spectrometer (TIMS) method. The Sr isotopic stability and homogeneity of these clinopyroxenes make them potential reference materials for in situ Sr microanalysis to correct instrumental fractionation or as quality control materials for analytical sessions. The new Sr isotope data provided here might be beneficial for microbeam analysis in the geochemical community.


2015 ◽  
Vol 77 (13) ◽  
Author(s):  
Nuraddeen Nasirum Garba ◽  
Ahmad Termizi Ramli ◽  
Muneer Aziz Saleh ◽  
Mohd Syazwan Mohd Sanusi ◽  
Hamman Tukur Gabdo ◽  
...  

Assessment of natural radionuclides (238U, 232Th, and 40K) and terrestrial gamma radiation dose rates (TGRD) in major rivers of Kelantan states, Malaysia were conducted. Measurements were carried out using a portable [NaI(TI)] micro roentgen (µR) survey meter and inductively coupled plasma mass spectrometer (ICP-MS) for in situ TGRD and the activity concentrations of 238U, 232Th, and 40K in water samples, respectively. The mean TGRD was found to be 312.98 nGy h-1 and from water samples analyzed, the mean activity concentrations of 238U, 232Th, and 40K was found to be 13.31 mBq L-1, 4.39 mBq L-1 and 1118.72 mBq L-1 which were about 3 times and slightly higher than the world average values of 5 mBq L-1 and 3 mBq L-1 respectively.


2019 ◽  
Vol 85 (4) ◽  
pp. 110-113
Author(s):  
Olexandr Ponomarenko ◽  
Anatolyi Samchuk ◽  
Kateryna Vovk ◽  
Igor Shvaika ◽  
Ganna Grodzinskaya

The analytical technologies of sample preparation of rocks and mushrooms using the microwave field for the determination of germanium by the method of mass spectrometry with inductively coupled plasma (ICP-MS analysis) have been developed. Germanium is a rare element. Germanium is homology of silicon and carbon. To date, the definition of low content of germanium in geological objects is a rather complex analytical task, which requires its concentration - extraction, co-precipitation, ion exchange. At present, the harmonious combination of the method of natural objects decomposition in the microwave field and germanium determination using ICP-MS analysis is particularly promising. Sample preparation of silicate rocks for ICP-MS determination of germanium was carried out by decomposition in a mixture of hydrofluoric, phosphate and nitric acids (5: 5: 2) in a microwave oven program at 240°C for 30 min. Sample preparation of mushrooms for ICP-MS germanium determination was carried out according to the following scheme. Initially, the dried sample was sealed in the presence of CaO, after dissolving it in a mixture of HNO3+HF+H3PO4 (6:6:1). Ge solution was extracted by Nazarenko V.A. extraction method. The developed analytical schemes have made it possible to significantly reduce the duration and labor intensity of sample preparation. The obtained solutions were analyzed using an inductively coupled plasma mass spectrometer. The developed method for determining germanium by ICP-MS analysis has been successfully tested on standard rock samples. The obtained results are in accordance with the accepted attribute, the relative standard deviation Sr ranges from 0.7-0.9. The data on the content and distribution of germanium in the Boletales fungi are obtained. They indicate wild mushrooms contain high levels of germanium, especially Boletus and Mushroom biospores. These studies are necessary because the essential properties of germanium and its compounds attract special attention of scientists today. Complementary Ge compounds which have hypotensive, bactericidal, antiviral and antitumor effects have already been synthesized.


2020 ◽  
Vol 58 (3) ◽  
pp. 293-311 ◽  
Author(s):  
Zeinab Azadbakht ◽  
David R. Lentz

ABSTRACT Biotite grains from 22 felsic intrusions in New Brunswick were mapped in situ using a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS). We investigated the extent to which biotite can retain its magmatic zoning patterns and, where zoning does exist, how it can be used to elucidate early to late stage, syn-magmatic to post-crystallization processes. Although the major element and halogen contents of the examined biotite phenocrysts are homogeneous, two-thirds of the grains display trace-element zoning for Ba, Rb, and Cs. The results also indicated that zoning is better retained in larger grains (i.e., > 500 × 500 μm) with minimal alteration and mineral inclusions. An exceptionally well-zoned Li-rich siderophyllite from the Pleasant Ridge topaz granite in southwestern New Brunswick shows Ti, Ta, Sn, W, Cs, Rb, and V (without Li or Ba) zoning. Cesium values increase from 200 to 1400 ppm from core to rim. Conversely, Sn and W values decrease toward the rim (50 to 10 and 100 to 10 ppm, respectively). Tantalum and Ti values show fewer variations but drop abruptly close to the rim of the grain (100 to 20 and 2000 to 500 ppm, respectively). These observations may indicate crystallization of mineral phases with high partition coefficients for these highly incompatible elements (except Ti) (e.g., cassiterite and rutile) followed by fractionation of a fluid phase at a later stage of magma crystallization. The preservation of zoning may indicate rapid cooling post-crystallization of the parent magma.


Minerals ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 890 ◽  
Author(s):  
Sergey Lipko ◽  
Vladimir Tauson ◽  
Valeriy Bychinskii

The characteristics of Au partitioning in a multiphase, multicomponent hydrothermal system at 450 °C and 1 kbar pressure were obtained using experimental and computational physicochemical modelling and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. Sphalerite and magnetite contained 0.1–0.16 ± 0.02 µg/g Au and coexisted with galena and bornite which contained up to 73 ± 5 and 42 ± 10 µg/g Au, respectively. Bornite and chalcopyrite were the most effective Au scavengers with cocrystallization coefficients Au/Fe and Au/Cu in mineral-fluid system n–n × 10−2. Sphalerite and magnetite were the weakest Au absorbers, although Fe impurity in sphalerite facilitated Au uptake. Using the phase composition correlation principle, Au solubility in minerals was estimated (µg/g Au): low-Fe sphalerite = 0.7, high-Fe sphalerite = 5, magnetite = 1, pyrite = 3, pyrite-Mn = 7, pyrite-Cu = 10, pyrrhotite = 21, chalcopyrite = 110, bornite = 140 and galena = 240. The sequence reflected increasing metallicity of chemical bonds. Gold segregation occurred at crystal defects, and on surfaces, and influenced Au distribution due to its segregation at crystal interblock boundaries enriched in Cu-containing submicron phases. The LA-ICP-MS analysis of bulk and surficial gold admixtures revealed elevated Au content in surficial crystal layers, especially for bornite and galena, indicating the presence of a superficial nonautonomous phase (NAP) and dualism in the distribution of gold. Thermodynamic calculations showed that changes in experimental conditions, primarily in sulfur regime, increased the content of the main gold species (AuCl2− and AuHS0) and decreased the content of FeCl20, the prevailing form of iron in the fluid phase. The elevation of S2 and H2S fugacity affected Au partitioning and cocrystallization coefficients. Using Au content in pyrite, chalcopyrite, magnetite and bornite from volcanic-sedimentary, skarn-hosted and magmatic-hydrothermal sulfide deposits, the ranges of metal ratios in fluids were estimated: Au/Fe = n × 10−4−n × 10−7 and Au/Cu = n × 10−4−n × 10−6. Pyrite and magnetite were crystallized from solutions enriched in Au compared to chalcopyrite and bornite. The presence of NAP, and associated dualism in distribution coefficients, strongly influenced Au partitioning, but this effect does not fully explain the high gold fractionation into mineral precipitates in low-temperature geothermal systems.


2017 ◽  
Vol 32 (5) ◽  
pp. 975-986 ◽  
Author(s):  
Lie-Wen Xie ◽  
Jin-Hui Yang ◽  
Qing-Zhu Yin ◽  
Yue-Heng Yang ◽  
Jing-Bo Liu ◽  
...  

A new LA-MIC-ICP-MS analytical technique has been developed for the rapid measurement of 206Pb/238U zircon age (<1%, 2s) at a high spatial resolution. We show that this technique can be routinely employed to date U–Pb in small and/or complex zircons, providing a powerful tool for geochronology.


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