Guiqin Wang

Separation of magnesium from meteorites and terrestrial silicate rocks for high-precision isotopic analysis using multiple collector-inductively coupled plasma-mass spectrometry

We report a modified procedure for separating Mg and Al from meteorites and terrestrial igneous rocks for high-precision analysis of Mg isotopes with multiple collector-inductively coupled plasma-mass spectrometry. The separating procedure was carried out in a single ion-exchange column filled with AG50W-X12 resin, and Mg was eluted with 1 M HNO3, followed by Al eluted with 4M HNO3. The modified procedure efficiently eliminates most matrix elements (except for Ni, Co, and Cu) with a recovery yield of Mg > 99%. Measurements of Ni-, Co-, and Cu-bearing simulation solutions revealed no detectable matrix effects. However, test runs demonstrated significant mass-dependent fractionation during the chromatographic process; consequently, a high recovery yield of Mg (>99%) is required to limit the deviation to less than 0.05‰. Furthermore, analysis of Mg standard solution with a wide range of concentrations demonstrated negligible deviation for samples with concentrations of 0.3–2.5 μg ml−1Mg relative to Mg standard solution concentrations of 1 μg ml−1Mg. The total procedure bank is less than 2 ng. The long-term reproducibility of instrumental measurements of Mg isotopes is ±0.05‰ for δ25Mg, ±0.10‰ for δ26Mg, and ±0.06‰ for δ26Mg* (2 SD, n = 211), based on analyzing five pure Mg standard solutions. Analysis of three chondrites and seven igneous rock standards showed ranges of δ26Mg(DSM3) from 0.02‰ to 0.30‰ for the former and from 0.03‰ to 0.30‰ for the latter. This method is simple and actionable.

Optimization techniques for improving the precision of isotopic analysis by thermal ionization mass spectrometry, taking strontium, neodymium, lead, and osmium as examples

ABSTRACT Several optimization techniques have been suggested to improve the signal and precision of analyses by thermal ionization mass spectrometry. Our work shows that tungsten filament is likely the most efficient for ionizing strontium when selecting from tungsten, rhenium, and tantalum filament. Deviations of isotopic ratios could be due to the degradation of the Faraday cups. This disadvantage could be avoided through eliminating the imperfect cup from the cup configuration. The high background produced from usage of rhenium filament could be decreased by cleaning the ion source and baking the source housing.

Calcium Isotopic Compositions of Normal Mid‐Ocean Ridge Basalts From the Southern Juan de Fuca Ridge

Mantle peridotites show that Ca is isotopically heterogeneous in Earths mantle, but the mechanism for such heterogeneity remains obscure. To investigate the effect of partial melting on Ca isotopic fractionation and the mechanism for Ca isotopic heterogeneity in the mantle, we report high-precision Ca isotopic compositions of the normal Mid-Ocean Ridge Basalts (N-MORB) from the southern Juan de Fuca Ridge. Ca-44/40 of these N-MORB samples display a small variation ranging from 0.750.05 to 0.860.03 (relative to NIST SRM 915a, a standard reference material produced by the National Institute of Standards and Technology), which are slightly lower than the estimated Upper Mantle value of 1.050.04 parts per thousand and the Bulk Silicate Earth (BSE) value of 0.94 +/- 0.05 parts per thousand. This phenomenon cannot be explained by fractional crystallization, because olivine and orthopyroxene fractional crystallization has limited influence on Ca-44/40 of N-MORB due to their low CaO contents, while plagioclase fractional crystallization cannot lead to light Ca isotopic compositions of the residue magma. Instead, the lower Ca-44/40 of N-MORB samples compared to their mantle source is most likely caused by partial melting. The offset in Ca-44/40 between N-MORB and BSE indicates that at least 0.1-0.2 parts per thousand fractionation would occur during partial melting and light Ca isotopes are preferred to be enriched in magma melt, which is in accordance with the fact that Ca-44/40 of melt-depleted peridotites are higher than fertile peridotites in literature. Therefore, partial melting is an important process that can decrease Ca-44/40 in basalts and induce Ca isotopic heterogeneity in Earths mantle.

A comparison using Faraday cups with 1013 Ω amplifiers and a secondary electron multiplier to measure Os isotopes by negative thermal ionization mass spectrometry

RATIONALE According to the Johnson-Nyquist noise equation, the value of electron noise is proportional to the square root of the resistor value. This relationship gives a theoretical improvement of 100 in the signal/noise ratio by going from 1011 Ω to 1013 Ω amplifiers for Faraday detection in thermal ionization mass spectrometry (TIMS). METHODS We measured Os isotopes using static Faraday cups with 1013 Ω amplifiers in negative thermal ionization mass spectrometry (NTIMS) and compared the results with those obtained with 1011 Ω amplifiers and by peak-hopping on a single secondary electron multiplier (SEM). We analysed large loads of Os (1 μg) at a range of intensities of 187 OsO3 (0.02-10 mV) in addition to small loads of Os (5-500 pg) to compare the results of the three methods. RESULTS Using 1013 Ω amplifiers, the long-term reproducibility determined from Merck Os was 187 Os/188 Os = 0.1211 ± 0.0086 and 0.120229 ± 0.000034 at 0.02 mV and 10 mV of 187 OsO3 intensities. Meanwhile, the analysed JMC Os loadings of 5 and 500 pg showed 187 Os/188 Os = 0.10669 ± 0.00036 and 0.106807 ± 0.000023. In comparison, the values measured by the SEM were 187 Os/188 Os = 0.10704 ± 0.00056 and 0.10690 ± 0.00013. All errors are in 2 standard deviation (SD). CONCLUSIONS Both the accuracy and the precision determined using the 1013 Ω amplifiers and the SEM are identical when the Os amounts are within 10-50 pg. However, the former analysis time can be shortened by approximately two-thirds. The SEM measurement is still the most precise method for Os amounts <10 pg, but the analyses using 1013 Ω amplifiers suggest they are significantly better than the SEM for Os amounts >50 pg.

Trace element analysis of extraterrestrial metal samples by inductively coupled plasma mass spectrometry: the standard solutions and digesting acids

RATIONALE Nearly 99% of the total content of extraterrestrial metals is composed of Fe and Ni, but with greatly variable trace element contents. The accuracy obtained in the inductively coupled plasma mass spectrometry (ICP-MS) analysis of solutions of these samples can be significantly influenced by matrix contents, polyatomic ion interference, and the concentrations of external standard solutions. METHODS An ICP-MS instrument (X Series 2) was used to determine 30 standard solutions with different concentrations of trace elements, and different matrix contents. Based on these measurements, the matrix effects were determined. Three iron meteorites were dissolved separately in aqua regia and HNO3. Deviations due to variation of matrix contents in the external standard solutions were evaluated and the analysis results of the two digestion methods for iron meteorites were assessed. RESULTS Our results show obvious deviations due to unmatched matrix contents in the external standard solutions. Furthermore, discrepancy in the measurement of some elements was found between the sample solutions prepared with aqua regia and HNO3, due to loss of chloride during sample preparation and/or incomplete digestion of highly siderophile elements in iron meteorites. CONCLUSIONS An accurate ICP-MS analysis method for extraterrestrial metal samples has been established using external standard solutions with matched matrix contents and digesting the samples with HNO3 and aqua regia. Using the data from this work, the Mundrabilla iron meteorite previously classified as IAB-ung is reclassified as IAB-MG.

A “peak cut” procedure of column separation for calcium isotope measurement using the double spike technique and thermal ionization mass spectrometry (TIMS)

Full recovery from column separation and matrix effects are the two factors that need to be considered for the high-precision analysis of stable Ca isotopes, but generally they are difficult to balance. In many cases, to get a pure Ca fraction, the interference of the matrix elements is reduced at the cost of discarding a fraction of Ca overlapping with other elements (e.g. Sr and K). However, quantitative evaluation using this approach is challenging but greatly needed. Our study investigates the influence of low Ca recovery on δ44/40Ca using thermal ionization mass spectrometry (TIMS) with the double spike technique. δ44/40Ca of IAPSO seawater, ML3B-G and BHVO-2 in different Ca subcuts (e.g. 0–20, 20–40, 40–60, 60–80 and 80–100%), display limited variation after iterative correction by 42Ca–43Ca double spike with the exponential law. Notably, δ44/40Ca of each Ca subcut with ∼20% recovery is consistent with that of the Ca cut with full recovery, within a margin of error. Our results indicate that 42Ca–43Ca double spike technique can simultaneously correct Ca isotopic fractionation, occurring during column separation, and TIMS determination, because both follow the exponential fractionation law well. Therefore, a “peak cut” procedure of column separation for Ca isotope measurement using the double spike technique on TIMS is proposed. Briefly, we can mix the double spike with the sample solution well before column separation, then collect the peak of the Ca cut and abandon both sides of the Ca eluate that may overlap with other elements. This procedure would eliminate matrix effects efficiently, especially for samples with low CaO contents which typically must be passed through the column twice (e.g. peridotite and dunite).