Next Article in Journal
Study of Radiation Resistance to Helium Swelling of Li2ZrO3/LiO and Li2ZrO3 Ceramics
Previous Article in Journal
Established Model on Polycrystalline Graphene Oxide and Analysis of Mechanical Characteristic
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Crystals
Volume 12
Issue 3
10.3390/cryst12030383
crystals-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Simultaneous Determination of δ18O and δ37Cl Isotopic Compositions and the Concentrations of F, Cl, and S in Apatite Using SIMS

by
Yu Liu
1,2,
Qiuli Li
1,2,3,*,
Guoqiang Tang
1,2,3 and
Xianhua Li
1,2,3
1
State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
2
Innovation Academy for Earth Science, Chinese Academy of Sciences, Beijing 100029, China
3
College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
*
Author to whom correspondence should be addressed.
Crystals 2022, 12(3), 383; https://doi.org/10.3390/cryst12030383
Submission received: 7 February 2022 / Revised: 9 March 2022 / Accepted: 10 March 2022 / Published: 12 March 2022
Browse Figures
Versions Notes

Abstract

:
Due to its ubiquity in rock types and ability to accommodate a wide range of trace elements, apatite is widely used to interpret magmatic evolution and track volatile elements in hydrothermal systems. Volatile elements and Cl–O isotopes make apatite an ideal mineral with which to record the chemical and textural signatures of geological processes. This study describes a new analytical procedure to obtain the F, Cl, and S contents and Cl and O isotopes simultaneously using secondary ion mass spectrometry (SIMS) within ~10 min of analysis time for each spot. The analytical precision of δ18O (2 SD (standard deviation) ~0.30‰) and δ37Cl (2 SD ~0.20‰) has no obvious trade-off compared with ordinary SIMS analysis. The new protocol is time-efficient and, more importantly, ensures the consistency of data sources. A set of apatite standards with different uses were determined using this new method to provide a complete set of recommended values.

1. Introduction

Apatite (Ca5(PO4)3(F, Cl, OH)) is a ubiquitous accessory mineral in almost all major rock types. The crystal structure of apatite allows for complex substitutions of various minor and trace elements, including volatile constituents (F, Cl, OH), rare earth elements, and redox-sensitive elements (e.g., S) (e.g., [1]). Apatite is stable over a wide range of temperatures and pressures and is highly resistant to weathering, alteration, and diffusion processes. The study of the halogen composition of apatite reveals information about the composition and evolution of the magmatic and hydrothermal fluid (e.g., [2]). Apatite sulfur content can be used as a proxy for the S oxidation state in the melt because S partitioning into apatite is highly dependent on the oxidation state of S in the silicate melt [3]. Apatite Cl isotope signatures, especially in lunar rocks, can provide unique insights into volatile processing (e.g., [4]). The apatite oxygen isotope present can be related to the formation environment—for example, the global climate record can be determined by the oxygen isotopes of conodont apatite [5,6]. Therefore, a set of volatile element contents and isotopes make apatite an ideal mineral with which to record the chemical and texture signatures of many geological processes.
Secondary ion mass spectrometry (SIMS) was developed as an excellent in situ technique to provide a high spatial resolution and high precision for extracting elemental and isotopic compositions [7,8,9,10]. The analytical protocols used for determining element contents and separating Cl and O isotopes in apatite were established using SIMS (e.g., [11,12]). It is common to use integrated data to discuss the geological processes involved. However, the data are generally derived from different grains or the domains of one grain. Possible mismatching has the potential to yield unsuitable interpretations. This study attempts to develop a SIMS analytical procedure to simultaneously obtain the F, Cl, and S content and Cl–O isotopes. This new protocol is more time-efficient and, more importantly, provides greater data robustness among the different analytical items.

2. Sample Preparation

The newly developed reference materials (RMs) for apatite oxygen isotopes, Qinghu-AP, Durango, five chlorine isotope RMs, MGMH#133648, MGMH#128441A, TUBAF#37, TUBAF#38, and TUBAF#40, were placed in the one-inch epoxy mount A. Additionally, IGG-Durango, AP1, AP2, MAD, NW-1, and Qinghu were cast in another epoxy mount B. The reference values of these samples are summarized in Table 1.

2.1. Qinghu

Qinghu apatite grains, with δ18OVSOMW = 5.59 ± 0.19‰ (the errors are 2 standard deviations (SDs) unless indicated otherwise) [12], were separated from Qinghu monzonite [13] near the border of Guangdong and Guangxi provinces, south China. The contents of Cl, F, and S (calculated by SO3 in this study) were determined to be 0.36%, 2.78%, and 0.01%, respectively [14].

2.2. Durango Apatite

Durango apatite crystals were purchased from the Fersman Mineralogical Museum, Russian Academy of Sciences in Moscow. They were determined to have a δ18OVSOMW = 9.70 ± 0.22‰ [12]. Durango apatite was also used as chlorine isotopic RM with δ37ClSMOC = 0.19 ± 0,12‰ [15]. Its Cl, F, and S contents of 0.4 ± 0.04%, 3.61 ± 0.33%, and 0.3 ± 0.05% [15] were used as references in this study.

2.3. MGMH#133648, MGMH#128441A, TUBAF#37, TUBAF#38, and TUBAF#40

These five apatite samples were obtained from www.iageo.com and described by Wudarska et al. [15] in detail. Here, only the determined values are provided. The δ37ClSMOC of the five samples are MGMH#133648 = 0.09 ± 0.16 (1s), TUBAF#38 = 0.09 ± 0.19(1s), TUBAF#40 = 0.20 ± 0.24 (1s), MGMH# 128441A = 0.42 ± 0.20 (1s), and TUBAF#37 = 0.20 ± 0.13 (1s) [15]. The Cl, F, and S contents and δ37ClSMOC values are summarized in Table 1 [15]. The samples were used as RMs to verify the precision and accuracy of the method described in this study.

2.4. AP1 and AP2

The two gem-quality apatite crystals AP1 and AP2, which were used as in-house apatite RMs for laser ablation Sr and Nd isotopic analyses, had Cl and F contents of 0.3% and 3.97% for AP1 and 0.2% and 4.16% for AP2 [16]. No oxygen or chlorine isotopic ratios were provided in the previous studies on this topic.

2.5. MAD Apatite

MAD (Madagascar) is a large fragment of a blue gem-quality apatite crystal from the 1st Mine Discovery in Madagascar. The Cl and F contents of MAD were 0.20% and 4.13% [16]. The MAD sample used in this study was a fraction of this crystal. According to Sun et al. [17], the δ18O of the Madagascar 1st Mine apatite has a range of 7.6−11.1‰ among nine crystals. The contents of Cl, F, and S were also determined by EMPA. The obtained values of 0.14% (Cl) and 4.45% (F) were in agreement with the findings of Yang et al. [16], and the concentration of S = 0.42% was used as a reference in this study.

2.6. NW-1 Apatite

NW-1 apatite was extracted from a carbonatite collected from the Prairie Lake alkaline carbonatite complex in Ontario, Canada [18,19]. It has been used as a U-Th-Pb geochronology RM for apatite with a best-estimated age of 1160 ± 5 Ma [19,20]. The determined Cl and F contents are 0.01% and 1.84%, respectively.
The sample mounts were polished to a mirror finish. After cleaning with deionized water and ethanol, they were coated with gold under a vacuum. Before the SIMS analysis, the mounts were stored in the vacuum chamber in the SIMS instrument for more than 24 h to minimize the isobaric interference from the hydride.

3. Instrument Settings

The SIMS measurements were conducted using a CAMECA IMS-1280 large-geometry SIMS instrument at the Institute of Geology and Geophysics, Chinese Academy of Sciences in Beijing, China. The analytical conditions used for the SIMS measurements are summarized in Table 2. A low-intensity Cs+ primary beam (<1 nA) was focused to a ~10 µm spot at +10 kV to adapt the variable Cl and F contents of the different samples. A 10 µm raster was used to avoid a deep crater. Before each analysis, a 20 µm sputter was performed for 30 s to achieve a stable secondary ion beam. The transfer ion optics of the secondary beam were tuned to obtain a 133 times magnification to optimize the beam intensity. The normal incidence electron gun (NEG) was used to compensate for the positive charge accumulation. It was tuned to a round shape with a diameter of ~120 µm and a maximum emission current of ~2 mA. The entrance slit of 150 µm, field aperture of 5500 µm, and energy slit of 45 eV bandwidth were opened to balance the mass resolution and ion transmission.
Four Faraday Cups (FC) in a multi-collection system located in L’2, L1, H1, and H’2 were used for collecting all the secondary ions. The detector arrangement is summarized in Table 3. The acquisition was divided into three steps. The first step used L’2 and H1 with pre-amplifiers of 1010 Ω and 1012 Ω to determine the oxygen isotopes (16O and 18O). The chlorine isotopes, 35Cl and 37Cl, were collected in the second step with L1 and H1. In the third step, 32S and 19F16O peaks were measured with L1 (1011 Ω) and H’2 (1011 Ω). The counting times for the three steps were 20 s, 20 s, and 4 s, respectively. Each analysis consisted of 7 cycles for ~10 min.
According to Wudarska et al. [15], the isobaric interference of 34S1H− with 35Cl− is negligible due to the very low signal intensity. The low mass resolution was sufficient for the Cl isotopic determination. In this study, the detector used for 35Cl− had a slit width of 500 µm and a mass resolution power (MRP) of ~2200 (50% peak height). The mass spectrum is shown in Figure 1. The mass peaks of 35Cl− and 37Cl− were sufficiently separated from the isobaric inferences 19F16O− and 19F18O−, with a flat top peak shape. The 32S− was separated from the high peak of 16O2− (MRP of 1800 required) with an MRP of ~2200 (50% peak height).

4. Results and Discussion

4.1. Oxygen Isotope

In the first session, mount A was determined using the combined isotopic and element analytical method. Durango was used as the oxygen isotope RM with δ18O = 9.7‰ [12]. The other six samples were calibrated; the δ18O values are shown in Table 4 and plotted in Figure 2. The error of each spot was combined from the analytical error and external repeatability of Durango in this session (0.30‰, 2SD). The analytical error of each spot can be found in the Supplementary tables. The corresponding δ18O of each sample was determined as follows: MGMH#133648 = 5.58 ± 0.19‰, MGMH#128441A = 7.91 ± 0.32‰, TUBAF#37 = 17.74 ± 0.25, TUBAF#38 = 9.74 ± 0.30‰, TUBAF#40 = 8.80 ± 0.15, and Qinghu = 5.31 ± 0.50‰. The results of Qinghu agree well with the recommended value of 5.5 ± 0.2‰ found by Chen et al. [6], the value of 5.44 ± 0.49‰ found by Yang et al. [14], and the value of 5.59 ± 0.19‰ found by Li et al. [12].
In the second session, the external repeatability of Durango was 0.18‰ (2 SD), which was also propagated to the internal error of each spot. The determined δ18O of the samples in mount B were AP1 = 10.33 ± 0.20‰, AP2 = 8.30 ± 0.18‰, MAD = 10.18 ± 0.26‰, NW-1 = 5.65 ± 0.25‰, and Qinghu = 5.43 ± 0.38‰ (Table 5).
It is worth noting that the 1012 Ω pre-amplifier for the H1 detector had a relatively long decay time (>15 s). The 18O− and 37Cl− signals shared the same detector in this study. According to the mass order, the step for 32S− and 19F16O− with an axial mass of ~32.3 a.m.u. should be measured before the Cl isotopes (axial mass of 35.7 a.m.u.). However, due to the high intensity of 37Cl− (105 to 107 cps depend on the Cl concentration) compared with the 18O− a signal of ~2 × 106 cps, the decay time of this 1012 Ω pre-amplifier could have a significant influence on the 18O− signal for the following cycles. Therefore, the step for Cl isotopes was set before the 32S− and 19F16O− step (no H1 was used in this step) to provide a sufficient time for signal decay.
The external repeatability of oxygen isotope determination for Durango apatite using SIMS is ~0.25‰ (2 SD) in general—i.e., 0.25‰ and 0.27‰ as determined by Yang et al. [14] and 0.25‰ as determined by Li et al. [11] The combined method described in this study can provide a similar external precision of 0.18‰ and 0.30‰ in two sessions, which indicates that this approach does not trade off its analytical precision. The recent study conducted by Wudarska et al. provided δ18O values for MGMH#133648 = 5.81 ± 0.93‰ and MGMH#128441A = 7.60 ± 0.48‰ by multi-laboratory analysis [21]. The large uncertainty of the given data is mainly due to the different sample processing methods used by the different laboratories. For instance, two different values were found for MGMH#133648, “phosphate δ18O” = 6.64 ± 0.22‰ (only oxygen in the PO4 was measured) and “bulk δ18O”s = 4.97 ± 0.21‰ (all the oxygen in PO4, OH, and CO3 was measured) [21]. The different values obtained using the different methods were the main problem faced in the apatite oxygen isotopic determination and application. The reported δ18O values should include detailed information on the analytical method and RM used for the calibration. For in situ application, particularly SIMS, a reference value obtained by SIMS is more valuable for use as a reference. In this study, the Durango-calibrated δ18O values for MGMH#133648 and MGMH#128441A were 5.58 ± 0.19‰ and 7.91 ± 0.32‰, respectively, which are generally within the value ranges reported by Wudarska et al. [21] A high-quality oxygen isotope RM of apatite should be established and widely used in all the SIMS laboratories involved. Based on the current study, the large crystal MGMH#133648 has an adequate homogeneity and mass for in situ oxygen isotopic analysis and should be used by the SIMS community as the common RM to unify the calibration standard.

4.2. Chlorine Isotopes

The Cl content varies from ~0.1% to a few percent for different samples. This range can affect the δ37Cl values considerably (matrix effect) [2,15,22]. A similar trend was also found in this study. The data of six samples, MGMH#133648, MGMH#128441A, TUBAF#37, TUBAF#38, TUBAF#40, and Durango (with IRMS determined values), were firstly calibrated against Durango without considering the instrument mass fractionation (IMF) variation caused by the matrix effect. The calibrated δ37Cl values are marked as Measured δ37Cl in Table 4 and Table 5. The difference between the directly calibrated δ37Cl values and the IRMS-determined δ37Cl values (δ37ClSIMS–δ37ClIRMS) was defined as ΔIMFCl in this study. The ΔIMFCl verse Cl% content of each sample is plotted in Figure 3. Linear fitting was performed, with an equation of y = −1.004x – 0.1504 obtained with an R2 = 0.8. The matrix δ37Cl data calibrated using the linear equation (marked as IMF corrected in the table) are listed in Table 4 and Table 5. The determined δ37Cl values of these RMs are consistent with the recommended values taking into account uncertainties (Figure 4). The calibrated δ37Cl of Qinghu is 0.24 ± 0.17‰ (2 SD), which could be used as a recommended value.
The same calibration method was used in the second session. The δ37Cl of Qinghu calibrated in this session was 0.22 ± 0.21‰ (2 SD), which agrees well with the value obtained in the previous session. The recommended δ37Cl value of 0.23 ± 0.19‰ (2SD) could be obtained by combining the data of Qinghu apatite obtained from two sessions. The values obtained for other samples were as follows: Durango = 0.38 ± 0.11‰, AP1 = 0.37 ± 0.25‰, AP2 = 0.50 ± 0.22‰, MAD = 0.78 ± 0.36‰, and NW-1 = 3.68 ± 3.42‰. The errors were 2 SD. For the samples with a Cl content of more than 0.17%, the external repeatability of 0.22‰ (2 SD) could be achieved. The δ37Cl determined for AP1, AP2, and MAD can be used as reference values for SIMS analysis.
Due to the magnitude difference in the Cl mass fraction of different samples, a relatively low primary beam intensity was used to make sure that the signals of all the samples were within the detection range. Thus, the intensity of 37Cl− could go as low as 105 cps for the low-concentration samples, which is very small compared with the detection range of the Faraday Cup detector with a pre-amplifier of 1012 Ω. Improper background subtraction creates an illusion of matrix effects related to Cl mass fractions. For instance, an inappropriate background was applied in Figure 5. If a 5000 cps miss-correction on H1 FC was used, the ΔIMF trend could change from negative to positive. In this study, the background of each detector was carefully subtracted, with both the primary beam and the electron beam turned off. The L1 FC (for 35Cl−) with 1011 Ω and H1 FC (for 37Cl−) with 1012 Ω were determined to have baselines of 675 ± 858 cps and −79 ± 378 cps (2SD, n = 8), respectively, after the subtraction of the background. Both detectors had readings of around zero within the errors.

4.3. Cl, F, and S Mass Fractions

The Cl, F, and S mass fractions could be obtained simultaneously in the combined analytical method. 16O was used as an internal standard for calibrating the Cl, F, and S mass fractions. The Durango apatite with homogeneous Cl, F, and S mass fractions (0.41 ± 0.02, 3.61 ± 0.05, and 0.30 ± 0.04, errors are 2 SD) was used as the calibration standard.
The calibrated Cl, F, and S mass fractions of the samples are listed in Table 4 and Table 5. For the samples of MGMH#133648, MGMH#128441A, TUBAF#37, TUBAF#38, and TUBAF#40, the values determined in this study agree well with the recommended values [15]. The maximum difference between them is only 0.26% w/w. For Qinghu apatite, the mass fractions of Cl, F, and S were 0.22 ± 0.08%, 3.43 ± 0.08%, and 5.9 × 10−4 ± 1.1 × 10−4%, respectively. In the second session, the Cl, F, and S mass fractions calibrated for AP1 were 0.26 ± 0.01%, 3.88 ± 0.04%, and 0.37 ± 0.02%; for AP2, they were 0.17 ± 0.02%, 3.98 ± 0.05, and 0.57 ± 0.09%; for MAD, they were 0.17 ± 0.005%, 3.96 ± 0.04%, and 0.45 ± 0.02%; and for NW-1, they were 0.01 ± 0.001%, 1.90 ± 0.03%, and 1.26 × 10−3 ± 4.6 × 10−4%. In this session, the Qinghu was determined to have Cl, F, and S concentrations of 0.21 ± 0.09, 3.43 ± 0.10%, and 1.05 × 10−3 ± 3.9 × 10−4%, which are consistent with the previous session within the error range. The recommended Cl, F, and S concentrations for Qinghu apatite in this study were 0.22 ± 0.08%, 3.43 ± 0.09%, and 8.3 × 10−4 ± 5.5 × 10−4%, respectively.
For the 32S− measurement (the signal intensity could go as low as 1 × 104 cps), the noise level was 1000 cps (2 SD) on the L1 detector, so the detection limit was ~3000 cps, corresponding to a concentration of 0.3 ppm under the current instrument settings.

5. Conclusions

A combined SIMS analytical method was established in this study. Multiple pieces of information, including the isotopic ratios (δ18O, δ37Cl) and contents of three volatile elements (Cl, F, and S), could be obtained simultaneously within ~10 min of analysis time for each spot. Compared with the ordinary isotope and elemental concentration determination method (each item cost ~3 min in general e.g., [11,14]), this method is more efficient as it diminishes the sample targeting time and pre-sputtering time. More importantly, the multiple pieces of information gathered on a single spot ensure the consistency of the data sources. The analytical precision of determining δ18O (2 SD ~0.30‰) and δ37Cl (2 SD ~0.20‰) has no obvious trade-off compared with the ordinary SIMS analytical protocol used for single information. The matrix effect for δ37Cl determination on apatite using SMS was confirmed, and the linear relationship was constructed for the IMF calibration. A set of apatite RMs (including Qinghu and Durango for oxygen isotopes; MGMH#133648, MGMH#128441A, TUBAF#37, TUBAF#38, and TUBAF#40 for chlorine isotopes; AP1, AP2, and MAD1 for Sr-Nd isotopes; and NW-1 for U-Pb dating) were measured and used to provide recommended values to complete the missing information. A summary of the recommended values of these RMs is shown in Table 6. The data were collected from this study and Wudarska et al., 2021 [15]; Li et al., 2021 [12]; Yang et al., 2019 [14]; Yang et al., 2014 [16]; Sun et al., 2016 [17]; Li et al., 2012 [19]; and Zhou 2013 [23].

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/cryst12030383/s1: Supplementary tables.

Author Contributions

Conceptualization, Q.L.; methodology, Y.L.; software, G.T.; validation, X.L.; formal analysis, Y.L.; investigation, Q.L.; resources, Q.L.; data curation, Y.L.; writing—original draft preparation, Y.L.; writing—review and editing, Q.L.; visualization, Y.L.; supervision, X.L.; project administration, X.L.; funding acquisition, X.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Key R&D Program of China (2018YFA0702600) and the Key Research Program of IGGCAS (IGGCAS-201901, IGGCAS-202101).

Institutional Review Board Statement

Not applicable.

Data Availability Statement

The data are contained within the article and supplementary material.

Acknowledgments

The authors would like to thank Yue-Heng Yang for providing the AP1, AP2, and MAD apatite samples. Ma Hong-Xia is thanked for her excellent skill in preparing the sample mounts. The work was supported by the National Key Research and Development Program of China (2018YFA0702600) and the Key Research Program of IGGCAS (IGGCAS-201901, IGGCAS-202101). We would like to thank the two anonymous reviewers for their helpful comments, which have greatly improved this manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Piccoli, P.M.; Candela, P.A. Apatite in Igneous Systems. Rev. Miner. Geochem. 2002, 48, 255–292. [Google Scholar] [CrossRef]
  2. Kusebauch, C.; John, T.; Whitehouse, M.; Engvik, A.K. Apatite as probe for the halogen composition of metamorphic fluids (Bamble Sector, SE Norway). Contrib. Miner. Pet. 2015, 170, 34. [Google Scholar] [CrossRef]
  3. Tang, M.; Lee, C.-T.A.; Ji, W.-Q.; Wang, R.; Costin, G. Crustal thickening and endogenic oxidation of magmatic sulfur. Sci. Adv. 2020, 6, eaba6342. [Google Scholar] [CrossRef] [PubMed]
  4. Stephant, A.; Anand, M.; Ashcroft, H.; Zhao, X.; Hu, S.; Korotev, R.; Strekopytov, S.; Greenwood, R.; Humphreys-Williams, E.; Liu, Y.; et al. An ancient reservoir of volatiles in the Moon sampled by lunar meteorite Northwest Africa 10989. Geochim. Cosmochim. Acta 2019, 266, 163–183. [Google Scholar] [CrossRef]
  5. Trotter, J.A.; Williams, I.S.; Barnes, C.R.; Lécuyer, C.; Nicoll, R.S. Did Cooling Oceans Trigger Ordovician Biodiversification? Evidence from Conodont Thermometry. Science 2008, 321, 550–554. [Google Scholar] [CrossRef] [PubMed]
  6. Chen, M.; Bagas, L.; Liao, X.; Zhang, Z.; Li, Q. Hydrothermal apatite SIMS ThPb dating: Constraints on the timing of low-temperature hydrothermal Au deposits in Nibao, SW China. Lithos 2019, 324–325, 418–428. [Google Scholar] [CrossRef]
  7. Fitzsimons, I.C.; Harte, B.; Clark, R.M. SIMS stable isotope measurement: Counting statistics and analytical precision. Mineral. Mag. 2000, 64, 59–83. [Google Scholar] [CrossRef]
  8. Hinton, R.W. Microprobe Techniques in the Earth Sciences; Chapman and Hall: London, UK, 1995; pp. 235–290. [Google Scholar]
  9. De Laeter, J.R. Applications of Inorganic Mass Spectrometry; John Wiley & Sons: Hoboken, NJ, USA, 2001; p. 474. [Google Scholar]
  10. Page, F.Z.; Ushikubo, T.; Kita, N.T.; Riciputi, L.R.; Valley, J.W. High precision oxygen isotope analysis of picogram samples reveals μm gradients and slow diffusion in zircon. Am. Mineral. 2007, 92, 1772–1775. [Google Scholar] [CrossRef]
  11. Li, Y.; Li, Q.-L.; Tang, G.-Q.; Gargano, A.; Sharp, Z.; Pitawala, A.; Zhao, L.; Zhai, M.-G.; Li, X.-H. Eppawala-AP, Sri Lanka, an Apatite Reference Material for High Precision Chlorine Isotope Analysis. At. Spectrosc. 2020, 41, 51–56. [Google Scholar] [CrossRef]
  12. Li, Y.; Tang, G.-Q.; Liu, Y.; He, S.; Chen, B.; Li, Q.-L.; Li, X.-H. Revisiting apatite SIMS oxygen isotope analysis and Qinghu-AP reference material. Chem. Geol. 2021, 582, 120445. [Google Scholar] [CrossRef]
  13. Li, X.H.; Tang, G.Q.; Gong, B.; Yang, Y.H.; Hou, K.J.; Hu, Z.C.; Li, Q.L.; Liu, Y.; Li, W.X. Qinghu zircon: A working reference for microbeam analysis of U-Pb age and Hf and O isotopes. Chin. Sci. Bull. 2013, 58, 4647–4654. [Google Scholar] [CrossRef]
  14. Yang, Q.; Xia, X.P.; Zhang, L.; Zhang, W.; Zhang, Y.; Chen, L.; Yang, Y.; He, M. Oxygen isotope homogeneity assessment for apatite U-Th-Pb geochronology reference materials. Surf. Interface Anal. 2019, 52, 197–213. [Google Scholar] [CrossRef]
  15. Wudarska, A.; Słaby, E.; Wiedenbeck, M.; Barnes, J.D.; Bonifacie, M.; Sturchio, N.C.; Bardoux, G.; Couffignal, F.; Glodny, J.; Heraty, L.; et al. Inter-laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis. Geostand. Geoanal. Res. 2021, 45, 121–142. [Google Scholar] [CrossRef]
  16. Yang, Y.-H.; Wu, F.-Y.; Yang, J.-H.; Chew, D.; Xie, L.-W.; Chu, Z.-Y.; Zhang, Y.-B.; Huang, C. Sr and Nd isotopic compositions of apatite reference materials used in U–Th–Pb geochronology. Chem. Geol. 2014, 385, 35–55. [Google Scholar] [CrossRef]
  17. Sun, Y.; Wiedenbeck, M.; Joachimski, M.M.; Beier, C.; Kemner, F.; Weinzierl, C. Chemical and oxygen isotope composition of gem-quality apatites: Implications for oxygen isotope reference materials for secondary ion mass spectrometry (SIMS). Chem. Geol. 2016, 440, 164–178. [Google Scholar] [CrossRef]
  18. Sano, Y.; Oyama, T.; Terada, K.; Hidaka, H. Ion microprobe U–Pb dating of apatite. Chem. Geol. 1999, 153, 249–258. [Google Scholar] [CrossRef]
  19. Li, Q.; Li, X.-H.; Wu, F.-Y.; Yin, Q.-Z.; Ye, H.-M.; Liu, Y.; Tang, G.-Q.; Zhang, C.-L. In-situ SIMS U–Pb dating of phanerozoic apatite with low U and high common Pb. Gondwana Res. 2012, 21, 745–756. [Google Scholar] [CrossRef]
  20. Wu, F.-Y.; Mitchell, R.H.; Li, Q.-L.; Zhang, C.; Yang, Y.-H. Emplacement age and isotopic composition of the Prairie Lake carbonatite complex, Northwestern Ontario, Canada. Geol. Mag. 2017, 154, 217–236. [Google Scholar] [CrossRef]
  21. Wudarska, A.; Wiedenbeck, M.; Słaby, E.; Lempart-Drozd, M.; Harris, C.; Joachimski, M.M.; Lécuyer, C.; MacLeod, K.G.; Pack, A.; Vennemann, T.; et al. Inter-laboratory Characterisation of Apatite Reference Materials for Oxygen Isotope Analysis and Associated Methodological Considerations. Geostand. Geoanal. Res. 2022. [Google Scholar] [CrossRef]
  22. Eiler, J.M.; Graham, C.; Valley, J. SIMS analysis of oxygen isotopes: Matrix effects in complex minerals and glasses. Chem. Geol. 1997, 138, 221–244. [Google Scholar] [CrossRef]
  23. Zhou, Q. In-Situ U–Pb Isotopic Dating of Accessory Minerals in Meteorites; University of Chinese Academy of Sciences: Beijing, China; Institute of Geology and Geophysics: Beijing, China; Chinese Academy of Sciences: Beijing, China, 2013; pp. 19–22. [Google Scholar]
Crystals 12 00383 g001 550
Figure 1. Mass spectrum of 35Cl−, 37Cl−, 19F16O−, and 32S− on apatite determined using SIMS.
Figure 1. Mass spectrum of 35Cl−, 37Cl−, 19F16O−, and 32S− on apatite determined using SIMS.
Crystals 12 00383 g001
Crystals 12 00383 g002 550
Figure 2. Probabilistic histograms of δ18O for the 11 samples used in this study, calibrated against Durango. The upper value in each diagram is the δ18O determined by SIMS in this study and the lower value is the recommended value. The errors are 2 SD.
Figure 2. Probabilistic histograms of δ18O for the 11 samples used in this study, calibrated against Durango. The upper value in each diagram is the δ18O determined by SIMS in this study and the lower value is the recommended value. The errors are 2 SD.
Crystals 12 00383 g002
Crystals 12 00383 g003 550
Figure 3. Matrix effect caused by the varying Cl content in different samples. A linear trend was found between ΔIMFCl (δ37ClSIMS−δ37ClIRMS) and Cl% in samples.
Figure 3. Matrix effect caused by the varying Cl content in different samples. A linear trend was found between ΔIMFCl (δ37ClSIMS−δ37ClIRMS) and Cl% in samples.
Crystals 12 00383 g003
Crystals 12 00383 g004 550
Figure 4. Probabilistic histograms of the δ37Cl of the 11 samples used in this study, calibrated against Durango.
Figure 4. Probabilistic histograms of the δ37Cl of the 11 samples used in this study, calibrated against Durango.
Crystals 12 00383 g004
Crystals 12 00383 g005 550
Figure 5. An inappropriate background subtraction could cause the ΔIMF trend to change from negative to positive. A 5000 cps was subtracted (or added) to the 37Cl− channel (H1) as an example.
Figure 5. An inappropriate background subtraction could cause the ΔIMF trend to change from negative to positive. A 5000 cps was subtracted (or added) to the 37Cl− channel (H1) as an example.
Crystals 12 00383 g005
Table
Table 1. The summarized Cl, F, and S concentrations and δ37Cl and δ18O of the samples used in this study.
Table 1. The summarized Cl, F, and S concentrations and δ37Cl and δ18O of the samples used in this study.
Sampleδ18O (‰)δ37Cl (‰)Cl (%)F (%)SO3 (%)
MGMHMedian-0.096.09<DL0.11
#1336481s-0.160.71-0.02
MGMHMedian-0.421.032.360.19
#128441A1s-0.200.020.120.02
TUBAF#37Median-0.200.263.630.34
1s-0.130.020.180.11
TUBAF#38Median-0.094.290.460.14
1s-0.190.190.060.02
TUBAF#40Median-0.201.431.930.11
1s-0.240.080.130.02
DurangoMedian9.70.190.43.610.3
1s0.220.120.040.330.05
QinghuMedian5.59-0.362.780.01
1s0.19----
AP1Median--0.33.97-
1s-----
AP2Median--0.24.16-
1s-----
NW-1Median--0.011.84
1s-----
MADMedian7.6−11.1-0.24.130.42
1s-----
Data for MGMH#133648, MGMH#128441A, TUBAF#37, TUBAF#38, and TUBAF#40 are summarized from Wudarska et al., 2021; Durango data are summarized from Li et al., 2021, and Wudarska et al., 2021; Qinghu data are summarized from Yang et al., 2019, and Li et al., 2021; AP1, AP2, and NW-1 data are summarized from Yang et al., 2014; MAD data are summarized from Yang et al., 2014, and Sun et al., 2016; <DL: below detection limit.
Table
Table 2. Analytical conditions used for SIMS determination.
Table 2. Analytical conditions used for SIMS determination.
Primary beamGaussian Cs+ beam, ~1 nA, ~10 µm diameter, with 10 µm raster, +10 kV potential
Secondary HV−10,000 V
Transfer opticsMagnification of 133×
NEGRound shape with ~120 µm diameter, maximum emission current 2 mA
Entrance slit150 µm
Energy slit45 eV bandwidth, with 5 eV gap
Field aperture5500 µm
16O intensity (cps)~1 × 109 cps
35Cl intensity (cps)~105 to 108 cps
19F16O intensity (cps)~104 to 106 cps
32S intensity (cps)~104 to 107 cps
Pre-sputtering20 µm, 30s
Table
Table 3. Configuration of the multi-collector used for simultaneous detection.
Table 3. Configuration of the multi-collector used for simultaneous detection.
DetectorL′2L1H1H′2Counting Time
Exit slit (µm)700500700500(s)
StepPre-amplifier1010 Ω1011 Ω1012 Ω1011 Ω
1 16O 18O 20
2 35Cl37Cl 20
3 32S 19F 16O4
Table
Table 4. Calibrated data of the seven apatite samples.
Table 4. Calibrated data of the seven apatite samples.
SampleIMF Corrected2σ *MeasuredIMF Corrected2σ *Cl%F%S%
δ18O (‰)(‰)δ 37Clδ 37Cl(‰)
136648@15.530.40−0.600.160.226.100.170.09
136648@25.600.41−0.660.100.236.190.150.07
136648@35.620.37−0.680.080.236.260.140.08
136648@45.610.38−0.720.040.246.250.140.07
136648@55.600.41−0.560.200.236.250.130.06
136648@65.530.35−0.690.070.246.270.140.08
136648@75.530.31−0.710.060.226.180.170.10
136648@85.710.39−0.620.150.226.250.140.08
136648@95.700.33−0.590.170.246.300.130.06
136648@105.610.40−0.670.100.236.220.150.08
136648@115.420.44−0.710.050.226.210.160.09
136648@125.550.38−0.690.070.236.280.150.08
136648@135.690.37−0.760.000.236.210.160.10
136648@145.370.40−0.700.060.246.280.130.07
136648@155.550.36−0.79−0.030.256.280.140.08
Average5.580.19 0.090.126.240.150.08
128441A@17.740.350.060.310.240.962.440.12
128441A@27.880.610.010.270.230.962.440.12
128441A@37.750.330.000.250.230.952.460.12
128441A@47.910.37−0.020.230.230.962.440.13
128441A@58.170.400.030.280.240.972.430.13
128441A@68.110.410.050.300.240.962.460.12
128441A@78.070.35−0.110.140.230.942.460.13
128441A@88.130.41−0.060.200.220.962.460.12
128441A@97.800.31−0.010.250.230.952.460.13
128441A@107.950.390.010.260.240.972.440.14
128441A@117.930.360.050.310.230.942.440.13
128441A@127.750.38−0.110.140.240.962.450.13
128441A@137.720.310.140.390.230.962.440.13
Average7.910.32 0.260.140.962.450.13
Durango@19.620.330.370.560.260.413.650.31
Durango@29.410.470.350.540.230.403.580.31
Durango@39.700.350.040.230.260.413.620.31
Durango@49.980.340.160.350.260.403.610.31
Durango@59.590.390.240.440.240.413.610.29
Durango@69.720.440.200.390.250.403.570.28
Durango@79.730.340.090.280.260.403.580.28
Durango@89.590.420.310.500.250.413.600.28
Durango@99.840.400.320.510.230.413.620.32
Durango@109.870.480.100.290.240.423.650.33
Durango@119.870.340.030.220.240.423.660.33
Durango@129.950.420.340.530.300.413.600.32
Durango@139.720.350.170.360.250.413.610.32
Durango@149.540.370.190.380.240.403.610.30
Durango@159.560.350.110.300.260.403.610.30
Durango@169.720.540.070.270.260.443.590.25
Durango@179.540.370.170.360.260.423.620.29
Durango@189.700.350.120.310.240.413.620.30
Durango@199.640.390.250.440.260.403.580.29
Average9.700.30 0.380.220.413.610.30
Qinghu@15.740.430.020.200.320.233.425.8 × 10−4
Qinghu@25.080.450.100.280.370.173.445.6 × 10−4
Qinghu@35.050.400.200.380.270.273.345.7 × 10−4
Qinghu@45.050.370.140.330.320.203.425.9 × 10−4
Qinghu@55.050.42−0.020.170.310.203.435.4 × 10−4
Qinghu@65.540.42−0.020.160.340.243.435.4 × 10−4
Qinghu@75.340.480.130.320.280.243.416.4 × 10−4
Qinghu@85.770.360.050.240.380.183.475.7 × 10−4
Qinghu@95.090.440.110.300.320.143.526.1 × 10−4
Qinghu@105.290.36−0.070.120.350.193.456.8 × 10−4
Qinghu@115.440.42−0.060.130.300.243.397.1 × 10−4
Qinghu@125.490.420.120.310.340.243.405.1 × 10−4
Qinghu@135.220.390.080.260.360.253.435.9 × 10−4
Qinghu@145.230.33−0.060.130.250.273.455.5 × 10−4
Average5.310.50 0.240.170.223.435.9 × 10−4
TUBAF37@117.590.390.100.280.270.253.570.18
TUBAF37@218.030.480.040.220.290.253.530.16
TUBAF37@317.710.47−0.050.130.260.243.590.14
TUBAF37@417.730.39−0.130.040.320.243.580.19
TUBAF37@517.720.38−0.030.150.280.253.540.18
TUBAF37@617.720.360.010.180.280.253.580.27
TUBAF37@717.850.430.070.250.350.233.590.20
TUBAF37@817.780.39−0.22−0.040.250.253.570.21
TUBAF37@917.630.35−0.19−0.010.270.283.520.53
TUBAF37@1017.660.340.180.360.360.253.530.19
Average17.740.25 0.150.260.253.560.22
TUBA38@19.460.40−0.59−0.010.224.050.740.10
TUBA38@29.830.32−0.500.090.224.190.700.09
TUBA38@39.810.43−0.340.240.234.070.710.10
TUBA38@410.000.46−0.380.200.244.090.700.10
TUBA38@59.980.40−0.340.240.224.140.680.11
TUBA38@69.840.35−0.570.010.224.150.700.11
TUBA38@79.850.39−0.370.210.233.920.790.08
TUBA38@89.600.42−0.580.000.234.050.720.10
TUBA38@99.830.35−0.560.020.244.170.710.10
TUBA38@109.600.35−0.560.020.233.950.770.11
TUBA38@119.660.38−0.440.140.244.100.710.11
TUBA38@129.680.37−0.360.220.234.020.740.10
TUBA38@139.620.42−0.490.090.234.110.700.11
TUBA38@149.740.43−0.340.240.234.130.700.10
TUBA38@159.670.38−0.400.180.233.990.770.10
Average9.740.30 0.130.204.080.720.10
TUBAF40@18.740.40−0.090.210.231.341.960.07
TUBAF40@28.980.35−0.110.180.231.371.970.08
TUBAF40@38.750.41−0.060.230.221.282.010.07
TUBAF40@48.770.32−0.220.070.221.322.020.07
TUBAF40@58.780.37−0.180.110.231.381.960.09
TUBAF40@68.860.34−0.170.120.231.332.000.08
TUBAF40@78.870.390.030.320.241.252.090.08
TUBAF40@88.710.59−0.020.280.231.361.970.07
TUBAF40@98.830.38−0.090.200.241.361.960.09
TUBAF40@108.790.31−0.010.280.261.321.970.08
TUBAF40@118.770.36−0.240.050.261.321.980.07
Average8.800.15 0.190.181.331.990.08
* The internal error was combined from the measured internal error and external repeatability of Durango (2SD = 0.3‰ for O and 0.22 for Cl).
Table
Table 5. Calibrated data from session 2.
Table 5. Calibrated data from session 2.
SampleIMF Corrected2σ *MeasuredIMF Corrected2σ *Cl%F%S%
δ18O (‰)(‰)δ 37Clδ 37Cl(‰)
Durango@19.740.200.150.350.330.403.630.23
Durango@29.620.300.250.440.340.403.620.24
Durango@39.590.330.300.490.130.403.610.24
Durango@49.700.300.220.410.190.413.580.28
Durango@59.540.310.170.360.220.423.630.33
Durango@69.570.330.190.390.150.423.600.34
Durango@79.650.240.120.310.170.413.600.30
Durango@89.730.260.150.340.150.413.600.31
Durango@99.750.320.120.310.130.413.600.32
Durango@109.720.340.190.380.170.413.580.32
Durango@119.690.240.130.320.120.413.610.31
Durango@129.760.320.190.380.600.413.600.31
Durango@139.780.320.170.360.210.413.650.31
Durango@149.750.300.280.470.240.413.590.31
Durango@159.910.290.250.440.120.413.610.30
Durango@169.750.270.170.360.200.423.630.33
Durango@179.660.340.190.380.160.423.630.33
Average9.700.18 0.380.110.413.610.30
AP1@110.100.280.050.230.300.263.870.36
AP1@210.270.300.000.180.180.273.920.38
AP1@310.420.340.070.240.220.263.880.38
AP1@410.190.330.250.420.120.263.860.36
AP1@510.370.240.130.310.240.263.880.38
AP1@610.350.260.390.570.320.263.840.39
AP1@710.430.250.140.320.160.263.850.37
AP1@810.370.270.330.500.500.263.880.37
AP1@910.380.310.110.290.270.263.900.37
AP1@1010.300.260.310.490.380.263.900.35
AP1@1110.460.320.270.450.270.253.900.37
AP1@1210.190.280.130.310.230.263.910.38
AP1@1310.400.310.390.560.150.263.890.36
AP1@1410.400.350.270.450.240.263.910.37
AP1@1510.340.270.120.300.240.263.880.35
Average10.330.20 0.370.250.263.880.37
AP2@18.440.330.320.490.160.173.970.62
AP2@28.440.250.150.320.290.183.980.60
AP2@38.270.320.300.470.420.183.940.57
AP2@48.380.360.180.350.250.173.960.50
AP2@58.300.360.260.430.340.183.960.60
AP2@68.330.280.380.550.480.183.990.60
AP2@78.340.210.560.730.340.163.980.44
AP2@88.230.270.350.520.250.183.980.59
AP2@98.180.320.400.570.320.174.020.58
AP2@108.340.310.420.590.160.184.020.59
AP2@118.360.260.320.490.380.184.000.58
AP2@128.120.260.250.410.350.174.030.57
AP2@138.180.340.370.540.170.163.980.56
AP2@148.280.270.490.660.190.173.990.56
AP2@158.270.310.380.550.200.193.940.57
AP2@168.300.320.220.390.290.183.950.56
Average8.300.18 0.500.220.173.980.57
MAD1@110.160.340.510.670.240.183.960.45
MAD1@210.230.290.420.590.300.173.960.45
MAD1@310.160.230.600.760.330.173.950.46
MAD1@410.080.290.550.720.250.173.940.44
MAD1@510.320.320.530.700.200.183.940.44
MAD1@610.200.290.670.830.350.173.930.44
MAD1@710.310.350.490.660.240.183.950.46
MAD1@810.240.330.941.110.260.183.990.46
MAD1@910.190.260.841.010.380.173.970.46
MAD1@1010.010.270.951.120.410.174.010.44
MAD1@1110.180.340.500.660.340.173.960.45
MAD1@1210.030.250.650.820.120.173.960.45
MAD1@1310.290.210.620.790.300.183.970.47
MAD1@149.900.220.320.490.240.173.960.46
MAD1@1510.390.210.600.760.210.173.950.45
Average10.180.26 0.780.360.173.960.45
NW-1@15.570.322.883.042.720.011.931.73 × 10−3
NW-1@25.680.261.281.441.490.011.921.46 × 10−3
NW-1@35.700.243.303.451.060.011.891.49 × 10−3
NW-1@45.490.254.144.292.260.011.881.50 × 10−3
NW-1@55.930.452.923.072.260.011.901.47 × 10−3
NW-1@65.600.363.053.212.870.011.881.29 × 10−3
NW-1@75.670.232.182.332.030.011.891.19 × 10−3
NW-1@85.540.302.532.681.680.011.911.17 × 10−3
NW-1@95.390.324.694.841.590.011.929.79 × 10−3
NW-1@105.710.25−0.30−0.152.090.011.901.19 × 10−3
NW-1@115.690.325.185.332.750.011.891.19 × 10−3
NW-1@125.610.274.995.142.720.011.889.74 × 10−4
NW-1@135.680.305.956.101.190.011.901.00 × 10−3
NW-1@145.790.245.425.573.560.011.911.05 × 10−3
NW-1@155.640.254.654.803.090.011.891.14 × 10−3
Average5.650.25 3.683.420.011.901.26 × 10−3
Qinghu@15.120.230.010.180.310.223.411.42 × 10−3
Qinghu@25.170.25−0.060.110.320.223.381.07 × 10−3
Qinghu@35.640.330.030.190.170.163.511.20 × 10−3
Qinghu@45.350.220.030.200.260.203.461.22 × 10−3
Qinghu@55.430.30−0.140.040.230.283.389.09 × 10−4
Qinghu@65.410.230.230.400.170.193.441.21 × 10−3
Qinghu@75.360.410.230.410.310.213.421.32 × 10−3
Qinghu@85.580.200.100.270.270.183.458.84 × 10−4
Qinghu@95.520.320.040.210.370.193.469.15 × 10−4
Qinghu@105.300.280.030.200.310.233.421.06 × 10−3
Qinghu@115.530.260.050.220.210.193.441.03 × 10−3
Qinghu@125.140.370.120.290.120.263.358.97 × 10−4
Qinghu@135.450.260.100.260.430.133.541.11 × 10−3
Qinghu@145.790.29−0.130.050.320.273.367.84 × 10−4
Qinghu@155.590.270.090.260.230.253.417.62 × 10−4
Average5.430.38 0.220.210.213.431.05 × 10−3
* The internal error was combined from measured internal error and external repeatability of Durango (2SD = 0.18‰ for O and 0.11‰ for Cl).
Table
Table 6. Recommend isotopic values for 11 apatite RMs.
Table 6. Recommend isotopic values for 11 apatite RMs.
Sampleδ18O (‰)δ37Cl (‰)Cl (%)F (%)SO3 (%)U-Pb age (Ma)
MGMHMedian5.58 *0.09 a6.09 a< DL a0.11 a-
#1336481s0.0950.160.71-0.02-
MGMHMedian7.91 *0.42 a1.03 a2.36 a0.19 a-
#128441A1s0.160.200.020.120.02-
TUBAF#37Median17.74 *0.20 a0.26 a3.63 a0.34 a-
1s0.130.130.020.180.11-
TUBAF#38Median9.74 *0.09 a4.29 a0.46 a0.14 a-
1s0.150.190.190.060.02-
TUBAF#40Median8.80 *0.20 a1.43 a1.93 a0.11 a-
1s0.080.240.080.130.02-
DurangoMedian9.70 b0.19 c0.40 c3.61 c0.3 c-
1s0.220.120.040.330.05-
QinghuMedian5.59 b0.23 *0.36 c2.78 c0.01 c-
1s0.190.09----
AP1Median10.33 *0.37 *0.3 d3.97 d0.37 *475 g
1s0.100.13--0.01
AP2Median8.30 *0.50 *0.2 d4.16 d0.57 *475 g
1s0.090.11--0.05
NW-1Median5.65 *3.68 *0.01 d1.84 d1.26 × 10−3 *1160 f
1s0.131.71--2.3 × 10−45
MADMedian7.6−11.1 e0.78 *0.2 d4.13 d0.42 d485.2 g
1s-0.18---0.8
a: Data were collected from Wudarska et al., 2021; b: Data were collected from Li et al., 2021; c: Data were collected from Yang et al., 2019; d: Data were collected from Yang et al., 2014; e: Data were collected from Sun et al., 2016; f: Data were collected from Li et al., 2012; g: 206Pb/238U age from Zhou 2013; Data labeled with * were determined in this study by SIMS.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Liu, Y.; Li, Q.; Tang, G.; Li, X. Simultaneous Determination of δ18O and δ37Cl Isotopic Compositions and the Concentrations of F, Cl, and S in Apatite Using SIMS. Crystals 2022, 12, 383. https://doi.org/10.3390/cryst12030383

AMA Style

Liu Y, Li Q, Tang G, Li X. Simultaneous Determination of δ18O and δ37Cl Isotopic Compositions and the Concentrations of F, Cl, and S in Apatite Using SIMS. Crystals. 2022; 12(3):383. https://doi.org/10.3390/cryst12030383

Chicago/Turabian Style

Liu, Yu, Qiuli Li, Guoqiang Tang, and Xianhua Li. 2022. "Simultaneous Determination of δ18O and δ37Cl Isotopic Compositions and the Concentrations of F, Cl, and S in Apatite Using SIMS" Crystals 12, no. 3: 383. https://doi.org/10.3390/cryst12030383

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop