High‐sensitivity sulfur isotopic measurements for Antarctic ice core analyses

Takahashi, Kazuya; Nakai, Yutaka; Motizuki, Yuko; Ino, Toshiyuki; Ito, Shigeru; Ohkubo, S.; Minami, Takeshi; Takaku, Yuichi; Yamaguchi, Yoshitaka; Tanaka, Miho; Motoyama, Hideaki

doi:10.1002/rcm.8275

Cited by 8 publications

(12 citation statements)

References 18 publications

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“…We performed sulfur isotope analyses of SO 4 2− in the ice core by isotope‐ratio mass spectrometry following the method of Takahashi et al. (2018) (Figure 1). In brief, SO 2 gas was first produced from the sample by combustion and subsequent reduction in an elemental analyzer (Vario ISOTOPE select, Elementar Analysensysteme GmbH, Langenselbold, Germany).…”

Section: Samples and Methodsmentioning

confidence: 99%

“…With this system, high-sensitivity δ 34 S measurements can be performed on samples containing only ∼2.5 nmol sulfur. Samples were prepared as described by Takahashi et al (2018). The linearity of the data and the stability of the calibration lines were well maintained for sulfur amounts between 5 and 40 nmol (signal intensities at m/z 64 ( 32 S 16 O 16 O + ) were 1.5-15 nA).…”

Section: Samples and Methodsmentioning

confidence: 99%

“…However, Takahashi et al. (2018) have developed a highly sensitive method of δ 34 S analysis that uses an improved analytical system and allows δ 34 S values to be determined from as little as 2.5 nmol sulfur with high accuracy. Using this system, Takahashi et al.…”

Section: Introductionmentioning

confidence: 99%

“…Using this system, Takahashi et al. (2018) successfully analyzed 15 5 mL samples from ice core DF01, a shallow ice core drilled at the Dome Fuji station in 2001, and presented a δ 34 S depth profile for the period from 1880 to 1890 with a 1‐year temporal resolution along with a [SO 4 2− ] profile with the same depth (temporal) resolution, obtained using ion chromatography to analyze the same samples. Then, by comparing the δ 34 S and [SO 4 2− ] nss profiles, they showed that an apparent decrease in δ 34 S coincided with the [SO 4 2− ] nss peak associated with the 1883 Krakatau (Indonesia) eruption.…”

Section: Introductionmentioning

confidence: 99%

“…In general, to analyze sulfur isotope ratios with a temporal resolution of about 1 year, ice-core samples of 10-20 g have been required. However, Takahashi et al (2018) have developed a highly sensitive method of δ 34 S analysis that uses an improved analytical system and allows δ 34 S values to be determined from as little as 2.5 nmol sulfur with high accuracy. Using this system, Takahashi et al (2018) successfully analyzed 15 5 mL samples from ice core DF01, a shallow ice core drilled at the Dome Fuji station in 2001, and presented a δ 34 S depth profile for the period from 1880 to 1890 with a 1-year temporal resolution along with a [SO 4…”

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Annually Resolved Profiles of δ³⁴S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

et al. 2022

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We report the results of a high‐sensitivity sulfur‐isotope (δ34S) analysis of samples from shallow ice core DF01 from Dome Fuji, East Antarctica, and present chronological profiles of the data with an annual resolution covering the entire nineteenth century. In the δ34S and non‐sea‐salt (nss)‐sulfate ([SO42−]nss) profiles, the signals of five well‐known nineteenth century volcanic eruptions were confirmed: Krakatau 1883 (and Tarawera 1886), Makian 1861, Cosiguina 1835, Tambora 1815, and Unknown 1809. Due to large influence of sulfate caused by volcanic eruptions in the first half of the nineteenth century, the averages of nss‐sulfur‐isotope composition (δ34Snss) and [SO42−]nss for the second half (+14.6‰ and 67.6 μg/L), calculated after excluding these prominent signals, were found to differ from those of the first half century (+9.1‰ and 84.1 μg/L). We also examined anomalous variations other than the five major volcanic signals in the δ34S and [SO42−]nss profiles based on not only variations in δ34S and [SO42−]nss but also variations in the concentrations of other ions. We then identified the presence of three additional volcanic signals: Babuyan 1831, Galunggung 1822, and an unknown volcanic eruption around 1807. The latter two signals confirmed for the first time in Antarctic ice cores. Other δ34S and [SO42−]nss anomalies may be related to an influx of coastal air masses, a nonstratospheric volcanic eruption near Antarctica or an increase in the relative contribution of a stratospheric component to the precipitation in inland Antarctica. These demonstrate the importance of obtaining the annually resolved, continuous δ34S profile over a certain period.

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Section: Samples and Methodsmentioning

confidence: 99%

Section: Samples and Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Annually Resolved Profiles of δ³⁴S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

et al. 2022

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Sequential measurement of ¹³C, ¹⁵N, and ³⁴S isotopic composition on nanomolar quantities of carbon, nitrogen, and sulfur using nano‐elemental analysis/isotope ratio mass spectrometry

Baczynski

Brodie

Kracht

et al. 2022

Rapid Comm Mass Spectrometry

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Rationale: We report modifications to a commercial elemental analyzer-isotope ratio mass spectrometer that permit high-precision isotopic analysis of nanomoles of carbon (C), nitrogen (N), and sulfur (S) on a single sample without chemical or cryogenic trapping of gases. The sample size required for measurement by our system is about two orders of magnitude less than that for conventional analyses. Methods: Our system builds on the analytical advancements offered by the EA IsoLink IRMS System and employs simple modifications to reduce the diameter of the flow path (reactors, water trap, and transfer lines), enhance peak separation (gas chromatography capillary column), and improve sample transfer to the ion source of the mass spectrometer (reduced flow rates).Results: Conventional precision (<0.2‰) can be achieved down to c. 500 nmol C, N, and S for samples analyzed without modification of the commercial system. Further reduction in sample size (<50 nmol C, N, and S) was achieved with minor modifications. There is a significant carbon blank and a small nitrogen blank that can be measured directly and a sulfur blank that can be calculated using regression. Only 30 nmol of N, 22 nmol of C, and 12 nmol of S are needed to achieve better than 1‰ precision (1σ) from a single measurement. Larger samples and more replicate measurements provide better precision. Conclusions:The nano-EA method described here reduces sample size requirements by two orders of magnitude compared to traditional approaches and improves the accuracy and precision of isotope measurements on sample sizes less than 1 μmol.These advancements simplify the analytical technique and broaden the range and type of samples amenable to EA analysis. | INTRODUCTIONIsotopic abundances for carbon (C), nitrogen (N), and sulfur (S) in bulk organic and inorganic materials are typically determined using an elemental analyzer coupled to an isotope ratio mass spectrometer.Samples are converted to gaseous CO 2 , N 2 , and SO 2 using combustion in the presence of excess oxygen in a reactor system (Dumas combustion). The gases are dried via a water trap, separated using a gas chromatography (GC) column, and delivered in discrete pulses using a carrier stream of helium into the ion source of the mass spectrometer. Conventional elemental analysis (EA)-isotope ratio mass spectrometry (IRMS) requires a minimum of 2 μmol C, N, or S

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A modified laser ablation‐isotope ratio mass spectrometry method for in situ analysis of sulfur isotope composition of sulfides

Guo,

Fan,

et al. 2024

Rapid Comm Mass Spectrometry

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RationaleA novel laser ablation‐isotope ratio mass spectrometry (LA‐IRMS) method for in situ analysis of sulfur isotopes in sulfides has been developed. Instead of the in situ reaction applied by the traditional laser microprobe, the analyte gas preparation in this method is separated temporally and spatially from the LA, resulting in improved precision and accuracy.MethodsOur LA‐IRMS system combines an ultraviolet LA system, an elemental analyzer (EA), a custom‐built cryogenic concentration system, a continuous‐flow interface, and an IRMS. The sulfide aerosol particles generated from LA were transferred by a helium carrier gas from the ablation cell into the reaction tube and were then converted into SO2. Subsequently, SO2 was enriched in two cold traps and was finally introduced into the ion source of the IRMS through the continuous‐flow interface.ResultsWe measured three synthetic and four natural sulfide reference materials to test the performance of this method. Precisions of ±0.25‰–±0.48‰ and ±0.32‰–±0.64‰ (1SD, n = 5) for δ34S values of synthetic and natural sulfide standards can be obtained for spot sizes ranging from 64 to 80 μm. Measured values and their recommended values showed a good linear relationship (R2 within 0.998 and 0.9995) with the slope of approaching unity (within 1.0509 and 1.1313).ConclusionsData from the measurement of reference materials showed that the precision and accuracy of our method were satisfactory. This method is a powerful tool for in situ sulfur isotope measurement of sulfides and can be further applied to in situ carbon and oxygen isotope analyses.

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High‐sensitivity sulfur isotopic measurements for Antarctic ice core analyses

Abstract: The analytical system developed herein is a powerful tool for trace sulfur isotopic analyses. The results obtained from the DF01 ice core samples are the first step towards elucidating high-time-resolution (less than 1 year) paleo-environmental changes by sulfur isotopic analyses.

Cited by 8 publications

References 18 publications

Annually Resolved Profiles of δ³⁴S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

Annually Resolved Profiles of δ³⁴S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

Sequential measurement of ¹³C, ¹⁵N, and ³⁴S isotopic composition on nanomolar quantities of carbon, nitrogen, and sulfur using nano‐elemental analysis/isotope ratio mass spectrometry

A modified laser ablation‐isotope ratio mass spectrometry method for in situ analysis of sulfur isotope composition of sulfides

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High‐sensitivity sulfur isotopic measurements for Antarctic ice core analyses

Abstract: The analytical system developed herein is a powerful tool for trace sulfur isotopic analyses. The results obtained from the DF01 ice core samples are the first step towards elucidating high-time-resolution (less than 1 year) paleo-environmental changes by sulfur isotopic analyses.

Cited by 8 publications

References 18 publications

Annually Resolved Profiles of δ34S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

Annually Resolved Profiles of δ34S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

Sequential measurement of 13C, 15N, and 34S isotopic composition on nanomolar quantities of carbon, nitrogen, and sulfur using nano‐elemental analysis/isotope ratio mass spectrometry

A modified laser ablation‐isotope ratio mass spectrometry method for in situ analysis of sulfur isotope composition of sulfides

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Annually Resolved Profiles of δ³⁴S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

Annually Resolved Profiles of δ³⁴S and Sulfate in Shallow Ice Core DF01 (Dome Fuji, Antarctica) Spanning the Nineteenth Century and Their Geochemical Implications

Sequential measurement of ¹³C, ¹⁵N, and ³⁴S isotopic composition on nanomolar quantities of carbon, nitrogen, and sulfur using nano‐elemental analysis/isotope ratio mass spectrometry