This study develops and optimizes a new protocol to measure lithium isotope ratios using a single collector quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) operated under hot plasma (1550 W) conditions with a sample–standard bracketing method. Our Q-ICP-MS method reduces sample consumption to 2.5 ng of Li and achieves a high long-term precision of 1.1‰ (2SD). This Q-ICP-MS method exhibits high matrix tolerance (Na/Li < 100), suitable for ng-sized and high-matrix geological samples. We also developed a dual-column system for Li separation, with large loading capacity (29.6 meq), complete recovery (∼100%) and satisfactory purification (Na/Li m m −1 < 1), as well as a fixed elution range for Li fractions (28–60 mL). This new chromatography method has been applied to chemically diverse materials, producing consistent results. In addition, we report the Li isotope compositions of 13 geostandards, and our measurements agree well with reported data within analytical uncertainties. This study documents that Li element concentration and Li isotope composition can be routinely measured using a single collector ICP-MS, which is convenient and commercially affordable for future Li isotope research across the fields of Earth and Environmental Sciences.
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An efficient method for high-precision potassium isotope analysis in carbonate materials
High-precision potassium (K) isotope measurements in marine carbonates allow using this novel geochemical proxy to constrain seawater chemistry through geologic time. However, these measurements are still scarce due to the challenges of low-K contents in carbonates during K ion chromatography, such as insufficient sample purification, non-quantitative yield, and high accumulative blank. Here we optimize a dual-column K purification method that addresses these challenges, achieving a satisfactory K separation using 100–150 mg carbonates for routine high-precision K isotope analysis on the Sapphire™ MC-ICP-MS. We then report K isotope compositions in multiple certified reference materials, including limestone, dolostone, coral, and basalt for future inter-laboratory comparisons. The optimized K purification method provides great potential for future K isotope studies of marine carbonates.
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- Award ID(s):
- 1848153
- NSF-PAR ID:
- 10389594
- Date Published:
- Journal Name:
- Journal of Analytical Atomic Spectrometry
- Volume:
- 37
- Issue:
- 11
- ISSN:
- 0267-9477
- Page Range / eLocation ID:
- 2410 to 2419
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Iodine intersects with the marine biogeochemical cycles of several major elements and can influence air quality through reactions with tropospheric ozone. Iodine is also an element of interest in paleoclimatology, whereby iodine-to-calcium ratios in marine carbonates are widely used as a proxy for past ocean redox state. While inorganic iodine in seawater is found predominantly in its reduced and oxidized anionic forms, iodide (I−) and iodate (IO3−), the rates, mechanisms and intermediate species by which iodine cycles between these inorganic pools are poorly understood. Here, we address these issues by characterizing the speciation, composition and cycling of iodine in the upper 1,000 m of the water column at Station ALOHA in the subtropical North Pacific Ocean. We first obtained high-precision profiles of iodine speciation using isotope dilution and anion exchange chromatography, with measurements performed using inductively coupled plasma mass spectrometry (ICP-MS). These profiles indicate an apparent iodine deficit in surface waters approaching 8% of the predicted total, which we ascribe partly to the existence of dissolved organic iodine that is not resolved during chromatography. To test this, we passed large volumes of seawater through solid phase extraction columns and analyzed the eluent using high-performance liquid chromatography ICP-MS. These analyses reveal a significant pool of dissolved organic iodine in open ocean seawater, the concentration and complexity of which diminish with increasing water depth. Finally, we analyzed the rates of IO3−formation using shipboard incubations of surface seawater amended with129I−. These experiments suggest that intermediate iodine species oxidize to IO3−much faster than I−does, and that rates of IO3−formation are dependent on the presence of particles, but not light levels. Our study documents the dynamics of iodine cycling in the subtropical ocean, highlighting the critical role of intermediates in mediating redox transformations between the major inorganic iodine species.
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Stable potassium (K) isotopes (41K/39K) have shown great promise as novel chemical tracers for a wide range of bio-, geo-, and cosmo-chemical processes, but high precision stable K isotope analysis remains a challenge for plasma source mass spectrometry due to intense argon-related interferences produced directly from argon plasma. Here we provide an assessment on the analytical figures of merit of a new generation collision-cell equipped multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS), Sapphire from Nu Instruments, for K isotope analysis based on our extensive tests over a duration of ~8 months. Because use of helium and hydrogen as collision/reaction gases can reduce argon-related interferences to negligible levels at optimal flow rates, the collision-cell mode can operate at low mass resolution during K isotope analysis, providing >2 orders of magnitude higher K sensitivity (>1000 V per μg mL-1 K), as compared to the widely used “cold plasma” method, and the capability for direct 40K measurement. One challenge of the collision/reaction cell analysis on Sapphire is its higher susceptibility to matrix effects, requiring effective sample purification prior to analysis. Also, the collision-cell mode on Sapphire shows a pronounced effect associated with concentration (or ion intensity) mismatch between the sample and the bracketing standard during analysis, and this effect may not be fully eliminated through conventional concentration matching practice. Instead, we developed a correction method for this concentration/ion intensity mismatch effect. Our method reduces the burden to the operator and increases sample throughput. This method allows for accurate K isotope analysis with an intermediate precision of ≤0.05 ‰ (2SD) to be routinely achieved using the collision cell on Sapphire, representing a major advance to stable K isotope analysis.more » « less
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Rationale The isotopic measurement of environmental sample CO2via isotope ratio mass spectrometry (IRMS) can present many analytical challenges. In many offline applications, exceedingly few samples can be prepared per day. In such applications, long‐term storage (months) of sample CO2is desirable, in order to accumulate enough samples to warrant a day of isotopic measurements. Conversely, traditional sample tube cracker systems for dual‐inlet IRMS offer a capacity for only 6–8 tubes and thus limit throughput. Here we present a simple method to alleviate these concerns using a Gas Bench II gas handling device coupled with continuous‐flow IRMS.
Methods Sample preparation entails the cryogenic purification and quantification of CO2on a vacuum line. Sample CO2splits are expanded from a known volume to several sample ports and allowed to isotopically equilibrate (homogenize). Equilibrated CO2splits are frozen into 3 mm outer diameter Pyrex break‐seals and sealed under vacuum with a torch to a length of 5.5 cm. Sample break‐seals are scored, placed into 12 mL Labco Exetainer®vials, purged with ultrahigh‐purity helium, cracked inside the capped helium‐flushed vials and subsequently measured via a Gas Bench equipped IRMS instrument using a CTC Analytics PAL autosampler.
Results Our δ13C results from NIST and internal isotopic standards, measured over a time period of several years, indicate that the sealed‐tube method produces accurate δ13C values to a precision of ±0.1‰ for samples containing 10–35 μgC. The tube cracking technique within Exetainer vials has been optimized over a period of 10 years, resulting in decreased sample failure rates from 5–10% to <1%.
Conclusions This technique offers an alternative method for δ13C analyses of CO2where offline isolation and long‐term storage are desired. The method features a much higher sample throughput than traditional dual‐inlet IRMS cracker setups at similar precision (±0.1‰).
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Rationale Nitrogen isotopic compositions (δ15N) of source and trophic amino acids (AAs) are crucial tracers of N sources and trophic enrichments in diverse fields, including archeology, astrobiochemistry, ecology, oceanography, and paleo‐sciences. The current analytical technique using gas chromatography‐combustion‐isotope ratio mass spectrometry (GC/C/IRMS) requires derivatization, which is not compatible with some key AAs. Another approach using high‐performance liquid chromatography‐elemental analyzer‐IRMS (HPLC/EA/IRMS) may experience coelution issues with other compounds in certain types of samples, and the highly sensitive nano‐EA/IRMS instrumentations are not widely available.
Methods We present a method for high‐precision δ15N measurements of AAs (δ15N‐AA) optimized for canonical source AA‐phenylalanine (Phe) and trophic AA‐glutamic acid (Glu). This offline approach entails purification and separation via high‐pressure ion‐exchange chromatography (IC) with automated fraction collection, the sequential chemical conversion of AA to nitrite and then to nitrous oxide (N2O), and the final determination of δ15N of the produced N2O via purge‐and‐trap continuous‐flow isotope ratio mass spectrometry (PT/CF/IRMS).
Results The cross‐plots of δ15N of Glu and Phe standards (four different natural‐abundance levels) generated by this method and their accepted values have a linear regression slope of 1 and small intercepts demonstrating high accuracy. The precisions were 0.36‰–0.67‰ for Phe standards and 0.27‰–0.35‰ for Glu standards. Our method and the GC/C/IRMS approach produced equivalent δ15N values for two lab standards (McCarthy Lab AA mixture and cyanobacteria) within error. We further tested our method on a wide range of natural sample matrices and obtained reasonable results.
Conclusions Our method provides a reliable alternative to the current methods for δ15N‐AA measurement as IC or HPLC‐based techniques that can collect underivatized AAs are widely available. Our chemical approach that converts AA to N2O can be easily implemented in laboratories currently analyzing δ15N of N2O using PT/CF/IRMS. This method will help promote the use of δ15N‐AA in important studies of N cycling and trophic ecology in a wide range of research areas.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2ja00170e
