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RationaleNitrogen 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. MethodsWe 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). ResultsThe 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. ConclusionsOur 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.
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This content will become publicly available on January 11, 2026
Using δ15N of Amino Acids and Nitrate to Investigate Particle Production and Transformation in the Ocean: A Case Study From the Eastern Tropical North Pacific Oxygen Deficient Zone
Abstract The eastern tropical North Pacific oxygen deficient zone (ETNP‐ODZ) exhibits a distinct physical and biological environment compared to other oxygenated water columns, leading to a unique scenario of particulate organic matter (POM) production and vertical transport. To elucidate these biological pump processes, we present the first comparison of δ15N values of nitrate, phenylalanine (Phe), and glutamic acid (Glu) within two distinct size fractions of particles collected along a productivity gradient in the ETNP‐ODZ. Low δ15NPheand δ15NGluvalues in both particle pools at sites with prominent secondary chlorophyll maximum (SCM), compared to the ambient δ15N‐NO3−, suggest the presence of recycled N‐utilizing primary producers distinct from those at the primary chlorophyll maximum and their contribution to export. We observed reduced15N enrichment of Phe in small particles and a narrower δ15NPhedisparity between the two particle size fractions compared to the results from oxic waters, likely due to slower heterotrophic microbial degradation of small particles. Unique δ15NPheand δ15NGlusignatures of particles were found at the lower oxycline, potentially attributable to chemoautotrophic production and zooplankton mediation. These findings underscore the need for further investigations targeting particles generated at the SCM, their subsequent alteration by zooplankton, and the new production by chemoautotrophs. This will allow for a better evaluation of the efficiency of the biological pump in the globally expanding ODZs under contemporary climate change.
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- Award ID(s):
- 1829947
- PAR ID:
- 10570165
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Global Biogeochemical Cycles
- Volume:
- 39
- Issue:
- 1
- ISSN:
- 0886-6236
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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