Large-Volume Injection and Assessment of Reference Standards for n-Alkane δD and δ13C Analysis via Gas Chromatography Isotope Ratio Mass Spectrometry

Abstract

Rationale

Compound-specific stable isotope analysis of hydrogen (δD) and carbon (δ¹³C) in organic compounds is a valuable tool in biogeochemical research. A key limitation of this method is the relatively large amount of sample required to achieve desirable precision.

Methods

We developed a large-volume (20 μL) injection method that allows for high throughput analysis of less concentrated samples and tested it for δ¹³C and δD measurements of n-alkanes. We also conducted a comparison of reference standards and assessed several methods to normalize and correct n-alkane δD and δ13C measurements.

Results

The mean precision of the δD method based on 233 environmental n-alkane samples (two to three replications per sample) is 4.0‰ (1σ, estimated from the weighted mean of the pooled unbiased standard deviations) and 0.46‰ (1σ) for δ¹³C from 37 environmental samples (two to three replications per sample). The evaluation of reference standards shows that the use of n-alkane standards with large offsets in δD values in adjacent n-alkane chains can lead to biases in measurement correction.

Conclusions

The large-volume injection method shows good reproducibility of δ¹³C and δD measurements of n-alkanes and reduces the required sample concentration by about 80%. We propose that for δD measurements, a reference standard set should be used in which each reference standard has a limited range of δD values and no adjacent n-alkane chains, to minimize memory effects.