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.

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. [ABSTRACT FROM AUTHOR]