An On-Line Technique for the Determination of the δ(18)O and δ(17)O of Gaseous and Dissolved Oxygen.

Few studies have used the stable isotopic composition of O(2) as a tracer of gas transport or biogeochemical processes in environmental research. Here we demonstrate field sampling techniques for gaseous and dissolved O(2) and describe an analytical method for measuring δ(18)O and δ(17)O values of O(2) in air, soil gas, and water samples using continuous-flow isotope-ratio mass spectrometry (CF-IRMS). A Micromass CF-IRMS was altered to accommodate a sample gas injection port prior to a CO(2) and H(2)O trap and GC column. The GC column was a 1-m, 5-Å molecular sieve column held at 35 °C. The resolved sample O(2) was introduced to the IRMS via an open split. δ(18)O and δ(17)O values were determined by measurement of O(2) isotopes at m/z 34/32 and 33/32 and comparison to a reference pulse of O(2). Repeated injections of atmospheric oxygen yielded a repeatability (±SD) of ±0.17‰ for δ(18)O and ±0.5‰ for δ(17)O. IRMS source linearity was excellent for O(2) over a sample size range of 60-400 μL. The smallest sample for routine δ(18)O and δ(17)O determinations was ∼80 μL of O(2), with a sample analysis time of 180 s. Preliminary results from a riverine and soil gas study illustrate natural oxygen isotope fractionation processes.