Use of argon to measure gas exchange in turbulent mountain streams

Abstract

Abstract. Gas exchange is a parameter needed in stream metabolism and trace gas emissions models. One way to estimate gas exchange is via measuring the decline of added tracer gases such as sulfur hexafluoride (SF6). Estimates of oxygen (O2) gas exchange derived from SF6 additions require scaling via Schmidt number (Sc) ratio, but this scaling is uncertain under conditions of high gas exchange via bubbles because scaling depends on gas solubility as well as Sc. Because argon (Ar) and O2 have nearly identical Schmidt numbers and solubility, Ar may be a useful tracer gas for estimating stream O2 exchange. Here we compared rates of gas exchange measured via Ar and SF6 for turbulent mountain streams in Wyoming, USA. We measured Ar as the ratio of Ar : N2 using a membrane inlet mass spectrometer (MIMS). Normalizing to N2 confers higher precision than simply measuring [Ar] alone. We consistently enriched streams with Ar from 1 to 18 % of ambient Ar concentration and could estimate gas exchange rate using an exponential decline model. The mean ratio of gas exchange of Ar relative to SF6 was 1.8 (credible interval 1.1 to 2.5) compared to the theoretical estimate 1.35, showing that using SF6 would have underestimated exchange of Ar. Steep streams (slopes 11–12 %) had high rates of gas exchange velocity normalized to Sc=600 (k600, 57–210 m d−1), and slope strongly predicted variation in k600 among all streams. We suggest that Ar is a useful tracer because it is easily measured, requires no scaling assumptions to estimate rates of O2 exchange, and is not an intense greenhouse gas as is SF6. We caution that scaling from rates of either Ar or SF6 gas exchange to CO2 is uncertain due to solubility effects in conditions of bubble-mediated gas transfer.