In-situ mass spectrometry improves the estimation of stream reaeration from gas-tracer tests

The estimation of gas-exchange rates between streams and the atmosphere is of great importance for the fate of volatile compounds in rivers. For dissolved oxygen, this exchange process is called reaeration, and its accurate and precise estimation is essential for the quantification of metabolic rates. A common method for the determination of gas-exchange rates is through artificial gas-tracer tests with a proxy gas. We present the implementation of a portable gas-equilibrium membrane inlet mass spectrometer (GE-MIMS) to record concentrations of krypton and propane injected as tracer compound in the context of a gas-tracer test. The field-compatible GE-MIMS uses signals of atmospheric measurements for concentration standardization, and allows recording the dissolved-gas concentrations at a high temporal resolution, leading to overall low measurement uncertainty. Furthermore, the in-situ approach avoids loss of gas during the steps of sampling, transport, storage, and analysis required for ex-situ gas measurements. We compare obtained gas-exchange rate coefficients, reaeration and derived metabolic rates from the in-situ measurements to results obtained from head-space sampling of propane followed by laboratory analysis, and find much lower uncertainties with the in-situ method.