Analyzing groundwater mixing ratios is crucial for many groundwater management tasks such as assessing sources of groundwater recharge and flow paths. However, estimating groundwater mixing ratios is affected by various uncertainties, which are related to analytical and measurement errors of tracers, the selection of end-members and finding the most suitable set of tracers. Although these uncertainties are well recognized, it is still not common practice to account for them. We address this issue by using a new set of tracers in combination with a Bayesian modeling approach, which explicitly considers the possibility of unknown end-members while fully accounting for tracer uncertainties. We apply the Bayesian model we developed to a tracer set which includes helium-4 analyzed on-site to determine mixing ratios in groundwater. Thereby, we identify an unknown end-member, that contributes up to 84% to the water mixture observed at our study site. For the helium-4 analysis, we use a newly developed Gas Equilibrium Membrane Inlet Mass Spectrometer (GE-MIMS), operated in the field. To test the reliability of on-site helium-4 analysis, we compare results obtained with the GE-MIMS to the conventional lab-based method, which is comparatively expensive and labor intensive. Our work demonstrates that (i) tracer-aided Bayesian mixing modeling can detect unknown water sources, thereby revealing valuable insights into the conceptual understanding of the groundwater system studied and ii) on-site helium-4 analysis with the GE-MIMS system is an accurate and reliable alternative to the lab-based analysis.
