Continual in-situ monitoring of pore water stable isotopes in the subsurface

The stable isotope signature of pore water provides an integral fingerprint of water origin, flow path, transport processes, and residence times and can thus serve as a powerful tracer of hydrological processes in the unsaturated and saturated zone. However, the full potential of stable isotopes to quantitatively characterize subsurface water dynamics is yet unfolded due to the difficulty in obtaining extensive detailed and continual measurements of spatiotemporally variable pore water signatures. With the development of field-deployable laser-based isotope analyzers, such measurements are now becoming feasible. This study presents the development and application of a functional, automatable, and cost-efficient system for non-destructive continual in-situ monitoring of pore water stable isotope signatures with high resolution. The monitoring system uses automatic-controllable valve arrays to continuously extract diluted soil air water vapor via a branching network of multiple small microporous probes into a commercial isotope analyzer. Soil temperature observations are used to convert obtained vapor phase into liquid phase water isotope signatures, but these can also be obtained based on vapor concentration measurements. In-situ sampling was conducted at six depths for each of three plots planted with varying vegetation on an experimental site in SW Germany. Two different methods based on advective and diffusive soil water vapor probing were employed suitable under unsaturated and all (including saturated) moisture conditions, respectively. The advective sampling method was applied using multiple permanently installed probes (continual mode) and using a single probe subsequently inserted to sample the various locations (push-in mode), while the diffusive sampling method was applied in push-in mode only. Using a specific identical treatment onsite calibration approach along with basic corrections for instrument bias and temperature dependent free water-vapor isotopic equilibrium fractionation, the monitoring system facilitated inference of normalized liquid pore water isotopic composition with sufficiently high accuracy and precision at sampling intervals of less than four minutes and resolved the isotopic variability along natural depth profiles. Comparison indicated that the presented in-situ approaches may be used interchangeably with each other and with concurrent laboratory-based direct equilibration measurements of destructively collected samples, such that the choice of method will depend upon the task and anticipated conditions of sampling. The introduced sampling techniques provide powerful tools towards a detailed quantitative understanding of dynamic and heterogeneous shallow subsurface and vadose zone processes.