Linear membrane-based gas sensors that can be advantageously applied for the measurement of a single gas component in large heterogeneous systems, e.g., for representative determination of CO2 in the subsurface, can be designed depending on the properties of the observation object. A resulting disadvantage is that the permeation-based sensor response depends on operating conditions, the individual site-adapted sensor geometry, the membrane material, and the target gas component. Therefore, calibration is needed, especially of the slope, which could change over several orders of magnitude. A calibration-free approach based on an internal gas standard is developed to overcome the multi-criterial slope dependency. This results in a normalization of sensor response and enables the sensor to assess the significance of measurement. The approach was proofed on the example of CO2 analysis in dry air with tubular PDMS membranes for various CO2 concentrations of an internal standard. Negligible temperature dependency was found within an 18 K range. The transformation behavior of the measurement signal and the influence of concentration variations of the internal standard on the measurement signal were shown. Offsets that were adjusted based on the stated theory for the given measurement conditions and material data from the literature were in agreement with the experimentally determined offsets. A measurement comparison with an NDIR reference sensor shows an unexpectedly low bias (<1%) of the non-calibrated sensor response, and comparable statistical uncertainty.
Core Ideas This new technology is suitable for field‐scale quantification of CO2 in soil. The measurement scale ranges from decimeters up to decameters. The concentrations from the soil water and air phases are averaged. Transient CO2 production and transport reflect plant growth. Biological activity in soil causes fluxes of O2 into and CO2 out of the soil with significant global relevance. Hence, the dynamics of CO2 concentrations in soil can be used as an indicator for biological activity. However, there is an enormous spatial and temporal variability in soil respiration, which has led to the notion of hotspots and hot moments. This variability is attributed to the spatiotemporal heterogeneity of both plant–soil–microbiome interactions and the local conditions governing gas transport. For the characterization of a given soil, the local heterogeneities should be replaced by some meaningful average. To this end, we introduce a line sensor based on tubular gas‐selective membranes that is applicable at the field scale for a wide range in water content. It provides the average CO2 concentration of the ambient soil along its length. The new technique corrects for fluctuating external conditions (i.e., temperature and air pressure) and the impact of water vapor without any further calibration. The new line sensor was tested in a laboratory mesocosm experiment where CO2 concentrations were monitored at two depths during the growth of barley (Hordeum vulgare L.). The results could be consistently related to plant development, plant density, and changing conditions for gas diffusion toward the soil surface. The comparison with an independent CO2 sensor confirmed that the new sensor is actually capable of determining meaningful average CO2 concentrations in a natural soil for long time periods.
Abstract. A miniaturized field-applicable sensor system was developed for the measurement of hydrogen (H2) in air in the concentration range 0.2–200 ppmv. The sensor system is based on the application of an yttria-stabilized zirconia (YSZ) solid electrolyte cell (SEC) as a coulometric detector with gas chromatographic (GC) pre-separation. The main system components for injection, chromatographic separation, and the oxygen pumping cell were significantly miniaturized and tested separately to characterize important measurement properties like selectivity, lower limit of detection, repeatability, and signal-to-noise ratio. Measurements were conducted under varying GC parameters and detector operating conditions. While changing the detector temperature influences the hydrogen peak significantly due to diffusion processes at the electrode–electrolyte interface; different oxygen-partial pressures at the measuring electrode have no visible effect. The combination of two packed columns with 1 m length, one filled with a molecular sieve (13X) and the other one with silica gel, enabled highly reproducible and selective H2 measurements with more than 90 % analyte turnover compared to Faraday's law. The resulting insights were used to define appropriate system parameters, construction guidelines, and material properties for the final test prototype.
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