Mass spectrometric multiple soil-gas flux measurement system with a portable high-resolution mass spectrometer (MULTUM) coupled to an automatic chamber for continuous field observations

Abstract

We developed a mass spectrometric soil-gas flux measurement system using a portable high-resolution multi-turn time-of-flight mass spectrometer, called MULTUM, and we combined it with an automated soil-gas flux chamber for the continuous field measurement of multiple gas concentrations with a high temporal resolution. The developed system continuously measures the concentrations of four different atmospheric gases (NO2, CH4, CO2, and field soil–atmosphere flux measurements of greenhouse gases (NO2, O2) ranging over 6 orders of magnitude at one time using a single gas sample. The measurements are performed every 2.5 min with an analytical precision (2 standard deviations) of ±34 ppbv for NO2; ±170 ppbv, CH4; ±16 ppmv, CO2; and ±0.60 vol %, O2 at their atmospheric concentrations. The developed system was used for the continuous field soil–atmosphere flux measurements of greenhouse gases (NO2, CH4, and CO2) and O2 with a 1 h resolution. The minimum quantitative fluxes (2 standard deviations) were estimated via a simulation as 70.2 µgNm-2h-1 for NO2; 139 µgCm-2h-1, CH4; 11.7 mg C m−2 h−1, CO2; and 9.8 g O2 m−2 h−1, O2. The estimated minimum detectable fluxes (2 standard deviations) were 17.2 µgNm-2h-1 for NO2; 35.4 µgCm-2h-1, CH4; 2.6 mg C m−2 h−1, CO2; and 2.9 g O2 m−2 h−1, O2. The developed system was deployed at the university farm of the Ehime University (Matsuyama, Ehime, Japan) for a field observation over 5 d. An abrupt increase in NO2 flux from 70 to 682 µgNm-2h-1 was observed a few hours after the first rainfall, whereas no obvious increase was observed in CO2 flux. No abrupt NO2 flux change was observed in succeeding rainfall events, and the observed temporal responses at the first rainfall were different from those observed in a laboratory experiment. The observed differences in temporal flux variation for each gas component show that gas production processes and their responses for each gas component in the soil are different. The results of this study indicate that continuous multiple gas concentration and flux measurements can be employed as a powerful tool for tracking and understanding underlying biological and physicochemical processes in the soil by measuring more tracer gases such as volatile organic carbon, reactive nitrogen, and noble gases, and by exploiting the broad versatility of mass spectrometry in detecting a broad range of gas species.