Mass spectrometric multiple soil-gas flux measurement system with portable high-resolution mass spectrometer MULTUM coupled to automatic chamber for continuous field observation

. We developed a mass spectrometric soil-gas flux measurement system using a portable high-resolution multiturn 20 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 (N 2 O, CH 4 , CO 2 , and O 2 ) ranging over six orders of magnitude at one time using a single gas sample. The measurements are performed every 2.5 min with an analytical precision (two standard deviations) of ±34 ppbv for N 2 O; ±170 ppbv, CH 4 ; ±16 ppmv, CO 2 ; and ±0.60 vol%, O 2 at their atmospheric 25 concentrations. The developed system was used for the continuous field soil–atmosphere flux measurements of greenhouse gases (N 2 O, CH 4 , and CO 2 ) and O 2 with a 1 h resolution. The minimum quantitative fluxes (two standard deviations) were estimated via a simulation as 70.2 µg N m − 2 h − 1 for N 2 O; 139 µg C m − 2 h − 1 , CH 4 ; 11.7 mg C m − 2 h − 1 , CO 2 ; and 9.8 g O 2 m − 2 h − 1 , O 2 . The estimated minimum detectable fluxes (two standard deviations) were 17.2 μ g N m − 2 h − 1 for N 2 O; 35.4 μ g C m − 2 h − 1 , CH 4 ; 2.6 mg C m − 2 h − 1 , CO 2 ; and 2.9 g O 2 m − 2 h − 1 , O 2 . The developed system was deployed in the university farm of the 30 Ehime University (Matsuyama, Ehime, Japan) for a field observation over five days. An abrupt increase in N 2 O flux from 70 to 682 µg N m − 2 h − 1 was observed a few hours after the first rainfall, whereas no obvious increase was observed in CO 2 flux. No abrupt N 2 O flux change was observed in succeeding rainfalls, 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.


Introduction 40
This makes it necessary to perform appropriate water vapor corrections for accurate measurement, and thus, it is not yet applied for the measurement of trace gases (e.g., NO, SF6), noble gases, and complex BVOCs in soil air.
Mass spectrometry (MS) provides high sensitivity and allows detecting a wide range of chemicals as it is widely used for 85 the trace analysis of various compounds including multiple BVOCs measurements with proton-transfer reaction mass spectrometry (PTR-MS) (Veres et al., 2014, Mancuso et al., 2015, references in Peñuelas et al., 2014, Yuan et al., 2017. However, the application of MS to the simultaneous measurement of various GHGs is limited by the difficulty in resolving each gas species. For instance, CO2 and N2O have considerably similar mass (43.989 and 44.001 u, respectively), and their ion peaks are difficult to distinguish using ordinary mass spectrometers such as quadrupole mass spectrometers that do not have 90 sufficient high-mass resolving power to resolve the ions. The independent detection of CO2 + and N2O + by MS requires a massresolving power above 10,000, which corresponds to high-resolution mass spectrometry that can be achieved by mass spectrometers used in laboratories.
Recently, simultaneous mass spectrometric measurement of multiple GHGs has become feasible (Anan et al., 2014), after the introduction of a portable high-resolution multiturn time-of-flight mass spectrometer (MULTUM; Shimma et al., 95 2010), which has dimensions comparable to that of a desktop PC (215 × 545 × 610 mm, 45 kg) and a high mass resolving power (30,000-50,000) for direct mass spectrometric separation of natural gas mixtures. Although MULTUM can resolve CO2 + and N2O + ion peaks, it is technically difficult to measure the two GHGs and major atmospheric gas components (N2 and O2) simultaneously. This is because their concentrations in air substantially differ by more than six orders of magnitude (78.1%, 20.9%, 405 ppmv, and 330 ppbv for average atmospheric N2, O2, CO2, and N2O, respectively) and because MULTUM a limited 100 dynamic range of ion detection and signal acquisition. In addition, suppression in the electron ionization source causes major gases to restrict the ionization of other trace gases, which undermines sensitivity to the latter. Even using MULTUM, these inherent restrictions in MS need to be mitigated for the simultaneous measurement of atmospheric gases such as N2O, CH4, CO2, and O2, for which the concentrations span over six orders of magnitude. Thus far, the lack of field portable high-resolution MS and technical difficulties in existing ion detectors and signal acquisition and processing prevented the simultaneous field 105 observation of multiple GHGs.
In this study, we combined MULTUM with a hybrid ion detection and signal processing technique to measure multiple gases with different concentrations over six orders of magnitude in a single measurement quantitatively and simultaneously.
We used the high-resolution MS system to measure the concentrations of N2O, CH4, CO2, and O2 every 2.5 min. The system was coupled with an automated open/closed chamber as the MULTUM-soil chamber system to obtain hourly soil-atmosphere 110 gas fluxes. We described the system and its characterization, including the simultaneous gas flux observations under both laboratory settings and at an agricultural field. Figure 1 illustrates the MULTUM-soil chamber system that comprises an automatic open/closed chamber, a sample/standard 115 gas injection unit, and a mass spectrometer. The chamber was developed at Hokkaido University. The gas-tight lid of the custom chamber (0.25 × 0.37 m, inner diameter × height, 0.02 m 3 internal volume) is opened or closed by a DC motor attached to the chamber. The lid aperture timing is controlled using an FPGA platform (DE0-Nano-SoC Development Kit, Terasic, Hsinchu, Taiwan) with a Linux shell script through the "curl" command on a workstation. The system clocks of both the embedded Linux software and the workstation are synchronized using the IEEE 1588-2008 protocol, which obtains a sub-120 microsecond time difference.

Simultaneous GHGs and O2 measurement using MULTUM
The soil gas in the chamber headspace is continuously circulated through stainless-steel tubing (1/8 inch × 10 m, outer diameter × length) between the chamber and the sample injection unit via an air pump Enomoto Micro Pump,Tokyo,Japan). The circulating soil gas continuously passes through a 100 µL sample loop (SL100CM, Valco Instruments, sample gas is analyzed with MULTUM (infiTOF-UHV, MSI Tokyo, Tokyo, Japan), the valve rotates and the soil gas sample is injected into a porous layer open tubular capillary column with a monolithic carbon layer (10 m × 0.320 mm, length × inner diameter, 3.0 µM; GS-Carbon PLOT, Agilent Technologies, Santa Clara, CA, USA) with a carrier He gas stream (2.5 mL min -1 ) for rough gas separation before feeding into MULTUM. Another six-port auto valve (V2) (SAV-VA-11-65, FLOM, Tokyo, Japan) switches soil-gas sampling and standard gas injection for calibration. Sample gas injection occurs every 2.5 min, and 130 both the sample and standard gas injections are controlled by the FPGA.
Although MULTUM has sufficient mass resolving power for completely separating CO2 + and N2O + ion peaks, we include the column to provide slight time lags between N2/O2, CO2, and N2O before injection into the system to improve quantification.
In fact, omitting the separation in the time domain (20-60 s) causes several intrinsic MS problems. For example, the N2O + is derived directly from co-existing N2 and O2 at the electron impact (EI) source reaction. Further, the ionization of atmospheric 135 trace gases with the main components of the atmosphere (e.g., N2, O2) restrict the ionization of co-existing trace gases in the ion source (ion-source saturation), which considerably worsens the detection limit of the trace gases. Finally, the dynamic ranges of the ion detector and signal acquisition are limited to two to three orders of magnitude, thereby impeding the simultaneous and accurate measurement of N2O and CO2 within a single gas sample wherein the concentrations differ by more than three orders of magnitude. Thus, we adopt a hybrid ion detection and signal processing technique that selects either 140 waveform averaging or ion counting to detect ions with intensities differing by six orders of magnitude (Kawai et al., 2018).
In the conventional waveform averaging mode, it is difficult to recognize considerably less abundant ions (e.g., N2O + ) as an ion peak because such low abundant ions are easily overwhelmed by background noise. In contrast, ion counting allows detecting scarce ions (Hoffmann and Stoobant, 2007) by regarding ion peaks above a pre-defined threshold intensity (−10 mV in this study) as a single ion. However, counting loss occurs for abundant ions when two or more ions arrive at the detector 145 within the minimum time resolution of the ion signal detection system. The present hybrid ion detection and signal processing scheme employs two detection modes using a single ion detector and recording system by selecting either waveform averaging or ion counting depending on the type of gas (at different periods from sample injection into the column) by changing the ion detector gain and real-time signal processing protocol . Thus, a column is required to create small temporal separations for the detection of target ions and to select the appropriate measurement mode in addition to averting ion-source 150 saturation. For the detection of CO2 + , the ion detector voltage is set to 2400 V, and the conventional waveform recording and averaging are conducted for the time-of-flight ion signal where the voltage is set to 2650 V for the detection of O + , CH4 + , and N2O + ; the real-time software thresholding (i.e., ion counting) is conducted for the acquired signal (Fig. 2). Though determination of Oxygen concentration would be more accurate using O2 + detection, Oxygen was detected as O + (not as O2 + ) using the ion counting mode because O + (m/z 15.99) can be simultaneously detected along with CH4 + (m/z 16.03). If oxygen 155 is observed as O2 + (m/z 32.00), another mass segment around m/z 32.00 needs to be analyzed, and less measurement time can be allocated for CH4 + and N2O + measurements, which results in lower sensitivity for CH4 + and N2O + measurements. The optimized high-voltage settings of MULTUM for this study are listed in Table 1.
The gases injected into MULTUM are ionized by electron ionization at an electron acceleration voltage of 30 V, and the produced ions are mass analyzed at a repetition rate of 1 kHz with 30 laps of circular ion flight; this yields a mass resolution 160 of approximately 10,000. After 30 laps, each ion is detected by an electron multiplier (ETP secondary electron multiplier 14882, ETP Ion Detect, Sydney, Australia). The ion signal from the ion detector is then amplified through a high-speed preamplifier (ORTEC 9301, Advanced Measurement Technology, Oak Ridge, TN, USA) and recorded and processed in real time with a high-speed 1 GS/s digitizer (U5303a, Keysight Technologies, Santa Rosa, CA, USA). Mass spectra are then transferred to a host PC (dual Intel 8-core/16-thread Xeon processor PC with Linux Debian 9.9 operating system). The data 165 acquisition system is controlled by the QtPlatz open-source-software (https://github.com/qtplatz) with its plugin developed for the infiTOF system . We calibrate the system with six different concentrations including blank gas (ultrapure N2), which are prepared from mixed standard gases (mixture of N2O, CH4, and CO2) and O2 standard gas by diluting with ultrapure N2 (>99.9995%, Takachiho Chemical Industrial, Tokyo, Japan). We use two certified standard gases (standard #1: N2O, 279 ppbv; CH4, 1.47 170 ppmv; CO2, 421 ppmv in N2; standard #2: N2O, 1752 ppbv; CH4, 2.97 ppmv; CO2, 1705 ppmv in N2; Sumitomo Seika Chemicals, Osaka, Japan) and O2 standard gas (20.9% in N2 balance gas; Takachiho Chemical Industrial, Tokyo, Japan). The gas mixing rates are adjusted using mass flow controllers (Model 8500 series, KOFLOC, Kojima Instruments, Kyoto, Japan) calibrated using a soap film flowmeter (HORIBA STEC, Kyoto, Japan).
We continuously measured the standard gases using the developed MULTUM-soil chamber system and estimated the 175 detection limits for N2O, CO2, CH4, and O2 based on the IUPAC criteria (Long and Winefordner, 1983) given as where k is a constant that determines the confidence level (we set k = 3 for a confidence level above 99%), RSD is the standard deviation of the ion count or peak area of the target gas when measuring ultrapure N2, and m is the slope of linear regression obtained from the measurement of the six above mentioned gas concentrations prepared from the standard gases and ultrapure 180 N2 based on 10 replicate measurements of each gas.

Flux measurement using MULTUM-soil chamber system
The fluxes of target soil gases are determined from the variation in the target gas concentration while the chamber is closed.
where ∆C/∆t is the concentration variation of the target gas (ppbv-N2O, ppmv-CH4 or ppmv-CO2 h -1 ) during the flux 190 measurement period, V is the chamber volume (m 3 ), A is the chamber area (m 2 ), ρ is the gas density (kg m -3 ), T is mean air temperature inside the chamber (°C), and α is a conversion factor to transform N2O into N, and CH4, CO2 into C. We determine ∆C/∆t by applying linear regression to the data obtained from the nine consecutive concentration measurements when the chamber is closed.
Besides the flux measurement, we monitor soil temperatures and moisture with a portable digital thermometer (EM50 Data 195 Logger, METER Group, Pullman, WA, USA). Further, we monitor the air temperature inside the chamber and the ambient temperature using a temperature data logger (Thermo Recorder TR-52i, T&D Corporation, Nagano, Japan).
The minimum detectable flux (MDF) of each soil gas can be estimated based on the derivations by Courtois et al. (2019) originally developed by Christiansen et al. (2015) and Nickerson (2016) where Aa,i is the analytical accuracy of MULTUM for gas i, tc is the closure time of the soil flux chamber per flux measurement (20 min), n is the number of gas concentration measurements to calculate the gas flux (i.e., nine measurements), V is the volume of the flux chamber (0.018 m 3 ), P is the atmospheric pressure in kPa, S is the inner surface area of the flux chamber (0.049 m 2 ), R is the ideal gas constant (8.314 m 3 Pa K −1 mol −1 ), and T is the ambient temperature surrounding the chamber in K.

6
The MDF metric is a common performance metric in flux measurements; in particular, it is used in flux measurement methods based on continuous gas concentration observation with the chamber technique. Because MDF is a useful metric for comparing results between the cavity ring-down spectroscopy (CRDS) and our MS-based instrument, we employed the MDF for the comparison. The device accuracy (Aa,i) is defined as the measurement accuracy of an instrument (Christiansen et al. 2015;Nickerson 2016). In the flux measurement with the CRDS instrument, they used the accuracy value provided by the 210 manufacturer. For our system, we define the analytical accuracy (Aa,i) as the analytical precision (measurement uncertainty) of MULTUM for gas i and use two standard deviations (2σ) obtained from 994 measurements of the gas in air. However, we found that the MDF was not proper metrics for our flux measurement and thus defined new metrics, minimum quantitative flux (MQF), for better assessment of the reliability. Since flux is the rate of increase or decrease in the gas concentration of interest in the closed chamber, we determine the flux by applying linear regression to every set of the nine consecutive gas 215 concentration measurements in the closed chamber period over 20 min. We noticed that the quality of the linear regression analysis was quite poor even when the flux values were above MDF and the determined flux values were not reliable enough for further scientific discussion. We thus additionally evaluated the MQFs for each gas species to examine quantitatively reliable fluxes in our study. The MQF is determined from the precision of the slopes (rates of gas concentration changes) in the flux measurement relative to the true slope. However, the true slopes are difficult to determine in actual field measurements, 220 and therefore, we conducted a simulation study to characterize the MQF of the current instrument for each gas species.
We first defined a true flux value of the gas for the model simulation assuming that the flux remained constant when the chamber is closed. Based on the defined true flux value and chamber dimension, true gas concentrations to be measured in the chamber were calculated over time when the chamber was closed. To simulate a realistic observation, a random measurement error based on the standard deviation derived from the atmospheric gas measurements was intentionally added to the predefined 225 true gas concentrations when the chamber was closed. The simulated nine consecutive observation data were then used for flux determination with linear regression analysis, whose results were further characterized for MQF estimation. For each defined flux value, 10,000 sets of flux measurements were simulated, 10,000 corresponding slopes were obtained, and the standard deviations of the slopes were characterized. The simulation was conducted on a scientific graphical data processing software (Igor Pro, WaveMetrics, Lake Oswego, OR, USA) and the random measurement error was generated with a built-in 230 Gaussian distribution noise generator.

Laboratory tests
We conducted laboratory flux measurement tests of N2O, CH4, CO2, and O2 using a soil sample collected at the university farm of Ehime University. The soil was collected from 0-10 cm below the soil surface. After sampling, the soil was sieved to The automated flux chamber was placed on a ridge in the upland field, as shown in the left panel of Fig. 4. The field test was conducted during the fallow period (i.e., bare field condition). The soil pH, electric conductivity, and texture were 5.3, 34.0 µS cm −1 , and sandy loam (sand, 75.6%; silt, 10.6%; clay, 13.8%), respectively. On September 2, ammonium sulfate (150 kg N ha −1 ) and dried cattle feces (10 Mg ha −1 of fresh weight) were added and incorporated into the soil surface (0-15 cm 250 depth). After plowing, the soil bulk density and porosity were 1.02 g cm −3 and 62.9%, respectively. The automated soil chamber was installed immediately after incorporation. The total carbon (C) and nitrogen (N) contents of the dried cattle feces were 36.1 and 2.08%, respectively. The other components of the MULTUM-soil chamber system (i.e., MULTUM platform, control, and data acquisition system) were installed at a nearby goat hut that had a room temperature of 27 ± 2°C. Two 5 m long stainless-steel tubes (1/8 inch outer diameter) were used to connect the chamber and the six-port auto valve in the gas injection 255 unit to circulate headspace gas within the chamber.

Laboratory characterization of MULTUM-soil chamber system performance
In the laboratory, we characterized the performance of the developed MULTUM-soil chamber system by introducing standard gases through the gas injection unit at six different concentrations and by following the procedure for field observations. As To verify the stability of the developed MULTUM-soil chamber system, we conducted continuous measurements of 265 atmospheric N2O, CH4, CO2, and O2 in the laboratory with the flux chamber open (Fig. 6). The set of N2O, CH4, CO2, and O2 measurements was repeated every 2.5 min over 42 h. In the laboratory, the room temperature was maintained at 23 ± 1 °C and the relative humidity was around 15% at the beginning of the measurement; it increased to 30-33% after the midnight of January 31, 2019. The atmospheric pressure during the laboratory measurement period ranged between 1005-1014 hPa. The variations of atmospheric N2O, CH4, CO2, and O2 measurements are shown as histograms in Fig. 7. Because the distributions 270 agree with Gaussian distributions plotted as dashed lines in Fig. 7, we calculated the standard deviations (2σ) of each gas from the measurements to obtain Aa,i. The Aa,i obtained from the atmospheric air measurements were 22 ppbv for N2O; 102 ppbv, CH4; 8.1 ppmv, CO2; and 0.38 vol%, O2. These variations may be subject to the natural variabilities of atmospheric concentrations; however, we consider that they are instrumental variations because their distributions demonstrated good agreements with Gaussian distributions (Fig. 7) and the analytical precision obtained from the measurements of standard#1 275 and O2 standard in the laboratory (±34 ppbv for N2O; ±170 ppbv, CH4; ±16 ppmv, CO2; and ±0.60 vol%, O2, 2σ) almost corresponded to those obtained from atmospheric air. Using the standard gas rather than ambient air usually yields better instrumental performance because ambient air contains considerably more complicated gas species including water vapor, which can affect the precision of mass spectrometric measurement. Our final goal in our instrumental development is to construct a new instrument for field observation; soil gas flux is determined from the change in gas concentration in the flux 280 chamber relative to its atmospheric concentration. Thus, we considered that using ambient air measurement for out instrumental performance test is more appropriate and practical for our research purpose.

Laboratory flux measurement test
Before the field campaign, we conducted a laboratory flux measurement test to confirm whether our newly developed instrument could capture each soil gas flux when water was added, which is a major fluctuation factor of soil gas flux. The 285 temporal variations of the measured gas concentrations when the chamber is closed is shown in Fig. 8. Only data acquired when the chamber is closed (flux measurement periods) is depicted for simplification; however, the system stability verification and calibration were conducted when the chamber is open. At 22 h, water (approximately 3 L) was sprayed on the soil surface as environmental perturbation resembling rainfall to reactivate the dormant soil biological processes. Immediately after water addition, the emission of N2O and CO2 began to change in different ways. For example, the CO2 emission rapidly 290 increased and reached its maximum 2 h after water addition and remained relatively high, whereas N2O emission gradually increased until 20 h after water addition at a seemingly constant rate.
Such increases in soil CO2 flux by rainfall or rewetting soil have been reported previously (Lee et al., 2002;Smith and Owens, 2010;Gelfand et al., 2015;Kostyanovsky et al., 2019); it enhances microbial activity and population and boosts the availability of carbon and nutrients because of either rewetting or the assemblages (Fierer and Schimel, 2003;Iovieno and 295 Bååth, 2008;Blazewicz et al., 2014). A similar increase in N2O flux on rewetting soil have been reported (Nobre et al., 2001;Dobbie and Smith, 2003;Smith and Owens, 2010;Gelfand et al., 2015;Schwenke and Haigh, 2016;Leitner et al., 2017;Barba et al., 2019;Kostyanovsky et al., 2019), although very few research reported the simultaneous response of N2O and CO2 fluxes upon artificial watering (Smith and Owens, 2010;Gelfand et al., 2015;Kostyanovsky et al., 2019). Only Kostyanovsky et al. (2019) reported short-term flux changes of both CO2 and N2O upon simulated rainfall with a time resolution of 2 h. They 300 showed that the simulated rainfall immediately triggered increases in both CO2 and N2O fluxes; however, the increase in CO2 flux continued till about 3 h after the simulated rainfall, while that in N2O flux continued till about 5 h after the simulated rainfall. In the present laboratory test, CO2 and N2O fluxes showed different temporal behaviors from those observed by Kostyanovsky et al. (2019), although the observed N2O flux change was similar to that observed by Leitner et al. (2017). We speculate that the slow increase in N2O flux may reflect a slow building-up of nitrification and denitrification microorganisms 305 after watering, although further studies that consider both the biological and physicochemical aspects of the soil gas formations are necessary for gain better understanding. The fluxes of CH4 and O2 during the laboratory test were below their MDFs.

Minimum detectable and minimum quantitative fluxes of GHGs and O2
In Fig. 7, the frequencies of atmospheric concentrations of N2O, CH4, CO2, and O2 observed with the MULTUM-soil chamber system during the laboratory stability check (Fig. 6) are compiled as histograms. Their frequency distributions agree well with 310 Gaussian distributions (plotted as dashed lines in Fig. 7), and thus, their standard deviations are considered to have the Aa,i of the MULTUM-soil chamber system for each gas. The Aa,i is defined as the analytical accuracy (measurement uncertainty) of MULTUM for gas i and the use of two standard deviations (2σ) obtained from 994 measurements of atmospheric gas as a reference.
We estimated the MDFs based on Eq. (3) using the Aa,i for each gas, and we obtained 17.2 μg N m −2 h −1 , 35.4 μg C m −2 h −1 , 315 2.6 mg C m −2 h −1 , and 2.9 g O2 m −2 h −1 for N2O, CH4, CO2, and O2, respectively. However, the MDF is not a practical measure for the reliable quantification of flux. Thus, we evaluated the MQF for each gas as the quantitatively reliable flux in our study via model simulation. ; 139 µg C m −2 h −1 , CH4; 11.7 mg C m −2 h −1 , CO2; and 9.8 g O2 m −2 h −1 , O2. We consider the observed fluxes below the MQFs as qualitatively uncertain, and we do not use them in subsequent data analyses for this study.
We conducted data quality checks for the filed observation flux data using coefficients of determination (R 2 ) in the linear 325 regression analysis for nine consecutive concentration measurements when the chamber was closed. Fig. 10 shows the relationships between observed fluxes and the corresponding R 2 in the N2O and CO2 flux derivation during field flux observation at Ehime University. The R 2 was approximately 0.4 at its MQF (70.2 µg N m −2 h −1 ) in the N2O flux observation.
The data with R 2 = 0.4 in its linear regression analysis is regarded to have a statistically significant correlation, which supports that MQF is a reasonable metric for reliable quantification. In the field N2O flux measurement, R 2 increased with an increase 330 in the observed flux, which indicates that the improvement of quality in N2O measurement (i.e., detection limit and sensitivity) is desirable for more reliable determination, and in particular, under a low N2O flux condition. All CO2 flux measurements showed R 2 > 0.9, indicating that the present system is reliable for CO2 flux determination. The observed fluxes of CH4 and O2 during the laboratory/field study were usually below their MDFs; however, during a different field campaign in March 2019 at the same field, the CH4 flux above the MDF was observed (Fig. 12). For O2 flux, the analytical precision for the current O2 335 concentration measurement was ± 0.60 vol% (± 6000 ppmv). The current flux observation was under a dark condition and the CO2 concentration change was caused by respiration of the soil organisms. Therefore, the increase in CO2 concentration in the flux chamber is roughly equal to the decrease in O2 concentration during flux measurement. As shown in Fig. 8, to capture the O2 flux, an analytical precision of more than three orders of magnitude is necessary because the CO2 concentration change is about 100 ppmv after water spraying. It is considerably difficult to achieve an improvement in measurement precision by more 340 than three orders of magnitude. Although quantitative O2 flux measurement is difficult, our developed instrument can detect the variation in O2 concentration as a tracer for the redox state in soil environments (Kaiser et al., 2018).

Field observation
The N2O fluxes were mostly below 300 µg N m −2 h −1 and generally dependent on soil moisture, which substantially affected the production, consumption, and atmospheric exchange of GHGs (Davidson and Swank, 1986, Dobbie and Smith, 2003, 345 Liebig et al. 2005, Ellert and Janzen 2008, Sainju et al., 2012). An interesting event was observed in the N2O flux on September 4. The N2O flux abruptly increased from 70 to 682 µg N m −2 h −1 within a few hours after rainfall, while a gradually increase in CO2 flux was observed. These observed responses exhibit sharp contrast with our laboratory flux measurement test, in which CO2 flux showed a rapid increase while N2O flux showed a slow sustained increase upon water spraying (Fig. 8). Various studies have reported an increase in the N2O flux after rainfall (Nobre et al., 2001;Dobbie and Smith, 2003;Smith and Owens, 350 2010;Gelfand et al., 2015;Schwenke and Haigh, 2016;Leitner et al., 2017;Barba et al., 2019;Kostyanovsky et al., 2019) and similar increases in CO2 flux after rainfall have also been reported (Lee et al., 2002;Smith and Owens, 2010;Gelfand et al., 2015;Kostyanovsky et al., 2019). However, no short-term responses of CO2 and N2O fluxes similar to our observation upon rainfall have been reported. Further, two heavier rainfalls occurred on September 5 and 7; however, the N2O flux showed no obvious increase similar to that after the first rainfall. The different responses in N2O flux may reflect the complexity in 355 microbial and nutrient dynamics initiated in the soil upon rainfall (Gordon et al., 2008;Blazewicz et al., 2014), although further detailed studies that investigate both biological and physicochemical aspects of the soil gas formations are necessary to determine the causes of the response. The CO2 flux, in contrast, remained constant except during rainfall periods, in which an abrupt decrease and quick recovery within several hours of the flux occurred. This can be attributed to the suppression of CO2 permeation within the soil column caused by a capping effect of wet soil and different vertical distributions within the 360 soil column; although these explanations are feasible, they require further temporal and spatial investigation.

Conclusion and Future perspectives
We developed a field-deployable MS-based multiple gas flux measurement system utilizing a portable high-resolution mass spectrometer (MULTUM) combined with an automated soil-gas chamber. The MULTUM was coupled with a short gas separation column to roughly separate atmospheric major and trace gases over a short period, and a new hybrid ion detection 365 and signal processing technique was employed to ensure a much wider dynamic range for quantitative and simultaneous measurement of multiple gas concentrations that differ by six orders of magnitude. The present hourly continuous gas flux measurement of multiple gas species clearly indicates its considerable advantage of capturing rapid and different temporal responses of different gas species toward sporadic abrupt environmental changes (e.g., sudden rainfall), which provides more detailed understanding of underlying soil biological and physicochemical processes. 370 Further improvement in the detection limit and analytical precision is required for the accurate measurements of low GHG fluxes, in particular, for N2O and CH4. We believe that the improvement in the sensitivity by one order of magnitude can be achieved relatively easily by retrofitting a larger vacuum pump to the MULTUM (from 50 l/s to 250 l/s), using a higher mass measurement rate (from current 1 kHz to 10 kHz), and using a flux chamber with a lower ratio of the height to bottom area.
The privilege of MS-based gas measurement in highly sensitive and wider range of detectable gas species, including reactive-375 nitrogen gases (e.g., NO, NO2), noble gases (e.g., Ar, Ne), inorganic gases (e.g., N2, H2, CO, H2S), small organic gases (e.g., ethylene) should be quite advantageous in providing deeper insights into soil microbiological ecosystems, physicochemical processes, and their responses to environmental perturbations. A wide variety of gas species such as He, Ar, and polychlorinated biphenyls have already applied by MULTUM (Jense et al.,2017, Kawai et al., 2018, Shimma et al., 2013. Coupling proton transfer reaction (PTR) ionization source with the MULTUM can help detect a wider range of individual 380 BVOCs and subsequently their soil-atmosphere fluxes, and our group is coupling a PTR ion source to MULTUM.
We expect that further instrumental improvements and further expansion in detectable gas species will boost providing deeper insights on the biological and physicochemical processes in soil and lead to more comprehensive their understanding.
Data Availability. Data are available upon request.
Author contributions. NN led this research project and conducted a major part of the study. YT coordinated the field campaign, 385 assisted with the field flux measurement, and provided valuable feedback and advice for the field measurements. YI assisted in conducting a field test. TH constructed the hybrid ion detection and signal processing technique as well as the data analysis tools. HF developed a prototype of the multiple-gas measurement, MULTUM, system. RH and MT created the conceptual framework of this study. All authors discussed the results and contributed to the preparation of the final manuscript.
Competing interests. The authors declare that they have no conflict of interest. 390  1. Schematic of developed mass spectrometric multiple soil-gas flux measurement system with a portable high-resolution multiturn time-of-flight mass spectrometer (MULTUM) coupled with an automated soil-gas flux chamber. The headspace gas in the chamber continuously circulates a sample loop in the gas injection unit through stainless-steel tubing. In each gas analysis, the headspace gas in the sample loop is injected into a capillary column for rough gas separation before analyzing each gas with MULTUM. (o.d., outer diameter; ss, stainless steel).

Figure 2.
Schematic of two-dimensional gas/ion separation for O2, CH4, CO2, and N2O in chromatographic and m/z domains using a short column for rough separation and high-resolution mass spectrometry (MULTUM) for further complete separation. O2, CH4, and N2O are detected as O + , CH4 + , and N2O + with ion counting mode, whereas CO2 is detected as CO2 + with waveform averaging mode. In the chromatographic domain, CO2 and N2O are not fully separated; however, in the m/z domain, residual contributions of CO2 + and N2O + are fully separated by high mass resolving power of MULTUM.  The coefficients of determination (R 2 ) for each linear regression were above 0.996 for all gases regardless huge concentration difference by six orders of magnitude. Each points were based on ten replicate injections.