water Article Soil CO2 Uptake in Deserts and Its Implications to the Groundwater Environment Wenfeng Wang 1 , Xi Chen 1, *, Hongwei Zheng 1 , Ruide Yu 1 , Jing Qian 2 , Yifan Zhang 3 and Jianjun Yu 4 1 2 3 4 * State Key Laboratory of Desert and Oasis Ecology, Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences, Urumqi 830011, China; [email protected] (W.W.); [email protected] (H.Z.); [email protected] (R.Y.) Center for Geo-Spatial Information, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China; [email protected] Department of Chemistry, Inha University, 100 Inharo, Incheon 402-751, Korea; [email protected] Environmental Change Institute, University of Oxford, Oxford OX1 3QY, UK; [email protected] Correspondence: [email protected]; Tel.: +86-0991-7885-303 Academic Editors: Y. Jun Xu, Guangxin Zhang and Hongyan Li Received: 30 June 2016; Accepted: 30 August 2016; Published: 5 September 2016 Abstract: Recent studies of soil carbon cycle in arid and semi-arid ecosystems demonstrated that there exists an abiotic CO2 absorption by saline-alkali soils (Aa ) at desert ecosystems and suggested potential contributions of CO2 dissolution beneath deserts to the terrestrial ecosystems carbon balance. However, the overall importance of such soil CO2 uptake is still undetermined and its implications to the groundwater environment remain unaddressed. In this manuscript, a simple method is proposed for the direct computation of Aa from the total soil CO2 flux (Fa ) as well as for the evaluation of Aa importance to Fa . An artificial soil-groundwater system was employed to investigate the implications to groundwater environment and it was found that soil CO2 uptake in deserts can contribute a possible influence on the evolution of the groundwater environment, providing that the absorbed CO2 largely remained in the soil-groundwater system. Keywords: abiotic CO2 absorption; soil CO2 flux; the soil-groundwater system 1. Introduction Global soil CO2 releases account for 20%–38% of the annual input of CO2 from terrestrial and marine sources to the atmosphere [1–11]. Therefore, soil CO2 flux (Fa ) is a significant determinant of the ecosystem carbon balance. Among the components of Fa , the biotic processes (including the root and microbial respiratory components) were thought to be significantly contributing to it [2–6], while the abiotic processes were always neglected [12–20]. However, a series of recent studies of deserts ecosystems have highlighted that the abiotic processes (including subterranean CO2 dissolution and other abiotic carbon sink beneath deserts) must be taken into account in the budget of Fa [7–10]. Some recent studies attributed the abiotic processes to the effects of the soil water dynamics on subterranean carbon cycle and presented theoretical and experimental analyses based on the biogeochemical reactive transport modeling [21,22]. This not only developed the methodology of the partition of Fa into the biotic and abiotic components across some special environments, but also highlighted that the subterranean dissolution of CO2 has been involved in the ecosystem carbon balance in deserts, and can even temporally dominate [7–11]. However, soil CO2 dissolution and effusion, as abiotic processes in deserts, are different from the considered processes in these previous studies. Especially in some experimental contrast, only the top few cm of the soil was considered. It became much more impressive after the abiotic CO2 absorption (Aa ) by the soil collected from a saline desert was directly observed after a minimizing-disturbance sterilization treatment on the Water 2016, 8, 379; doi:10.3390/w8090379 www.mdpi.com/journal/water Water 2016, 8, 379 2 of 12 soil [8]. This demonstrated that there exists an abiotic CO2 uptake by saline-alkali soils (Aa ) at desert ecosystems and suggested a potential contribution of such soil CO2 uptake to the ecosystem carbon balance in deserts [8,10]. There is strong evidence suggesting that Aa can contribute significantly to Fa and the net ecosystem carbon balance, but the overall importance of the soil CO2 uptake to Fa is still undetermined. Presently, both the field observations and the laboratory experiments are still limited on site scales. Because of the lack of large-scale experiments, the magnitude of such CO2 uptake is still a matter of controversy. Some recent publications have further presented the laboratory data on the soil abiotic CO2 absorption and the field data on the net CO2 exchange in desert ecosystems [23,24], whereas it is still imperative to have a simple method for a direct computation of the abiotic soil CO2 uptake from the total soil CO2 flux and for quantifying its overall importance to Fa . The minimizing-disturbance sterilization treatment on soils has been widely recognized as an experimental method for separating Aa [10]. Since the significance of CO2 dissolution and effusion as the abiotic processes has become much more impressive after the soil CO2 uptake was directly observed after such a sterilization treatment on the soil [8,10], another subsequent unresolved issue is whether the beneath CO2 dissolution has a non-negligible implication to the groundwater environment beneath deserts, providing that the dissolved and absorbed CO2 largely remained in the soil-groundwater system. This certainly desires a further investigation but remains unaddressed. This manuscript aims to design a simple method for a direct computation of the abiotic soil CO2 uptake from the total soil CO2 flux and proposed a simple approach to quantify its overall importance to Fa . After a special treatment, Fa is reconciled as a simple function of Aa , which is implemented in two different approaches. In the experimental approach, all Aa data are collected after the minimizing-disturbance sterilization treatment on the soils, while in the other semi-experimental approach, most of the Aa data are directly calculated from a simple regressive model. The potential implications of Aa and the beneath CO2 dissolution to the groundwater environment are also preliminarily discussed. 2. Materials and Methods 2.1. Data Sources Sampling data of soil CO2 fluxes were collected from Xie et al. [8]. The measurements were conducted in the Gurbantunggut Desert, which is located at hinterland of the Eurasian Continent (87◦ 560 E, 44◦ 170 N; elevation: 461 m), with an arid, windy climate (sunshine: 3079 h; precipitation: 144.7 mm; evapotranspiration: 2020 mm; radiation: 5439 MJ/m2 ; velocity: 2.6 m/s). Note that two LI-8100s (LI-COR, Lincoln, Nebraska, NE, USA) have been employed for the valid comparison between the flux data measured at the sterilized and unsterilized samples. It should be noted that the soil was smashed, roots-sieved, air-dried and the many sinks and sources of CO2 in the subsurface environment have been excluded. After sterilization, the net soil CO2 fluxes were negative and the CO2 exchange was abiotic. In order to highlight the soil CO2 uptake, such abiotic exchange is hence defined as “soil abiotic CO2 absorption” throughout this manuscript (Figure 1). Consequently, the variations of Fa were largely determined by Aa and the soil microbial respiration (Rm ). With the purpose of a preliminary discussion on the potential implications of the beneath CO2 dissolution to the groundwater environment, an artificial soil-groundwater system was employed and the groundwater were sampled with six replications (Figure 2). The groundwater pH and the concentration of dissolved inorganic carbon (DIC) in the artificial soil-groundwater system were measured, where the concentration of DIC (symbolized as (DIC) was defined as the sum of the concentration of the dissolved carbonate ion and bicarbonate ion. Water 2016, 8, 379 Water 2016, 8, 379 3 of 12 3 of 12 Water 2016, 8, 379 3 of 12 CO2 flux averaged from sampled days[ mol m-2 s-1] CO2 flux averaged from sampled days[ mol m-2 s-1] 2.5 flux data measured before sterilization flux data measured after sterilization flux data measured before sterilization flux data measured after sterilization 2.5 2 1.5 2 1.5 1 1 0.5 0.5 0 0 -0.5 -0.5 -1 -1 -1.5 0 -1.5 0 1 1 2 2 3 3 4 4 5 5 Time [d] Time [d] 6 7 6 7 8 8 9 9 Figure 1. Contrast of mean CO Figure 1. Contrast of mean CO222 flux before/after sterilization. flux before/after sterilization. Figure 1. Contrast of mean CO flux before/after sterilization. Figure 2. diagram theartificial artificial soil-groundwater soil‐groundwater system. collected from #1, #1, Figure 2. A A A diagram ofof the system.The Thesamples sampleswere were collected from Figure 2. diagram of the artificial soil‐groundwater system. The samples were collected from #1, with 6 replications. with 6 replications. with 6 replications. 2.2. Modeling Approach 2.2. Modeling Approach 2.2. Modeling Approach Neglecting Aa, it is well‐known that Fa can be formulated as an exponential function of the soil Neglecting Aaa, it is well‐known that F , it is well-known that Faa can be formulated as an exponential function of the soil can be formulated as an exponential function of the soil Neglecting A surface temperature or the ambient air temperature [19]: surface temperature or the ambient air temperature [19]: surface temperature or the ambient air temperature [19]: Fa Fa 20 Q10(TS 20)/10 (1) ( 20 (TTSS− 20) )/10 /10 F Q FaF= F × Q (1) (1) a20 10 a a 20 10 where Fa20 is measured Fa at 20 °C, TS is the soil temperature (here it is measured at 0–10 cm), and Q10 is the relative change in F a20 is measured F 10 where F where Fa20 is measured Faa at 20 °C, T ata with 10 °C increases. 20 ◦ C, TSS is the soil temperature (here it is measured at 0–10 cm), and Q is the soil temperature (here it is measured at 0–10 cm), and Q10 R m is formulated as in [20]: is the relative change in F is the relative change in Faa with 10 °C increases. with 10 ◦ C increases. R m is formulated as in [20]: Rm is formulated as in [20]: R m R m20 Q10(TS 20)/10 (2) )/10 S −20 Rm = Rm20 · Q10 (T(T (2) S 20)/10 R m R m20 Q10 (2) where Rm20 is the measured value of Rm at 20 °C. where RTaking into account A of Rm at 20 ◦ C. m20 is the measured value a, Fa is reconciled as, m at 20 °C. where Rm20 is the measured value of R Taking into account Aa , Fa is reconciled as, Taking into account Aa, Fa is reconciled as, Fa R m A a (3) FFa = Rm + Aa (3) (3) a R m Aa Water 2016, 8, 379 4 of 12 The experimental method separates Aa by the sterilization treatment on the soils and hence Rm20 can be estimated as follows: Rm20 = Fa20 − Aa20 (4) where Aa20 are measured Aa at 20 ◦ C. Substituting Equation (2) into Equation (4), Rm is reconciled as: Rm = (Fa20 − A20 ) · Q10 (TS −20)/10 (5) Correspondingly, Fa can be finally reconciled as: Fa = (Fa20 − A20 ) · Q10 (TS −20)/10 + Aa (6) Unfortunately, extensive time is required during the minimizing-disturbance sterilization treatment on the soil. At large scales, it is necessary to couple with other methodologies. Development of a semi-experimental method for the rough partition of Aa is thus necessary. Similar to semi-experimental approaches for the partition of the biotic components of Fa [12], the relationship between Aa and Fa could be assumed to be represented by a simple linear regressive model and written as: Aa = β0 Fa + β1 (7) where β0 and β1 are determined by the contributions of Aa to Fa . Under this assumption, Rm is reconciled as: Rm = (1 − β0 )Fa − β1 (8) Rm10 = (1 − β0 )Fa10 − β1 (9) and correspondingly By Equation (2), the Q10 value for Rm can be estimated by Rm = [(1 − β0 )Fa10 − β1 ] · Q10 (TS −10)/10 (10) Combining Equations (8) and (10), the soil CO2 flux could be finally reconciled as Fa = [Fa10 − β1 β1 ] · Q10 (TS −10)/10 + 1 − β0 1 − β0 (11) The parameters β0 and β1 can be estimated by Equation (7) after a few experiments and a large magnitude of time will be saved in the partition of Aa . Regarding the first approach, the relationship between the groundwater pH and (DIC) are analyzed by utilizing an exponentially regressive model: pH = λ0 eλ1 (DIC) (12) where λ0 and λ1 are determined by the contributions of (DIC) to the groundwater pH. 3. Results and Discussion 3.1. Separated Biotic and Abiotic Components of Soil CO2 Fluxes The aforementioned parameters of β0 and β1 are estimated using the measured values of Aa and Fa on two clear days in two typical desert ecosystems, saline desert and oasis farmland (Figure 3). Water 2016, 8, x 5 of 13 The aforementioned parameters of β 0 and β1 are estimated using the measured values of Aa and Water 2016, 8, 379 5 of 12 Fa on two clear days in two typical desert ecosystems, saline desert and oasis farmland (Figure 3). Water 2016, 8, 379 5 of 12 0 0.2 Data Fit Confidence bounds -0.2 a Data Fit Confidence bounds 0.1 0 -0.4 b -0.1 -0.2 y y -0.6 -0.8 -0.3 -0.4 -0.5 -1 -0.6 -1.2 -0.7 -1.4 -1 -0.5 x 0 -0.8 0.5 0 0.5 1 x 1.5 2 2.5 Figure 3. Parameters β0 and β1 estimated at desert ecosystems (a) and oasis farmland (b). Figure 3. Parameters β0 and β1 estimated at desert ecosystems (a) and oasis farmland (b). Figure 3. Parameters β0 and β1 estimated at desert ecosystems (a) and oasis farmland (b). The estimated parameters of β00 and β and β11 are then applied to the semi‐experimental separation of are then applied to the semi-experimental separation of The estimated parameters of β The estimated parameters of β 0 and β1 are then applied to the semi‐experimental separation of AaAata at the corresponding ecosystems in a drought period of one growing season in 2006, taking into the corresponding ecosystems in a drought period of one growing season in 2006, taking into Aa at the corresponding ecosystems in a drought period of one growing season in 2006, taking into account their difference for different ecosystems (the estimated β00 and β and β1 from saline desert are also account their difference for different ecosystems (the estimated β 1 from saline desert are also account their difference for different ecosystems (the estimated β0 and β1 from saline desert are also applied to its neighbor abandoned farmland, as provided in Table 1). applied to its neighbor abandoned farmland, as provided in Table 1). applied to its neighbor abandoned farmland, as provided in Table 1). Table 1. Suitable parameters for the isolation of Aa. a . Table 1. Suitable parameters for the isolation of A Table 1. Suitable parameters for the isolation of Aa. Study Sites Parameters Applied in Semi‐Experimental Method Study Sites Parameters Applied in Semi-Experimental Method Study Sites Parameters Applied in Semi‐Experimental Method Saline desert β0 = 0.5284 β1 = −0.8975 Saline desert β0 = 0.5284 = −0.8975 Saline desert β0 β= 0.5284 βββ1 1 1= −0.8975 Abandoned farmland 0 = 0.5284 = −0.8975 Abandoned farmland β0 = 0.5284 β1 = −0.8975 Abandoned farmland β0 β= 0.5284 ββ1 1 = −0.8975 0 = 0.4266 = −0.8330 Oasis farmland Oasis farmland β = 0.4266 β = −0.8330 0 1 Oasis farmland β0 = 0.4266 β1 = −0.8330 It is obvious that Aa separated in both the experimental and semi‐experimental approaches acts It is obvious that Aa aseparated in both the experimental and semi-experimental approaches acts It is obvious that A separated in both the experimental and semi‐experimental approaches acts as a CO 2 sink. Aa separated into two approaches varies in a similar pattern during the considered as drought period. Through comparison with the total soil CO a CO sink. A separated into two approaches varies in a similar pattern during the considered a a separated into two approaches varies in a similar pattern during the considered 2 2 sink. A as a CO 2 flux Fa, it was found that most Fa data drought period. Through comparison with the total soil COa, the microbial soil respiration R flux Faa, it was found that most F , it was found that most a data drought period. Through comparison with the total soil CO 22 flux F aF data are positive. This implies that the other flux component of F m, plays area dominant role within this period (Figure 4) positive. This implies that the other flux component of F , the microbial soil respiration R , m plays are positive. This implies that the other flux component of Fa, the microbial soil respiration Rm, plays a dominant role within this period (Figure 4) a dominant role within this period (Figure 4) 4 -2 -1 -2 m hourly CO2[ flux mol mol[ m hourly meanmean CO2 flux s-1] s ] 24 Total soil CO2 flux Fa 02 Total soil CO2 flux Fa -20 0 -2 10 01 -10 -2 -1 0 -2 10 01 -10 -2 -1 0 -2 0 50 50 Experimental isolation of Aa 100 150 200 250 100 150 200 250 100 150 200 250 100 150 200 250 150 200 250 150 200 250 Experimental isolation of Aa 50 50 Semi-experimental isolation of Aa Semi-experimental isolation of Aa 50 100 50 100 Time [h] Time [h] Figure 4. Isolated Aa by experimental/semi‐experimental method. Figure 4. Isolated Aa by experimental/semi‐experimental method. Figure 4. Isolated Aa by experimental/semi-experimental method. Considering that β0 and β1 are determined by the contributions of Aa to Fa, they might be very Considering that β0 and β1 area is not very different, but F determined by the contributions of Aa to Fa , they might be very different in various ecosystems (A a can be very different). Choosing soil different in various ecosystems (Aa is not very different, but Fa can be very different). Choosing soil sites for the few sampled experiments should be done cautiously. sites forThe the values few sampled shouldsoil be respiration done cautiously. of Q10 experiments for the microbial Rm might also be different in various The values of Q for the microbial soil respiration also be different in various m might 10 visualization of the separated RmR ecosystems. From the in considered drought period by a ecosystems. From the visualization of the separated Rm in considered drought period by a continuous Water 2016, 8, 379 Water 2016, 8, 379 Water 2016, 8, 379 6 of 12 6 of 12 6 of 12 -2 -2-1 -1 Estimated Rm byby experimental method [ [mol mm s s] ] mol Estimated Rm experimental method curve, the gradient of Rm in some sites and sampling days might not be evident. For to this reason, only continuous curve, the gradient of R m in some sites and sampling days might not be evident. For to continuous curve, the gradient of R m in some sites and sampling days might not be evident. For to the separated results of R on nine sampled presented here andare three kinds ofhere ecosystems are this reason, only the separated results of Rdays m on are nine sampled days presented and three m this reason, only the separated results of Rm on nine sampled days are presented here and three selected the comparison, the saline desert, abandoned farmland and oasis farmland.farmland It could also kinds of for ecosystems are selected for the comparison, the saline desert, abandoned and kinds of ecosystems are selected for the comparison, the saline desert, abandoned farmland and facilitate the validIt and explicit between the separated results of Rmbetween from thethe experimental oasis farmland. could also comparison facilitate the valid and explicit comparison separated oasis farmland. It could also facilitate the valid and explicit comparison between the separated method and semi-experimental method. Obviously, the separated Rm inmethod. the semi-experimental results of Rmthe from the experimental method and the semi‐experimental Obviously, the results of Rm from the experimental method and the semi‐experimental method. Obviously, the and experimental approaches show similar patterns. The diurnal dynamics on nine sampled days also separated Rm in the semi‐experimental and experimental approaches show similar patterns. The separated Rm in the semi‐experimental and experimental approaches show similar patterns. The reveal a duplicated variability (Figures 5 and 6). diurnal dynamics on nine sampled days also reveal a duplicated variability (Figures 5 and 6). diurnal dynamics on nine sampled days also reveal a duplicated variability (Figures 5 and 6). 1 1 0.8 0.8 0.6 0.6 0.4 0.4 0 0 0.9 0.9 0.8 0.8 0.7 0.7 0.6 0.6 0 0 2.2 2.2 2 2 1.8 1.8 1.6 1.6 0 0 a a 10 10 20 20 30 30 d d 10 10 20 20 30 30 g g 1 1 0.8 0.8 0.6 0.6 0.4 0.4 0 0 0.9 0.9 0.8 0.8 0.7 0.7 0.6 0.6 0 0 b b 10 10 20 20 30 30 e e 10 10 20 20 2.2 2.2 30 30 h h 2 2 10 10 20 20 30 30 1.8 1.8 0 0 10 20 10Time [h]20 Time [h] 30 30 1 1 0.8 0.8 0.6 0.6 0.4 0.4 0 0 0.9 0.9 0.8 0.8 0.7 0.7 0.6 0.6 0 0 2.2 2.2 2.1 2.1 2 2 1.9 1.9 0 0 c c 10 10 20 20 30 30 f f 10 10 20 20 30 30 i i 10 10 20 20 30 30 -2 -2-1 -1 Estimated bybysemi-experimental [ [mol mm s s] ] mol EstimatedRm Rm semi-experimentalmethod method Figure 5. Isolated RR m by experimental method (a–c: saline desert; d–f: abandoned farmland; g–i: Figure 5. Isolated IsolatedR experimental method (a–c: saline desert; abandoned farmland; Figure 5. m m by by experimental method (a–c: saline desert; d–f: d–f: abandoned farmland; g–i: oasis farmland). g–i: oasis farmland). oasis farmland). 1 1 0.8 0.8 0.6 0.6 0 0 1 1 0.9 0.9 0.8 0.8 0.7 0.7 0 0 2 2 1.8 1.8 1.6 1.6 1.4 1.4 0 0 1 1 0.8 0.8 0.6 0.6 a a 10 10 20 20 30 30 d d 10 10 20 20 20 20 10 10 20 20 30 30 0.6 0.6 0 0 2 2 10 10 20 20 1.6 1.6 0 0 10 20 10Time [h]20 Time [h] 1 1 0.8 0.8 0.6 0.6 0.4 0.4 0 0 1 1 c c 10 10 20 20 30 30 0.6 0.6 0 0 2 2 10 10 20 20 1.6 1.6 0 0 30 30 i i 1.8 1.8 30 30 30 30 f f 0.8 0.8 h h 1.8 1.8 30 30 30 30 e e 0.8 0.8 g g 10 10 0 0 1 1 b b 10 10 20 20 30 30 Figure 6. Isolated Rm by semi‐experimental method (a–c: saline desert; d–f: abandoned farmland; g–i: Figure 6. Isolated R by semi‐experimental method (a–c: saline desert; d–f: abandoned farmland; g–i: Figure 6. Isolated Rmm by semi-experimental method (a–c: saline desert; d–f: abandoned farmland; oasis farmland). oasis farmland). g–i: oasis farmland). The separated results of Rm in the former two ecosystems are almost the same (Table 2), which The separated results of Rm in the former two ecosystems are almost the same (Table 2), which The separated results of Rm in the former two ecosystems are almost the same (Table 2), which are are all different with the oasis farmland. This might be the reason that the soil microbial activity in are all different with the oasis farmland. This might be the reason that the soil microbial activity in all different with the oasis farmland. This might be the reason that the soil microbial activity in the the saline desert is very different to that in oasis farmland. the saline desert is very different to that in oasis farmland. salineThe desert is very different to that in oasis farmland. separated A a from the semi‐experimental approach represents about 80% of that from the The separated Aa from the semi‐experimental approach represents about 80% of that from the The separated Aa from the semi-experimental approach 80%7). of that from the experimental approach, which indicates a reliable cross represents validation about (Figure In fact, the experimental approach, which indicates a reliable cross validation (Figure 7). In fact, the experimental approach, which indicates a reliable cross validation (Figure 7). In fact, the experimental experimental method should still be used with much caution since it indicates a large magnitude of experimental method should still be used with much caution since it indicates a large magnitude of method should still used with much caution[10,14]. Thus, since it indicates large validations magnitude of carbon sink intwo the carbon sink in the be most barren ecosystems the across between these carbon sink in the most barren ecosystems [10,14]. Thus, the cross validations between these two most barren ecosystems [10,14]. Thus, the cross validations between these two methods are necessary. methods are necessary. methods are necessary. Water 2016, 8, 379 7 of 12 Water 2016, 8, 379 Water 2016, 8, 379 7 of 12 7 of 12 -2 -1 isolated by semi-experimental method [ mol isolated Aa A bya semi-experimental method [ mol m-2ms-1]s ] Table 2. Q10 values for isolated Rm by two methods. Table 2. Q10 values for isolated Rm by two methods. Table 2. Q10 values for isolated Rm by two methods. Study Sites Semi-Experimental Method Experimental Method Study Sites Semi‐Experimental Method Experimental Method Study Sites Semi‐Experimental Method Experimental Method Saline desert 0.53200 0.58711 Saline desert 0.53200 0.58711 Saline desert 0.53200 0.58711 Abandoned farmland 0.81835 0.77012 Abandoned farmland 0.81835 0.77012 Abandoned farmland 0.81835 0.77012 Oasis farmland 1.21009 1.19123 Oasis farmland 1.21009 1.19123 Oasis farmland 1.21009 1.19123 1.5 1.5 1 1 Slope =0.81 Slope =0.81 RMSE =0.29 RMSE =0.29 0.5 0.5 0 0 -0.5 -0.5 -1 -1 -1.5 -1.5 -2 -2 -2 -2 -1.5 -1.5 -1 -0.5 0 0.5 -1 -1 -0.5 0 [ mol m-2 s0.5 method ] isolated Aa by experimental isolated Aa by experimental method [ mol m-2 s-1] 1 1 1.5 1.5 Figure 7. Reliability of semi‐experimental partition method Figure 7. Reliability of semi-experimental partition method(the (thegreen green line line is is the the linear linear regression regression Figure 7. Reliability of semi‐experimental partition method (the green line is the linear regression line determined by the observed values and the simulated values) utilizing a linear regression curve line determined by the observed values and the simulated values) utilizing a linear regression curve line determined by the observed values and the simulated values) utilizing a linear regression curve (the green line). The diagonal blue line is taken as a reference. (the green line). The diagonal blue line is taken as a reference. (the green line). The diagonal blue line is taken as a reference. -1 s-1] isolated by two methods [ mol-2m-2 isolated RmRby m two methods [ mol m s ] Employing the estimated β0 and β1 in Equation (10) and fitted Q10 provided in Table 2, the Employing the estimated estimated ββ00 and andββ Equation (10) and fitted in Table 2, 1 in 10 provided Employing the 1 in Equation (10) and fitted Q10 Qprovided in Table 2, the separated R m by the semi‐experimental method explain well the variability of separated Rm by the the separated R by the semi-experimental method explain well the variability of separated R m m separated Rm by the semi‐experimental method explain well the variability of separated R m by the experimental method (Figure 8). Both semi‐experimental and experimental methods reconcile F a as a by the experimental method (Figure 8). Both semi-experimental and experimental methods reconcile experimental method (Figure 8). Both semi‐experimental and experimental methods reconcile F a as a direct sum of Aa and Rm, rendering the cross validation of reconciled Fa using these two methods Fdirect sum of A of Ama , rendering and Rm , rendering the cross validation of reconciled a as a direct sum a using these two a and R the cross validation of reconciled F a using F these two methods necessary. In Figure 9, it is also found that F a reconciled by Equation (11) using the semi‐experimental methods necessary. In Figure 9, it is also found that F reconciled by Equation (11) using the a necessary. In Figure 9, it is also found that F a reconciled by Equation (11) using the semi‐experimental approach almost coincides with that reconciled by Equation (6) in the experimental approach. The semi-experimental approach almost coincides with that reconciled bythe experimental approach. The Equation (6) in the experimental approach almost coincides with that reconciled by Equation (6) in aforementioned results of cross validation also show that the semi‐experimental separations of Rm approach. The aforementioned results of cross validation also show that the semi-experimentalm aforementioned results of cross validation also show that the semi‐experimental separations of R a proposed in Section 2 are both feasible and reliable (Table 3). and A separations of Rm and Aa proposed in Section 2 are both feasible and reliable (Table 3). and Aa proposed in Section 2 are both feasible and reliable (Table 3). 1.5 1.5 saline desert: saline desert: experimental method experimental method semi-experimental method semi-experimental method 1 1 0.5 0.5 0 0 0 0 1 1 R2=0.99973 R2=0.99973 10 10 RMSE=0.077922 RMSE=0.077922 20 30 20 30 abandoned farmland: abandoned farmland: 0.8 0.8 0.6 0.6 0 0 R2=0.99969 R2=0.99969 20 20 RMSE=0.081291 RMSE=0.081291 40 60 40 60 40 40 3 3 2.5 2.5 2 2 1.5 1.5 1 80 0 1 80 Time [h] 0 Time [h] 50 50 60 60 70 70 80 80 oasis farmland: oasis farmland: R2=0.99998 R2=0.99998 20 20 RMSE=0.22938 RMSE=0.22938 40 60 40 Figure 8. Cross validation of isolated Rm by two methods. Figure 8. Cross validation of isolated R Figure 8. Cross validation of isolated Rmm by two methods. by two methods. 60 80 80 reconciled Fa by semi-experimental method [ mol m-2 s-1] Water 2016, 8, 379 Water 2016, 8, 379 8 of 12 8 of 12 2.5 Slope =0.91 RMSE =0.25 2 1.5 1 0.5 0 -0.5 -1 -1 -0.5 0 0.5 1 1.5 reconciled Fa by experimental method [ mol m-2 s-1] 2 2.5 Figure 9. Cross validation of reconciled Fa by two methods, utilizing a linear regression curve (the Figure 9. Cross validation of reconciled Fa by two methods, utilizing a linear regression curve (the green green line). The diagonal blue line is taken as a reference. line). The diagonal blue line is taken as a reference. Table 3. Fitted relationships between isolated components by two methods. Table 3. Fitted relationships between isolated components by two methods. Flux Components Slope Flux Components Alkaline absorption Slope 0.80630 Alkaline absorption Microbial respiration Microbial respiration 2 flux Reconciled soil CO Reconciled soil CO2 flux 0.80630 0.71842 0.71842 0.91428 0.91428 RMSE RMSE 0.29089 0.29089 0.14753 0.14753 0.25061 0.25061 3.2. Implications of Soil CO2 Uptake to the Groundwater Environment 3.2. Implications of Soil CO2 Uptake to the Groundwater Environment Although soil CO2 uptake in deserts has been investigated in many previous studies, its Although soil CO2 uptake in deserts has been investigated in many previous studies, its potential potential influences on the groundwater environment remain unaddressed [25–39]. This is partially influences on the groundwater environment remain unaddressed [25–39]. This is partially due to the due to the lack of a simple method for the separation and quantification of such CO 2 uptake. This lack of a simple method for the separation and quantification of such CO uptake. This study presents 2 study presents a simple yet efficient method for partitioning CO2 influxes to and efflux from bare asaline‐alkali soils, implying a time to consider the implications of such CO simple yet efficient method for partitioning CO2 influxes to and efflux from bare saline-alkali soils, 2 uptake beneath deserts implying a time to consider the implications of such CO uptake beneath deserts to the groundwater 2 where the absorbed CO to the groundwater environment. An unresolved issue, 2 has gone, still environment. An unresolved issue, where the absorbed CO has gone, still remains. Most studies 2 remains. Most studies assumed that these absorbed CO2 are partially dissolved in the soil‐groundwater assumed that these absorbed CO2 are partially dissolved in the soil-groundwater system. However, system. However, the magnitude of the beneath CO 2 dissolution remains undetermined [25–30]. the magnitude of the beneath CO dissolution remains undetermined [25–30]. 2 Furthermore, the experimental partition method is still desired for further improvement. Based Furthermore, the experimental partition method is still desired for further2 influx and efflux when improvement. Based on on some recent studies, there exists little difference between abiotic soil CO some recent studies, there exists little difference between abiotic soil CO influx and efflux when 2 excluding the role of groundwater and soil is left to absorb/release CO2 naturally [28]. The excluding the role of groundwater and soil is left to absorb/release CO naturally [28]. The difference 2 difference might be attributed to the extent of the sterilization treatment on the soil and the might be attributed to the extent of the sterilization treatment on the soil and the existence of msome soila. existence of some soil microbial respiration (R m), or the interaction between the existing R and A microbial respiration (R ), or the interaction between the existing R and A . Future studies must m m a Future studies must keep a most cautious mind in extending the results from the laboratory keep a most cautious mind in extending the results from the laboratory experiments tothe field research. experiments to field research. In reality, the conditions are much more complex and additional In reality, the conditions are much more complex and the additional confounding factors for many flux confounding factors for many flux components exist and might interact with each other. components existwidely and might interact that withthe each other. magnitude of CO2 dissolution beneath deserts It has been recognized overall It has been widely recognized that the overall magnitude of CO2 dissolution beneath deserts and its contributions to the ecosystem carbon balance can be huge [30–39], but its effect on the local and its contributions to the ecosystem balanceto can be huge but its on CO the2 environment are seldom reported. As a carbon first attempt analyze the [30–39], implications of effect the soil local environment are seldom reported. As a first attempt to analyze the implications of the soil uptake to the groundwater environment, the present study simply assumes that the absorbed CO2 CO uptakelargely to the groundwater the present study simply that the absorbed has 2 been dissolved in environment, the soil‐groundwater system beneath assumes the deserts. Under this CO has been largely dissolved in the soil-groundwater system beneath the deserts. Under this 2 assumption, an artificial soil‐groundwater system has been incubated for a long period in the assumption, an artificial soil-groundwater system has been incubated for a long period in the laboratory. laboratory. Collected data at the first stage confirm that the implications to the water environment Collected data at the first stage confirm that the implications to the water environment should be taken should be taken into account (Figure 10). into account (Figure 10). Water 2016, 8, 379 9 of 12 Water 2016, 8, 379 9 of 12 The concentration of DIC (μmol/kg) 4000 y = 0.0008e1.3841x R² = 0.3664 3500 3000 2500 2000 1500 1000 500 0 9.60 9.80 10.00 10.20 10.40 10.60 10.80 11.00 The groundwater pH Figure 10. 10. The The relationship between the groundwater pH the concentration of dissolved Figure relationship between the groundwater pH and theand concentration of dissolved inorganic inorganic carbon (DIC) in the artificial soil‐groundwater system. carbon (DIC) in the artificial soil-groundwater system. Since the potential contributions of these abiotic components to the total soil CO2 fluxes were Since the potential contributions of these abiotic components to the total soil CO2 fluxes non‐negligible, the implication of the biotic CO2 effluxes and abiotic CO2 influxes to the were non-negligible, the implication of the biotic CO2 effluxes and abiotic CO2 influxes to the soil‐groundwater environment cycle is a subsequent problem. Despite the recent studies of soil soil-groundwater environment cycle is a subsequent problem. Despite the recent studies of soil carbon carbon cycle in the desert ecosystems and the biogeochemical investigations in the arid ecosystems cycle in the desert ecosystems and the biogeochemical investigations in the arid ecosystems [40–49], [40–49], the dynamics of beneath CO2 dissolution [7,10] is still not well‐understood. Furthermore, the dynamics of beneath CO2 dissolution [7,10] is still not well-understood. Furthermore, even the even the mechanisms of subterranean abiotic processes are still not wholly known. It is worth mechanisms of subterranean abiotic processes are still not wholly known. It is worth noting that the noting that the groundwater pH is essentially significant for the local water environment and has groundwater pH is essentially significant for the local water environment and has attracted a wide attracted a wide attention [50–60]. Attaining a reliable quantification for the contributions of soil attention [50–60]. Attaining a reliable quantification for the contributions of soil CO2 uptake to the CO2 uptake to the groundwater environment remains one major challenge and hence should be a groundwater environment remains one major challenge and hence should be a research priority. research priority. Because the mechanisms for the abiotic CO2 absorption and the overall magnitude of the soil CO2 Because the mechanisms for the abiotic CO2 absorption and the overall magnitude of the soil uptake are still not well-understood, there are still considerable uncertainties in more explicit analyses CO2 uptake are still not well‐understood, there are still considerable uncertainties in more explicit of the contributions of such soil CO2 uptake to the groundwater environment [8,10,14]. Additionally, analyses of the contributions of such soil CO2 uptake to the groundwater environment [8,10,14]. the data required by the present experimental method can only be collected from the top few cm of the Additionally, the data required by the present experimental method can only be collected from the soil. The whole atmospheric exchange of CO2 requires some further investigations towards better and top few cm of the soil. The whole atmospheric exchange of CO2 requires some further investigations more suitable experimental and non-experimental methodologies. towards better and more suitable experimental and non‐experimental methodologies. 4. Conclusions 4. Conclusions This study presented a simple yet efficient method to work out the magnitude of soil abiotic CO2 This study presented a simple yet efficient method to work out the magnitude of soil abiotic absorption in deserts from the data set of soil CO2 fluxes, along with a first approach to illustrate its CO 2 absorption in deserts from the data set of soil CO2 fluxes, along with a first approach to potential role in influencing environments in an artificial soil-groundwater system. The first approach illustrate its potential role in influencing environments in an artificial soil‐groundwater system. The highlighted significant events where an evident variation of the groundwater pH, provided that first approach highlighted significant events where an evident variation of the groundwater pH, the absorbed CO 2 largely remained in the soil-groundwater system. Considering the CO2 sink size provided that the absorbed CO 2 largely remained in the soil‐groundwater system. Considering the across different environments remains unknown, there are still considerable uncertainties and further CO 2 sink size across different environments remains unknown, there are still considerable investigations are necessary. uncertainties and further investigations are necessary. Acknowledgments: This research was financially supported by the National Natural Science Foundation of China Acknowledgments: This research was financially supported by the National Natural Science Foundation of (41571299), the “Thousand Talents” plan (Y474161), the CAS “Light of West China” Program (XBBS-2014-16) China the “Thousand Talents” plan (Y474161), the CAS “Light of West China” Program and the(41571299), Shenzhen Basic Research Project (JCYJ20150630114942260). Essential geodata were collected from (XBBS‐2014‐16) and the Shenzhen Basic Research Project (JCYJ20150630114942260). Essential geodata were National Science and Technology Infrastructure Center-Earth System Science Data Sharing Infrastructure of (www.geodata.cn). collected from National Science and Technology Infrastructure Center‐Earth System Science Data Sharing Infrastructure of (www.geodata.cn). Author Contributions: Xi Chen and Wenfeng Wang conceived and designed the experiments; Wenfeng Wang performed the experiments; Xi Chen, Wenfeng Wang and Jing Qian analyzed the data; Hongwei Zheng, Ruide Yu, Yifan Zhang and Jianjun Yu contributed analysis tools; and Wenfeng Wang wrote the paper. Water 2016, 8, 379 10 of 12 Author Contributions: Xi Chen and Wenfeng Wang conceived and designed the experiments; Wenfeng Wang performed the experiments; Xi Chen, Wenfeng Wang and Jing Qian analyzed the data; Hongwei Zheng, Ruide Yu, Yifan Zhang and Jianjun Yu contributed analysis tools; and Wenfeng Wang wrote the paper. Conflicts of Interest: The authors declare no conflict of interest. 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