Citation: | LAN Gao-yong, WANG Zhi-jun, YIN Jian-jun, TANG Wei, WU Xia, YANG Hui. Study on Carbon Dioxide Outgassing in a Karst Spring-fed Surface Stream[J]. Rock and Mineral Analysis, 2021, 40(5): 720-730. doi: 10.15898/j.cnki.11-2131/td.202107310088 |
Chemical weathering of carbonates (i.e.karstification) involves considerable uptake of atmospheric CO2 which is converted to dissolve inorganic carbon (DIC), thereby acting as one of the important terrestrial carbon sinks. This karst-related carbon sink could contribute greatly to the global carbon budget and have the potential to be an increasing carbon sink on land. However, its stability has long been debated because CO2 sequestered by the dissolution of carbonate could return to the atmosphere through CO2 outgassing from groundwater-feeding surface waters, which can cause uncertainties for the estimation of the karst-related carbon sink.
In order to better understand the processes responsible for CO2 outgassing and the flux and influencing factors of CO2 outgassing, and provide more insights into the stability of the karst-related carbon sink.
Hydrochemical and isotopic techniques were used to monitor the change of water chemistry and carbon isotopic composition of dissolved inorganic δ13CDIC along the flow path. Based on the downstream variations of hydrochemical indicators and δ13CDIC, the flux and influencing factors of CO2 outgassing along the stream were analyzed.
From the spring (C1) to site C14, the stream channel (270m-long) had a steep gradient of~10°, and pH, calcite saturation index and δ13CDIC of stream water increased by 0.9, 0.9 and 1.8‰, respectively, whereas CO2 partial pressure, electrical conductivity, Ca2+ and DIC concentrations decreased by 85%, 34μS/cm, 0.2mmol/L and 0.7mmol/L, respectively. These observations indicated the occurrence of significant CO2 degassing and calcium carbonate precipitation in the channel. In contrast, less downstream variations in water chemistry and δ13CDIC of stream water occurred along C18-C26 segment (about 2.1km long, slope gradient < 1°) in the plain area, suggesting weak CO2 outgassing and very limited calcite precipitation. Furthermore, the hydrochemical and isotopic compositions of stream water were likely to be affected by tributary mixing and dilution in the downstream area, and consequently the pH value of the stream and calcite saturation index decreased to some degrees, which inhibited the occurrence of CO2 degassing.
The downstream variation in hydrochemical and isotopic compositions suggest that the stream CO2 degassing is chiefly affected by topographically controlled hydrological conditions. At Changliushui, the CO2 degassing in streams partly counteracts the atmospheric CO2 sequestered by carbonate weathering, but causes 29% of the total amount of CO2 sequestered in DIC of the feeding spring water to be released back to the atmosphere. For streams/rivers from low-relief areas fed by karst springs/underground rivers that have a large discharge rate, the CO2 degassing should have limited impact on the stability of karst-related carbon sinks. In addition, the possibly enhanced "carbon pump" effects of aquatic phototrophs would make the karst-related carbon sink more stable.
[1] | Gao Y, Yu G R, Yang T T, et al. New insight into global blue carbon estimation under human activity in land-sea interaction area: A case study of China[J]. Earth-Science Reviews, 2016, 159: 36-46. doi: 10.1016/j.earscirev.2016.05.003 |
[2] | Liu Z, Dreybrodt W, Wang H. A new direction in effective accounting for the atmospheric CO2 budget: Considering the combined action of carbonate dissolution, the global water cycle and photosynthetic uptake of DIC by aquatic organisms[J]. Earth-Science Reviews, 2010, 99: 162-172. doi: 10.1016/j.earscirev.2010.03.001 |
[3] | Gombert P. Role of karstic dissolution in global carbon cycle[J]. Global and Planetary Change, 2002, 33(1): 177-184. |
[4] | 刘再华, Dreybrodt W, 王海静. 一种由全球水循环产生的可能重要的CO2汇[J]. 科学通报, 2007, 52(20): 2418-2422. doi: 10.3321/j.issn:0023-074x.2007.20.013 Liu Z H, Dreybrodt W, Wang H J. A possible important CO2 sink by the global water cycle[J]. Chinese Science Bulletin, 2007, 52(20): 2418-2422. doi: 10.3321/j.issn:0023-074x.2007.20.013 |
[5] | Liu Z, Macpherson G L, Groves C, et al. Large and active CO2 uptake by coupled carbonate weathering[J]. Earth-Science Reviews, 2018, 182: 42-49. doi: 10.1016/j.earscirev.2018.05.007 |
[6] | Liu Z, Dreybrodt W. Significance of the carbon sink pro-duced by H2O-carbonate-CO2-aquatic phototroph interaction on land[J]. Science Bulletin, 2015, 60(2): 182-191. doi: 10.1007/s11434-014-0682-y |
[7] | Liu Z H, Dreybrodt W, Liu H. Atmospheric CO2 sink: Silicate weathering or carbonate weathering?[J]. Applied Geochemistry, 2011, 26: 292-294. doi: 10.1016/j.apgeochem.2011.03.085 |
[8] | Liu Z, Li Q, Sun H, Wang J. Seasonal, diurnal and storm-scale hydrochemical variations of typical epikarst springs in subtropical karst areas of SW China: Soil CO2 and dilution effects[J]. Journal of Hydrology, 2007, 337(1): 207-223. |
[9] | Wang Z, Yin J J, Pu J, et al. Integrated understanding of the critical zone processes in a subtropical karst watershed (Qingmuguan, southwestern China): Hydro-chemical and isotopic constraints[J]. Science of The Total Environment, 2020, 749: 141257. doi: 10.1016/j.scitotenv.2020.141257 |
[10] | Zeng S, Liu Z, Kaufmann G. Sensitivity of the global carbonate weathering carbon-sink flux to climate and land-use changes[J]. Nature Communications, 2019, 10(1): 5749. doi: 10.1038/s41467-019-13772-4 |
[11] | 曾思博, 蒋勇军. 土地利用对岩溶作用碳汇的影响研究综述[J]. 中国岩溶, 2016, 36(2): 153-163. Zeng S B, Jiang Y J. Impact of land-use and land-cover change on the carbon sink produced by karst processes: A review[J]. Carsologica Sinica, 2016, 36(2): 153-163. |
[12] | Curl R L. Carbon shifted but not sequestered[J]. Science, 2012, 335(6069): 655. |
[13] | Hoffer-French K J, Herman J S. Evaluation of hydrological and biological influences on CO2 fluxes from a karst stream[J]. Journal of Hydrology, 1989, 108: 189-212. doi: 10.1016/0022-1694(89)90283-7 |
[14] | Wang Z, Yin J J, Pu J, et al. Flux and influencing factors of CO2 outgassing in a karst spring-fed creek: Implications for carbonate weathering-related carbon sink assessment[J]. Journal of Hydrology, 2020, 596: 125710. |
[15] | 周小萍, 沈立成, 王鹏, 等. 表层岩溶地下水出露地表后的脱气作用——以重庆市南川区柏树湾表层岩溶泉溪流为例[J]. 中国岩溶, 2011, 30(4): 1014-1021. Zhou X P, Shen L C, Wang P, et al. Degasification of the outcropped epikarst water: A case study on the Baishuwan Spring in Nanchuan, Chongqing[J]. Carsologica Sinica, 2013, 30(4): 1014-1021. |
[16] | 周小萍, 蓝家程, 张笑微, 等. 岩溶溪流的脱气作用及碳酸钙沉积——以重庆市南川区柏树湾泉溪流为例[J]. 沉积学报, 2013, 31(6): 1014-1021. Zhou X P, Lan J C, Zhang X W, et al. CO2 outgassing and precipitation of calcium carbonate in a karst stream: A case study of Baishuwan Spring in Nanchuan, Chongqing[J]. Acta Sedimentologica Sinica, 2013, 31(6): 1014-1021. |
[17] | Drysdale R N, Taylor M P, Ihlenfeld C. Factors con-trolling the chemical evolution of travertine-depositing rivers of the Barkly karst, northern Australia[J]. Hydrological Processes, 2002, 16(15): 2941-2962. doi: 10.1002/hyp.1078 |
[18] | 陈波, 杨睿, 刘再华, 等. 水生光合生物对茂兰拉桥泉及其下游水化学和δ13CDIC昼夜变化的影响[J]. 地球化学, 2014, 43(4): 375-385. Chen B, Yang R, Liu Z H, et al. Effects of aquatic phototrophs on diurnal hydrochemical and δ13CDIC variations in an epikarst spring and two spring-fed ponds of Laqiao, Maolan, SW China[J]. Geochimica, 2014, 43(4): 375-385. |
[19] | Pu J, Li J, Khadka M B, et al. In-stream metabolism and atmospheric carbon sequestration in a groundwater-fed karst stream[J]. Science of The Total Environment, 2017, 579: 1343-1355. doi: 10.1016/j.scitotenv.2016.11.132 |
[20] | 李丽, 蒲俊兵, 李建鸿, 等. 岩溶地下水补给的地表溪流溶解无机碳及其稳定同位素组成的时空变化[J]. 环境科学, 2017, 38(2): 527-534. Li L, Pu J B, Li J H, et al. Temporal and spatial variations of dissolved inorganic carbon and its stable isotopic composition in the surface stream of karst ground water recharge[J]. Environmental Science, 2017, 38(2): 527-534. |
[21] | 张陶, 李建鸿, 蒲俊兵, 等. 桂江典型断面夏季水-气界面CO2交换的碳源与机制[J]. 第四纪研究, 2020, 40(4): 1048-1057. Zhang T, Li J H, Pu J B, et al. Sources and controlling mechanisms of CO2 exchange across water-air interface in summer in two typical transects of Guijiang River, China[J]. Quaternary Sciences, 2020, 40(4): 1048-1057. |
[22] | Zhang T, Li J, Pu J, et al. Carbon dioxide exchanges and their controlling factors in Guijiang River, SW China[J]. Journal of Hydrology, 2019, 578: 124073. doi: 10.1016/j.jhydrol.2019.124073 |
[23] | 唐伟, 王华, 蓝高勇, 等. Gas BenchⅡ-IRMS磷酸法在线测定水中溶解无机碳碳同位素分析条件及影响因素[J]. 中国岩溶, 2017, 36(3): 419-426. Tang W, Wang H, Lan G Y, et al. A study on the test conditions and influence factors in online-phosphoric acid method for carbon isotopes of dissolved inorganic carbon compounds in water samples by GasBenchⅡ-IRMS[J]. Carsologica Sinica, 2017, 36(3): 419-426. |
[24] | 黄芬, 吴夏, 杨慧, 等. 桂林毛村地下河流域岩溶关键带碳循环研究[J]. 广西科学, 2018, 25(5): 515-523. Huang F, Wu X, Yang H, et al. Study on carbon cycle of karst critical zone in Maocun subterranean river basin of Guilin[J]. Guangxi Sciences, 2018, 25(5): 515-523. |
[25] | Zeng C, Liu Z, Zhao M, et al. Hydrologically-driven variations in the karst-related carbon sink fluxes: Insights from high-resolution monitoring of three karst catchments in southwest China[J]. Journal of Hydrology, 2016, 533: 74-90. doi: 10.1016/j.jhydrol.2015.11.049 |
[26] | 吴夏, 朱晓燕, 张美良, 等. 桂林岩溶表层带土壤CO2体积分数时空变化规律及其意义[J]. 生态环境学报, 2012, 21(5): 834-839. Wu X, Zhu X Y, Zhang M L, et al. Variation of soil CO2 concentration content and its significance in epikarst of Guilin[J]. Ecology and Environmental Sciences, 2012, 21(5): 834-839. |
[27] | Dreybrodt W. Physics and chemistry of CO2 outgassing from a solution precipitating calcite to a speleothem: Implication to 13C, 18O, and clumped 13C18O isotope composition in DIC and calcite[J]. Acta Carsologica, 2019, 48: 59-68. |
[28] | Runnells D D. Diagenesis, chemical sediments, and the mixing of natural waters[J]. Journal of Sedimentary Research, 1969, 36: 1188-1201. |
[29] | Pei W, Hu Q, Hui Y, et al. Preliminary study on the utilization of Ca2+ and HCO3- in karst water by different sources of Chlorella vulgaris[J]. Carbonates and Evaporites, 2014, 29(2): 203-210. doi: 10.1007/s13146-013-0170-5 |
[30] | Clark I D, Fritz P. Environmental isotopes in hydrogeo-logy[M]. New York: Lewis Publishers, 1997. |
[31] | Shin W J, Chung G S, Lee D, et al. Dissolved inorganic carbon export from carbonate and silicate catchments estimated from carbonate chemistry and δ13CDIC[J]. Hydrology and Earth System Sciences, 2011, 15(8): 2551-2560. doi: 10.5194/hess-15-2551-2011 |
[32] | Yan H, Liu Z, Sun H. Large degrees of carbon isotope dis-equilibrium during precipitation-associated degassing of CO2 in a mountain stream[J]. Geochimica Et Cosmochimica Acta, 2020, 273: 244-256. doi: 10.1016/j.gca.2020.01.012 |
[33] | Jiang Y, Hu Y, Schirmer M. Biogeochemical controls on daily cycling of hydrochemistry and δ13C of dissolved inorganic carbon in a karst spring-fed pool[J]. Journal of Hydrology, 2013, 478: 157-168. doi: 10.1016/j.jhydrol.2012.12.001 |
[34] | 蒲俊兵. 重庆地区岩溶地下河水溶解无机碳及其稳定同位素特征[J]. 中国岩溶, 2013, 32(2): 123-132. Pu J B. Dissolved inorganic carbon and stable carbon isotope in karst subterranean streams in Chongqing, China[J]. Carsologica Sinica, 2013, 32(2): 123-132. |
[35] | Liu Z, Svensson U, Dreybrodt W, et al. Hydrodynamic control of inorganic calcite precipitation in Huanglong Ravine, China: Field measurements and theoretical prediction of deposition rates[J]. Geochimica Et Cosmochimica Acta, 1995, 59(15): 3087-3097. doi: 10.1016/0016-7037(95)00198-9 |
[36] | 曾成, 刘再华, 孙海龙, 等. 水力坡度对溪流钙华沉积的影响[J]. 地球与环境, 2009, 37(2): 103-110. Zeng C, Liu Z H, Sun H L, et al. Influence of hydraulic gradient on the travertine deposition in the Baishuitai Canal, Yunnan Province[J]. Earth and Environment, 2009, 37(2): 103-110. |
[37] | 赵海娟, 肖琼, 吴夏, 等. 人类活动对漓江地表水体水-岩作用的影响[J]. 环境科学, 2017, 38(10): 4108-4119. Zhao H, Xiao Q, Wu X, et al. Impact of human activities on water-rock interactions in surface water of Lijiang River[J]. Environmental Science, 2017, 38(10): 4108-4119. |
[38] | 李建鸿, 蒲俊兵, 袁道先, 等. 岩溶区地下水补给型水库表层无机碳时空变化特征及影响因素[J]. 环境科学, 2015, 36(8): 2833-2842. Li J H, Pu J B, Yuan D X, et al. Variations of inorganic carbon and its impact factors in surface-layer waters in a groundwater-fed reservoir in karst area, SW China[J]. Environmental Science, 2015, 36(8): 2833-2842. |
[39] | Huang S, Pu J, Li J, et al. Sources, variations, and flux of settling particulate organic matter in a subtropical karst reservoir in southwest China[J]. Journal of Hydrology, 2020, 586: 124882. doi: 10.1016/j.jhydrol.2020.124882 |
[40] | Jiang Y, Lei J, Hu L, et al. Biogeochemical and physical controls on the evolution of dissolved inorganic carbon (DIC) and δ13CDIC in karst spring-waters exposed to atmospheric CO2(g): Insights from laboratory experiments[J]. Journal of Hydrology, 2020, 583: 124294. doi: 10.1016/j.jhydrol.2019.124294 |
[41] | 宋昂, 彭文杰, 何若雪, 等. 好氧不产氧光合细菌反馈作用下的五里峡水库坝前水体化学特征研究[J]. 岩矿测试, 2017, 36(2): 171-179. Song A, Peng W J, He R X, et al. Hydrochemistry characteristics in front of the Wulixia Reservoir dam associated with feedback from aerobic anoxygenic phototrophic bacteria[J]. Rock and Mineral Analysis, 2017, 36(2): 171-179. |
[42] | 李强, 黄雅丹, 何若雪, 等. 岩溶水体惰性有机碳含量及其存在机理[J]. 岩矿测试, 2018, 37(5): 475-478. Li Q, Huang Y D, He R X, et al. The concentration of recalcitrant dissolved organic carbon in the karst hydrosphere and its existing mechanism[J]. Rock and Mineral Analysis, 2018, 37(5): 475-478. |
[43] | Jiao N, Herndl G J, Hansell D A, et al. Microbial pro-duction of recalcitrant dissolved organic matter: Long-term carbon storage in the global ocean[J]. Nature Reviews Microbiology, 2010, 8(8): 593-599. |
[44] | 陈崇瑛, 刘再华. 喀斯特地表水生生态系统生物碳泵的碳汇和水环境改善效应[J]. 科学通报, 2017, 62(30): 38-48. Chen C Y, Liu Z H. The role of biological carbon pump in the carbon sink and water environment improvement in karst surface aquatic ecosystems[J]. Chinese Science Bulletin, 2017, 62(30): 38-48. |
Locations of the Changliushui spring and sampling sites along the stream of Guilin City, Guangxi Autonomous Region
Downstream variations in the hydrogeochemistry of stream water
Correlationship between δ13CDIC values and HCO3- concentrations