Carbon Cycle Characteristics in Karst Cave System of Xueyu Cave from 2012 to 2013
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摘要: 重庆雪玉洞洞内CO2浓度之高，在国内外皆罕见，但此洞穴系统碳循环特征及控制因素仍不清楚.利用土壤二氧化碳分压(PCO2-soil)、洞内大气二氧化碳分压(PCO2-cave)、地下河水二氧化碳分压(PCO2-eq)、方解石饱和指数(SIc)、地下河水溶解无机碳同位素(δ13CDIC)等指标来研究雪玉洞洞内CO2浓度变化、控制因素以及地下河对洞内碳循环的影响.结果表明：雪玉洞上覆PCO2-soil雨季高，旱季低；降雨量是控制上覆PCO2-soil的重要因子.雪玉洞PCO2-cave变化规律明显，暖季高，冷季低；温度变化导致洞内外气流频繁交换是PCO2-cave突变的重要原因，地下河水CO2脱气能够在短时间内让PCO2-cave上升到较高值.雨季由于土壤CO2效应，地下河水具有低SIc、高PCO2-eq特性，矿化度较高，并且部分月份地下河水具有溶蚀性；旱季由于土壤CO2效应及降雨较少，地下河水呈现高SIc、低PCO2-eq特性，矿化度较低，以沉积为主.Abstract: The high CO2 concentration in Xueyue cave, Chongqing, is rare at home and abroad. However, the circulation characteristics of carbon and its controlling factors in this cave system remain unknown. PCO2-soil, PCO2-cave, PCO2-eq, SIc, and δ13CDIC of subterranean stream were analyzed to investigate the laws of CO2 concentration variations in Xueyu cave and its contolling factors, as well as the impact on carbon cycle in this cave by subterranean stream. It is found that soil PCO2 mainly controlled by precipitation in subtropical areas was higher in rainy season than that of dry season. Cave air PCO2 exhibited seasonal variations, high cave air PCO2 typically occurred during warm periods, and low cave air PCO2 were typical of cold periods. It was ventilation driven by the temperature difference between cave and outside air that resulted in a sharp transition of cave air PCO2. Meanwhile, cave air PCO2 could rise to high level in a short period of time because of CO2 degassing from subterranean stream. Due to soil CO2 effect, groundwater became more mineralized water with low SIc and high water PCO2-eq, and dissolution in some months in rainy season. With the reduction of soil CO2 and precipitation, groundwater had low degree of mineralization with high SIc and low water PCO2-eq in dry season.
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Key words:
- karst cave system /
- carbon cycle /
- CO2 partial pressure /
- calcite saturation index /
- Xueyu cave /
- climate change
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图 3 开放系统中方解石溶解的基本物理化学过程
[H2CO3*]指水中的CO2与H2CO3活度之和
Fig. 3. Dissolution of calcite in an open karst system
图 5 研究区土壤PCO2、洞穴PCO2随时间变化规律
Fig. 5. The variation relationships of PCO2-soil and PCO2-cave with time in study area
图 6 地下河水-lg(PCO2-eq) vs. SIc模型输出结果
Fig. 6. Results of subterranean stream in -lg(PCO2-eq) vs. SIc
图 7 土壤PCO2与降雨量、温度的相关性
Fig. 7. Correlations of PCO2-soil vs. precipitation and PCO2-soil vs. temperature
图 8 雪玉洞冷季、暖季气流交换示意
图中黑色粗箭头为洞外气流，灰色虚箭头为洞内气流，灰色实箭头为土壤气流
Fig. 8. Schematic summary of the two main types of air circulation in Xueyu cave
图 9 雪玉洞内各相PCO2变化
Fig. 9. Evolution of equilibrium and saturation values of PCO2 from water in Xueyu cave
表 1 文中术语
Table 1. The nomenclature in article
表达式 代表意义 表达式 代表意义 [Ca2+] 钙离子活度 SIc 方解石饱和指数 (Ca2+) 钙离子摩尔当量 PCO2 二氧化碳分压 [HCO3-] 碳酸氢根离子活度 PCO2-eq 水-气平衡时二氧化碳分压 (HCO3-) 碳酸氢根离子摩尔当量 PCO2-sat SIc=0时的二氧化碳分压 γCa2+ 钙离子活度系数 PCO2-cave 洞穴内大气二氧化碳分压 γHCO3- 碳酸氢根离子活度系数 PCO2-soil 土壤二氧化碳分压 G & D 吸气脱气直线 pH 酸碱指标 K0 亨利气体溶解平衡常数 pHm 实际测试的pH值 K1 碳酸的一次离解常数 pHsat SIc=0时的pH值 K2 碳酸的二次离解常数 Model-HCO3- (-lg(PCO2-eq) vs. SIc)模型得出的HCO3-浓度 Kc CaCO3溶解时平衡常数 Model-PCO2-sat (-lg(PCO2-eq) vs. SIc)模型得出的PCO2-sat 
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表 2 地下河水上下游二氧化碳分压(%)
Table 2. Water PCO2 in upstream and downstream water of subterranean river (%)
日期 下游PCO2-eq 上游PCO2-eq △PCO2-eq PCO2-cave PCO2-cave增加/减少量 2013-11-02 0.14 0.15 0.01 0.39 - 2013-11-03 0.20 0.24 0.04 0.50 0.11 2013-11-04 0.18 0.31 0.13 0.60 0.10 2013-11-05 0.34 0.43 0.09 0.73 0.13 2013-11-06 0.33 0.34 0.01 0.54 -0.19 2013-11-07 0.36 0.49 0.14 0.66 0.12 2013-11-08 0.61 0.76 0.15 0.91 0.25 2013-11-09 0.67 0.96 0.29 0.98 0.07 平均值 0.35 0.46 0.11 0.70 0.09 注：PCO2-cave为4个洞穴大气监测点的平均值；PCO2-cave增加/减少量为相邻2天数据之差.
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