Influence process of thermal structure variations of a karst water reservoir on dissolved inorganic carbon and its stable carbon isotope
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摘要: 以中国南方亚热带地区典型的地下水补给型水库——大龙洞水库为对象，于2018年1月、4月、7月、10月、12月分别在上、中、下游三个监测点进行采样，探究水库热结构变化对于水体无机碳及其同位素的影响过程及机理。结果表明：（1）大龙洞水库水体在一个水文年中呈现周期性的混合期—分层期—混合期的热结构变化，4月热分层开始显现，7月逐渐显著呈现完整的热分层，10月以后热分层逐渐消失，水体逐渐实现混合；（2）水体热分层是溶解无机碳（DIC）浓度与碳稳定同位素（δ13CDIC）值变化的主要驱动力。表水层中DIC主要受水—气界面二氧化碳脱气、水生生物光合作用控制，其DIC浓度与δ13CDIC值分别为3.22 mmol·L−1和−9.15‰；温跃层中DIC主要受有机质降解过程影响，其DIC浓度与δ13CDIC值分别为3.43 mmol·L−1和−9.70‰；底水层中DIC主要受碳酸盐沉淀过程影响，其DIC浓度与δ13CDIC值分别为4.32 mmol·L−1和−11.89‰；（3）三种过程伴随水库热结构的变化而变化，驱动DIC浓度及其同位素的变化梯度 G (DIC)与 G (δ13CDIC)的变化，表现为底水层＜表水层＜温跃层。热分层结束进入混合期后，DIC浓度与δ13CDIC值的时空差异均逐渐消失，最终表现出DIC浓度与δ13CDIC值的均一化。Abstract: Dalongdong Reservoir, a typical groundwater recharge reservoir in karst area of southwest China, is located at 23°30′01″−23°40′08″N and 108°30′02″−108°36′04″E in Shanglin county, Nanning City, Guangxi. This large reservoir was built mainly for irrigation and power generation by blocking caves, sinkholes and some fissures in a karst valley in 1958. It covers a rainwater collecting area of 310 km2, totaling storage capacity of 151 million m3. Approximately 95% of the recharge water comes from two karst subterranean streams. The principal strata in the reservoir catchment are carbonate rocks of Carboniferous (C1) and Devonian (D2d3) era. Influenced by the subtropical monsoon climate, the average temperature in the reservoir area is 21℃ and the average rainfall is 1,837.3 mm. The rainy season in this area is from April to September. Samples were collected respectively by the plankton method at the upper, middle and downstream monitoring sites in January, April, July, October and December, 2018. Based on DIC concentration, δ13CDIC value, water temperature, DO, SIC, partial pressure of carbon dioxide, carbon dioxide diffusion flux and other indicators, the thermal structure change on DIC concentrations and isotope composition δ13CDIC in each water layer of reservoir and its influencing factors are systematically studied. The gradient differences of DIC concentrations and isotopic composition δ13CDIC in different water layers and their causes are also discussed.In order to provide scientific and technological support for accurate assessment of carbon budget of land and water, the carbon cycle process of karst reservoirs was deeply revealed. The results show that Dalongdong reservoir presents periodic thermal structure changes in the mixing stage−stratification stage−in a hydrological year. The thermal stratification begins to appear in April, gradually presents complete thermal stratification in July, and gradually disappears after October.Besides, thermal stratification is an important driving force of DIC concentration and δ13CDIC value. After the formation of thermal stratification, DIC concentrations in the upper, middle and lower reaches show the same characteristics as those of the δ13CDIC values at the same layer, and DIC concentrations increase with depth, while δ13CDIC values become negative. DIC concentrations and δ13CDIC values are respectively 3.22 mmol·L−1 and −9.15‰ in surface water, 3.43 mmol·L−1 and −9.70‰ in thermocline, and 4.32 mmol·L−1 and −11.89‰ in bottom water. After thermal stratification, the vertical, horizontal and seasonal variations of DIC concentrations and δ13CDIC values gradually disappear, and finally show their homogenization.Finally, carbon dioxide degassing and photosynthesis dominate the water-air interface in the surface water layer. Degradation of organic matter is the main process in thermocline, and carbonate precipitation can be mostly found in the bottom water layer. The change of these three processes with the reservoir thermal structure may drive the variation of DIC concentrations and isotope gradient G (DIC) and G (δ13CDIC), which shows the characteristics of bottom water layer < surface water layer < thermocline layer.
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图 1 大龙洞水库采样点分布图
a.大龙洞水库遥感图 b.大龙洞水库实景图注：a图中的红星为采样点，SU、SM、SD分别代表水库上、中、下游；带箭头和弧线的蓝色短虚线代表地下河流，蓝色细虚线表示间歇性地表水流，右下部蓝色实线代表人工水渠，曲线上部的虚线代表引水涵洞，水库通过底部涵洞引水和发电，并排泄到下游水渠中，供灌溉使用。
Figure 1. Map of sampling points of Dalongdong reservoir
图 2 大龙洞水库水温分布
注：热分层期间4、7、10月水体从上至下分别为表水层、底水层；表水层、温跃层、底水层；表水层、底水层。
Figure 2. Vertical distribution of water temperatures in Dalongdong reservoir in different seasons
图 3 大龙洞水库各采样点水体表层DIC浓度与δ13CDIC值分布特征
Figure 3. Distribution of DIC concentrations and δ13CDIC values in the surface water of each sampling point in Dalongdong reservoir
图 4 大龙洞水库水体DIC及δ13CDIC季节变化图
Figure 4. Diagram of the seasonal variation of DIC concentrations and δ13CDIC values in Dalongdong reservoir
图 5 大龙洞水库样品DIC浓度及δ13CDIC垂向分布
Figure 5. Vertical distribution of DIC concentrations and δ13CDIC values in Dalongdong reservoir
图 6 热分层期间各分层DIC浓度及δ13CDIC值变化梯度
Figure 6. Gradient differences of DIC concentrations and δ13CDIC values in each depth during thermal stratification
图 8 大龙洞水库各采样点水气界面CO2交换通量
Figure 8. CO2 exchange flux at the water-air interface at each sampling site in Dalongdong reservoir
图 9 大龙洞水库各采样点分层期间各水层DIC浓度及δ13CDIC值与主要指标相关关系
Figure 9. Correlation between DIC concentrations and δ13CDIC values and the main parameters during the thermal stratification period in Dalongdong reservoir
（a：1.y=1.58x+30.07,r=0.43；2.y=2.40x+41.27，r=0.58；3.y=1.79x+29.09，r=0.20；4.y=−4.66x+30.60，r=−0.38；5.y=−6.11x+38.82，r=−0.54；6.y=−12.34x+60.77，r=−0.63； b：7.y=−1 090.13x−5 182.74，r=−0.71；8.y=−1 609.28x−9 414.79，r=−0.96；9.y=−2 106.46x−11 434.47，r=−0.32；10.y=4 009.81x−8 096.79，r=0.79；11.y=3 871.66x−7 035.17，r=0.85；12.y=12 545x−40 210.48，r=0.88； c：13.y=0.80x+14.52，r=0.70；14.y=0.91x+16.39，r=0.79；15.y=0.65x+10.11，r=0.30；16.y=−2.68x+15.81，r=−0.70；17.y=−1.85x+13.93，r=−0.59；18.y=−0.38x+3.93，r=−0.08； d：19.y=0.047x+0.84，r=0.54；20.y=0.047x+0.82，r=0.75；21.y=−0.01x−0.01，r=−0.06；22.y=−0.15x+0.88，r=−0.52；23.y=−0.01x+0.70，r=−0.58；24.y=−0.06x+0.36，r=−0.21）
图 10 大龙洞水库各采样点剖面叶绿素分布
Figure 10. Vertical distribution of chlorophyll in each sampling site in Dalongdong reservoir
图 11 大龙洞水库各采样点剖面SIC与Ca2+浓度分布
Figure 11. Concentration distribution of SIC and Ca2+ in the profile of each sampling site in Dalongdong reservoir
表 1 监测期间各水层物理化学参数平均值
Table 1. Mean values of physical and chemical parameters of each water layer during monitoring
位置 T/ pH DIC/ δ13CDIC/ Ca2+/ DO/ Chl-a/ pCO2/ SIC ℃ mmol·L−1 ‰ mg·L−1 mg·L−1 μg·L−1 μatm
1月SU-Mix 16.64 8.25 3.64 −9.55 68.80 9.27 34.36 1072.16 0.85 SM-Mix 16.77 8.16 3.75 −10.35 74.00 8.23 25.66 1339.14 0.80 SD-Mix 17.09 8.04 3.83 −11.29 73.43 7.12 20.02 1763.48 0.69
4月SU-E 23.47 7.91 2.70 −6.95 48.00 6.70 20.43 5255.04 0.28 SM-E 22.70 7.84 2.93 −7.61 52.67 6.29 27.53 4347.72 0.32 SM-H 17.60 7.38 3.97 −11.64 70.67 1.43 15.07 8917.20 0.06 SD-E 22.23 7.93 3.07 −8.01 54.67 7.49 29.97 3614.85 0.42 SD-H 17.23 7.46 3.83 −11.49 71.33 1.63 13.37 7139.43 0.13
7月SU-E 29.00 8.60 1.40 −3.96 23.00 9.98 22.52 215.41 0.54 SU-T 26.70 7.99 2.80 −8.15 50.00 8.02 12.50 4384.21 0.39 SU-H 24.15 7.38 4.30 −11.30 89.00 6.58 2.95 10550.32 0.27 SM-E 28.75 8.11 2.30 −6.18 43.00 9.68 22.75 1758.55 0.49 SM-T 26.20 7.59 3.60 −9.83 63.00 7.36 17.75 6356.10 0.30 SM-H 23.23 7.21 4.50 −11.53 82.00 3.10 4.67 16852.67 0.08 SD-E 28.75 8.16 2.80 −7.68 50.00 11.17 21.80 1409.36 0.69 SD-T 26.05 7.63 3.85 −11.12 68.00 7.40 23.60 7838.70 0.39 SD-H 21.73 7.16 4.30 −12.33 81.00 1.69 7.65 16850.80 −0.01
10月SU-E 22.82 7.63 3.51 −10.74 65.17 6.19 6.88 5528.57 0.30 SM-E 22.88 7.70 3.82 −11.39 70.00 6.78 9.60 5976.82 0.43 SD-E 22.97 7.66 3.83 −10.96 73.67 6.12 8.12 7099.00 0.42 SD-H 21.33 7.15 4.87 −12.85 90.33 1.09 1.43 19570.08 0.06
12月SU-Mix
SM-Mix
SD-Mix17.18
17.38
17.638.20
8.02
7.923.55
3.59
3.76−10.21
−10.73
−11.4177.20
75.00
79.439.05
7.47
6.5223.50
12.90
8.601178.11
1791.03
2441.430.82
0.67
0.62注：SU（上游）， SM（中游）， SD（下游）， E（表水层）， T（温跃层）， H（底水层），Mix(混合期)。 
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表 2 观测期间大龙洞水库各水层DIC浓度与δ13CDIC值变化梯度
Table 2. Gradient differences of DIC concentrations and δ13CDIC values at each water depth during study period (G (DIC), G (δ13CDIC)
1月 4月 7月 10月 12月
混合期
表水层SU
SM
SD
SU(0.04，0.23)
(0.01，0.14)
(0.01，0.16)
(0.54，1.67)
(0，0.82)
(0.08，0.21)(0.01，0.03)
(0.03，0.07)
(0.01，0.02)SM (0.36，1.63) (0.56，1.68) (0.10，0.22) SD (0.38，1.53) (0.48，0.72) (0.09，0.23)
温跃层SU (1.11，2.54) SM (0.48，1.23) SD (0.36，2.03)
底水层SU (0.08，0.02) SM (0.04，0.06) (0.12，0.38) SD (0.02，0.17) (0.04，0.40) (0.12，0.01)
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