云南白水台泉水地球化学特征及其气候环境指示意义

赵茜; 徐洪阳; 甘海伶; 叶爱华; 周立旻; 郑祥民

doi:10.11932/karst20240304

云南白水台泉水地球化学特征及其气候环境指示意义

doi: 10.11932/karst20240304

华东师范大学地理科学学院地理信息科学教育部重点实验室, 上海 200241

基金项目: 国家自然科学基金面上项目（41871015）；国家自然科学基金面上项目（41971020）

详细信息

作者简介:
赵茜(1999－)，女，硕士研究生，自然地理学专业。E-mail：51213901041@stu.ecnu.edu.cn

通讯作者:
郑祥民(1959－)，男，教授，主要从事自然地理学和环境演变等方面研究。E-mail：xmzheng@re.ecnu.edu.cn。

中图分类号: P641.3
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- 被引次数: 0
出版历程
- 收稿日期: 2024-01-01
- 录用日期: 2023-07-20
- 修回日期: 2023-07-17
- 网络出版日期: 2024-08-15
- 刊出日期: 2024-06-25

Geochemical characteristics of spring water in Baishuitai of Yunnan and their indicative significance on climatic environment

Key Laboratory of Geographic Information Science, Ministry of Education, School of Geographic Sciences, East China Normal University, Shanghai 200241, China

摘要

摘要: 为研究岩溶地下水的水文地球化学演化特征，对云南白水台地区雨水和泉水中氢氧稳定同位素（δD、δ¹⁸O）组成和微量元素含量进行了为期近5年（2018年1月至2022年10月）以月为频率的连续监测。结果表明：（1）白水台雨水中δD、δ¹⁸O具有明显的季节性变化特征，均表现为雨季偏轻，旱季偏重，主要受到水汽来源与蒸发条件的影响；（2）白水台泉水受当地大气降水补给，其δD、δ¹⁸O经历了石灰岩基层中不同通道、裂隙网络中的新、老水混合导致的同位素调蓄平滑作用以及与深部来源CO₂的氧同位素交换作用，修正性继承了雨水中δD、δ¹⁸O的部分特征；（3）泉水中Ca、Mg、Sr、Ba、Si等元素主要来源于喀斯特水体侵蚀下围岩的溶解，其含量变化可能指示了降水量的变化；而Fe、Al、Mn等元素主要来源于大气降水对上覆土壤的淋滤作用，其浓度变化可能反映了降水强度的变化。
- 氢氧稳定同位素 /
- 微量元素 /
- 泉水 /
- 钙华 /
- 云南白水台
Abstract: Understanding the geochemical characteristics and dynamic changes of groundwater (e.g., springs, etc.) is an important scientific reference for accurately interpreting the paleoclimatic and environmental information on karst deposits (e.g., stalagmites, travertine, etc.). In this study, we continuously collected local rainwater samples and S3 spring water in Baishuitai area of Yunnan Province on a monthly frequency for nearly 5 years (January 2018 to October 2022). We analyzed the temporal variations of stable isotopes of hydrogen and oxygen (δD and δ¹⁸O) compositions and trace element contents in the two types of water bodies to identify the recharge source and hydrogeochemical evolution process of Baishuitai spring water, and to reveal the source differences of trace elements in spring water and their indicative significance on climate and environment. The results showed as follows. (1) Values of stable isotope composition of rainwater in Baishuitai region of Yunnan had obvious seasonal variation characteristics—high in the dry season and low in the rainy season. This result was mainly affected by water vapor source and evaporation conditions. During the dry season, water vapor mainly came from the stable continental air mass, and the evaporation effect was strong, which resulted in the enrichment of D and ¹⁸O in the remaining water vapor mass. During the rainy season, multiple fractionation and condensation processes occurred when water vapor migrated from the sea to the land, due to the influence of the southwest monsoon and the southeast monsoon. D and ¹⁸O were severely scoured, thus making δD and δ¹⁸O light in rain during the precipitation process. (2) The stable isotopic compositions of hydrogen and oxygen in Baishuitai spring water were on or near the atmospheric precipitation line, indicating that the spring water was mainly supplied by atmospheric precipitation. During the infiltration of atmospheric precipitation into the zone of shallow circulation runoff, new and old water from different channels and fissure networks was continuously mixed to regulate and store hydrogen and oxygen isotopes in groundwater, resulting a much smaller variation amplitude of δD and δ¹⁸O in spring water than in rainfall. During the rainy season in 2018, 2019 and 2022, δD and δ¹⁸O in spring water witnessed a similar trend to δD and δ¹⁸O in rainwater with a lag of about one month, indicating that δD and δ¹⁸O in water evolved to some extent in underground runoff, so that δD and δ¹⁸O in spring water correctly inherited some of the characteristics of δD and δ¹⁸O in rainwater. The δD-δ¹⁸O scatter points of spring water in Baishuitai region all shifted to the area near the left side of the atmospheric precipitation line. This means that δ¹⁸O in spring water became lighter under the exchange of lighter oxygen isotopes with CO₂ gas from deep sources, while δD basically did not change, indicating that atmospheric precipitation was fully mixed with deep source CO₂ during the infiltration process. The smoothing effect of isotope regulation and storage generated by the mixing of old water, as well as the exchange of oxygen isotope with CO₂ from deep sources, indicated that the Baishuitai region contains a wide spring area, numerous underground passageways and fissures, and intricate karst features. (3) The trace elements in Baishuitai spring water show two types of dynamic change characteristics. Elements such as Ca, Mg, Sr, Ba, and Si constitute one category, mainly originating from the dissolution of surrounding rocks under karst water erosion. After entering the rainy season, the water–rock interaction was weakened by the dilution of rainfall. Concentrations of these elements decreased to varying degrees in the early rainy season, and increased in the late rainy season to the transition from the rainy season to the rainy and dry season, while these concentrations stayed stable or slightly fluctuated in the dry season. The decrease in precipitation promoted the precipitation of calcium carbonate caused by degassing, which increased the values of Mg/Ca, Sr/Ca and Ba/Ca. At the same time, water within the fractures between soil and bedrock was less disturbed by fresh water inputs. This reduction in the rate of water migration enhanced the interaction between water and rock, resulting in a preferential leaching of elements such as Sr and Ba. The consequent differential changes in the concentrations of these elements suggest that variations in their levels could be indicative of shifts in precipitation patterns. Elements like Fe, Al, and Mn constitute another category, primarily originating from the leaching effects of atmospheric precipitation on the overlying soil. The occurrence of peaks in these elements during the rainy season corresponds to periods of heavy annual precipitation, while peaks observed in the dry season may be associated with the pulse-like action triggered by a single instance of heavy precipitation.
- hydrogen and oxygen stable isotopes /
- trace element /
- spring water /
- travertine /
- Baishuitai of Yunnan

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图 1 a：云南白水台采样点分布图 b：泉水采样点实景图 c：雨水采样点实景图

Figure 1. a: Distribution of sampling points in Baishuitai of Yunnan; b: Reality images of sampling points of spring water; c: Reality images of sampling points of rainwater

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图 2 2018—2022年白水台地区雨水与S3号泉水氢氧稳定同位素动态变化趋势图

a. 丽江站站点月平均降水量 b. δD c. δ¹⁸O d. 氘盈余(d-excess)注：阴影部分代表雨季(5-10月)，2020年1月数据缺失是由于该月未采样。

Figure 2. Dynamic trend of hydrogen and oxygen stable isotopes of rainwater and S3 spring water in the Baishuitai region from 2018 to 2022

a. average monthly precipitation of Lijiang station b. δD c. δ¹⁸O d. deuterium excess (d-excess). Note: Shaded portion indicates the rainy season from May to October; the date of January, 2020 is absent because samples were not collected.

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图 3 云南白水台地区雨水、泉水δD-δ¹⁸O关系图

a.白水台雨水线与全球、昆明雨水线对比 b. 图(a)中方框部分放大图，箭头为泉水δD、δ¹⁸O相对于白水台雨水线的偏移方向

Figure 3. δD-δ¹⁸O relationship between rain water and spring water in Baishuitai, Yunnan Province

a. Comparison of Baishuitai rainwater line with global rainwater line and Kunming rainwater line; b is the enlarged picture of box portion in figure (a), and the arrow indicates the deviation direction of δD and δ¹⁸O of spring water relative to the rainwater line of Baishuitai.

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图 4 2018-2022年云南白水台S3号泉泉水微量元素动态变化趋势图

a. 丽江站站点月平均降水量 b. Ca c. Mg d. Sr e. Ba f. Si g. Na h. K i. Fe j. Mn k. Al，注：阴影部分代表雨季(5—10月) ，2020年1月数据缺失是由于该月未采样)

Figure 4. Dynamic trend of trace elements in spring water of S3 spring, Baishuitai, Yunnan, from 2018 to 2022

a. average monthly precipitation of Lijiang station; b. Ca; c. Mg; d. Sr; e. Ba; f. Si; g. Na; h. K; i. Fe; j. Mn; k. Al. Note: Shaded portion indicates the rainy season from May to October; the date of January, 2020 is absent because samples were not collected

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图 5 云南白水台地区地质剖面图（据刘再华等，2002改绘）

Figure 5. Geological profile of the Baishuitai area, Yunnan Province (modified in 2002 based on Liu Zaihua, etc.)

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图 6 云南白水台S3号泉泉水微量元素的系统聚类分析树状图

Figure 6. Tree diagram of systematic cluster analysis of trace elements in spring water of S3 spring in Baishuitai, Yunnan Province

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图 7 2018-2022年云南白水台S3号泉泉水微量元素比值动态变化趋势图

((a) Mg/Ca；(b)Sr/ Ca；(c) Ba/Ca；注：黄实线为雨/旱季平均值，阴影部分代表雨季(5-10月)，2020年1月数据缺失是由于该月未采样)

Figure 7. Dynamic trend of trace element ratio in S3 spring water in Baishuitai, Yunnan Province from 2018 to 2022

((a) Mg/Ca; (b)Sr/Ca; (c) Ba/Ca; Note: The yellow solid line is the average value in the rain/dry season; the shadowed portion indicates the rainy season from May to October; the data of January, 2020 is absent because smaples were not collected)

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表 1 2018-2022年云南白水台雨水和泉水中常微量元素浓度分布

Table 1. Concentration distribution of normal and trace elements in rainwater and spring water of Baishuitai, Yunnan, from 2018 to 2022

元素种类	雨水（n=21）				泉水（n=55）
元素种类	极小值	极大值	均值	变异系数	极小值	极大值	均值	变异系数
Ca/mg·L⁻¹	0.00	6.65	2.71	0.77	147.56	219.07	190.20	0.07
Mg/mg·L⁻¹	0.32	11.32	1.13	2.74	11.74	15.79	14.29	0.06
Na/mg·L⁻¹	0.12	10.38	0.67	3.17	4.03	6.28	5.22	0.10
Si/mg·L⁻¹	\	\	\	\	1.32	2.54	1.80	0.15
Sr/mg·L⁻¹	0.00	0.06	0.01	1.16	1.46	2.16	1.95	0.07
K/μg·L⁻¹	35.56	7 361.82	1 055.81	1.74	500.21	984.13	603.85	0.12
Fe/μg·L⁻¹	0.00	256.47	61.54	0.99	0.79	510.88	55.27	1.42
Ba/μg·L⁻¹	0.12	200.98	33.27	1.84	43.67	69.21	62.11	0.07
Al/μg·L⁻¹	5.32	184.24	52.59	0.89	0.00	126.57	19.39	0.96
Mn/μg·L⁻¹	0.42	29.31	7.27	1.05	0.28	26.73	2.55	1.57

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