非岩溶水和硫酸参与溶蚀对湘南地区地下河流域岩溶碳汇通量的影响

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黄奇波, 覃小群, 刘朋雨, 张连凯, 苏春田. 非岩溶水和硫酸参与溶蚀对湘南地区地下河流域岩溶碳汇通量的影响. 地球科学进展, 2017, 32(3): 307-318
Huang Qibo, Qin Xiaoqun, Liu Pengyu, Zhang Liankai, Su Chuntian. The Influence of Allogenic Water and Sulfuric Acid to Karst Carbon Sink in Karst Subterranean River in Southern Hu’nan. Advances in Earth Science, 2017, 32(3): 307-318 复制到剪切板

Doi:10.11867/j.issn.1001-8166.2017.03.0307
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非岩溶水和硫酸参与溶蚀对湘南地区地下河流域岩溶碳汇通量的影响

黄奇波^1,^2,³, 覃小群^2,^3,^*, 刘朋雨^2,³, 张连凯^2,³, 苏春田^1,^2,³

1.中国地质大学环境学院,湖北武汉 430074

2.中国地质科学院岩溶地质研究所, 广西桂林 541004

3.国土资源部广西岩溶动力学重点实验室,广西桂林 541004

*通信作者:覃小群(1961-),女,广西梧州人,研究员,主要从事岩溶水文地质研究.E-mail:qxq@karst.ac.cn

作者简介:黄奇波(1982-),男,江西萍乡人,副研究员,主要从事岩溶水文地质、岩溶环境与全球变化研究.E-mail:qbohuang@karst.ac.cn

基金:中国地质调查局地质调查项目“西江中下游岩溶峰林区1∶ 5万水文地质环境地质调查”(编号:121201107000150005); 国家自然科学基金项目“半干旱岩溶区溶蚀作用季节分异与影响机制”(编号:41302211)资助

摘要

研究非岩溶水和硫酸参与溶蚀对地下河流域岩溶碳汇通量的影响,有助于提高岩石风化碳汇通量估算精度,对于推进地质作用与全球气候变化研究意义重大。选取湘南北江上游武水河流域内4条典型地下河为对象,通过水化学对比分析,揭示硅酸盐岩风化对流域地下水化学的重要影响。运用Galy方法计算流域非岩溶地层中的硅酸盐岩风化消耗大气/土壤CO₂对岩石风化碳汇的重要贡献,并评价了H₂SO₄参与下碳汇通量的扣除比例。结果显示:①流域内有非岩溶地层的L01,L02地下河, Na⁺,K⁺和SiO₂浓度明显高于纯碳酸盐L03和L04地下河,非岩溶地层中的硅酸盐的风化对地下河水中K⁺,Na⁺,SiO₂浓度有一定贡献;② 4条地下河的[Ca²⁺+Mg²⁺]/[HCO₃^-]当量比值为1.05~1.15,[Ca²⁺+Mg²⁺]/[HCO₃^-+SO₄^2-]的当量比值为0.99~1.08,Ca²⁺+Mg²⁺相对于HCO₃^-过量,过量的Ca²⁺+Mg²⁺与SO₄^2-相平衡,证实硫酸参与流域碳酸盐岩的溶蚀;③L01和L02地下河岩石风化消耗的CO₂通量中非岩溶地层中的硅酸盐风化消耗所占比例分别为3.36%和2.22%,而L03和L04地下河中硅酸盐风化消耗比例小于0.50%,表明有非岩溶地层存在的地下河流域,其岩石风化消耗的CO₂通量中硅酸盐风化消耗占有一定比例;④在考虑硫酸参与碳酸盐岩溶蚀时,4条地下河的碳汇通量分别扣除4.84%,4.52%,6.20%和9.36%。

关键词: 地下河; 碳酸盐岩风化; 硅酸盐岩风化; 碳汇通量; 硫酸

中图分类号:P641.134 文献标志码:A 文章编号:1001-8166(2017)03-0307-12

The Influence of Allogenic Water and Sulfuric Acid to Karst Carbon Sink in Karst Subterranean River in Southern Hu’nan

Huang Qibo^1,^2,³, Qin Xiaoqun^2,³, Liu Pengyu^2,³, Zhang Liankai^2,³, Su Chuntian^1,^2,³

1.Environmental School,China University of Geosciences, Wuhan 430074, China

2.Institute of Karst Geology, Chinese Academy of Geological Sciences,Guilin 541004, China

3.Karst Laboratory of Karst Dynamics, Ministry of Land and Resources & Guangxi Zhuang Autonomous Region, Guilin 541004, China

*Corresponding author:Qin Xiaoqun(1961-), female, Wuzhou City, Guangxi Zhuang Autonomous Region, Professor. Research areas include karst geo-hydrology.E-mail:qxq@karst.ac.cn

First author:Huang Qibo(1982-), male, Pingxiang City, Jiangxi Province, Associate Professor. Research areas include karst geo-hydrology and Karst environment with global chang.E-mail:qbohuang@karst.ac.cn

Fund:Project supported by the China Geology Survey “Hydrogeological and environmental geological survey of 1∶ 50 000 in peak-forest karst area of the middle and lower reaches of the Xijiang River Basin” (No.121201107000150005); The National Natural Science Foundation of China “Seasonal different and influence mechanism of the dissolution in the semi-arid karst area”(No.41302211)

Abstract

Evaluating the impact of allogenic water and sulfuric acid on karst carbon sink not only helps to improve the accurate calculation of soil CO₂ uptake by rock weathering, but also obtains a complete understanding of the global carbon cycle. Groundwater samples were collected from four karst subterranean rivers watershed within different lithology strata in Wushui Basin, upstream of Beijiang Basin, Hunan Province, for revealing the important impact of silicate weathering on hydrochemistry of groundwater. To estimate the contribution of soil CO₂ uptake by silicate weathering to CO₂ uptake by rock weathering, the Galy model was employed in this article. The important impact of sulfuric acid on CO₂ uptake by carbonate weathering resulting from the substitution of carbonic acid by protons from sulfuric acid was investigated. Our results showed that the concentration of Na⁺, K⁺ and SiO₂ in L01,L02 subterranean river with silicate strata in watershed were higher than that in L03,L04 subterranean river without silicate strata in watershed, which implied that the contribution of silicate weathering to Na⁺,K⁺ and SiO₂ was very important in watershed within silicate strata . The changeable equivalent ratio between (Ca²⁺+Mg²⁺) and HCO₃^- was 1.05 to 1.15, and the value of [Ca²⁺+Mg²⁺]/[HCO₃^-+SO₄^2-] was 0.99 to 1.08. The concentrations of Ca²⁺ and Mg²⁺ exceeded the equivalent concentrations of HC₃^-, and the excess of Ca²⁺ and Mg²⁺cations were compensated by SO₄^2-, which suggested that sulfuric acid has an important influence on carbonate dissolution. The contribution of soil CO₂uptake by silicate weathering to CO₂ consumption in L01 and L02 subterranean river were 3.36% and 2.22%, respectively, whereas the contribution in L03, L04 subterranean river were less than 0.50%, indicating that the contribution of soil CO₂ uptake by silicate weathering was important in the subterranean river basin within silicate strata. Due to the contributions made by sulfuric acid, the CO₂ consumption in four subterranean rivers decreased by 4.84%, 4.52%, 6.20%, 9.36%, respectively.

Keyword: Karst subterranean rivers; Carbonate weathering; Silicate weathering; CO2 consumption flux; Sulfuric acid.

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岩石化学风化能够回收大气/土壤中的CO₂产生碳汇效应, 积极参与全球碳循环^[1~4]。由于方解石快速的溶解反应动力学机制, 碳酸盐岩风化碳汇是岩石风化碳汇的主要组成部分^[5~9]。碳酸盐岩溶蚀形成的岩溶水中 HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 有一半来源于大气/土壤 CO₂, 一半来源于碳酸盐岩^{[10, 11]}, 计算岩溶碳汇通量较为通用的方法是根据地下水流量和水中HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 浓度的水化学径流法^[12~14]。完整的岩溶流域内经常存在非岩溶地层或夹层^[15], 流经非岩溶地层或夹层的非岩溶水补给岩溶水的同时, 也带来了一部分HC $\begin{matrix} O_{3}^{-} \end{matrix}$ , 该部分HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 是碳酸溶蚀硅酸盐岩所产生的, 均源于大气/土壤 C $\begin{matrix} {O_{2}}^{[16, 17]} \end{matrix}$ , 造成流域出口岩溶地下水中HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 来源于大气/土壤 CO₂的量大于50%^[15]。运用水化学径流法计算岩溶碳汇通量时由于忽略了非岩溶水带来的HC $\begin{matrix} O_{3}^{-} \end{matrix}$ , 这可能会造成碳汇效应被低估^[18]。另一方面, 西南岩溶区大气酸沉降较为严重, 硫酸(H₂SO₄)参与碳酸盐岩溶蚀已被大量的研究所证实^[19~22], 硫酸参与碳酸盐岩的溶蚀并不消耗大气或土壤中的CO₂, 但会增加碳酸盐岩的溶蚀量并增加水体中HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 的含量^{[23, 24]}, 如何扣除地下水中来源于硫酸溶蚀成因的HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 也成为准确计算岩溶碳汇通量的关键^[25~27]。

Galy方法是Galy和France-Lanord用来估算Ganges-Brahmaputra流域的侵蚀速率和岩石风化消耗大气/土壤CO₂通量的重要方法^[28]。该方法将河流水化学离子组分归因于不同岩石端元的溶解, 根据河水中元素比值关系, 运用水化学计量方法来估算不同岩石端员风化对河水溶质的贡献。在我国云贵高原的乌江流域、南盘江、北盘江流域, 韩贵琳等^[29]和刘丛强等^[30]运用Galy方法计算了硅酸盐岩和碳酸盐岩风化速率及消耗大气/土壤CO₂通量, 并评估了硫酸参与碳酸盐岩溶蚀的比例及对岩溶碳汇效应的影响程度。覃小群等^[31]运用Galy方法计算出珠江流域平均岩石风化速率和由岩石风化作用引起的大气CO₂消耗通量, 并证实由于碳酸盐岩风化溶蚀速率是硅酸盐岩的10.8 倍, 碳酸盐岩风化是流域碳汇过程及效应的主体。张连凯等^[32]利用Galy方法研究了长江流域岩石化学风化与大气CO₂消耗, 并估算了在考虑硫酸参与碳酸盐岩溶蚀时, 流域岩石风化碳汇通量应扣除约14%。然而, 将Galy方法用于计算典型地下河流域岩石风化碳汇通量的文献十分少见。

本研究选取湘南北江上游武水河流域内具有不同岩性条件的4条典型地下河为对象, 通过水化学组分对比分析, 揭示非岩溶地层中的硅酸盐岩风化对地下河水化学组成的重要影响。运用Galy方法计算岩溶流域内非岩溶地层中的硅酸盐岩风化消耗大气/土壤CO₂通量对岩石风化碳汇通量的重要贡献, 并评价在硫酸的参与下, 流域碳汇通量的扣除比例。本研究为存在非岩溶水补给和外源酸参与溶蚀的地下河流域如何准确计算碳汇通量提供参考, 有助于提高岩石风化碳汇通量估算精度, 对于推进地质作用与全球气候变化研究意义重大。

1 研究区概况

研究区位于湖南省南部, 为长江流域与珠江流域分水岭地带, 归属珠江水系北江流域, 属亚热带季风性湿润气候区, 因南北气流受南岭山脉影响, 形成了气候温暖、四季分明、热量充足、雨水集中、春暖多变、夏秋多旱、严寒期短、暑期热长的气候特征。区内降水具有时空分布不均、年际变化大、雨量集中、前多而涝、后少而旱的特征, 上半年占全年降雨量的63.2%, 下半年为36.8%, 降水主要集中在4~6月, 占全年降水量的43.5%。湖南省是全国严重的酸雨污染区之一, 2004 年湖南省14 个城市的降水监测结果显示, pH≤ 5.6 的酸雨样占76.4%, pH≤ 4.5 的酸雨样占39.4%, 酸雨中硝酸的含量不及硫酸的10%, 主要为硫酸型酸雨^[33]。

研究区为基岩山区, 主要出露泥盆系的棋子桥组(Dq)、锡矿山组(Dx)、孟公坳组(Dm), 石炭系的马栏边组(Cm)、天鹅坪组(Ct)、石凳子组(Cs)、测水组(Cc)、梓门桥组(Cz), 二叠系的栖霞组(Pq)、孤峰组(Pg), 其中泥盆系的孟公坳组(Dm)、石炭系的测水组(Cc)及二叠系的孤峰组(Pg)岩性为页岩和砂页岩, 其他地层的岩性为灰岩夹少量白云岩, 碳酸盐岩面积占80%以上(图1)。山体海拔850~900 m, 地貌特征是北高南低、西高东低, 地表岩溶形态呈丘陵和洼地组合, 裸露基岩表层石芽、溶沟、溶槽广泛发育; 洼地底部浅平, 常有漏斗及落水洞发育, 以丘顶面和坡面发育较多, 为接受降水补给的通道; 受南北向断层和向斜构造控制, 地下河发育主要呈南北向和东西向; 南北向地下河规模大, 管道发育长10~12 km; 东西向地下河向东部金江河排泄, 规模较小, 长度1~3 km(图1)。

选取流域内的L01(邓家地下河)、L02(百里地下河)、L03(大泉地下河)、L04(夏家地下河)为研究对象(图1), 4条地下河的岩性及流域面积由野外实际调查圈定, 流量为建观测站后的实测流量, 采取每5天测1次流量, 遇雨天加密到1天1次的观测方法, 观测期为2015年5月至2016年6月。流域内有非岩溶地层出露的地下河为L01和L02, 其出露面积分别占流域面积比例的17.33%和13.00%, 而L03和L04地下河流域内均为碳酸盐岩地层。4条地下河的流量季节动态特征和岩性条件见表1。

2 研究方法

在2015年3月、6月、8月、11月对4条地下河进行了现场和取样回实验室分析测试。主要采用仪器现场测试、现场滴定和样品室内测试相结合的研究方法。野外现场利用德国WTW公司生产pH/Cond340i测试仪测试各样点水的pH值和水温, 分辨率分别为0.1 pH和 0.1 ℃; 使用德国Aquamerck公司生产的碱度计和硬度计测定河水的HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 和Ca²⁺质量浓度, 分辨率分别为6 mg/L和1 mg/L。样品在现场进行过滤(< 0.22 μ m Millipore滤膜)后再装入100 mL聚乙烯瓶中。用于阳离子(Ca²⁺, Mg²⁺, K⁺和Na⁺)测定的样品立即加入超纯盐酸酸化至 pH< 2, 密封于暗箱中保存; 用于测定阴离子的样品直接密封于暗箱中保存。样品带回实验室后, 用原子吸收光谱法 (Atomic Absorption Spectroscopy, AAS)测定阳离子(Mg²⁺, K⁺和Na⁺)含量。阴离子含量 (S $\begin{matrix} O_{4}^{2 +} \end{matrix}$ , Cl^-和N $\begin{matrix} O_{3}^{-} \end{matrix}$ )用高效液相色谱(HPLC)仪测定。阴阳离子电荷平衡之差< 5%。

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	图1 研究区水地质图Fig.1 Gological sketch map of study area

采用钼酸盐光度法测量(硅钼黄法)水体中的SiO₂浓度, 其原理:在酸性环境中, 钼酸铵与水中SiO反应, 生成黄色可溶的硅钼杂多酸络合物, 在一定深度范围内, 其黄色与SiO₂的浓度成正比, 通过测定其吸光度并与硅标准曲线对照可求得SiO₂浓度。测试精度为0.50 mg/L。测试结果如表2所示。

表1 4条地下河的流量和岩性特征 Table 1 The characteristic of lithology and discharge in four kart subterranean rivers

表2 4条地下河不同月主要离子组成 Table 2 Major ionic concentrations in different seasons from four karst subterranean rivers

名称	时间	T/ ℃	pH	Ca²⁺	Mg²⁺	Na⁺	K⁺	HC $\begin{matrix} O_{3}^{-} \end{matrix}$	Cl^-	S $\begin{matrix} O_{4}^{2 -} \end{matrix}$	N $\begin{matrix} O_{3}^{-} \end{matrix}$		TDS	SI_C	pCO₂/ Pa	NICB 含量/%	Ca²⁺ 含量/%	Mg²⁺ 含量/%	HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 含量/%	S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 含量/%
名称	时间	T/ ℃	pH	/(mmol/L)								/(mg/L)		SI_C	pCO₂/ Pa	NICB 含量/%	Ca²⁺ 含量/%	Mg²⁺ 含量/%	HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 含量/%	S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 含量/%
L01(邓家地下河)	3月	17.5	7.63	1.823	0.731	0.070	0.027	4.844	0.079	0.146	0.091	5.40	257.72	0.39	6 026	-0.96	68.8	27.6	93.9	2.8
	6月	17.8	7.43	1.778	0.910	0.090	0.039	4.876	0.080	0.115	0.114	5.31	259.21	0.18	9 661	1.90	63.1	32.3	94.0	2.2
	8月	18.0	7.15	1.718	0.864	0.085	0.052	4.530	0.104	0.132	0.130	5.64	247.99	-0.14	17 258	2.63	63.2	31.8	92.5	2.7
	11月	17.6	7.21	1.566	0.876	0.062	0.027	4.386	0.054	0.095	0.092	5.74	230.97	-0.13	14 488	2.59	61.8	34.6	94.8	2.1
	平均值	17.7	7.36	1.721	0.845	0.077	0.037	4.659	0.079	0.122	0.107	5.52	248.97	0.08	11 858	1.54	64.2	31.6	93.8	2.5
L02(百里地下河)	3月	17.2	7.65	1.783	0.485	0.074	0.012	4.290	0.050	0.118	0.055	5.21	229.14	0.35	5 105	-0.09	75.7	20.6	95.1	2.6
	6月	17.5	7.24	1.768	0.534	0.037	0.022	4.342	0.041	0.073	0.057	6.16	226.11	0.05	6 486	0.84	74.9	22.6	96.2	1.6
	8月	17.7	7.32	1.798	0.306	0.052	0.039	3.838	0.078	0.140	0.085	6.07	215.30	-0.05	13 428	0.22	81.9	13.9	92.7	3.4
	11月	17.2	7.47	1.571	0.353	0.044	0.019	3.553	0.041	0.106	0.065	5.29	193.00	-0.01	9 931	0.51	79.1	17.8	94.4	2.8
	平均值	17.4	7.42	1.730	0.420	0.052	0.023	4.006	0.052	0.109	0.065	5.68	215.89	0.09	8 738	0.37	77.9	18.7	94.6	2.6
L03(大泉地下河)	3月	18.0	7.73	2.049	0.177	0.023	0.010	4.114	0.056	0.133	0.099	4.74	227.39	0.49	4 111	-0.57	90.7	7.8	93.5	3.0
	6月	18.1	7.57	2.033	0.167	0.025	0.019	3.975	0.046	0.128	0.104	5.23	221.74	0.31	5 768	0.73	90.6	7.4	93.5	3.0
	8月	18.5	6.99	1.912	0.173	0.051	0.024	3.618	0.066	0.123	0.112	5.46	207.30	-0.32	20 277	2.44	88.5	8.0	92.3	3.1
	11月	18.0	7.14	2.089	0.184	0.038	0.014	4.108	0.041	0.111	0.076	5.30	226.81	-0.09	16 106	1.66	89.8	7.9	94.7	2.6
	平均值	18.2	7.36	2.021	0.175	0.034	0.017	3.954	0.052	0.124	0.098	5.18	220.81	0.10	11 566	1.07	89.9	7.8	93.5	2.9
L04(夏家地下河)	3月	17.7	7.87	1.702	0.399	0.023	0.011	3.648	0.052	0.208	0.111	4.12	211.68	0.49	2 630	0.12	79.7	18.7	90.8	5.2
	6月	18.0	7.73	1.785	0.398	0.026	0.019	3.875	0.042	0.181	0.108	5.48	219.30	0.40	3 873	0.28	80.1	17.8	92.1	4.3
	8月	18.1	7.65	1.867	0.446	0.038	0.019	4.090	0.073	0.201	0.132	5.08	233.60	0.36	4 920	-0.13	78.7	18.8	91.0	4.5
	11月	17.8	7.60	1.806	0.409	0.036	0.013	3.942	0.037	0.148	0.087	5.14	219.06	0.28	5 321	1.34	79.8	18.1	93.6	3.5
	平均值	17.9	7.71	1.790	0.413	0.031	0.016	3.888	0.051	0.184	0.109	4.96	220.91	0.38	4 186	0.40	79.6	18.4	91.9	4.4

注:NICB为标准无机离子平衡, NICB=(TZ⁺-TZ^-)× 100/(TZ⁺+TZ^-)

表2 4条地下河不同月主要离子组成 Table 2 Major ionic concentrations in different seasons from four karst subterranean rivers

	Figure Option View Download New Window
	图2 主要离子Piper图Fig.2 Piper diagram of ionic concentration in the samplers

3 结果

从表2可以看出, 4条地下河不同月份的pH值变化范围为6.99~7.87, 呈弱碱性, 显示出典型的岩溶地下水化学特征^[34]。4条地下河6月和8月的水温大于3月和11月, 年均水温分别为17.7 ℃, 18.2 ℃, 17.9 ℃和17.4 ℃, 与当地年均气温基本一致。总体上, 4条地下河水温的季节动态变幅比当地气温的变幅小, 反映出岩溶地下水水温既受外部气温控制又对外部温度具有调蓄作用。4条地下河不同月份总溶解性固体(Total Dissolved Solids, TDS)含量的变化范围为193.00~259.21 mg/L, 平均分别为248.97, 215.89, 220.81, 220.91 mg/L, 远高于世界河流平均值(69 mg/L)^[35], 显示了岩溶地下河流域剧烈的岩石化学侵蚀作用^[36]。

由水化学数据作出Piper三线图(图2), 可知4条地下河不同月份均以Ca²⁺, Mg²⁺和HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 为主要离子, 其他阴阳离子相对较少。水化学类型为低矿化度HCO₃-Ca型水, 具有典型的“ 高钙富碳” 岩溶水特征^[37]。阳离子中, 4条地下河均是Ca²⁺所占比重最高, Ca²⁺占阳离子总量的62.8%~90.7%; Mg²⁺次之, 占总量的7.4%~34.6%; K⁺和Na⁺离子含量很低, 两者仅占阳离子总量的1.5%~5.1%。阴离子中, 4条地下河均是HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 所占比重最高, 占阴离子总量的90.8%~96.2%; 其次为S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ , 占总量的1.6%~5.2%; Cl^-, N $\begin{matrix} O_{3}^{-} \end{matrix}$ 含量低, 大多低于0.1 mmol/L, 因此本研究不考虑HNO₃对碳酸盐岩的风化作用。4条地下河不同月份中的SiO₂含量范围为4.12~7.16 mg/L, 平均浓度分别为 5.52, 6.68, 5.18, 4.96 mg/L。

利用FREECH软件计算出方解石饱和指数(SIc)和水体二氧化碳分压(pCO₂)(表1)。发现4条地下河河水的SIc具有季节动态, 3月和6月SIc较大, 8月和11月较小, 其中L01, L02和L03地下河的SIc在3月和6月大于0, 8月和11月均小于0。4条地下河不同月份水体pCO₂的变化范围为2 630~20 277 Pa, 显著高于大气二氧化碳分压(32 Pa), 这缘于大气降水下渗过程中溶解了更多的土壤CO₂, 使岩溶地下水具有较高的HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 含量和水体pC $\begin{matrix} {O_{2}}^{[27, 38, 39]} \end{matrix}$ 。从图3可以看出, 4条地下河不同月份SIc和水体pCO₂具有较强的负相关关系(R²=0.89, p< 0.05), 意味着二者的变化均受同一个因素即水中CO₂浓度的控制^[40]。

4 讨论

4.1 岩石风化端元鉴别

4.1.1 硅酸盐岩风化

4条地下河均是以大气降水为补给来源, 大气降水对岩溶地下水化学组分有一定影响。大气降水对地下水化学影响的研究, 通常选择 Cl^-作为参照元素, 它是雨水中的主要成分且来源相对简单, 在水的循环过程中 Cl^-的行为也相对保持稳定, 一般认为其主要通过降雨从海洋输送而来, 受人类活动的贡献相对较少^[41]。4条地下河不同月份中Cl^-和K⁺, Na⁺离子所占阴阳离子比例均小于10%, Na⁺与Cl^-比值(Na⁺/Cl^-)范围为0.41~1.47, 平均值为0.83, 接近标准海水的Na⁺/Cl^-值(0.86)^[42]; 且从图4可以看出, K⁺, Na⁺与Cl^-存在一定的相关性, 意味着K⁺和Na⁺的来源与Cl^-一致, 大部分来源于大气降水, 人类活动对4条地下河的K⁺和Na⁺影响较小; 这可从4条地下河不同月份水中S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 和N $\begin{matrix} O_{3}^{-} \end{matrix}$ 离子的浓度低得到证实。另一方面, 在0.05检测水平下, Na⁺与Cl^-相关系数R²小于0.5, K⁺与Cl^-的相关系数R²小于0.7, 这意味着K⁺和Na⁺的来源与Cl^-又有所差异, 除大气降雨外, 应该还有其他来源。大量的研究结果显示, K⁺和Na⁺可来源于非岩溶地层中的硅酸盐岩矿物的风化^[43], 如Na⁺可来源于石盐的溶解和硅酸盐风化; K⁺可来源于钾长石和云母的风化^[42]。研究区L01和L02地下河流域内均有一定比例的非岩溶地层出露(表1), 其Na⁺(平均值为0.077 和0.052 mmol/L)和K⁺浓度(平均值为0.037 和0.023 mmol/L)明显高于纯碳酸盐岩L03和L04地下河(平均值为0.034, 0.031和0.017, 0.016 mmol/L)(表2), 表明地下河流域内非岩溶地层中硅酸盐的风化对地下河的K⁺和Na⁺具有一定贡献, 由于L01地下河流域中非岩溶地层的出露面积比例大于L02, 其K⁺和Na⁺浓度也明显高于L02。

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	图3 地下河水饱和指数(SI_C)与pCO₂的关系Fig.3 The correlation between SI_C and pCO₂ in karst subterranean river

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	图4 4条地下河中Cl^-与Na⁺的关系(a)和与K⁺的关系(b)Fig.4 Variationsof Cl^- vs. Na⁺ (a)and vs. K⁺ (b) in four karst subterranean river

地下水中SiO₂主要来源于非岩溶地层中的硅酸盐的风化^[41]。4条地下河不同月份的SiO₂的含量与珠江^[31]、乌江^[26]及长江主河道^[32]水体相比, 明显偏小, 主要原因是4条地下河流域主要为碳酸盐岩, 非岩溶地层比例最高的L01也不超过18%, 而珠江流域、乌江流域和长江流域非岩溶地层出露面积均大于50%。另一方面, 研究区Cl^-主要来源于大气降水, 而K⁺和Na⁺除大气降雨外, 还来源于非岩溶地层中硅酸盐岩矿物的风化, 因此, 可用(Na⁺+K⁺)/(Na⁺+K⁺+Cl^-)值的大小来指示非岩溶地层中硅酸盐岩矿物风化对地下水贡献大小^[34]。从图5可以看出, 4条地下河SiO₂含量与(Na⁺+K⁺)/(Na⁺+K⁺+Cl^-)具有较好的正相关关系(R²=0.42, p< 0.05), 这是由于非岩溶地层中的硅酸盐岩矿物的风化使地下水中SiO₂含量与(Na⁺+K⁺)/(Na⁺+K⁺+Cl^-)同步增加, 进一步证实了流域内非岩溶地层中硅酸盐岩矿物的风化对地下河的K⁺, Na⁺, SiO₂具有一定贡献的认识。由于L01和L02地下河流域内有一定面积的非岩溶地层出露, 其SiO₂的平均浓度(分别为5.52和5.68 mg/L)高于纯碳酸盐岩的L03和L04地下河流域(5.18和4.96 mg/L)。

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	图5 SiO₂含量与(Na⁺+K⁺)/(Na⁺+K⁺+Cl^-)变化关系Fig.5 Variations of SiO₂ vs. (Na⁺+K⁺)/(Na⁺+K⁺+Cl^-) in karst subterranean river

4.1.2 碳酸盐岩风化

Ca²⁺, Mg²⁺和HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 在4条地下河的阴阳离子中占有绝对优势, 碳酸盐岩的溶蚀对地下水化学组分具有控制作用^[44]。开放的岩溶动力系统中, CO₂是岩溶作用发生的重要驱动力^[45], CO₂进入岩溶动力系统促进碳酸盐岩的溶解, 表现为地下水中Ca²⁺, HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 浓度和水体pCO₂增加, SIc减少。反之, 若CO₂从系统逸出, 将发生碳酸盐岩的沉积, 水中Ca²⁺, HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 浓度和水体pCO₂减少, SIc增加。因此, 通常情况下地下水中SIc和水体pCO₂具有负相关关系^[40], 图3很好地证实了这一点。从季节动态看, 4条地下河SIc的平均值和水体pCO₂平均值也具有很强的对应关系(图6)。3月气温低, 降雨稀少, 土壤覆被的生产力和生物量相对较小, 土壤有机质含量较低, 土壤微生物含量较少, 土壤有机质分解产生CO₂浓度低, 造成降雨下渗吸收的CO₂含量少, 地下水的pCO₂低, 水的侵蚀性低, SIc高; 6月随着气温回升, 降雨量增大, 土壤微生物活沃, 土壤覆被的生产力和生物量增加, 土壤有机质含量增高, 土壤CO₂浓度升高, 地下水下渗能够吸收较多的土壤CO₂, 水体pCO₂增加, 对碳酸盐岩的溶蚀能力增加, SIc减小。8月气温最高, 生物活动最强, 地下水中pCO₂达到最大, SIc最低; 11月随着气温回落, 生物活动减弱, 地下水中pCO₂减小, SIc增加。

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	图6 地下水SIc和pCO₂季节动态Fig.6 Temporal change of SIc and pCO₂ in karst subterranean river

4.1.3 人为活动输入

人为活动产物可以通过废物直接排放和通过大气输入这2种途径输入水体^[44]。其中, 以工业活动和农业活动的影响最为显著。地下水中N $\begin{matrix} O_{3}^{-} \end{matrix}$ 主要来源于农业活动, 如大气输入、农肥、人畜的排泄物和“ 三废” ^[37], 而S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 多来自于大气酸沉降和工矿业活动^[46], 因此, 一般情况下, 水中的 N $\begin{matrix} O_{3}^{-} \end{matrix}$ 和 S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 浓度的变化主要反映来自农业活动和工业活动的影响。

4条地下河N $\begin{matrix} O_{3}^{-} \end{matrix}$ 浓度为0.055~0.132 mmol/L, 平均值分别为0.107, 0.065, 0.098, 0.109 mmol/L, S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 浓度为0.073~0.208 mmol/L, 平均值分别为0.122, 0.109, 0.124, 0.184 mmol/L。N $\begin{matrix} O_{3}^{-} \end{matrix}$ 和 S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 浓度远小于受酸雨和工业活动影响较大的乌江流域地表水和地下水^[26], 也小于人类活动频繁的长江流域主河道水体^[32]。另外, 所有样点的N $\begin{matrix} O_{3}^{-} \end{matrix}$ /Cl^-与S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ /Cl^-具有较好的相关性(相关系数R²=0.69, p< 0.01)(图7), 其取值范围分别为1.1~2.6和 1.3~4.3, 也明显小于乌江上游段地表水体中的N $\begin{matrix} O_{3}^{-} \end{matrix}$ /Cl^-与S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ /Cl^-值^[44], 表明4条地下河受农业和工业活动影响较轻。这与野外调查基本吻合, 4条地下河补给区为海拔850~900 m一级岩溶峰丛顶面, 岩溶发育, 以盲谷、落水洞发育较好(图1), 溶蚀洼地呈深盆状。人口相对稀少, 只在少量的洼地中种植玉米、花生, 因此人类生产、生活对地下水的影响有限。但研究区位于湖南南部, 湖南是受严重的酸雨污染区之一, 酸雨发生频率高, 但不同季节又存在明显差异的酸雨频率^[47], 这可能是引起研究区4条地下河中不同季节S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 差异的主要原因。

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	图7 4条地下河中N $\begin{matrix} O_{3}^{-} \end{matrix}$ /Cl^-与S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ /Cl^-的关系Fig.7 Four variations of N $\begin{matrix} O_{3}^{-} \end{matrix}$ /Cl^- vs. S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ /Cl^-in four karst subterranean river

4.2 H₂SO₄参与碳酸盐岩溶蚀

根据H₂CO₃风化碳酸盐岩的方程^[13]:

Ca_(1-_x₎Mg_xCO₃+CO₂+H₂O =(1-x)Ca²⁺+xMg²⁺+2HC $\begin{matrix} O_{3}^{-} \end{matrix}$

仅有H₂CO₃参与岩溶作用时, 溶蚀产物主要为Ca²⁺, Mg²⁺, HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 。此时, [Ca²⁺+Mg²⁺]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ ]的当量比值为1, [S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ ]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ ]的当量比值为0。实测4条地下河的[Ca²⁺+Mg²⁺]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ ]当量比值为1.05~1.15, 表明Ca²⁺+Mg²⁺相对于HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 过量, 除HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 外还有其他阴离子来平衡Ca²⁺+Mg²⁺。图8表示了4条地下河中[Ca²⁺+Mg²⁺]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ +S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ ]的当量比值关系, 所有样品的[Ca²⁺+Mg²⁺]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ +S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ ]的当量比值为0.99~1.08, 平均值为1.04, 说明地下水中多余的Ca²⁺ 和Mg²⁺ 应当是S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 离子来加以平衡的, 进而说明4条地下河中, 除了H₂CO₃参与碳酸盐岩的侵蚀以外, H₂SO₄也对碳酸盐岩的风化过程产生作用。

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	图8 地下河Ca²⁺+Mg²⁺与HC $\begin{matrix} O_{3}^{-} \end{matrix}$ + S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 关系Fig.8 Ca²⁺+Mg²⁺ vs.HC $\begin{matrix} O_{3}^{-} \end{matrix}$ + S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ in karst subterranean river

另一方面, 当H₂SO₄+H₂CO₃共同风化碳酸盐时, 溶蚀方程可表示为^[31]:3Ca_(1-_x₎Mg_xCO₃+ H₂SO₄+H₂CO₃= 3(1-x)Ca²⁺+3xMg²⁺+S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ +4HC $\begin{matrix} O_{3}^{-} \end{matrix}$ , 溶蚀产物主要为Ca²⁺, Mg²⁺, HC $\begin{matrix} O_{3}^{-} \end{matrix}$ , S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 。此时, [Ca²⁺+Mg²⁺]/HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 的当量比为1.5, [S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ ]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ ]的当量比为0.5。图9显示, 4条地下河均分布于H₂CO₃和H₂SO₄+H₂CO₃溶蚀碳酸盐岩2个端元组成之间, 说明除H₂CO₃外, H₂SO₄也参与了流域岩石化学风化过程。但所有样点更靠近H₂CO₃风化端元一侧, 意味着4条地下河主要受H₂CO₃风化控制, H₂SO₄风化贡献有限。

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图9 [Ca²⁺+Mg²⁺]/[HC

\begin{matrix} O_{3}^{-} \end{matrix}

]与[S

\begin{matrix} O_{4}^{2 -} \end{matrix}

]/[HC

\begin{matrix} O_{3}^{-} \end{matrix}

]的当量比值关系Fig.9 Equivalent ratios of [ Ca²⁺+ Mg²⁺]/[ HC

\begin{matrix} O_{3}^{-} \end{matrix}

] vs.[ S

\begin{matrix} O_{4}^{2 -} \end{matrix}

] /[ HC

\begin{matrix} O_{3}^{-} \end{matrix}

] in karst subterranean rivers

4.3 不同端元风化贡献比例及CO₂消耗通量

由以上分析可知, 4条地下河既受非岩溶地层中的硅酸盐岩风化影响, 又受H₂SO₄溶蚀的控制, 本研究利用地下河不同季度的流量(表1)和水化学数据(表2), 根据地下河元素比值之间的关系, 采用Galy 的模型^[28], 并运用参考文献[31]中的公式(1)~(16)计算出4 条地下河中碳酸盐岩和非岩溶地层中硅酸盐岩风化消耗的CO₂通量, 计算结果如表3所示。

从表3可以看出, 4条地下河岩石风化消耗的CO₂通量中硅酸盐岩风化消耗所占比例最大的为 L01地下河, 其硅酸盐岩风化消耗通量为27.93× 10³ mmol/(km²· a), 占岩石风化CO₂消耗通量(815.72× 10³ mmol/(km²· a))的3.36%; 其次为L02地下河, 其硅酸盐岩风化消耗通量为16.13× 10³ mmol/(km²· a), 占岩石风化CO₂消耗通量(727.78× 10³ mmol/(km²· a)) 的2.22%。最小为L03和L04地下河, 硅酸盐岩风化消耗通量分别为4.55× 10³ mmol/(km²· a)和2.81× 10³ mmol/(km²· a), 分别占岩石风化CO₂消耗通量(1 109.09× 10³ mmol/(km²· a)和859.27× 10³ mmol/(km²· a))的0.41%和0.33%; 可见, 非岩溶地层中的硅酸盐岩风化消耗CO₂通量和贡献比例大小受流域内非岩溶地层面积比例控制; 由于L01地下河流域内非岩溶地层面积比例最大, 为17.33%; 其次为L02, 非岩溶地层面积比例为13.00%; 2条地下河中硅酸盐风化消耗CO₂通量所占比例大于2%。而L03和L04地下河流域内由于没有非岩溶地层, 其硅酸盐风化消耗CO₂通量所占比例均小于0.5%。

仅考虑碳酸溶蚀作用时, L01, L02, L03和L04地下河岩石风化(碳酸盐岩和硅酸盐岩)消耗CO₂速率分别为857.17× 10³, 762.26× 10³, 1 182.43× 10³和947.98× 10³ mol/(km²· a); 在硫酸与碳酸共同作用下, 4条地下河岩石风化吸收CO₂速率分别为815.72× 10³, 727.78× 10³, 1 109.09× 10³, 859.27× 10³ mol/(km²· a)。可见在硫酸的参与下, 岩石风化消耗的CO₂通量降低。在考虑硫酸参与碳酸盐岩溶蚀时, 4条地下河的碳汇通量分别扣除4.84%, 4.52%, 6.20%, 9.36%。但总体上, 4条地下河受硫酸影响较小, 其扣除的比例均小于10%。刘丛强等^[30]的研究结果显示在硫酸参与下, 西南地区岩溶碳汇通量应扣除33%, 本研究的扣除比例明显小于该值, 这缘于本研究中的4条地下河流域受人类活动影响较小。

表3 4条地下河岩石风化CO₂通量计算结果 Table 3 CO₂consumption flux by rock weathering in four karst subterranean rivers

5 结论

流域内有非岩溶地层分布的L01和L02地下河其Na⁺ , K⁺ , SiO₂浓度高于流域内为纯碳酸盐岩地层的L03和L04地下河, 地下河流域内非岩溶地层中硅酸盐的风化对地下河的K⁺, Na⁺, SiO₂有一定贡献。4条地下河的[Ca²⁺+Mg²⁺]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ ]当量比值为1.05~1.15, [Ca²⁺+Mg²⁺]/[HC $\begin{matrix} O_{3}^{-} \end{matrix}$ +S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ ]的当量比值为0.99~1.08, 表明Ca²⁺+Mg²⁺相对于HC $\begin{matrix} O_{3}^{-} \end{matrix}$ 过量, 过量的Ca²⁺+Mg²⁺与S $\begin{matrix} O_{4}^{2 -} \end{matrix}$ 相平衡, 证实硫酸参与流域碳酸盐岩的溶蚀。

L01和L02地下河岩石风化消耗的CO₂通量中非岩溶地层中的硅酸盐风化消耗所占比例分别为3.36%和2.22%, 而L03和L04地下河中硅酸盐风化消耗比例小于0.50%。有非岩溶地层存在的地下河流域, 其硅酸盐风化消耗CO₂通量对岩石风化碳汇通量有一定贡献, 且贡献比例大小受流域内出露的非岩溶地层面积比例大小控制。在考虑硫酸参与碳酸盐岩溶蚀时, 4条地下河的碳汇通量分别扣除4.84%, 4.52%, 6.20%, 9.36%。证实硫酸参与岩石风化过程, 并减少岩石风化碳汇通量。

The authors have declared that no competing interests exist.

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. 2014, 29(12):1 333-1 340 DOI:doi:10.11867/j.issn.1001-8166.2014.12.1333

Research progresses and prospect of chimney effect about carbon cycle in the Karst cave system

喀斯特洞穴系统碳循环的烟囱效应研究现状及展望

Luo Weijun , Wang Shijie , Liu Xiuming.

罗维均, 王世杰, 刘秀明

对全球碳循环的系统研究已有几十年的历史,至今已取得很多重要成果,但对占整个地球陆地面积约10％的喀斯特地区碳循环的研究却在近10 ～ 20年来才逐渐受到重视.近年来的研究表明,岩溶作用对全球碳循环具有重要影响.目前,科学家们对影响喀斯特地区碳循环的各种因素有了较为全面系统的认识,并对碳源或碳汇量进行了估算.然而,与非喀斯特地区不同,喀斯特地区普遍发育着大小和形态各异的溶洞/裂隙,为喀斯特地区地—气交换增加了一个通道(窗口),其在喀斯特地区碳循环过程中扮演着什么样的角色,至今还少有报道.已有研究显示,喀斯特洞穴具有明显的烟囱效应,是不可忽略的.综述前人的研究发现,洞穴系统碳循环研究还存在诸多问题有待进一步研究,如烟囱效应对区域和全球大气CO2的贡献;烟囱效应的区域差异、季节变化及其原因(驱动力);烟囱效应对当地生态系统的影响等.随着现代科学技术(如涡度相关、大孔径闪烁和同位素)的发展,为解决上述问题提供了可能.因此,有必要运用现有的先进手段对洞穴系统碳循环进行自动连续监测和研究,这对喀斯特地区碳循环,甚至全球碳循环研究均具有重要意义.

... 岩石化学风化能够回收大气/土壤中的CO₂产生碳汇效应,积极参与全球碳循环^[1~4] ...

1997

0.0

... 由于方解石快速的溶解反应动力学机制,碳酸盐岩风化碳汇是岩石风化碳汇的主要组成部分^[5~9] ...

2010

0.0

2012

0.0

. 2012, 57(2/3):95-102

New progress and prospects in the study of rock-weathering-related carbon sinks

岩石风化碳汇研究的最新进展和展望

Liu Zaihua.

刘再华

2015

0.0

. 2015, 30(10):1 081-1 090

Some opinions on rock-weathering-related carbon sinks from the IPCC fifth assessment report

岩石风化碳汇研究进展:基于 IPCC 第五次气候变化评估报告的分析

Pu Junbing , Jiang Zhongcheng , Yuan Daoxian

蒲俊兵, 蒋忠诚, 袁道先

2011

0.0

. 2011, 31(3):426-430 DOI:10.3969/j.issn.1001-7410.2011.03.04

Atmospheric CO₂ sink: Silicate weathering or carbonate weathering?

刘洹. 大气CO 2 汇:硅酸盐风化还是碳酸盐风化的贡献?

Liu Zaihua , Dreybrodt W , Liu Huan.

刘再华

①State Key Laboratory of Environmental Geochemistry,Institute of Geochemistry,Chinese Academy of Sciences,Guiyang550002; ②Karst Dynamics Laboratory of Ministry of Land and Resources,Institute of Karst Geology,Chinese Academy of Geological Sciences,Guilin541004; ③Institute of Experimental Physics,University of Bremen,Bremen28359, Germany; ④College of Environmental Science and Engineering,Guilin University of Technology,Guilin541004

It is widely accepted that the chemical weathering of Ca-silicate rocks could potentially control long-term climate change by providing feedback interaction with atmospheric CO 2 drawdown by means of the precipitation of carbonate and that in contrast the weathering of carbonate rocks has not an equivalent impact because all of the CO 2 consumed in the carbonate dissolution is returned to the atmosphere by the comparatively rapid precipitation of carbonates in the oceans.Here we show that the rapid kinetics of carbonate dissolution and the importance of small amounts of carbonate minerals in controlling the dissolved inorganic carbon(DIC)of silicate watersheds coupled with aquatic photosynthetic uptake of the weathering-related DIC and burial of the resulting organic carbon suggest that the atmospheric CO 2 sink by carbonate weathering may previously have been greatly underestimated with a factor of about 3 amounting to 0.477 Pg C/a.This indicates that the contribution of silicate weathering to atmospheric CO 2 sink may be only 6 ％ while the other 94 ％ is by carbonate weathering.Therefore the atmospheric CO 2 sink by carbonate weatheringmight be significant in controlling both the short-term and long-term climate changes.

至今人们仍普遍认为: 是硅酸盐的化学风化碳汇作用在控制着长时间尺度的气候变化,而碳酸盐的化学风化作用不具有这一功能,因为碳酸盐溶解过程中消耗的所有CO 2 又通过海洋中相对快速的碳酸盐沉积而返回大气。本研究发现,碳酸盐溶解的快速动力学特性(比硅酸盐快100倍以上)以及硅酸盐流域中少量碳酸盐矿物在控制流域溶解无机碳(DIC)上的重要作用,再加上水生生物光合作用对DIC的利用,使得由碳酸盐风化形成的大气CO 2 汇以往被严重地低估至实际值的 1/3 左右,达到4.77亿吨 C/a,从而使得碳酸盐风化碳汇占整个岩石风化碳汇达到94％,而硅酸盐风化碳汇仅6％左右。因此,我们认为碳酸盐风化碳汇不仅控制了人类社会目前关注的短时间尺度的气候变化,而且在自水生光合生物出现以来的地质长时间尺度气候变化的控制上可能也是主要的。这无疑对传统的观点,即"只有钙硅酸盐风化才能形成长久的碳汇并控制地质长时间尺度的气候变化"提出了质疑。

... 由于方解石快速的溶解反应动力学机制,碳酸盐岩风化碳汇是岩石风化碳汇的主要组成部分^[5~9] ...

1997

0.0

... 碳酸盐岩溶蚀形成的岩溶水中 HC O3-有一半来源于大气/土壤 CO₂, 一半来源于碳酸盐岩^[10,11],计算岩溶碳汇通量较为通用的方法是根据地下水流量和水中HC O3-浓度的水化学径流法^[12~14] ...

1999

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1997

0.0

. 1997, 42(9):953-956 DOI:doi:10.1360/csb1997-42-9-953

Preliminary estimate the relationship between Karstification and CO₂ sources and sink

我国岩溶作用与大气温室气体CO 2 源汇关系的初步估算

Xu Shengyou , Jiang Zhongcheng.

徐胜友, 蒋忠诚

摘　要：

2008

0.0

. 2008, 29(3):355-365 DOI:doi:10.3321/j.issn:1006-3021.2008.03.009

Karst dynamics theory in China and its practice

岩溶动力学的理论探索与实践

Yuan Daoxian , Zhang Cheng.

袁道先, 章程

IGCP-513 "Karst Aquifers and Water Resources"(2005-2009) is a karst-related IGCP project that continues the trend of international karst geology research. Since 1990,three karst-related IGCP Projects(IGCP 299,IGCP 379 and IGCP 448) have been implemented successively with Prof.Yuan Daoxian from the Institute of Karst Geology,CAGS,as Leader of the International Working Group.All these four projects have provided opportunities for karst research communities worldwide to study together and solve resources and environment problems in the fields of karst formation,carbon cycle,karst ecology and water resources.Earth System Science has been introduced into the study of modern karstology,and Karst Dynamics Theory has been established,thus improving the development of karst science.The achievements of these projects have laid a solid foundation for the establishment of the International Research Centre on Karst(IRCK) under the auspice of UNESCO in Guilin,China.From this point,this paper presents a review of the development of Karst Dynamics Theory in China during the past couple of decades.The major scientific achievements are summarized,and the perspectives of their practical utilization are illustrated.The importance of Earth System Sciences and Global View in the development of modern karstology in China is emphasized.The history of the development of Karst Dynamics Theory in China can be traced back to 20 years ago in the study of karst geochemistry,in which a series of field portable facilities were used to reveal the behaviors of Karst Dynamics System as well as the directions(dissolution or deposition) and intensity of karst processes,thus providing the methodological background for the development of the Karst Dynamics Theory.The Karst Dynamics Theory is defined as the discipline for studying structures,behaviors,functions and types of the karst dynamics system(KDS) in the world.The KDS is the karst system of material,the energy transfer in the forms of carbon cycling,water cycling,calcium and other element cycling on the interfaces between lithosphere,atmosphere,hydrosphere and biosphere.Consequently,the major functions of KDS are: ①the forcing of the formation of karst;②the regulation of the greenhouse gas in the atmosphere and environment acidification;③the promotion of the migration or deposition of elements,thus forming mineral deposits and bringing about impacts on human life;④to record the processes of climate and environmental changes.As the KDS is influenced by geological,hydrological,climatic and biological processes,there are different types of KDS in the world.The idea of Karst Feature Complex(KFC) is an important part of the Karst Dynamics Theory.The KFC is defined as a group of karst features which include macroscopic and microscopic forms,surface and subterranean forms,and dissolution forms as well as depositional forms developed under similar environments.The idea of KFC helps karst researchers avoid the confusion of isomorphism,thus benefiting the global karst comparison and the smooth running of IGCP299.Through years of monitoring on dozens of typical karst dynamic system sites both in China and abroad,the differences in the behaviors of different types of KDS as well as their relationships with rainfall,especially thunderstorm events,vegetation,and soil condition were revealed.The largest carbon reservoir(carbonate rock mass) obviously remains active in global carbon cycle, the data from the site automatic records indicate that KDS is highly sensitive to environmental change,and the response time scale may be hours or even minutes.Continuous site observation shows that the seasonal and diurnal hydrochemical variations tend to co-vary with thunderstorm events.Hydrogeochemical sampling strategies for epikarst springs in karst areas with monsoon climate like southwest China should be redesigned,and continuous hydrogeochemical observation is needed for accurate evaluation of karstification intensity and carbon cycle.It is also found that the consideration of only water-rock interaction is not sufficient for understanding the hydrochemical variation in karst systems,that the variable effects of CO2 on the system should be evaluated,and that the consideration of water-rock-gas interaction as a whole is thus a must in understanding the regularity of the spatial and temporal variations in KDS.Taking the advantage of the CO2 involvement in karst processes,the Karst Dynamics Theory contributes to the global change study in 2 ways: ①Concerning the carbon sink or carbon source of the atmospheric CO2 through the karst process,it is estimated that about 17.74×106 t of carbon is removed by dissolution of carbonate rocks from the atmosphere in the karst regions of China,whereas the amount from the atmosphere in global karst regions is 6.08×108 t,i.e.,about 1/3 of the missing carbon sink.On the other hand,a lot of CO2 outgassing points from active tectonism were identified along the Tethys zone from Tibet westward to France,which become an important source of atmospheric CO2;②For the purpose of providing high resolution past climate change proxies from karst sediments,especially speleothemes for the test of GCM,some abrupt changes in paleomonsoon on termination I,II were revealed.A lot of papers in this aspect have been published in important international journals such as Science,Holocene and Quaternary International.For example,thorium-230 ages and oxygen isotope ratios of stalagmites from Dongge Cave in China characterize the Asian Monsoon and low-latitude precipitation over the past 160000 years.Numerous abrupt changes in 18O/16O values result from changes in tropical and subtropical precipitation driven by insolation and millennial-scale circulation shifts.The Last Interglacial Monsoon lasted 9.7 ± 1.1 thousand years,beginning with an abrupt(less than 200 years) drop in 18O/16O values 129.3 ± 0.9 thousand years ago and ending at an abrupt(less than 300 years) rise in 18O/16O values 119.6 ± 0.6 thousand years ago.The start coincides with insolation rise and measurements of full interglacial conditions,indicating that insolation triggered the final rise to full interglacial conditions.The paleoclimate environment evolution since 2300 years ago in Libo,China,was reconstructed by lots of paleoclimatological records of stalagmite.Many cold Heinrich events H1-H5 since the last glacial stage and abrupt events such as Younger Dry events are clearly recorded by stalagmites of south China.The Karst Dynamics Theory has been applied to the sustainable development of karst regions in China,especially to the rehabilitation of the rock desertification areas in southwest China which covers about 100000 km2 with a population of about 30 millions.Because of the leakage of water resources,the shortage of soil,and the alkaline background of carbonate rocks,the karst ecosystems are characterized by petrophile,xerophile,and calciphile on the surface.The lack of sunshine,the rather stable temperature,and slow underground metabolism constrain the biodiversity in karst areas.Under the guidance of karst dynamics,plants that enjoy both ecological and economic benefits are selected under the particular KDS geochemical background to be used in the rehabilitation of rock desertification areas,and water resources in thousands of underground streams in southwest China are managed in accordance with the special behaviors of KDS.The development and utilization of Karst Dynamics Theory is designated as a principal target of the newly approved International Research Centre on Karst(IRCK) in Guilin under the auspices of UNESCO.This discipline will be developed continuously under the joint effects of karst scientists both from China and abroad.

国土资源部岩溶动力学重点实验室的研究群体自1990年以来连续成功实施了3个国际岩溶对比计划项目,包括IGCP299、IGCP379、IGCP448,在岩溶形成、碳循环、岩溶生态和水资源等领域,为国际岩溶学术界提供了共同解决岩溶地区资源环境问题的机会,将地球系统科学思想引入现代岩溶学,建立岩溶动力学理论,有力地推动了国际岩溶学科的发展.目前正在执行的IGCP513"岩溶含水层与水资源"项目继续引领国际岩溶地质研究方向.相关成果为在中国桂林建立联合国教科文组织"国际岩溶研究中心"(IRCK)奠定了坚实基础.由此回顾了20多年来岩溶动力学理论在中国的发展过程.概述了其主要的科学成果和应用前景.指出了地球系统科学的引入、全球视野的研究和及时将理论用于解决岩溶地区的资源环境问题在现代岩溶学发展中的重要意义.经过20余年的不断探索,形成了岩溶动力学理论的基本思路,并创造性地总结了一套捕捉碳、水、钙循环的行踪的工作方法.通过全球对比,提出"岩溶形态组合"概念,将岩溶形态组合与岩溶形成环境条件建立对应关系,解决异质同相、同质异相这一令岩溶学者迷惘的问题.将岩溶学引入伞球变化研究,一方面把岩溶作用与全球碳循环紧密的联系在一起,通过对CO2H2O-CaCO3系统(岩溶动力系统)的定位观测,发现全球最大的碳库-碳酸盐岩体在伞球碳循环中仍甚活跃;另一方面,岩溶动力系统(KDS)对环境变化十分敏感,响应及时,其相关沉积物可记录全球变化.将岩溶地质过程与生态学联系在一起,将现代岩溶学理论的研究推向应用,与生产实践结合.在岩溶动力系统运行机制和运行规律、我国岩溶动力系统的类型划分和分布规律、在表生岩溶系统碳循环与大气CO2源汇关系、利用石笋记录重建古气候、古环境变化过程及中国西南岩溶生态系统研究等方面均获得了突出成果,如首次估算了我国和全球因碳酸盐岩溶蚀回收大气CO2的量,中国为1.774×107t/a,而全球为6.08×105t/a;证实了西南岩溶区典型表层岩溶泉水化学的季节、日变化与暴雨动态,表层岩溶泉水化学取样的频率需要重新审定,而且水文水化学的连续监测对于岩溶作用强度和岩溶作用碳循环的高精度评价是十分必要的;要了解岩溶系统水化学的变化,仅考虑水-岩相互作用是不够的,我们还必须重视CO2气体对岩溶系统中水化学变化的影响,即岩溶系统水化学动态的变化是CaCO3-H2O-CO2三者相瓦作用引起的,水-岩-气相互作用的概念必须引入岩溶水化学的研究中;揭示了过去0.16 Ma来亚洲季风和低纬度地区降雨变化的特征,说明太阳辐射强度增高,驱动了盛间冰期的出现,重建了荔波地区2.3 ka来古气候环境的演变历史,贵州董哥洞石笋提供了低纬度、低海拔地区,可较好定年,更接近水汽来源区的古气候变化的替代指标;石笋记录发现末次冰期以来存在有多次冷事件-Heinrich冷事件H1～H5跃变事件,新仙女木事件在我国南方的洞穴沉积物中具有显著的反映.对西南8省区市岩溶县、石漠化严重县统计和空间分布特征的分析研究表明地质地貌条件对岩溶区资源、环境和社会经济具有制约作用,认为西南岩溶区石漠化综合治理首先要在岩溶地质条件的基础上,结合气候、水文和社会经济状况,才能深入分析岩溶区石漠化的成因、危害和类型.划分出岩溶区石漠化综合治理区域8大区成为"西南岩溶石漠化综合治理规划大纲"编写的重要基础.

... 2 H₂SO₄参与碳酸盐岩溶蚀根据H₂CO₃风化碳酸盐岩的方程^[13]: ...

2011

0.0

. 2011, 30(4):437-442

The characteristics of karst carbon sink in the Guijiang Catchment

桂江流域岩溶碳汇特征

Huang Qibo , Liu Pengyu , Qin Xiaoqun

黄奇波, 刘朋雨, 覃小群

2011

0.0

... 完整的岩溶流域内经常存在非岩溶地层或夹层^[15],流经非岩溶地层或夹层的非岩溶水补给岩溶水的同时,也带来了一部分HC O3-,该部分HC O3-是碳酸溶蚀硅酸盐岩所产生的,均源于大气/土壤 C O216,17,造成流域出口岩溶地下水中HC O3-来源于大气/土壤 CO₂的量大于50%^[15] ...

1995

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1999

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2011

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. 2011, 41(5):1 542-1 547

The main controlling factor of karst carbon sequestration: About water cycle

岩溶碳汇的主控因子#cod#x02014;#cod#x02014;水循环

Kang Zhiqiang , Yuan Daoxian , Chang Yong

康志强, 袁道先, 常勇

1.Environmental School, China University of Geosciences, Wuhan430074, China; 2.Karst Institute of Geology, Chinese Academy of Geological Sciences/Key Laboratory of Karst Dynamics, Ministry of Land and Resources, Guilin541004, Guangxi|China; 3.International Research Centre on Karst, United Nations Educational, Scientific and Cultural Organization, Guilin541004,Guangxi|China; 4.College of Geographical Sciences, Southwest University, Chongqing400715, China; 5.College of Life Science, Guangxi Normal University, Guilin541004, Guangxi, China; 6.The Management of Maolan National Nature Reserve of Guizhou, Libo558400, Guizhou, China

The karst process is important composition of global carbon cycle because it can take-up CO 2 from atmosphere. To calculate karst carbon sequestration ( Kcs ) is useful to complete the theory of global carbon cycle. By the karst dynamic system theory, the Kcs is controlled by groundwater discharge and HCO - 3 mass concentration. The Banzhai River catchment, located in Maolan National Nature Reserve of Guizhou, was chosen as the study area. By the auto-monitoring technique, the discharge and water chemistry data of Banzhai River catchment were obtained. Based on the analysis of relationship between discharge, HCO - 3 concentration and karst carbon sequestration under different precipitation conditions including storm period, no/weak precipitation period and dry season. Kcs has positive correlation with discharge and negative correlation with HCO - 3 concentration. It shows that the discharge of catchment is main factor of Kcs rather than HCO - 3 concentration. The larger discharge of karst catchment, the larger Kcs from atmosphere.

精确地计算岩溶碳汇量，有助于全球碳循环模型理论的进一步完善。因而在实际工作中，排泄量和HCO - 3 质量浓度是岩溶碳汇监测评价的主要指标。选取贵州茂兰国家级自然保护区的板寨河流域为研究对象，基于自动化在线监测技术，获取了该域排泄量及水化学指标的实时监测数据。对比分析暴雨期、无或弱降水期以及枯水期等不同降水条件下HCO - 3 质量浓度、流域排泄量及岩溶碳汇量的动态过程曲线，发现流域排泄量与岩溶碳汇量呈良好的正相关关系，而与HCO - 3 质量浓度则呈负相关。这说明相比地下水中HCO - 3 浓度，流域排泄量才是影响岩溶碳汇的主控因素,同时也说明水循环方式是影响岩溶碳汇的主控因子，即流域排泄量愈大，流域内岩溶作用对大气CO 2 形成的“汇”值愈大。

... 运用水化学径流法计算岩溶碳汇通量时由于忽略了非岩溶水带来的HC O3-,这可能会造成碳汇效应被低估^[18] ...

2004

0.0

... 另一方面,西南岩溶区大气酸沉降较为严重,硫酸(H₂SO₄)参与碳酸盐岩溶蚀已被大量的研究所证实^[19~22],硫酸参与碳酸盐岩的溶蚀并不消耗大气或土壤中的CO₂,但会增加碳酸盐岩的溶蚀量并增加水体中HC O3-的含量^[23,24],如何扣除地下水中来源于硫酸溶蚀成因的HC O3-也成为准确计算岩溶碳汇通量的关键^[25~27] ...

2008

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2010

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2011

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2014

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. 2014, 34(5):1 044-1 053 DOI:10.3969/j.issn.1001-7410.2014.05.13

Geochemical tracers to characterize effects of urbanization on karst groundwater quality from Nanshan underground river system, SW China

城市发展对岩溶地下水质影响的地球化学示踪#cod#x02014;#cod#x02014;以重庆南山老龙洞地下河系统为例

Jiang Yongjun , Yuan Daoxian.

蒋勇军, 袁道先

① School of Geographical Sciences of Southwest University, Chongqing 400715; ② Karst Dynamics Laboratory, Ministry of Land and Resources/Guangxi, Institute of Karst Geology, Chinese Academy of Geological Sciences, International Research Center on Karst under the Auspices of UNESCO, Guilin 541004

With the expansion of urbanization, population in cities or suburbs has increased in number where sewage discharge from residential areas has deteriorated karst groundwater quality of drainage basins across the globe. The chemical and stable isotopic compositions of strontium, sulfur and carbon from groundwater are used to evaluate the contributions of urbanization to karst groundwater quality of Laolongdong Underground River in the Nanshan karst trough valley(29°28'~29°33'N, 106°35'~106°37'E) of Chongqing, SW China. The groundwater monitored from January to December in 2012, was characterized by hydrochemical facies of HCO 3 -SO 4 -Ca. The contributions of carbonate dissolution by carbonic acid to total(Ca 2+ +Mg 2+ )and HCO 3 - in groundwater ranged from 38% to 68% (average 53%), and from 55% to 81% (average 68%), in different months. While the contributions of carbonate dissolution by sulphuric acid to total(Ca 2+ +Mg 2+ ) and HCO 3 - in groundwater varied from 32% to 62% with an average of 47%, and 19% to 45% with an average of 32%, respectively. The 87 Sr/ 86 Sr ratios of groundwater ranged from 0.70800 to 0.70900, higher than that derived from the dissolution of calcite, suggesting the natural 87 Sr/ 86 Sr ratios of groundwater controlled by water-rock interaction has been significantly elevated by detergents derived from domestic sewage water. The δ 34 S-SO 4 2- of the groundwater varied from+7.8‰ to +12.0‰ with high SO 4 2- concentrations, indicating that the sulfate was mainly originated from detergents(domestic sewage water), rainwater and the dissolution of gypsum. The δ 13 C DIC in groundwater, varying from -11.2‰ to -7.3‰ with a changeable molar ratio between(Ca 2+ +Mg 2+ )and HCO 3 - of 0.60 to 0.71, suggested that the groundwater quality was controlled by processes that carbonate rocks are dissolved by CO 2 from C 3 vegetation under open system conditions which the δ 13 C DIC of groundwater has a value of around -14‰ with a molar ratio between(Ca 2+ +Mg 2+ ) and HCO 3 - of around 0.5 in groundwater, and H 2 SO 4 introduced by urbanization which the δ 13 C DIC of groundwater approaches a value of around 0‰ with a molar ratio between(Ca 2+ +Mg 2+ ) and HCO 3 - of around 1 in groundwater.

随着城市化的快速发展，大量生活废水的排放严重影响岩溶地下水质。本文尝试利用重庆南山老龙洞流域2012年每月地下水、雨水和生活污水的水化学数据与环境同位素 87 Sr/ 86 Sr 、 δ 34 S-SO 4 2- 和 δ 13 C DIC 来研究城市发展对岩溶地下水质的影响，结果表明：1）城市化过程带来的硫酸改变了岩溶地质过程，不同月份碳酸溶蚀碳酸盐岩对地下水中（Ca 2+ +Mg 2+ ）和HCO 3 - 的贡献率分别变化于38%~68%（平均贡献率为53%）和55%~81%（平均贡献率为68%），而硫酸溶蚀碳酸盐岩对地下水（Ca 2+ +Mg 2+ ）和HCO 3 - 的贡献率分别变化于32%~62%（平均贡献率为47%）和19%~45%（平均贡献率为32%）；2）生活废水的输入改变了流域地下水锶同位素的地球化学特征，地下水 87 Sr/ 86 Sr 变化于0.70800~0.70900，明显高于雨水和石灰岩溶解来源的 87 Sr/ 86 Sr 值，而低于生活废水的 87 Sr/ 86 Sr 值，表明流域地下水质受水-岩作用和污水输入的共同影响；3）地下水 δ 34 S-SO 4 2- 变化于7.8‰~12.0‰ 之间，SO 4 2- 主要来源于生活污水和雨水的输入与石膏的溶解；4）地下水 δ 13 C DIC 变化于-11.2‰~-7.3‰ 之间，且地下水（Ca 2+ +Mg 2+ ）/HCO 3 - 摩尔比率介于0.60~0.71，流域地下水质一方面受控于CO 2 对碳酸盐岩溶解的自然过程，另一方面则受城市化过程产生的硫酸对碳酸盐岩溶解的控制。

2012

0.0

. 2012, 27(4):466-476

Agricultural activities and carbon cycling in karst areas in Southwest China: Dissolving carbonate rocks and CO₂ sink

农业活动对岩溶作用碳汇的影响: 以重庆青木关地下河流域为例

Zhang Xingbo , Jiang Yongjun , Qiu Shulan

张兴波, 蒋勇军, 邱述兰

2013

0.0

2015

0.0

... 4条地下河不同月份的SiO₂的含量与珠江^[31]、乌江^[26]及长江主河道^[32]水体相比,明显偏小,主要原因是4条地下河流域主要为碳酸盐岩,非岩溶地层比例最高的L01也不超过18%,而珠江流域、乌江流域和长江流域非岩溶地层出露面积均大于50% ...

... N O3-和 S O42-浓度远小于受酸雨和工业活动影响较大的乌江流域地表水和地下水^[26],也小于人类活动频繁的长江流域主河道水体^[32] ...

2016

0.0

. 2016, 36(6):1 358-1 369 DOI:10.11928/j.issn.1001-7410.2016.06.02

The impact of human activities to #cod#x003b4;¹³C_DIC of karst groundwater and carbon sink in the upper and middle reaches of of Wu River

人为活动对乌江中上游段岩溶地下水#cod#x003b4; 13 C DIC 及碳汇效应的影响

Huang Qibo , Qin Xiaoqun , Liu Pengyu

黄奇波, 覃小群, 刘朋雨

1 Institute of Karst Geology, Chinese Academy of Geological Sciences, Guilin 541004; 2 Key Laboratory of Karst Dynamics, Ministry of Land and Resources & Guangxi Zhuang Autonomous Region, Guilin 541004

Quantitative evaluation of the impact of human activities to karst carbon sink not only helps to improve the estimation accuracy of karst carbon sinks,but also is significant for the current research on global climate change.The Wujiang River,the largest river in Guizhou Province,is a tributary of the Yangtze River with a highest proportion of carbonate.Recently,with the fast population proliferation and rapid economic growth,the drainage basin is intensively interfered by anthropogenic activities and shows an increasing SO 4 2- and NO 3 - concentration.For investigating the hydrochemical characteristics and the main influencing factors,the hydrochemistry and Carbon isotope in dissolved inorganic carbon (DIC) from 42 and 26 karst groundwater samples were sampled and analyzed during the rainy (July,2013) and dry (October,2013) seasons,respectively,from the Upper and Middle reaches of Wujiang River.The contribution of atmospheric/soil CO 2 (CO 2ATM-SOIL ) to the total HCO 3 - (CO 2ATM-SOIL /total HCO 3 - ) were calculated using the stoichiometry method.The results showed that the advantage cations of groundwater and surface water were Ca 2+ and Mg 2+ ,which accounted for more than 55%,and the advantage anions were HCO 3- and SO 4 2- ,accounting for more than 85%.The concentrations of Ca 2+ and Mg 2+ exceeded the equivalent concentrations of HCO 3 - ,which the excess of Ca 2+ and Mg 2+ cations were compensated by SO 4 2- +NO 3 - .The δ 13 C DIC of karst groundwater in the rainy and dry seasons,ranged from -14.19‰ to -8.27‰ and from -12.98‰ to -9.09‰,respectively,with a more depleted value in rainy season.A good positive correlation between δ 13 C DIC value and [SO 4 2- +NO 3 - ]/[HCO 3 - ] indicated that sulphuric and nitric acid might play a relatively important role in carbonate weathering and has an important influence on δ 13 C DIC value.The average contribution of atmospheric/soil CO 2 (CO 2ATM-SOIL ) to the total HCO 3 - (CO 2ATM-SOIL /total HCO 3 - ) is 33.83% for rainy season,and 35.84% for post-rainy reason,which corresponds to a mean decrease of 16.17% and 14.16% compared to natural environmental conditions (50%),respectively.As a consequence,in study area,the equal deficit of soil CO 2 uptake by carbonate weathering reach 32.34% and 28.32% when nitric and sulfuric acids were involved in.

定量评价人为活动对岩溶碳汇效应的影响有助于提高岩石风化碳汇通量估算精度，对当前全球气候变化研究意义重大。本文选取乌江中上游段岩溶区为研究对象，在雨季和旱季对研究区68个岩溶地下水（雨季42个，旱季26个）的水化学、溶解无机碳（DIC）同位素组成（ δ 13 C DIC ）进行了测试，利用化学计量法计算了H 2 SO 4 和HNO 3 对流域岩溶碳汇效应的影响程度。结果表明：1）雨季和旱季岩溶地下水中阴离子均以HCO 3 - 和SO 4 2- 为主，两者占总阴离子的85%以上；阳离子以Ca 2+ 和Mg 2+ 为主，两者占总阳离子的55%以上。Ca 2+ +Mg 2+ 相对于HCO 3 - 过量，过量的Ca 2+ +Mg 2+ 与SO 4 2- +NO 3 - 相平衡。2）雨季和旱季岩溶地下水的 δ 13 C DIC 值分别介于-14.19‰~-8.27‰和-12.98‰~-9.09‰之间。总体上，雨季的 δ 13 C DIC 更为偏负，且变化范围较大，均与[SO 4 2- +NO 3 - ]/[HCO 3 - ]呈正相关性，证实H 2 SO 4 和HNO 3 参与了流域碳酸盐岩的溶蚀并使 δ 13 C DIC 值增加。3）由于H 2 SO 4 和HNO 3 参与，雨季碳酸盐岩溶蚀消耗的CO 2 （CO 2ATM-SOIL ）占水中HCO 3 - 的比例（CO 2ATM-SOIL /total HCO 3 - ）平均值为33.83%，旱季平均值为35.84%，与H 2 CO 3 溶蚀碳酸盐岩的CO 2ATM-SOIL /total HCO 3 - 理论值（50%）相比，分别减少16.17%和14.16%。因此，雨季岩溶碳汇效应将减少32.34%，旱季将减少28.32%。

1999

0.0

... Galy方法是Galy和France-Lanord用来估算Ganges-Brahmaputra流域的侵蚀速率和岩石风化消耗大气/土壤CO₂通量的重要方法^[28] ...

... 3 不同端元风化贡献比例及CO₂消耗通量由以上分析可知,4条地下河既受非岩溶地层中的硅酸盐岩风化影响,又受H₂SO₄溶蚀的控制,本研究利用地下河不同季度的流量(表1)和水化学数据(表2),根据地下河元素比值之间的关系,采用Galy 的模型^[28],并运用参考文献[31]中的公式(1)~(16)计算出4 条地下河中碳酸盐岩和非岩溶地层中硅酸盐岩风化消耗的CO₂通量,计算结果如表3所示 ...

2005

0.0

. 2005, 20(4):394-406

Hydrogechemistry of rivers in Guizhou Province China: Constraints on crustal weathering in karst terrain

贵州喀斯特地区河流的研究#cod#x02014;#cod#x02014;碳酸盐岩溶解控制的水文地球化学特征

Han Guilin , Liu Congqiang.

韩贵琳, 刘丛强

The State Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guizhou 550002, China

Major ions and Sr2+ concentrations and Sr isotopic compositions of two major river systems were measured in Guizhou karst region. The chemical composition of these rivers in the karst region represents that of river water from the typical carbonate areas. Its hydrogeochemical characteristics are different from those of global major rivers: The river and its tributaries have high total dissolved solid concentrations, with Ca 2+ and HCO -3 being dominant, Ma 2+ and SO 2- 4 coming next. Both Na + +K + and Cl - +Si account for 5%~10% of the cations and anions, respectively. These rivers have high total concentration (TZ + ) ranging from 2.0 to 5.5 meq/L, which are significantly higher than those of the global river averge (TZ + =0.725meq/L). The chemical and isotopic compositions of these rivers are largely under controll by the geological signatures of their drainage areas. The Wujiang River system draining carbonate strata show high Sr 2+ concentrations(1.07~9.70) and lower 87 Sr/ 86 Sr ratios of 0.7077~0.7110, as compared with the Yuanjiang River system ( 87 Sr/ 86 Sr=0.7090~0.7145, Sr 2+ =0.39~1.32) draining detrital strata. The end-member identification by the intercorrelations between chemical and isotopic ratios shows three main sources, which are derived from weathering of limestone, dolomite and silicates. The Wujiang River system has characterized by low Na/Ca, Mg/Ca mole ratios (0.05~0.34 and 0.18~0.79, respectively), showing a strong influence of limestone, about 96% of solutes derived from the weathering of carbonate. On the other hand, the Yuanjiang river system show high Na/Ca mole ratio from 0.06~1.80, Mg/Ca from 0.23~1.30, suggestive of a strong influence of limestone and dolomite weathering, about 90% of solutes derived from the weathering of dolomite in the Wuyanghe river system and about 54% of solutes derived from the weathering of limestone in the Qingshuijiang river system.

测量了喀斯特地区乌江、沅江两大水系的河流枯水期的主元素、Sr 2+ 离子浓度和Sr同位素比值。这些河流的化学组成代表了流经碳酸盐岩地层的河水的化学组成。这些河流及其支流有高的溶解盐，TZ + 变化范围为：2.1～6.3 meq/L，高于全球河流的平均值(TZ + =0.725 meq/L)。河水含有较高的溶质浓度，河水水化学组成以Ca 2+ 和HCO -3 为主，其次为Mg 2+ 和SO 2- 4 ，Na + +K + 和Cl - +Si分别只占阳离子和阴离子组成的5%～10%。这些河流的化学和同位素组成主要受其自流盆地的地质特征控制。流经碳酸盐岩地层的乌江水系河流具有较高的Sr浓度（1.1～9.70 mol/L）和较低的 87 Sr/ 86 Sr比值（0.7077～0.7110），与流经碎屑岩地层的沅江水系的清水江河流中较高的 87 Sr/ 86 Sr比值（0.7090～0.7145）及较低的Sr浓度（0.28～1.32 mol/L）形成鲜明的对比。流域盆地的地理岩性控制了河水的化学组成和同位素组成。对河水的化学计量分析表明河水化学组成受碳酸盐岩溶解控制，而碳酸盐岩主要受碳酸和硫酸作用而溶解。乌江流域受硫酸作用特别明显，表明硫酸主要来源于燃煤或流域盆地硫化物矿物氧化而形成的大气输入。化学元素和同位素比值之间的相互关系表明3个主要来源为：石灰岩、白云岩和硅酸盐岩的风化。同时估计了碳酸盐岩和硅酸盐岩的化学风化速率，结果表明流域盆地的碳酸盐岩风化速率远远高于许多世界大河。岩石风化过程中硫酸的出现或土地的过度使用或土壤植被的退化等都可能是导致流域的碳酸盐岩风化速率如此高的原因。 

... 在我国云贵高原的乌江流域、南盘江、北盘江流域,韩贵琳等^[29]和刘丛强等^[30]运用Galy方法计算了硅酸盐岩和碳酸盐岩风化速率及消耗大气/土壤CO₂通量,并评估了硫酸参与碳酸盐岩溶蚀的比例及对岩溶碳汇效应的影响程度 ...

2008

0.0

. 2008, 37(4):404-414

Chemical weathering of carbonate rocks by sulfuric acid and the carbon cycling in Southwest China

西南喀斯特流域碳酸盐岩的硫酸侵蚀与碳循环

Liu Congqiang , Jiang Yingkui , Tao Faxiang

刘丛强, 蒋颖魁, 陶发祥

... 刘丛强等^[30]的研究结果显示在硫酸参与下,西南地区岩溶碳汇通量应扣除33%,本研究的扣除比例明显小于该值,这缘于本研究中的4条地下河流域受人类活动影响较小 ...

2015

0.0

. 2015, 34(9):1 749-1 757

The difference of the weathering rate between carbonate rocks and silicate rocks and its effects on the atmospheric CO₂ consumption in the Pearl River Basin

珠江流域碳酸盐岩与硅酸盐岩风化对大气CO 2 汇的效应

Qin Xiaoqun , Jiang Zhongcheng , Zhang Liankai

覃小群, 蒋忠诚, 张连凯

对珠江流域11个测站的河水1个水文年4次取样进行水化学和同位素测试分析，揭示无论是碳酸盐岩区还是硅酸盐岩区，岩石风化均使河流的离子成分以HCO3-、Ca2+、Mg2+为主，碳酸盐岩风化溶蚀速率和由碳酸盐岩风化溶蚀引起的大气CO2消耗量分别为27.60mm/ka和540.21x103mol/(km2?a-1),是硅酸盐岩风化速率和由硅酸盐岩风化引起的大气CO2消耗量的10.8倍和6.7倍，说明碳酸盐岩风化是流域碳汇过程及效应的主体。由于有利的水热条件和高的碳酸盐岩面积比例，珠江流域平均岩石风化速率和由岩石风化作用引起的大气CO2消耗量分别为30.15mm/ka和620.36×103mol/(km2?a-1)，为全球60条河流平均值的2.6倍。

... 覃小群等^[31]运用Galy方法计算出珠江流域平均岩石风化速率和由岩石风化作用引起的大气CO₂消耗通量,并证实由于碳酸盐岩风化溶蚀速率是硅酸盐岩的10 ...

... 另一方面,当H₂SO₄+H₂CO₃共同风化碳酸盐时,溶蚀方程可表示为^[31]:3Ca_(1-_x₎Mg_xCO₃+ H₂SO₄+H₂CO₃= 3(1-x)Ca²⁺+3xMg²⁺+S O42-+4HC O3-,溶蚀产物主要为Ca²⁺,Mg²⁺,HC O3-,S O42- ...

2016

0.0

... 张连凯等^[32]利用Galy方法研究了长江流域岩石化学风化与大气CO₂消耗,并估算了在考虑硫酸参与碳酸盐岩溶蚀时,流域岩石风化碳汇通量应扣除约14% ...

... N O3-和 S O42-浓度远小于受酸雨和工业活动影响较大的乌江流域地表水和地下水^[26],也小于人类活动频繁的长江流域主河道水体^[32] ...

2006

0.0

. 2006, 25(10):28-30 DOI:doi:10.3969/j.issn.1006-8937-B.2006.10.011

The present situation, cause of formation and countermeasure research of the acid rain in Hunan Province

湖南省酸雨现状、成因及对策研究

Zhu Xuanxiang.

朱选祥

摘　要：文章在全面介绍酸雨的基本概念和特征的基础上，对湖南地区的酸雨污染特征和变化趋势进行了研究，收集了最新的酸雨监测数据，并分析了酸雨成因，提出了防治酸雨污染的对策和建议。

... 4%,酸雨中硝酸的含量不及硫酸的10%,主要为硫酸型酸雨^[33] ...

1999

0.0

. 1999, 35(6):786-793 DOI:doi:10.3321/j.issn:0479-8023.1999.06.009

Chemical characteristics and genesis of major ions in the Pearl River Basin

珠江水系河水主要离子化学特征及成因

Chen Jingsheng , He Dawei.

陈静生, 何大伟

摘　要：对珠江水系１０９个水文站１９５４－１９８４年的水化学资料的研究表明，在组成珠江水系的３条河流中，以东江离子总量为最低西江的离子总量为最高，前者的化学类型为重碳酸盐钠型水，后者为重碳酸盐钙型水。

... 87,呈弱碱性,显示出典型的岩溶地下水化学特征^[34] ...

... 另一方面,研究区Cl^-主要来源于大气降水,而K⁺和Na⁺除大气降雨外,还来源于非岩溶地层中硅酸盐岩矿物的风化,因此,可用(Na⁺+K⁺)/(Na⁺+K⁺+Cl^-)值的大小来指示非岩溶地层中硅酸盐岩矿物风化对地下水贡献大小^[34] ...

1981

0.0

... 91 mg/L,远高于世界河流平均值(69 mg/L)^[35],显示了岩溶地下河流域剧烈的岩石化学侵蚀作用^[36] ...

2010

0.0

. 2010, 39(4):305-313

The impacts of chemical weathering of carbonate rock by sulfuric acid on the cycling of dissolved inorganic carbon in Changjiang River water

硫酸侵蚀碳酸盐岩对长江河水DIC循环的影响

Li Jun , Liu Congqiang , Li Longbo

李军, 刘丛强, 李龙波

... 91 mg/L,远高于世界河流平均值(69 mg/L)^[35],显示了岩溶地下河流域剧烈的岩石化学侵蚀作用^[36] ...

2010

0.0

. 2010, 21(5):628-636

Hydrogeochemistry and environmental meaning of Chongqing subterranean karst streams in China

重庆岩溶地下河水文地球化学特征及环境意义

Pu Junbing , Yuan Daoxian , Jiang Yongjun

蒲俊兵, 袁道先, 蒋勇军

... 岩溶水特征^[37] ...

... ^[37],而S O42-多来自于大气酸沉降和工矿业活动^[46],因此,一般情况下,水中的 N O3-和 S O42-浓度的变化主要反映来自农业活动和工业活动的影响 ...

2015

0.0

2016

0.0

2013

0.0

. 2013, 32(2):123-132 DOI:doi:10.3969/j.issn.1001-4810.2013.02.001

Dissolved inorganic carbon and stable carbon isotope in karst subterranean streams in Chongqing, China

重庆地区岩溶地下河水溶解无机碳及其稳定同位素特征

Pu Junbing.

蒲俊兵

Stable carbon isotope is a useful and powerful tool for tracing the origin and transformation of carbon in karst dynamics system. For obtaining the characteristics of hydrochemistry and isotope, groundwater samples in wet and dry seasons from 63 karst subterranean streams in Chongqing are collected in this study. The results show that the HCO3- is the dominant species of the DIC in ground waters and the concentration of HCO3- is lower in wet season than dry season due to dilution. δ13C-DIC (V-PDB) in karst subterranean streams in Chongqing varies from -15.34 ‰～-5.89 ‰ in dry season and from -17.40 ‰～-4.23 ‰ in wet season. The widely variations of δ13C in wet season show the complex origins of carbon in karst subterranean streams in wet season. Based on the δ13C isotope mass balance equation, the amount of DIC that comes from the carbonate rock dissolution is calculated in this study. The calculated results show that 45.1 %～79.7 % of the DIC in the dry season and 34.6 %～82.1 % in the wet season is from dissolution of carbonate rocks in karst groundwater. The calculated results also shows that the DIC and the corresponding δ13C proportion originated from the carbonate rock dissolution is not necessarily 50 % according to the molar ration of karst chemical reaction equation, but has a changes range at some extend. As a result, this study suggests that we should deduct first the DIC originated from the carbonate rock dissolution using the δ13C when we calculate the carbon sink of karst processes, and then calculate further the karst carbon sink.��

稳定碳同位素是指示岩溶动力系统碳来源及转化的重要指标。为揭示重庆地区岩溶地下水中溶解无机碳基本特征和碳来源，本文对该地区63条岩溶地下河水样进行了水化学和碳同位素分析。研究结果表明，重庆地区地下河水溶解无机碳主要表现形式为HCO3-，雨季由于稀释作用其浓度低于旱季。重庆岩溶地下河水δ13C-DIC（V-PDB）旱季变化范围为-15.34 ‰～-5.89 ‰，雨季变化范围为-17.40 ‰～-4.23 ‰。根据δ13C同位素质量平衡方法，计算得到重庆地下河旱季碳酸盐岩溶蚀对DIC贡献为45.1 % ～79.7 %，雨季平均为34.6 %～82.1 % 。计算结果表明，在人类活动不断增强的情况下，岩溶水体DIC通量中碳酸盐岩溶解来源的DIC和其参与岩溶地下水δ13C值的形成并不一定是岩溶作用理论方程中所计算的50 %，而是有一定的变化范围。因此在计算岩溶作用碳汇时，建议通过δ13C值扣除碳酸盐岩溶蚀形成DIC的通量后再来推算岩溶作用形成的碳汇量。

... 05),意味着二者的变化均受同一个因素即水中CO₂浓度的控制^[40] ...

... 因此,通常情况下地下水中SIc和水体pCO₂具有负相关关系^[40],图3很好地证实了这一点 ...

2015

0.0

. 2015, 36(5):1 565-1 572 DOI:doi:10.13227/j.hjkx.2015.05.008

Hydrochemical characteristics and sources of Qingshuijiang River Basin at wet season in Guizhou Province

贵州清水江流域丰水期水化学特征及离子来源分析

L#cod#x000fc; Jiemei , An Yanling , Wu Qixin

吕婕梅, 安艳玲, 吴起鑫

对清水江流域丰水期河水离子浓度及组成特征分析表明,流域水化学组成以Ca2+、HCO-3离子为主,其次为Mg2+、SO2-4;TDS均值213.96 mg·L-1,高于世界流域均值.根据海盐校正分析得出,研究区大气降水中海盐输入对流域水化学的贡献率为2.23%,低于世界河流均值3%.Gibbs图结合离子比值分析表明,流域水化学主要受碳酸盐岩风化影响,越往下游硅酸盐岩化学风化贡献越明显,碳酸和硫酸同时参与了流域岩石风化过程.离子来源分析表明,Ca2+、Mg2+、HCO-3离子主要来自于白云石、方解石等碳酸盐岩风化溶解,Na+、K+、Cl-主要来源于硅酸盐岩风化;SO2-4和NO-3主要来源于大气酸沉降和城镇废水输入.人为活动影响分析表明上游工矿企业活动对清水江流域水化学影响明显.

... 大气降水对地下水化学影响的研究,通常选择 Cl^-作为参照元素,它是雨水中的主要成分且来源相对简单,在水的循环过程中 Cl^-的行为也相对保持稳定,一般认为其主要通过降雨从海洋输送而来,受人类活动的贡献相对较少^[41] ...

... 地下水中SiO₂主要来源于非岩溶地层中的硅酸盐的风化^[41] ...

2013

0.0

. 2013, 34(3):874-881

Characteristics and evolution of hydrochemical compositions of freshwater lake in Tibetan Plateau

青藏高原淡水湖泊水化学组成特征及其演化

Wang Peng , Shang Yingnan , Shen Licheng

王鹏, 尚英男, 沈立成

青藏高原淡水湖具有高生态价值和高脆弱性并存的特点.以海拔 5080 m±10 m的打加芒错湖水为研究对象,测试及分析了湖水化学组分,探讨了其主要离子来源、控制因子和湖泊水化学演化趋势.结果表明,湖水阳离子以Ca2和Na+为主,阴离子以HCO3-为主,为HCO3-Ca型水；TDS为71.2～199.8 mg·L-1,矿化度低；受地表径流的稀释作用和富铝贫钙的地质背病约束湖区东南部水体的EC、Ca2+和HCO3-浓度均较低.湖水的Na+/(Na+ +Ca2+)为0.08～ 0.75,Cl /(Cl +HCO3-)为0.11 ～0.35,Ca/Na值为0.58,Mg/Ca值为0.12,HCO3/Na值为1.46,据Gibbs模型和元素化学计量分析表明,其化学组成主要受硅酸盐岩风化控制.湖区流域参与风化的矿物岩石包括斜长石(钙长石、钠长石)、钾长石、云母、石膏、盐岩等,但以斜长石风化为主,湖水的K/Na值平均为 0.059,表明流域钾长石风化程度较低.湖水中方解石、白云石、石英、石膏等矿物饱和指数(SI)大于0,石盐的SI则小于0,揭示了青藏高原上淡水湖泊演变成咸水湖的变化趋势.

... 86)^[42] ...

... K⁺可来源于钾长石和云母的风化^[42] ...

2006

0.0

... 大量的研究结果显示,K⁺和Na⁺可来源于非岩溶地层中的硅酸盐岩矿物的风化^[43],如Na⁺可来源于石盐的溶解和硅酸盐风化 ...

2016

0.0

. 2016, 37(5):1 779-1 787

Major ionic features and their controlled factor in the Upper- Middle Reaches of Wu River

乌江中上游段河水主要离子化学特征及控制因素

Huang Qibo , Qin Xiaoqun , Liu Pengyu

黄奇波, 覃小群, 刘朋雨

... Ca²⁺,Mg²⁺和HC O3-在4条地下河的阴阳离子中占有绝对优势,碳酸盐岩的溶蚀对地下水化学组分具有控制作用^[44] ...

... 人为活动产物可以通过废物直接排放和通过大气输入这2种途径输入水体^[44] ...

... 3,也明显小于乌江上游段地表水体中的N O3-/Cl^-与S O42-/Cl^-值^[44],表明4条地下河受农业和工业活动影响较轻 ...

2000

0.0

. 2000, 45(21):2 348-2 351

Two important atmospheric CO₂ sinks

大气CO 2 两个重要的汇

Liu Zaihua.

刘再华

对扬子克拉通太古宙高级区域变质岩系变质事件进行了Sm-Nd同位素定年(1 939~ 1 958 Ma), 综合区内同类岩石的SHRIMP锆石U-Pb等相关年龄数据和地质事件, 确认这一时期构造热事件的存在并对其地质意义进行了解析. 通过与扬子克拉通其他地区早期基底岩系形成时代的对比分析, 表明古元古代晚期在整个扬子克拉通范围内存在一次重要的构造热事件, 并导致了扬子陆块统一基底的形成.

... 开放的岩溶动力系统中,CO₂是岩溶作用发生的重要驱动力^[45],CO₂进入岩溶动力系统促进碳酸盐岩的溶解,表现为地下水中Ca²⁺,HC O3-浓度和水体pCO₂增加,SIc减少 ...

2013

0.0

. 2013, 24(3):418-426

Sources of riverine sulfate in Yellow River and its tributaries determined by sulfur and oxygen isotopes

硫和氧同位素示踪黄河及支流河水硫酸盐来源

Zhang Dong , Huang Xingyu , Li Chengjie.

张东, 黄兴宇, 李成杰

Determining the cycle of riverine sulfate, affected by natural weathering and anthropogenic activities, is necessary for surface water management. Mainstream and tributaries of Yellow River from Xiaolangdi Reservoir, including Qinhe River and Yiluo River, were selected. River water samples were collected during different seasons, and dual isotopes of dissolved sulfate were measured, together with hydrochemical compositions of surface water and isotopic compositions of potential sources. Based on these, sources of dissolved sulfate in Yellow River and its tributaries with the mixing ratios of different sources in Qinhe River could be identified. The results indicate that: ① dissolved sulfate in Yellow River mainly derived from Quaternary loess, and the mean sulfate content was 2.23 mmol/L, with the mean δ 34 S SO 4 and δ 18 O SO 4 values of +8.9‰ and +10.4‰, respectively; ② during flood season, 24% of dissolved sulfate in Qinhe River derived from rain water, 61 percent of dissolved sulfate derived from soil, and 15 percent of dissolved sulfate derived from gypsum dissolution. During temperate season, the mixing ratios of rain water, soil and gypsum were 39%, 36% and 25%, respectively. The mean sulfate concentration was 2.44 mmol/L, and mean δ 34 S SO 4 and δ 18 O SO 4 values were +9.8‰ and +9.7‰, respectively; and, ③ dissolved sulfate in Luohe River more derived from sewage water and that in Yihe River was mainly controlled by soil and fertilizer. The mean sulfate concentration in Yiluo River was 1.27 mmol/L, and mean δ 34 S SO 4 and δ 18 O SO 4 values were +10.4‰ and +6.5‰, respectively. Dissolved sulfate in local river water was mainly controlled by natural weathering processes, such as dissolution of evaporites minerals and soil sulfate. At the same time, it should not be ignored that anthropogenic activities had altered the hydrochemical composition of the water Yiluo River, which should be paid more attention by local surface water managers.

为了准确识别河水硫酸盐受自然风化和人为活动影响的过程,做好地表水资源管理,选择黄河小浪底水库以下干流和支流河水为主要研究对象,分期采集河水样品,采用硫酸盐硫和氧同位素,结合水化学组成及潜在硫酸盐来源硫和氧同位素范围,判定黄河及支流河水硫酸盐的来源及混入比例。结果表明:① 研究区黄河河水硫酸盐主要来源于第四纪黄土中易溶硫酸盐,干流河水SO 4 2- 含量均值为2.23 mmol/L,δ 34 S SO 4 和δ 18 O SO 4 均值分别为+8.9‰和+10.4‰;② 研究区沁河丰水期河水硫酸盐24%来源于大气降水,61%来源于土壤硫酸盐溶解,15%来自于石膏溶解;平水期河水硫酸盐39%来源于大气降水,36%来源于土壤硫酸盐溶解,25%来源于石膏溶解。沁河河水SO 4 2- 含量均值为2.44 mmol/L,δ 34 S SO 4 和δ 18 O SO 4 均值分别为+9.8‰和+9.7‰;③ 研究区洛河河水硫酸盐受生活污水影响较大,伊河河水硫酸盐受到土壤硫酸盐溶解和化学肥料溶解的共同影响,伊洛河河水SO 4 2- 含量均值为1.27 mmol/L,δ 34 S SO 4 和δ 18 O SO 4 均值分别为+10.4‰和+6.5‰。蒸发盐类矿物溶解以及土壤硫酸盐溶解等自然风化过程是控制区域河水硫酸盐来源的重要过程,人为活动对伊洛河河水硫酸盐的贡献不容忽视。

... ^[37],而S O42-多来自于大气酸沉降和工矿业活动^[46],因此,一般情况下,水中的 N O3-和 S O42-浓度的变化主要反映来自农业活动和工业活动的影响 ...

2011

0.0

. 2011, 30(4):135-139 DOI:doi:10.3969/j.issn.1001-3644.2011.04.029

Analysis of the distribution and causes of acid rain in southern China

中国南方酸雨的分布特征及其成因分析

Xu Xinhui , Gao Hongwen.

许新辉, 郜洪文

本文阐述了酸雨的危害、近几年中国南方地区酸雨的污染的时空分布状况、酸雨的成因等3方面的内容。研究表明:我国南方酸雨区的酸雨污染状况基本上处在一个稳定的时期。降水pH5的区域有从长江中上游向长江中下游发展的趋势;在时间分布上,秋季冬季降水pH低,酸雨发生的频率高;春季夏季降水pH高,酸雨发生的频率低。在酸雨的成因上,着重讨论了大气性质、污染物的迁移和扩散、气候条件、大气中颗粒物浓度以及土壤性质对酸雨形成的影响。

... 但研究区位于湖南南部,湖南是受严重的酸雨污染区之一,酸雨发生频率高,但不同季节又存在明显差异的酸雨频率^[47],这可能是引起研究区4条地下河中不同季节S O42-差异的主要原因 ...