酸雨对桂林枯水期岩溶地下水δ13CDIC及碳汇效应的影响

黄奇波; 覃小群; 刘朋雨; 唐萍萍

doi:10.3799/dqkx.2015.103

酸雨对桂林枯水期岩溶地下水δ¹³C_DIC及碳汇效应的影响

doi: 10.3799/dqkx.2015.103

黄奇波^{1, 2, 3,},
覃小群^{2, 3},
刘朋雨^{2, 3},
唐萍萍^{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

基金项目:

中国地质调查项目 12120113005200

国家自然科学基金项目 41302211

详细信息

作者简介:
黄奇波(1982-), 男, 博士研究生, 主要从事岩溶水文地质科研工作.E-mail: qbohuang0108@163.com

中图分类号: P631
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出版历程
- 收稿日期: 2014-12-06
- 刊出日期: 2015-07-15

Impact of Acid Rain to δ¹³C_DIC of Karst Groundwater and Carbon Sink in Dry Season in Guilin

Huang Qibo^{1, 2, 3
,},
Qin Xiaoqun^{2, 3},
Liu Pengyu^{2, 3},
Tang Pingping^{2, 3}

1.
School of Environmental Studies, China University of Geosciences, Wuhan 430074, China
2.
Institute of Karst Geology, Chinese Academy of Geological Sciences, Guilin 541004, China
3.
Guangxi Key Laboratory of Karst Dynamics, Ministry of Land and Resources, Guilin 541004, China

摘要

摘要: 定量评价硫酸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.选取受酸雨影响的桂林岩溶区为研究对象, 在枯水期对研究区14个岩溶大泉和15条地下河水化学成分和碳同位素进行了测试分析, 结果表明: 岩溶大泉和地下河中阳离子以Mg²⁺和Ca²⁺为主, 阴离子以HCO₃^-为主, 分别占阳离子和阴离子组成的90%以上, SO₄^2-含量较低, 其含量范围为0.004~0.213mmol/L; 所占阴离子组成比例为0.12%~6.11%;δ¹³C_DIC、[Ca²⁺+Mg²⁺]/[HCO₃^-]更偏向于碳酸溶解端元, 离硫酸溶解端元距离远, 证实硫酸参与碳酸盐岩的溶解对地下水无机碳(dissolved inorganic carbon, 简称DIC)及δ¹³C_DIC的影响有限; 与Sr²⁺/Ca²⁺值一样, δ¹³C_DIC主要受径流条件控制, 其大小可以反映地下水径流条件的强弱.利用化学计量关系计算出由硫酸溶蚀碳酸盐岩的平均比例为22.64%, 产生的DIC(HCO₃^-_H₂SO₄)占总DIC的平均比例为13.04%, 碳酸产生的DIC(HCO₃^-_H₂CO₃)占地下水总DIC的比例为86.96%, 其中来源于土壤大气中的HCO₃^-比例为43.48%.因此, 扣除硫酸对地下水中DIC的贡献后, 岩溶碳汇效应将减少13.04%.
- 岩溶碳汇 /
- 硫酸 /
- 溶解无机碳同位素 /
- Sr²⁺/Ca²⁺桂林岩溶区 /
- 地下水 /
Abstract: Quantitative evaluation of the impact of sulfuric acid to karst carbon sink not only improves the estimation accuracy of karst carbon sinks, but also facilitates research on global climate change. In this paper, Guilin karst area affected by acid rain is selected for studying. The results of testing and analysis of the chemical composition and inorganic carbon isotope in 14 karst spring and 15 subterraneans show that in both karst spring and subterranean, Mg²⁺ and Ca²⁺ are the main negative ions, and HCO₃^- is the main positive ion, which were accounted for more than 90% of negative ion and positive ion respectively, and SO₄^2- has a lower content, which content range was 0.004-0.213mmol/L and the composition ratio was 0.12%-6.11%; The δ¹³C_DIC, [Ca²⁺+Mg²⁺]/[HCO₃^-] are more inclined to carbonate dissolution endmember, and the longer distance from sulfuric acid dissolution endmember indicates the limited impact of sulfuric acid dissolution of carbonate rocks involved in groundwater inorganic carbon (DIC) and δ¹³C_DIC. Same as the situation of Sr²⁺/Ca²⁺ values, δ¹³C_DIC could reflect the run-off condition of groundwater to some degree. Using the stoichiometry method calculate, the average proportion of DIC(HCO₃^-_H₂SO₄) produced by sulfuric acid gained by stoichiometric relationship is 22.64%, accounts for 13.04%, while that produced by carbonic acid accounts for 86.96%, of which 43.48% comes from the soil atmosphere. Deducting DIC contribution of sulfuric acid to the groundwater, 13.04% karst carbon sink will be reduced.
- karst carbon sink /
- sulfuric acid /
- C isotope of dissolved inorganic carbon /
- Sr²⁺/Ca²⁺ /
- Guilin karst area /
- groundwater

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图 1 桂林水文地质图

1.灰岩；2.灰岩与白云岩互层；3.碳酸盐岩夹碎屑岩；4.非碳酸盐岩；5.地层分布界线；6.岩溶泉及编号；7.地表河流；8.地下河及出口和编号

Fig. 1. Hydrogeological map of Guilin

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图 2 地下水主要离子三角图

Fig. 2. Ternary diagrams of groundwater chemical composition

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图 3 地下水中Sr²⁺/Ca²⁺与δ¹³C_DIC之间的关系

Fig. 3. Co-variation of inorganic carbon isotope (δ¹³C_DIC) value vs. Sr²⁺/Ca²⁺ value in groundwater

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图 4 地下水[Ca²⁺+Mg²⁺]/[HCO₃^-]与[SO₄^2-]/[HCO₃^-]的当量比值关系

Fig. 4. Equivalent ratios of [Ca²⁺+Mg²⁺]/[HCO₃^-] vs. [SO₄^2-]/[HCO₃^-] in groundwater

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图 5 地下水δ¹³C_DIC与[Ca²⁺+Mg²⁺]/[HCO₃^-]比值相互变化特征

Fig. 5. Variations of δ¹³C_DIC vs. [Ca²⁺+Mg²⁺]/[HCO₃^-] in karst groundwater

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图 6 SO₄^2-浓度与硫酸溶蚀碳酸盐岩的比例((Ca_(1-x)Mg_x)CO_3H₂SO₄)关系(a)和与硫酸产生的HCO₃^-(HCO₃^-_H₂SO₄)占总[HCO₃^-]的比例关系(b)

Fig. 6. Co-variation of SO₄^2- vs. proportion of carbonate rock produced by sulfuric acid (a) and DIC(HCO₃^-_H₂SO₄) produced by sulfuric acid (b)

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表 1 桂林地区岩溶地下水水化学特征

Table 1. The chemical compositions of karst groundwater in Guilin

类型	编号	经度	纬度	pH	水温(℃)	电导率(μs/cm)	K⁺(mmol/L)	Na⁺(mmol/L)	Ca²⁺ (mmol/L)	Mg²⁺ (mmol/L)	Cl^- (mmol/L)	SO₄^2- (mmol/L)	HCO₃^- (mmol/L)	Sr²⁺ (μmol/L)	Sr²⁺/Ca²⁺ (10^-3)	ZT⁺(%)	ZT^-(%)	NICB (%)	δ¹³C_DIC (‰)	硫酸溶蚀碳酸盐岩的比例(%)	[HCO₃^-]/[H₂CO₃]的比例(%)
岩溶大泉	A01	110°14′18″	25°27′36″	7.30	20.3	288	0.010	0.031	1.609	0.071	0.125	0.087	2.796	0.696	0.433	3.40	3.09	4.7	-12.29	29.16	17.07
	A02	110°23′18″	25°28′21″	7.48	20.7	301	0.040	0.064	1.542	0.103	0.174	0.084	2.889	0.695	0.451	3.40	3.23	2.5	-10.79	19.60	10.86
	A03	110°18′26″	25°26′48″	7.39	19.6	378	0.015	0.033	2.085	0.062	0.174	0.140	3.821	0.735	0.353	4.34	4.27	0.8	-14.20	18.30	10.07
	A04	110°22′01″	25°04′03″	7.50	15.8	341	0.005	0.009	1.850	0.200	0.075	0.128	3.541	0.667	0.360	4.11	3.87	3.0	-13.43	23.43	13.27
	A05	110°33′06″	24°56′21″	7.25	21.4	419	0.015	0.062	1.887	0.560	0.174	0.193	4.100	0.716	0.379	4.97	4.66	3.2	-11.94	29.37	17.21
	A06	111°20′10″	24°15′00″	7.28	21.2	316	0.012	0.016	1.551	0.355	0.125	0.087	3.308	0.621	0.400	3.84	3.61	3.1	-10.66	22.37	12.59
	A07	111°15′42″	24°23′58″	7.87	13.9	492	0.056	0.120	2.291	0.565	0.349	0.163	4.846	0.688	0.300	5.89	5.52	3.2	-11.10	27.61	16.02
	A08	111°02′22″	24°24′38″	7.14	21.6	385	0.017	0.035	1.815	0.443	0.224	0.107	3.821	0.621	0.342	4.57	4.26	3.5	-12.88	27.37	15.85
	A09	111°07′00″	24°29′35″	7.39	21.9	271	0.030	0.086	1.138	0.434	0.174	0.027	2.842	0.480	0.422	3.26	3.07	3.0	-9.48	14.01	7.53
	A10	111°01′30″	25°06′45″	7.43	20.5	309	0.025	0.043	1.527	0.246	0.174	0.008	3.215	1.374	0.900	3.61	3.41	3.0	-9.24	14.00	7.53
	A11	110°53′20″	25°06′50″	7.61	21.4	266	0.011	0.028	1.296	0.247	0.174	0.028	2.749	0.391	0.302	3.13	2.98	2.4	-10.90	16.61	9.06
	A12	110°42′27″	24°41′22″	7.04	21.1	365	0.007	0.014	1.760	0.408	0.100	0.064	3.867	0.968	0.550	4.36	4.10	3.1	-11.81	17.95	9.86
	A13	110°21′25″	24°37′53″	7.18	21.7	326	0.031	0.060	1.486	0.588	0.249	0.143	3.495	0.727	0.489	4.24	4.03	2.5	-12.28	27.85	16.17
	A14	110°23′09″	24°15′03″	7.66	16.5	412	0.018	0.057	1.975	0.405	0.199	0.100	4.147	0.714	0.362	4.83	4.55	3.1	-11.67	22.43	12.63
地下河	B01	110°37′14″	25°34′26″	8.09	14.4	201	0.014	0.025	0.909	0.162	0.174	0.060	1.677	0.475	0.523	2.18	1.97	5.0	-12.33	36.61	22.40
	B02	110°33′23″	25°14′11″	7.65	18.3	373	0.017	0.029	2.024	0.190	0.125	0.105	3.867	0.752	0.372	4.47	4.20	3.1	-14.41	21.73	12.19
	B03	110°31′06″	25°11′23″	7.61	19.8	297	0.015	0.023	1.512	0.547	0.150	0.117	3.518	0.479	0.317	4.16	3.90	3.1	-12.70	25.42	14.56
	B04	110°31′35″	25°11′38″	8.25	17.5	358	0.013	0.022	1.341	0.448	0.174	0.004	3.122	0.566	0.422	3.61	3.30	4.5	-12.38	21.12	11.81
	B05	110°30′53″	25°04′45″	8.00	19.0	317	0.011	0.016	1.524	0.184	0.125	0.005	3.169	0.579	0.380	3.44	3.30	2.1	-13.83	9.56	5.02
	B06	110°59′41″	24°30′19″	7.15	20.7	428	0.018	0.052	2.164	0.295	0.199	0.080	4.333	0.787	0.364	4.99	4.69	3.0	-13.29	20.56	11.46
	B07	110°55′37″	24°38′07″	7.50	18.9	202	0.041	0.123	0.889	0.183	0.100	0.007	2.050	0.413	0.465	2.31	2.16	3.2	-12.23	0.37	0.19
	B08	110°42′26″	24°41′22″	7.44	20.6	485	0.022	0.038	2.080	0.783	0.150	0.104	5.079	0.695	0.334	5.79	5.44	3.1	-14.03	19.86	11.02
	B09	110°26′58″	24°58′55″	7.56	20.7	454	0.011	0.016	2.376	0.361	0.125	0.107	4.846	0.713	0.300	5.50	5.18	3.0	-15.03	20.04	11.14
	B10	110°56′53″	25°10′43″	7.67	16.8	217	0.000	0.029	0.995	0.276	0.100	0.087	2.190	0.450	0.452	2.57	2.46	2.1	-11.53	21.49	12.04
	B11	110°20′12″	24°24′37″	8.06	18.7	232	0.019	0.033	1.020	0.322	0.125	0.139	2.004	0.657	0.645	2.74	2.41	6.4	-12.41	45.62	29.55
	B12	110°22′33″	24°24′26″	7.45	18.4	422	0.030	0.056	1.822	0.568	0.199	0.213	3.774	1.116	0.613	4.87	4.40	5.0	-11.59	39.14	24.33
	B13	110°24′19″	24°47′36″	7.77	19.5	441	0.015	0.036	1.957	0.634	0.224	0.146	4.403	0.638	0.326	5.23	4.92	3.1	-13.16	27.10	15.67
	B14	110°33′48″	24°54′31″	7.79	17.1	402	0.009	0.019	1.619	0.799	0.125	0.067	4.380	0.782	0.483	4.86	4.64	2.4	-13.53	15.48	8.39
	B15	110°27′07″	25°03′07″	8.21	16.6	301	0.015	0.027	1.562	0.162	0.125	0.087	2.982	0.680	0.436	3.49	3.28	3.1	-12.77	22.47	12.66

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表 2 不同溶蚀条件下HCO₃^-所占比例

Table 2. Proportion of HCO₃^- in different corrosion conditions

溶蚀条件	H₂SO₄溶蚀比例(%)	HCO₃^-_H₂SO₄(%)	HCO₃^-_H₂CO₃(%)	HCO₃_{土壤大气(%)}^-
硫酸、碳酸溶蚀碳酸盐岩	22.64	13.04	86.96	43.48
碳酸溶蚀碳酸盐岩	0	0	100.00	50.00

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