石灰土对硫酸型酸雨缓冲过程模拟及碳汇效应研究

赵光帅; 黄奇波; 朱义年; 李腾芳; 普政功

doi:10.11932/karst20220504

石灰土对硫酸型酸雨缓冲过程模拟及碳汇效应研究

1.
桂林理工大学环境科学与工程学院, 广西桂林 541004

2.
中国地质科学院岩溶地质研究所/自然资源部、广西岩溶动力学重点实验室, 广西桂林 541004

3.
联合国教科文组织国际岩溶研究中心/岩溶动力系统与全球变化国际联合研究中心, 广西桂林 541004

4.
广西岩溶资源环境工程技术研究中心, 广西桂林 541004

基金项目: 广西自然科学基金重点基金项目(2018GXNSFDA281036)；中国地质调查项目(DD20221758)

详细信息

作者简介: 赵光帅(1989－），男，博士研究生，助理研究员，主要从事岩溶碳循环与全球变化研究。E-mail: zhaoguangshuai@mail.cgs.gov.cn

通讯作者: 黄奇波（1982－），男，博士，研究员，主要从事岩溶水文地质、岩溶碳循环与全球变化研究。E-mail: qbohuang0108@163.com

中图分类号: X517；X142

收稿日期: 2022-03-20

刊出日期: 2022-10-25

Simulation of buffering process and carbon sink effect of lime soil on sulfuric acid rain

1.
College of Environmental Science and Engineering, Guilin University of Technology, Guilin, Guangxi 541004，China

2.
Institute of Karst Geology, CAGS / Key Laboratory of Karst Dynamics, MNR & GZAR, Guilin, Guangxi 541004,China

3.
International Research Centre on Karst under the Auspices of UNESCO/National Center for International Research on Karst Dynamic System and Global Change, Guilin, Guangxi 541004,China

4.
Guangxi Karst Resources and Environment Research Center of Engineering Technology, Guilin, 541004, Guangxi, China

More Information

Corresponding author: HUANG Qibo, qbohuang0108@163.com

Received Date: 20 March 2022

Publish Date: 25 October 2022

摘要

摘要:
硫酸型酸雨沉降至地表经石灰土缓冲后，参与碳酸盐岩溶蚀及对岩溶碳汇的影响尚不明确，严重制约了我国岩溶碳汇效应的准确评估。本研究通过设置不同土层厚度条件下pH 4.5的硫酸型酸雨淋滤实验，以明确石灰土对硫酸型酸雨的缓冲过程及关键控制因素。结果表明：石灰土对酸雨的缓冲作用主要发生在表层(10 cm)，淋出液中Ca²⁺、Mg²⁺、${\rm{HCO}}_3^{-}$含量在淋溶初期均表现快速降低，当淋溶量(土壤水达饱和后)为1 020 mL时Ca²⁺、Mg²⁺、${\rm{HCO}}_{{3}}^{-}$淋失量趋于稳定，稳定淋失量分别为20 mg·L⁻¹、6 mg·L⁻¹、40 mg·L⁻¹。淋出液中被酸雨H⁺交换出的Ca²⁺、Mg²⁺仅占很小一部分，土壤水溶性Ca²⁺、Mg²⁺是淋出液中Ca²⁺、Mg²⁺的主要部分，开放系统中，大气和土壤CO₂溶于降雨形成H₂CO₃不仅增加碳汇，且H₂CO₃解离产生的H⁺交换土壤中交换态Ca²⁺、Mg²⁺，造成Ca²⁺、Mg²⁺的淋失量不容忽视。不同厚度石灰土中交换性钙镁可缓冲酸雨容量均大于土壤碳酸钙矿物可缓冲容量，前者是后者的1.17~1.59倍。相同酸度、同一降雨量(土壤水达饱和后)下土壤盐基离子参与酸雨缓冲产生的碳汇量约为碳酸盐矿物风化缓冲产生碳汇量的2.1倍，不同厚度(≥10 cm)石灰土产生的碳汇量大致相等。根据本次实验及桂林市降雨数据计算，桂林市质纯石灰岩风化残积土壤区(土层厚度≥10 cm)，土壤盐基离子参与酸雨缓冲每年可产生0.59 ~0.93 mol·m⁻²的碳汇通量。
- 石灰土 /
- 硫酸型酸雨 /
- 盐基离子 /
- 缓冲机制 /
- 碳汇通量
Abstract:
After sulfuric acid rain settles to the surface and is buffered by lime soil, its participation in carbonate rock erosion and its impact on karst carbon sink are still unclear, which seriously restricts the accurate assessment of karst carbon sink effect in China. In order to clarify the buffering process and key control factors of lime soil to sulfuric acid rain, we conducted leaching experiments of sulfuric acid rain with pH=4.5 under different soil thicknesses. Results show that contents of Ca²⁺, Mg²⁺ and ${\rm{HCO}}_3^{-}$ in leaching solution decrease rapidly at the initial stage of leaching. When the leaching amount (after soil water reaches saturation) reaches 1,020 mL, the leaching loss of Ca²⁺, Mg²⁺ and ${\rm{HCO}}_3^{-}$ tends to be stable, and stable leaching amounts are 20 mg·L⁻¹, 6 mg·L⁻¹ and 40 mg·L⁻¹ respectively. The same ion in leaching solution of different thicknesses of soil columns shows the same trend, which indicates that the lime soil buffering of acid rain may mainly occur in the 10 cm (surface) soil layer. Ca²⁺ and Mg²⁺ exchanged by acid rain H⁺ in leaching solution only accounts for a small part, and the soil water-soluble Ca²⁺ and Mg²⁺ is the main part of Ca²⁺ and Mg²⁺ in leaching solution. In an open system, atmospheric and soil CO₂ dissolves in rainfall to form H₂CO₃, which not only increases carbon sink, but also exchanges Ca²⁺ and Mg²⁺ in soil with H+ generated by the dissociation of H₂CO₃. The leaching amount of Ca²⁺ and Mg²⁺as a result cannot be ignored. The special physical structure of topsoil may produce preferential flow, which will significantly reduce the exchangeable point of H⁺ in leachate, causing dissolution of carbonate minerals to assist the buffering of H⁺ in leachate. The karst area is the main place for carbon loss in terrestrial ecosystems, and the most intense carbon leaching occurs in surface soil. Exchangeable calcium, exchangeable magnesium and carbonate minerals in lime soil are principal reactants for buffering acid rain. The buffering capacity of exchangeable calcium and magnesium in lime soil with different thicknesses is greater than that of soil calcium carbonate minerals, and the former is 1.17-1.59 times as large as that of the latter. Under the same acidity and the same rainfall (after the soil water reaches saturation), the carbon sink generated by soil base ions participating in acid rain buffering is about 2.1 times as large as that generated by weathering buffering of carbonate minerals. Under the same rainfall conditions, the existence of lime soil can significantly increase carbon sink, and the carbon sink generated by lime soil with different thicknesses (≥10 cm) is roughly equal. According to this experiment and the rainfall data of Guilin, in the weathered residual soil area of pure limestone in Guilin (soil thickness greater than 10 cm), the participation of soil base ions in acid rain buffering can produce 0.59-0.93 mol·m⁻² carbon sink flux per year.
- lime soil /
- sulfuric acid rain /
- base ions /
- buffer mechanism /
- carbon sink flux

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图 1 供试土壤自然剖面

Figure 1.

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图 2 淋滤实验装置

Figure 2.

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图 1 Ca²⁺、Mg²⁺淋溶动态变化

Figure 1.

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图 2 ${\rm{HCO}}_3^{-}$、${\rm{SO}}_4^{2-}$淋溶动态变化

Figure 2.

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图 3 淋出液[Ca²⁺+Mg²⁺]与${\rm{HCO}}_3^{-}$毫克当量关系

Figure 3.

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表 1 供试土壤基本理化性质

Table 1. Physico-chemical properties of soil samples

	石灰土厚度/cm
	10	20	30	40	50	60	70	80
pH	6.62	6.66	6.51	6.63	6.62	6.52	6.54	6.92
容重/g·cm⁻³	1.47	1.37	1.24	1.33	1.58	1.68	1.63	1.62
含水率/%	23.2	26.6	24.7	27.9	29.7	27.0	25.6	27.4
水溶性Ca²⁺/×10^-6	5.75	11.70	8.97	10.90	8.89	3.10	11.80	8.02
交换性钙/cmol·kg⁻¹	7.4	4.7	4.2	4.6	6.4	4.8	5.0	5.3
水溶性Mg²⁺/×10^-9	3.48	3.89	4.77	6.42	5.90	4.69	5.90	6.02
交换性镁/cmol·kg⁻¹	2.4	1.9	1.7	2.1	2.4	2.5	2.7	2.9
碳酸钙/×10^-3	6.83	8.34	2.77	3.00	3.70	5.55	7.30	5.09

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表 2 石灰土淋出液水化学分析结果 (mg·L⁻¹)

Table 2. Hydrochemical analysis results of leachate from lime soil (mg·L⁻¹)

土层厚度/cm		pH	Ca²⁺	Mg²⁺	K⁺	Na⁺				Cl⁻
10 (n=30)	最大值	7.71	127.79	44.44	8.06	6.90	60.63	33.35	547.59	13.94
	最小值	7.15	15.68	5.72	2.97	0.59	28.29	19.83	3.99	1.48
	平均值	7.52	27.68	10.00	3.69	1.30	50.26	24.31	61.33	3.18
	标准差	0.17	27.07	9.87	1.33	1.32	9.52	3.11	138.60	3.18
	变异系数	2.30	97.79	98.61	36.18	101.77	18.94	12.79	225.98	100.30
20 (n=30)	最大值	7.46	69.97	16.61	12.51	5.36	44.46	34.83	249.84	14.56
	最小值	6.42	17.08	4.40	6.21	0.77	16.17	17.14	4.86	1.90
	平均值	7.00	30.20	7.84	8.48	1.61	31.60	28.01	81.15	4.36
	标准差	0.28	15.34	4.02	2.27	0.97	9.25	6.61	86.15	2.77
	变异系数	4.00	50.79	51.32	26.83	60.20	29.26	23.61	106.15	63.56
30 (n=30)	最大值	7.53	55.79	12.04	6.77	5.05	44.46	40.76	175.98	10.50
	最小值	6.73	19.04	4.64	4.10	0.92	28.29	20.44	4.77	1.90
	平均值	7.18	33.79	8.19	5.42	1.79	39.28	30.34	77.23	4.62
	标准差	0.25	10.54	2.47	0.94	0.86	4.40	7.17	54.16	1.86
	变异系数	3.51	31.18	30.16	17.30	48.09	11.20	23.63	70.13	40.40
40 (n=30)	最大值	7.57	48.20	9.30	4.82	5.24	60.63	29.72	119.70	7.74
	最小值	6.88	21.55	5.29	3.36	1.26	34.36	16.52	13.02	3.11
	平均值	7.23	29.60	7.10	3.99	2.01	42.98	21.73	59.98	4.37
	标准差	0.14	7.49	1.53	0.54	0.92	5.38	4.51	41.55	1.04
	变异系数	1.95	25.32	21.54	13.43	45.68	12.53	20.77	69.28	23.75
50 (n=30)	最大值	7.60	50.54	9.54	4.37	6.03	64.67	30.32	115.02	8.77
	最小值	6.82	19.55	4.74	2.81	1.16	36.38	16.77	5.72	3.10
	平均值	7.23	25.58	6.14	3.25	2.08	44.53	20.69	41.80	4.14
	标准差	0.22	6.91	1.22	0.41	1.08	6.24	3.24	31.25	1.43
	变异系数	3.10	26.99	19.89	12.70	51.97	14.02	15.67	74.76	34.54
60 (n=30)	最大值	7.50	47.84	10.43	3.72	7.26	52.55	33.96	125.59	9.41
	最小值	6.85	19.24	5.16	2.28	1.38	32.34	16.60	3.52	3.60
	平均值	7.16	24.84	6.67	2.74	2.23	42.84	20.78	39.90	4.63
	标准差	0.18	6.28	1.27	0.36	1.20	6.59	3.87	32.11	1.48
	变异系数	2.45	25.29	19.10	12.97	53.78	15.39	18.64	80.48	32.06
70 (n=30)	最大值	7.45	43.18	11.03	2.62	5.87	48.50	32.28	109.33	9.60
	最小值	6.89	17.63	5.56	1.63	1.39	28.29	18.60	3.30	3.60
	平均值	7.21	22.93	7.11	1.92	2.19	38.74	21.66	40.08	4.92
	标准差	0.15	5.43	1.27	0.22	0.95	7.60	3.10	29.48	1.42
	变异系数	2.02	23.68	17.87	11.46	43.28	19.62	14.32	73.56	28.88
80 (n=30)	最大值	7.38	30.82	8.25	1.08	3.38	44.46	18.78	62.97	8.53
	最小值	6.74	17.10	6.04	0.75	1.60	28.29	14.33	16.36	4.88
	平均值	7.08	21.31	7.39	0.89	2.02	35.30	15.41	45.09	5.81
	标准差	0.19	2.89	0.66	0.07	0.38	4.49	1.08	15.33	0.87
	变异系数	2.64	13.54	8.90	8.33	18.84	12.73	7.01	33.99	15.03
注：n为样品数量。

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表 3 不同厚度土壤Ca²⁺、Mg²⁺含量及可参与淋溶量

Table 3. Contents of Ca²⁺ and Mg²⁺ in soil with different thicknesses and the amount that can be involved in leaching

	石灰土厚度/cm
	10	20	30	40	50	60	70	80
单层水溶性Ca²⁺/mg	21.48	39.78	28.03	35.61	34.04	12.84	48.12	32.04
累积水溶性Ca²⁺/mg	21.48	61.26	89.29	124.90	158.94	171.78	219.90	251.94
水溶性Ca²⁺可参与淋溶量/L	1.07	3.06	4.46	6.24	7.95	8.59	11.00	12.60
单层水溶性Mg²⁺/mg	13.00	13.23	14.91	20.97	22.59	19.43	24.06	24.05
累积水溶性Mg²⁺/mg	13.00	26.22	41.13	62.10	84.70	104.13	128.19	152.24
水溶性Mg²⁺可参与淋溶量/L	2.17	4.37	6.86	10.35	14.12	17.36	21.37	25.37

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表 4 不同厚度土壤累积Ca²⁺、Mg²⁺含量及淋失比

Table 4. Accumulative content of Ca²⁺ and Mg²⁺ in soil with different thicknesses and its leaching-loss ratio

	石灰土厚度/cm
	10	20	30	40	50	60	70	80
累积土壤水溶性Ca²⁺/meq	1.07	3.06	4.46	6.24	7.95	8.59	11.00	12.60
累积土壤水溶性Mg²⁺/meq	1.08	2.19	3.43	5.18	7.06	8.68	10.68	12.69
累积土壤水溶性Ca²⁺+Mg²⁺/meq	2.16	5.25	7.89	11.42	15.00	17.27	21.68	25.28
淋出液水溶性Ca²⁺+Mg²⁺/meq	6.95	8.23	8.65	6.81	5.25	5.43	5.47	5.46
水溶性Ca²⁺+Mg²⁺淋失比/%	321.76	156.76	109.63	59.63	35.00	31.44	25.23	21.60
累积土壤交换性Ca²⁺/mg	11056	17448	22698	28709	38511	46466	54622	63091
累积土壤交换性Ca²⁺/meq	553	872	1135	1435	1926	2323	2731	3155
累积土壤交换性Mg²⁺/mg	2151	3702	4977	6623	8829	11315	13957	16738
累积土壤交换性Mg²⁺/meq	179	308	415	552	736	943	1163	1395
累积土壤交换性Ca²⁺+Mg²⁺/meq	732	1180	1550	1987	2662	3266	3894	4550
淋出液交换性Ca²⁺+Mg²⁺/meq	4.36	2.80	3.44	3.75	3.88	3.74	3.40	3.11
交换性Ca²⁺+Mg²⁺淋失比/%	0.60	0.24	0.22	0.19	0.15	0.11	0.09	0.07

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表 5 不同厚度石灰土可缓冲酸雨(pH＝4.5)容量

Table 5. Capacity of buffer acid rain(pH＝4.5) in different thicknesses of lime

	石灰土厚度/cm
	10	20	30	40	50	60	70	80
土壤交换性Ca²⁺+Mg²⁺/meq	732	1 180	1 550	1 987	2 662	3 266	3 894	4 550
淋出液交换性Ca²⁺+Mg²⁺/meq	4.36	2.80	3.44	3.75	3.88	3.74	3.40	3.11
H_交换态/mm(pH＝4.5)	27 269	68 449	73 184	86 061	111 434	141 836	186 019	237 625
土壤碳酸钙_以钙计/g	10.20	21.55	25.01	28.93	34.60	43.79	55.70	63.84
溶蚀矿物态钙/g	0.09	0.06	0.07	0.08	0.08	0.07	0.07	0.06
H_矿物态/mm(pH＝4.5)	18408	58 336	58 030	58 735	70 247	101 606	129 240	172 815
H_交换态/ H_矿物态	1.48	1.17	1.26	1.47	1.59	1.40	1.44	1.38

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表 6 酸雨沉降下不同厚度石灰土产生的碳汇通量

Table 6. The carbon sink flux of lime soil with different thicknesses caused by acid rain deposition

	石灰土厚度/cm
	10	20	30	40	50	60	70	80
碳汇量b_y/mmol	4.20	2.64	3.28	3.59	3.72	3.58	3.24	2.95
碳汇量b_t/mmol	2.02	1.24	1.56	1.72	1.78	1.71	1.54	1.40
碳汇量b_y/碳汇量b_t	2.08	2.13	2.10	2.09	2.09	2.09	2.10	2.11
碳汇量C_Y/mol·m⁻²·y⁻¹	0.93	0.59	0.73	0.80	0.83	0.79	0.72	0.65
碳汇量C_T/mol·m⁻²·y⁻¹	0.45	0.28	0.35	0.38	0.39	0.38	0.34	0.31

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石灰土对硫酸型酸雨缓冲过程模拟及碳汇效应研究

作者简介: 赵光帅(1989－），男，博士研究生，助理研究员，主要从事岩溶碳循环与全球变化研究。E-mail: zhaoguangshuai@mail.cgs.gov.cn

通讯作者: 黄奇波（1982－），男，博士，研究员，主要从事岩溶水文地质、岩溶碳循环与全球变化研究。E-mail: qbohuang0108@163.com

Simulation of buffering process and carbon sink effect of lime soil on sulfuric acid rain

Corresponding author: HUANG Qibo, qbohuang0108@163.com

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