Characteristics and Sources of Dissolved Inorganic Carbon and Nitrate in Lijiang River Basin
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摘要: 以漓江流域境内地表河和地下河为研究对象，通过测定、分析水体中的水化学组成以及δ13CDIC、δ15N-NO3-、δ18O-NO3-等，利用同位素质量平衡混合模型，初步探讨了漓江流域境内DIC、硝酸盐的分布特征及其来源.结果表明：漓江流域DIC（即HCO3-）浓度和无机碳稳定同位素（δ13CDIC）分别在12.20~402.60 mg·L-1和-17.29‰~-10.01‰，平均值分别为140.3 mg·L-1和-13.06‰.NO3-浓度在2.37~35.38 mg·L-1，δ15N-NO3-在0.99‰~11.09‰，均展现出明显的空间变异特征.有机肥和污水对漓江流域硝酸盐的贡献最为显著，贡献比达57.00%.其次是化肥、降雨中的NH4+和土壤N，贡献比分别是36.45%，6.55%.流域内DIC主要来源于碳酸盐岩的风化和土壤CO2的溶解，同时也受硝酸溶蚀碳酸盐岩和大气CO2的影响.结果可为定制有效的控制硝酸盐的输入途径，净化水质测略提供依据.Abstract: The distribution characteristics and sources of DIC and nitrate in the Lijiang River basin are studied using isotope mass balance models, by which the hydrochemical composition of the surface and underground rivers in the Lijiang River basin, δ13CDIC, δ15N-NO3- and δ18O-NO3- are measured and analyzed. The results show that the concentration of DIC (HCO3-) and inorganic carbon stable isotopes (δ13CDIC) in Lijiang River basin range from 12.20 to 402.60 mg·L-1, and from -17.29‰ to -10.01‰ respectively, with the average value of 140.3 mg·L-1 and -13.06‰ respectively. The concentration of NO3- is between 2.37 and 35.38 mg·L-1, and δ15N-NO3- is between 0.99‰ and 11.09‰, both showing obvious spatial variation characteristics. It is concluded that organic manure and sewage have the most significant contribution to nitrate in the Lijiang River basin, with a contribution ratio of 57.00%, which is followed by NH4+ in fertilizer and precipitation, and soil N, with contribution ratios of 36.45% and 6.55% respectively. The source of DIC in the drainage basin is mainly due to the weathering of carbonate rocks and the dissolution of soil CO2, which is also affected by the corrosion of carbonate rocks by nitric acid and atmospheric CO2. The corrosion intensity of nitric acid on carbonate rocks is controlled not only by the degree of nitrogen pollution in water, but also by the source of nitrogen pollution. The results can provide a basis for customizing effective nitrate input channels and purifying water quality.
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Key words:
- Lijiang River /
- δ13CDIC /
- dissolved inorganic carbon (DIC) /
- δ15N-NO3- /
- δ18O-NO3- /
- nitrate /
- hydrogeology
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图 1 漓江流域水文地质图与取样点位置
Fig. 1. Hydrogeological map and sampling locations of the Lijiang River basin
图 4 不同来源硝酸盐的δ15N-NO3-和δ18O-NO3-典型值
据Desimone and Howes（1998）和Wu et al.（2018）
Fig. 4. Typical ranges δ15N-NO3- and δ18O-NO3- values of nitrate of different sources
图 8 δ13CDIC和(Ca2++Mg2+) /HCO3-、NO3-之间的关系
Fig. 8. Plots of δ13CDIC values vs. (Ca2++Mg2+) /HCO3- and NO3- molar ratio in the Lijiang River basin
表 1 漓江流域各子流域水文特征信息
Table 1. Hydrological characteristics of sub-catchments of the Lijiang River basin
子流域名称 分叉比Rb 河长比RL 水系分维Db 河网密度(km-2) 径流系数 子流域面积(km2) 漓江干流 3.35 2.49 1.33 0.56 0.748 1 272.08 溶江 3.79 2..41 1.51 0.51 0.714 719.37 小溶江 4.93 2.57 1.69 0.50 0.637 272.54 甘棠河 3.88 1.99 1.97 0.51 0.707 796.11 灵渠 4.19 2.12 1.91 0.54 0.746 245.75 桃花江 4.55 1.54 2.00 0.53 0.800 277.54 良丰河 4.30 1.73 2.00 0.58 0.797 560.94 潮田河 3.57 1.61 2.00 0.50 0.752 461.55 黄沙河 4.33 2.24 1.82 0.57 0.785 213.87 遇龙河 4.00 1.77 2.00 0.56 0.735 341.04 金宝河 5.20 1.57 2.00 0.54 0.711 219.59 大源河 3.83 1.68 2.00 0.52 0.746 137.72 其他 4.02 2.49 1.53 0.49 0.743 305.44 均值 4.15 2.02 1.83 0.53 — — 
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表 2 漓江流域水样测试数据
Table 2. Data results of water samples from the Lijiang River basin
采样点 pH EC HCO3- Cl- NO3- SO42- Ca2+ Mg2+ K+ Na+ δ13CDIC δ18O-NO3- δ15N-NO3- 土地利用方式 （μS·cm -1） （mg·L-1） （‰） 1XR 7.23 156 67.10 1.98 7.97 7.12 24.27 1.16 2.09 0.78 -14.41 3.74 2.97 G 2XS 7.05 404 244.00 2.61 8.05 36.41 93.83 3.35 1.45 1.42 -14.54 -6.02 6.32 G 3BC 6.87 38 18.30 1.46 4.74 4.67 5.48 1.09 0.82 1.25 -13.99 — — NKA 4BF 6.33 48 12.20 1.28 3.27 4.19 2.92 0.68 0.69 1.31 -14.7 4.80 1.41 F 5BS 6.21 72 18.30 1.58 3.29 5.59 5.45 0.84 1.17 1.97 -16.43 4.32 3.27 F 6BL 6.90 32 18.30 1.35 2.37 4.93 5.20 0.84 1.01 1.93 -14.93 7.92 0.99 NKA 7BT 6.61 46 18.30 1.54 7.11 7.55 6.74 1.75 0.99 1.25 -10.13 3.52 2.04 F 8BN 7.07 39 18.30 1.44 6.48 6.63 5.66 1.50 0.77 1.00 -10.12 5.06 2.33 F 9XG 7.68 226 158.60 1.42 7.25 5.39 53.51 1.76 0.51 0.80 -12.76 -0.72 1.87 G 10BS 7.29 215 122.00 3.38 10.53 16.16 45.98 1.87 2.26 1.84 -13.31 6.38 5.39 KA 11BR 6.97 49 24.40 1.58 4.89 6.62 8.36 1.33 1.02 1.40 -13.15 4.94 3.84 NKA 12BL 7.46 169 91.50 2.80 9.08 12.82 34.97 1.73 1.84 1.64 -12.77 4.54 5.84 KA 13XL 6.21 248 67.10 8.28 35.48 18.48 41.14 2.42 2.44 3.00 -17.24 6.51 11.09 G 14BD 7.44 115 54.90 2.20 7.30 9.04 20.47 1.47 1.65 1.67 -12.97 3.47 5.45 KA 15BN 7.29 100 48.80 2.08 6.77 8.57 19.46 1.41 1.47 1.45 -12.53 4.16 4.88 KA 16BN 6.69 60 18.30 1.34 3.77 4.26 6.29 0.98 0.78 1.19 -14.72 3.35 3.07 F 17BH 6.65 44 24.40 1.41 3.95 4.54 7.37 1.06 0.76 1.23 -15.12 3.53 3.70 NKA 18BX 7.43 78 36.60 1.81 5.75 7.21 14.69 1.36 1.29 1.58 -13.03 2.86 5.05 NKA 19BD 7.23 41 42.70 1.85 5.73 7.44 15.56 1.36 1.18 1.48 -11.95 2.41 6.35 NKA 20BY 7.54 149 85.40 2.95 8.62 12.52 31.10 1.50 1.76 1.97 -11.4 3.34 8.11 C 21BC 7.73 122 54.90 1.99 5.98 7.23 16.68 1.21 0.90 2.25 -10.01 4.86 6.15 KA 22BC 7.47 165 91.50 2.72 7.57 12.77 32.57 2.47 2.51 1.73 -11.04 0.53 6.83 KA 23BM 7.15 215 85.40 4.80 9.13 32.46 35.78 2.75 4.85 3.51 -10.02 0.65 7.18 KA 24BN 7.35 235 103.70 8.36 13.79 43.69 50.96 3.35 5.87 7.16 -10.63 1.10 8.97 C 25BJ 7.77 334 201.30 5.49 15.14 18.66 65.37 7.64 3.75 2.48 -11.88 4.38 9.64 KA 26BY 7.73 355 219.60 6.29 18.57 20.17 72.86 6.92 3.72 3.55 -11.32 2.59 8.80 C 27BL 7.34 151 67.10 4.84 7.97 12.88 26.21 1.75 2.25 4.29 -11.34 4.67 7.38 C 28BS 7.60 386 231.80 5.22 16.29 22.79 90.00 2.77 3.54 2.21 -12.33 0.64 8.99 KA 29BD 7.91 381 225.70 5.66 20.45 26.18 87.05 3.38 3.42 2.64 -11.48 1.59 8.08 KA 30BC 7.95 234 158.60 2.24 11.02 8.88 48.77 4.34 1.00 1.26 -12.83 3.43 6.02 KA 32XZ 7.02 407 268.40 4.02 26.24 12.75 95.20 3.57 1.35 2.11 -13.45 2.13 7.05 G 33XZ 7.28 390 274.50 2.43 11.79 8.52 92.20 4.10 0.72 0.95 -15.38 1.05 7.24 G 34BD 7.26 75 42.70 1.70 6.37 7.29 12.01 3.50 0.72 1.44 -10.04 4.06 6.14 NKA 35XD 7.01 482 366.00 2.03 19.83 7.35 124.00 2.84 0.35 0.74 -16.22 2.43 3.96 G 36XZ 6.60 529 396.50 1.75 12.75 9.07 133.70 5.60 0.36 0.77 -17.05 1.83 5.34 G 37XN 7.45 368 274.50 1.93 6.66 5.94 88.67 2.94 0.40 0.58 -15.19 2.22 6.02 G 38BL 7.33 190 97.60 4.04 10.12 13.67 36.65 2.62 2.22 3.27 -11.17 1.93 7.51 KA 39XL 6.89 452 286.70 2.10 20.13 8.32 106.10 7.44 0.70 0.68 -15.96 — — G 40XT 6.54 520 402.60 4.26 25.62 15.36 149.70 6.80 0.76 1.23 -17.29 1.07 3.59 G 41XJ 7.16 372 237.90 2.89 21.04 14.77 74.03 9.93 0.73 1.96 -13.11 4.23 6.94 G 42BJ 7.67 243 152.50 2.09 16.05 10.45 51.39 5.21 0.79 1.33 -12.71 3.01 7.13 KA 43BX 8.24 254 152.50 2.33 16.27 10.81 53.33 6.87 1.05 1.62 -13.64 2.26 4.69 KA 44BY 8.02 211 115.90 3.89 10.52 12.91 40.35 3.26 1.97 3.19 -11.46 — — C 45BS 8.10 261 134.20 3.09 11.11 10.82 48.37 7.43 1.78 2.20 -11.68 2.48 7.08 C 46BZ 7.92 277 183.00 2.93 11.55 9.22 56.62 8.16 1.20 1.97 -12.23 3.59 7.19 KA 47BD 7.45 149 79.30 2.99 10.18 11.33 24.52 5.56 2.27 1.87 -10.55 3.24 7.04 KA 48BD 7.44 81 42.70 2.38 9.83 7.57 13.02 3.48 1.43 1.67 -10.4 2.88 6.39 NKA 49XM 7.34 434 280.60 2.96 11.65 35.44 78.69 13.42 0.62 12.64 -14.1 2.53 6.67 G 50BC 7.91 277 183.00 2.78 11.26 9.63 54.07 8.27 1.05 1.91 -12.29 4.91 6.38 KA 51XW 7.12 354 237.90 2.36 14.03 10.79 75.51 7.88 1.42 0.92 -13.38 2.97 5.60 G 52XJ 7.08 267 183.00 2.63 9.13 8.99 46.70 12.19 1.51 1.32 -14.16 5.19 7.38 G 注：C代表城镇区；G代表地下水区；F代表森林区；KA代表岩溶农业区；NKA代表非岩溶农业区；“—”表示数据缺失.
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表 3 不同土地利用方式下的水化学组分和同位素值
Table 3. Chemical data and isotope values according to land use in the Lijiang River basin
土地利用方式 pH EC Ca2+ Mg2+ K+ Na+ Cl- NO3- HCO3- SO42- δ13CDIC δ18O-NO3- δ15N-NO3- (μS·cm -1) (mg·L-1) (‰) 森林区（5） 最大值 7.07 72.00 6.74 1.75 1.14 1.97 1.58 7.11 18.3 7.55 -10.12 5.06 3.27 最小值 6.21 39.00 2.92 0.68 0.67 1.00 1.28 3.27 12.20 4.19 -16.43 3.35 1.41 平均值 6.58 53.00 5.41 1.15 0.86 1.34 1.43 4.78 17.08 5.64 -13.22 4.21 2.42 地下水区（16） 最大值 7.89 529.00 149.70 13.42 2.38 12.64 8.28 35.48 402.60 36.41 -12.76 6.51 11.09 最小值 6.21 156.00 24.27 1.16 0.34 0.58 1.42 6.66 67.10 5.39 -17.29 -6.02 1.87 平均值 7.09 374.06 84.81 6.00 0.98 1.92 2.80 15.10 251.24 13.12 -14.93 2.02 5.89 城镇区（6） 最大值 8.10 355.00 72.86 7.43 5.72 7.16 8.36 18.57 219.60 43.69 -10.63 4.67 8.97 最小值 7.34 149.00 26.21 1.50 1.72 1.97 2.95 7.97 67.10 10.82 -11.68 1.10 7.08 平均值 7.68 227.00 44.98 4.03 2.82 3.73 4.90 11.76 120.98 18.83 -11.31 2.84 8.07 岩溶农业区（17） 最大值 8.24 386.00 90.00 8.27 4.73 3.51 5.66 20.45 231.80 32.46 -10.01 6.38 9.64 最小值 7.15 100.00 16.68 1.21 0.77 1.26 1.99 5.98 48.80 7.23 -13.31 0.53 3.84 平均值 7.62 225.06 45.51 3.98 2.05 2.04 3.28 11.45 130.25 14.16 -11.96 3.18 6.74 非岩溶农业区（8） 最大值 7.44 81.00 15.56 3.50 1.40 1.93 2.38 9.83 42.70 7.57 -10.04 7.92 6.39 最小值 6.65 32.00 5.20 0.84 0.70 1.23 1.35 2.37 18.30 4.54 -15.12 2.41 0.99 平均值 7.09 54.75 10.21 1.75 1.00 1.50 1.69 5.45 31.26 6.28 -12.77 3.91 4.87
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表 4 不同硝酸盐来源的δ15N值和δ18O值
Table 4. δ15N and δ18O values of various NO3- sources
CPN SN MS δ15N（‰） -1.1 3.5 10.6 δ18O（‰） 1.3 1.3 4.3
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表 5 主要阴离子与同位素相关性系数
Table 5. Correlation coefficient of main anion and isotope correlation coefficient
NO3- HCO3- SO42- δ13CDIC δ18O-NO3- δ15N-NO3- NO3- 1 HCO3- 0.545** 1 SO42- 0.348* 0.254 1 δ13CDIC -0.214 -0.426** 0.192 1 δ18O-NO3- -0.066 -0.444** -0.455** 0.001 1 δ15N-NO3- 0.576** 0.265 0.542** 0.245 -0.152 1 注：**表示在0.01级别（双侧），相关性显著；*表示在0.05级别（双侧），相关性显著.
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