Transformation Relationship of Different Water Body in Donggong River Basin Based on Hydrochemistry and Hydrogen-Oxygen Isotopes
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摘要: 为明晰秦皇岛东宫河流域水环境特征，以该流域大气降水、地下水及地表水为研究对象，通过对水化学和氢氧稳定同位素样品测试及特征分析，揭示其时空变化特征及大气降水、地下水和地表水的相互转化关系.结果表明：①东宫河流域地下水（第四系孔隙水、岩溶水、裂隙水）和地表水（河水、泉水）的水化学类型，枯水期较丰水期丰富.丰水期水化学类型主要以HCO3-Ca型、HCO3·SO4-Ca型和HCO3-Ca·Mg型为主；枯水期水化学类型以HCO3-Ca型、HCO3-Ca·Mg型、HCO3·SO4-Ca型、HCO3·SO4-Ca·Mg型为主.②研究区第四系孔隙水和泉水的离子含量变化受季节影响较大，枯水期离子含量变化较丰水期显著；岩溶水和裂隙水各离子含量变幅较小，基本趋于稳定.岩溶含水层和裂隙含水层中富含石膏，为SO42-的主要来源；Na+和Cl-主要来源于易溶解盐NaCl，Ca2+和Mg2+主要来源于方解石的风化溶解.③东宫河流域地下水、地表水及大气降水之间存在密切的水力联系，针对氢氧同位素的组成分析表明，大气降水为地下水和河水的主要来源；不同泉水补给来源存在差异性，泉水主要接受岩溶水补给，同时也受蒸发作用影响；第四系孔隙水接受大气降水和河水的双重补给；裂隙水主要接受山区降水径流补给.研究显示，东宫河流域不同水体中离子含量受降雨量、温度和地质背景等影响，不同水体间联系密切，相互补给排泄.Abstract: In order to ascertain the water environment characteristics of the Donggong River Basin in Qinhuangdao, the atmospheric precipitation, groundwater and surface water in this basin were taken as the research objects. Through the analysis of its water chemistry and hydrogen-oxygen stable isotopic characteristics, the characteristics of its temporal and spatial changes and the characteristics of atmospheric precipitation, groundwater and surface water are revealed. The results show that: (1) The water chemistry of groundwater (Quaternary pore water, karst water, fissure water) and surface water (river water, spring water) in the Donggong River Basin are more abundant in dry periods than in wet periods. The water chemistry types in the rich season are HCO3-Ca type, HCO3·SO4-Ca type and HCO3-Ca·Mg type mainly; the water chemistry types in the dry season are HCO3-Ca type, HCO3-Ca·Mg type, HCO3·SO4-Ca type, HCO3·SO4-Ca·Mg type mainly. (2) The change of ion content in Quaternary pore water and spring water in the study area is greatly affected by the season, and the change in ion content in dry season is more significant than in wet season; the ions in karst water and fissure water have a small change range and tend to be stable. The karst aquifer and bedrock fissure aquifer are rich in gypsum, which is the main source of SO42-; Na+ and Cl- mainly come from the easily soluble salts NaCl, Ca2+ and Mg2+ mainly come from the weathering dissolution of calcite. (3) There is a close hydraulic relationship between groundwater, surface water and atmospheric precipitation in the Donggong River Basin, analysis of the composition of hydrogen and oxygen isotopes shows that atmospheric precipitation is the main source of groundwater and river water, and the spring water mainly comes from karst water replenishment and is affected by evaporation; pores water receives dual recharges from atmospheric precipitation and river water; fissure water is mainly recharged from mountain runoff. The studies have shown that the ion content in different water bodies of the Donggong River Basin is affected by rainfall, temperature and geological background. Different water bodies are closely connected and complement each other for excretion.
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图 2 东宫河流域地下水中主要离子随时间变化
Figure 2. Temporal variations in major ions of groundwater in the Donggong River Basin
图 3 东宫河流域岩溶水中主要离子含量沿程变化
Figure 3. Spatial variations in major ions of karst water in the Donggong River Basin
图 4 东宫河流域各水体中离子比例关系
Figure 4. Ionic ratio plots of major ions in groundwater, spring and river in the Donggong River Basin
图 5 东宫河流域大气降水中δD、δ18O的组成特征
注：GLMWL为全球大气降水线；LMWL为当地大气降水线.
Figure 5. Relationship between δD and δ18O for precipitation in the Donggong River Basin
图 6 2015年东宫河流域大气降水中氢氧稳定同位素的时间变化特征
Figure 6. Temporal variation in δD and δ18O for precipitation in the Donggong River Basin, 2015
图 7 东宫河流域各水体中氢氧同位素组成与大气降水线的关系
Figure 7. Relationship between δD and δ18O in groundwater, spring, river and precipitation in the Donggong River Basin
图 8 东宫河流域各水体氢氧同位素变化特征
Figure 8. Spatial variation in δD and δ18O at sampling sites in the Donggong River Basin
表 1 东宫河流域地下水水化学与同位素组成特征
Table 1. Results of hydrochemistry and isotopic compositions in groundwater in the Donggong River Basin
时间 地下水类型 编号 pH ρ(TDS)/
(mg/L)EC/
(μS/cm)ρ(DO)/
(mg/L)Eh/ mV ρ(Ca+)/
(mg/L)ρ(K+)/
(mg/L)ρ(Mg2+)/
(mg/L)ρ(Na+)/
(mg/L)ρ(HCO3-)/
(mg/L)ρ(Cl-)/
(mg/L)ρ(SO42-)/
(mg/L)δ18O/‰ δD/‰ 水化学类型 2014年7月 岩溶水 w8 7.49 442.0 663 — — 95.90 24.20 23.00 24.10 265.00 38.70 83.70 -8.4 -59 HCO3-Ca w9 7.56 488.8 733 — — 115.00 5.95 34.70 19.10 352.00 38.10 83.50 -8.2 -58 HCO3-Ca·Mg w10 7.45 362.3 543 — — 83.60 8.77 18.60 23.20 165.00 38.20 84.20 -8.1 -58 HCO3·SO4-Ca w11 7.46 276.3 414 — — 65.60 4.36 15.40 13.90 174.00 20.40 57.90 -8.2 -59 HCO3·SO4-Ca w15 7.49 491.4 737 — — 93.80 25.30 30.40 34.00 266.00 43.10 105.00 -8.0 -57 HCO3·SO4-Ca·Mg 第四系孔隙水 w16 7.54 866.0 1 299 — — 89.70 169.00 36.80 89.30 360.00 141.00 107.00 -8.1 -56 HCO3·Cl-Na·Ca w20 7.44 369.4 554 — — 128.00 20.60 41.30 26.80 128.00 20.60 41.30 -8.2 -59 HCO3-Ca·Mg 裂隙水 w21 7.57 268.2 402 — — 56.30 2.34 21.90 13.40 270.00 9.45 29.80 -8.5 -61 HCO3-Ca·Mg 2015年7月 岩溶水 w1 7.42 228.2 326 7.2 — 51.76 1.59 8.93 6.91 132.74 8.52 57.04 -8.4 -59 HCO3·SO4-Ca w4 7.22 460.8 727 6.5 — 120.60 9.38 16.47 11.10 306.46 14.51 55.78 -8.1 -60 HCO3-Ca w5 7.28 396.2 590 8.7 — 87.00 11.57 19.88 13.55 245.95 20.22 63.51 -8.1 -59 HCO3-Ca w8 7.30 593.7 823 7.6 — 89.02 38.42 25.12 35.25 288.90 33.86 75.06 -7.5 -59 HCO3-Ca·Na w9 7.12 561.4 858 8.1 — 117.80 3.69 36.01 19.53 372.83 32.66 79.68 -7.8 -59 HCO3-Ca·Mg 第四系孔隙水 w17 7.27 835.6 1 152 7.2 — 106.20 40.07 29.13 72.88 247.90 61.80 115.13 -8.3 -59 HCO3·SO4-Ca·Na w18 6.78 1 210.1 1 662 4.1 — 143.80 65.66 47.92 108.70 370.88 158.64 132.30 -7.6 -56 HCO3·Cl-Ca·Mg w19 7.23 710.4 950 8.0 — 103.50 8.43 40.17 45.93 263.52 72.36 80.24 -8.3 -59 HCO3·Cl-Ca·Mg 裂隙水 w21 7.41 247.0 498 4.1 — 50.99 2.11 20.82 13.79 238.14 8.86 30.31 -8.3 -60 HCO3-Ca·Mg 2015年10月 岩溶水 w1 7.64 268.9 439 7.0 196 68.33 1.21 11.86 7.76 160.06 10.65 61.68 -8.3 -58 HCO3·SO4-Ca w2 7.13 387.4 663 7.1 216 106.70 2.62 16.23 10.64 308.42 9.79 47.57 -8.0 -61 HCO3-Ca w3 7.60 273.9 456 7.0 223 73.69 3.30 9.51 7.85 171.78 8.20 60.38 -8.3 -58 HCO3·SO4-Ca w6 7.51 245.4 419 3.8 228 56.89 4.21 11.76 14.02 156.16 10.78 47.31 -7.5 -56 HCO3·SO4-Ca w7 7.25 450.9 667 6.4 189 60.57 42.79 16.69 26.98 175.68 26.30 77.17 -8.3 -58 HCO3·SO4-Ca·Na w9 7.44 439.1 727 6.1 177 94.33 3.24 28.74 14.74 306.46 21.13 67.97 -8.1 -58 HCO3-Ca·Mg w10 7.50 260.5 445 5.5 213 58.60 4.22 13.03 13.57 167.87 10.84 47.52 -7.8 -57 HCO3-Ca w12 7.72 302.1 496 7.7 208 66.31 2.23 18.00 10.61 189.34 10.61 50.39 -8.0 -59 HCO3-Ca·Mg w13 7.52 334.2 535 7.1 206 65.55 12.33 17.93 13.99 185.44 13.23 55.74 -7.7 -62 HCO3·SO4-Ca·Mg w14 7.55 306.9 540 7.3 219 66.32 2.47 17.68 10.62 212.77 9.83 51.27 -8.2 -60 HCO3-Ca·Mg 第四系孔隙水 w17 7.39 738.4 1 079 3.2 187 102.20 30.00 28.18 66.64 261.57 68.72 82.30 -8.1 -57 HCO3-Ca·Na w20 7.30 742.7 1 051 7.3 207 115.30 26.61 37.15 32.57 284.99 41.61 87.34 -8.4 -58 HCO3-Ca·Mg 裂隙水 w21 7.59 288.7 472 2.7 167 56.94 2.14 21.48 14.15 310.37 8.57 29.29 -8.1 -60 HCO3-Ca·Mg w22 7.51 526.2 797 6.0 226 86.95 36.84 18.17 34.53 222.53 35.31 73.64 -8.3 -61 HCO3-Ca·Na w23 7.35 322.6 514 4.7 224 72.30 4.95 12.62 18.17 187.39 13.28 39.31 -8.1 -59 HCO3-Ca w24 7.31 354.6 584 4.6 242 65.85 25.77 15.48 21.89 208.86 19.76 61.29 — — HCO3-Ca·Na 2016年4月 岩溶水 w1 7.29 274.8 416 8.5 86 69.50 0.71 12.09 6.31 175.43 11.44 63.91 -8.5 -59 HCO3·SO4-Ca w2 7.34 287.6 429 8.9 96 76.92 2.10 9.70 6.60 187.64 12.18 62.38 -8.5 -59 HCO3·SO4-Ca w7 7.27 262.8 408 7.1 212 49.06 17.69 12.73 11.42 164.75 14.96 57.05 -7.3 -55 HCO3·SO4-Ca w9 7.63 442.1 669 11.1 182 92.96 2.68 27.75 14.97 250.18 29.91 68.83 -8.1 -59 HCO3-Ca·Mg w10 7.21 263.4 409 8.0 54 60.39 2.04 13.66 9.63 170.86 13.70 53.77 -7.9 -56 HCO3·SO4-Ca w11 7.48 270.7 427 7.0 34 61.74 3.39 12.56 12.17 166.28 16.90 54.63 -7.7 -55 HCO3·SO4-Ca w12 7.78 380.6 498 8.3 54 120.64 2.16 19.19 10.30 218.15 15.98 59.56 -8.2 -58 HCO3-Ca w13 7.31 334.2 512 9.1 201 68.83 9.17 19.06 10.81 212.04 16.25 58.38 -8.3 -58 HCO3-Ca·Mg w14 7.67 316.5 489 9.9 214 75.38 0.71 18.64 7.14 218.15 13.39 57.67 -8.3 -59 HCO3-Ca·Mg 第四系孔隙水 w20 7.27 435.1 640 8.0 112 86.79 4.83 26.05 14.56 242.55 25.17 53.32 -8.5 -59 HCO3-Ca·Mg 裂隙水 w21 7.26 271.7 464 2.7 205 60.29 2.19 22.09 13.01 253.23 11.74 34.55 -8.3 -61 HCO3-Ca·Mg w23 7.04 329.1 489 5.7 130 75.53 3.55 13.03 15.45 196.79 20.48 49.33 -8.2 -58 HCO3-Ca w24 7.16 368.2 576 7.7 154 81.27 17.38 18.60 16.08 239.50 27.27 71.61 — — HCO3-Ca 
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表 2 东宫河流域泉水和河水水化学与同位素组成特征
Table 2. Results of hydrochemistry and isotopic compositions in spring and river in the Donggong River Basin
时间 地下水类型 编号 pH ρ(TDS)/
(mg/L)EC/
(μS/cm)ρ(DO)/
(mg/L)Eh/ mV ρ(Ca+)/
(mg/L)ρ(K+)/
(mg/L)ρ(Mg2+)/
(mg/L)ρ(Na+)/
(mg/L)ρ(HCO3-)/
(mg/L)ρ(Cl-)/
(mg/L)ρ(SO42-)/
(mg/L)δ18O/‰ δD/‰ 水化学类型 2014年7月 泉水 s1 7.61 286.2 429 — — 68.30 2.52 19.10 10.70 212.00 15.50 55.30 -8.2 -58 HCO3-Ca·Mg 河水 r1 7.56 201.5 302 — — 52.60 2.33 12.20 7.89 79.10 9.37 73.30 -8.6 -62 SO4·HCO3-Ca·Mg r3 7.45 149.3 224 — — 32.50 2.36 8.17 8.59 50.30 8.26 56.70 -8.9 -63 SO4·HCO3-Ca r4 7.46 192.3 288 — — 46.60 2.63 10.80 8.71 101.00 9.34 56.70 -8.9 -63 HCO3·SO4-Ca r5 7.49 209.4 314 — — 54.00 0.82 11.60 6.14 145.00 5.92 54.30 -9.0 -64 HCO3·SO4-Ca r6 7.54 209.9 315 — — 49.60 2.73 11.40 8.68 122.00 9.82 59.60 -8.8 -62 HCO3·SO4-Ca 2015年7月 泉水 s1 7.42 303.2 388 14.0 — 69.33 1.78 16.78 9.51 187.39 10.36 53.14 -8.0 -58 HCO3-Ca·Mg s2 7.22 332.3 468 6.6 — 68.59 2.08 17.81 11.09 185.44 33.36 94.31 -8.1 -60 HCO3·SO4-Ca·Mg s3 7.28 291.2 408 — — 68.36 1.83 18.00 9.94 162.02 11.49 50.82 -8.0 -59 HCO3·SO4-Ca·Mg s4 7.30 326.7 478 6.9 — 68.68 1.85 18.43 10.08 203.01 13.02 57.54 -8.7 -58 HCO3-Ca·Mg 河水 r1 7.79 301.3 438 8.3 — 66.57 2.44 13.16 9.24 169.82 12.95 61.97 -8.0 -58 HCO3·SO4-Ca r2 8.80 218.9 352 11.7 — 45.53 3.69 9.25 10.97 97.60 8.40 50.21 -8.2 -56 HCO3·SO4-Ca r4 8.33 248.8 388 14.0 — 43.47 2.81 12.84 10.88 142.50 10.61 54.62 -7.9 -59 HCO3·SO4-Ca·Mg 2015年10月 泉水 s1 7.74 286.4 486 9.0 216 59.36 0.86 18.69 8.28 177.63 10.93 52.34 -8.3 -59 HCO3·SO4-Ca·Mg s2 7.52 304.7 487 5.4 225 65.34 2.95 17.19 11.61 173.73 13.14 54.56 -8.2 -59 HCO3·SO4-Ca·Mg s3 7.63 299.4 487 7.6 215 66.27 2.51 17.79 10.78 187.39 10.46 49.95 -8.1 -60 HCO3·SO4-Ca s4 7.60 301.3 487 5.9 217 65.34 2.83 17.44 11.89 181.54 11.11 51.34 -8.4 -58 HCO3·SO4-Ca 河水 r1 8.19 298.4 512 10.0 183 73.08 4.57 14.84 12.24 203.01 10.34 61.69 -8.1 -58 HCO3·SO4-Ca r3 9.08 164.1 285 12.3 207 32.61 2.80 8.35 12.11 81.98 9.96 44.95 -7.2 -54 HCO3·SO4-Ca r4 7.53 263.9 499 3.8 226 53.64 1.54 12.48 10.51 206.91 10.95 53.68 -7.7 -58 HCO3-Ca 2016年4月 泉水 s1 8.17 256.5 416 4.5 97.1 46.79 3.98 19.12 14.03 167.81 18.52 60.88 — — HCO3·SO4-Ca·Mg s3 7.88 319.3 482 13.5 186 71.08 2.70 18.99 10.90 202.89 16.14 58.80 -8.2 -57 HCO3-Ca·Mg s4 7.48 323.5 501 5.9 89 72.15 2.42 18.95 10.69 204.42 15.85 58.14 -8.4 -58 HCO3-Ca·Mg 河水 r1 7.51 236.2 387 11.9 238 57.66 3.17 11.78 8.13 154.08 11.96 57.19 -7.3 -54 HCO3-Ca·Mg r3 8.69 125.5 286 14.7 168 1.98 0.59 0.42 0.45 96.11 12.65 50.53 -7.0 -51 HCO3·SO4-Ca r4 7.90 280.9 454 13.5 191 67.03 0.97 11.72 8.22 180.01 15.43 66.76 -8.1 -58 HCO3·SO4-Ca
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