Hydrogeochemical Characteristics and Genesis of Luohe Iron Deposit
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摘要: 作为庐枞盆地较早开展勘探工作的罗河铁矿, 矿区揭露的地下水可分为潜水和承压水2类, 潜水表现为弱碱性HCO3--Ca+·Mg2+型水; 区域构造和凝灰岩阻隔了潜水和承压水的水力联系, 承压水以SO42--Ca2+型微咸温水为主, 水化学成分不受外界因素变化影响.离子比例系数和相关性分析说明承压水中主要水化学反应包括硫酸盐矿物溶解和阳离子交换.PHREEQC反向模拟SO42--Ca2+型承压水的成因主要是砖桥组下段次生石英岩中大量硬石膏、石英和水云母的原位溶解; 与此同时, 地下水中沉淀生成了方解石和绿泥石, 石膏溶解的Ca2+离子吸附交换粘土矿物中的Na+离子, 少量黄铁矿还发生了氧化还原反应.分析结果验证了罗河铁矿深部地下水相对封闭, 补给有限, 以静储量为主.Abstract: As one well-explored region of Luzong Mesozoic volcanic basin, the groundwater revealed in Luohe iron deposit can be divided into two types, namely, unconfined and confined groundwater. The unconfined groundwater is alkalescent HCO3--Ca+·Mg2+ water, while the confined groundwater is the SO42--Ca2+ brackish warm water due to the fact that their hydrochemical compositions are almost not affected by external changes because of the water blocking properties of regional structure and volcanic tuff. Ion proportionality coefficients and correlation analyses illustrate that major hydrochemical reactions in confined groundwater are sulfate mineral solution and cation exchange. PHREEQC inverse simulation shows that the cause of SO42--Ca2+ confined groundwater is the numerous anhydrite, quartz and hydromica solution in site, at the same time, some calcite and chlorite precipitate as the secondary minerals. Meanwhile, Ca2+that was dissolved from anhydrite absorbs and exchanges with Na+ in clay mineral, and few pyrites have redox reaction. The analysis verifies the hydrogeological condition of relative closed, limited recharge and static reserves of deep groundwater in Luohe iron deposit.
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Key words:
- geochemistry /
- inverse simulation /
- cluster analysis /
- ore deposits /
- Luohe iron deposit
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图 1 罗河铁矿构造简图及取样点位置
Fig. 1. Regional tectonic map of Luohe iron deposit and sampling sites
图 4 砖桥组地下水水化学成分随深度变化剖面图
Fig. 4. Sections of chemical compositions of goundwater changes with depth of Zhuanqiao Formation
图 5 承压水水化学成分随时间变化曲线
Fig. 5. Curves of chemical composition changes with time of confined groundwater
图 6 砖桥组承压水TDS-γNa+/γCl-、γCa2+/γSO42-关系
Fig. 6. Relations of TDS-γNa+/γCl-、γCa2+/γSO42- of confined groundwater of Zhuanqiao Formation
图 7 砖桥组承压水SO42--(Ca2++Na+)关系
Fig. 7. Relation of SO42- and Ca2++Na+ of confined groundwater of Zhuanqiao Formation
表 1 罗河铁矿地下水水化学测试结果
Table 1. Groundwater hydrochemical test data of Luohe iron deposit
编号 取样点 类型 K+ Na+ Ca2+ Mg2+ Cl- SO42- HCO3- pH TDS 1 ZK1312 矿层水 21.500 155.000 541.480 22.370 10.280 1 626.780 119.600 7.20 2.60 2 ZK12 砖桥组承压水 16.270 287.800 598.800 38.670 9.220 1 978.490 244.690 7.80 3.39 3 ZK22 17.920 225.210 614.430 39.160 7.450 1 987.130 233.090 6.40 2.88 4 ZK14 19.580 381.340 588.370 40.690 13.120 2 233.620 218.450 6.40 3.39 5 ZK211 9.300 42.290 634.900 27.000 2.800 1 435.480 221.530 6.70 2.35 6 ZK09 14.110 151.970 522.310 33.410 20.210 1 594.560 201.040 7.20 2.66 7 ZK24 2.800 89.600 607.750 102.320 7.520 1 875.000 179.740 6.70 2.49 8 ZK25 24.200 198.000 617.020 40.760 4.380 1 866.450 218.940 6.90 4.80 9 ZK28 17.300 168.000 542.280 33.200 4.250 1 639.740 201.360 6.90 3.04 10 ZK2112 13.400 50.000 630.700 28.680 2.190 1 529.490 198.920 6.80 2.50 11 ZK2112 12.200 49.000 636.870 23.220 1.060 1 570.580 190.990 7.20 2.39 12 ZK916 12.000 70.000 476.150 24.190 3.100 1 321.000 113.500 6.90 2.02 13 ZK19 16.600 246.380 612.020 36.240 4.250 1 973.550 217.830 6.90 3.11 14 ZK26 8.300 240.380 593.180 33.320 5.320 1 915.200 214.180 7.30 2.88 15 ZK08 16.600 158.000 623.010 36.820 7.800 1 837.920 216.620 7.60 2.90 16 ZK03 13.280 253.730 602.000 42.200 7.800 2 021.760 201.970 7.80 3.06 17 ZK15 17.760 231.440 667.810 38.670 9.220 1 940.630 230.040 6.40 2.90 18 ZK15 21.000 164.000 635.050 37.400 3.490 1 866.450 209.300 7.00 3.03 19 ZK15 16.200 150.000 628.450 23.330 8.510 1 822.560 218.450 7.50 2.89 20 ZK132 19.500 151.320 605.210 30.700 11.730 1 768.700 193.470 7.30 2.70 21 ZK1712 14.940 51.930 573.950 21.280 7.800 1 468.200 155.600 7.30 2.25 22 ZK176 18.800 65.000 564.530 18.970 4.960 1 430.300 191.760 7.50 2.35 23 废石井 10.000 86.400 383.390 19.440 17.340 1 001.090 206.370 7.10 1.70 24 副井 15.000 130.000 556.430 35.730 24.280 1 537.400 250.980 7.50 2.49 25 进风井 7.500 51.560 402.780 24.420 24.280 1 018.960 153.400 7.50 1.64 26 进风井 21.040 47.070 526.300 34.360 5.270 1 358.290 109.360 7.50 2.12 27 进风井 7.860 47.400 527.000 16.500 6.930 1 329.000 130.100 7.50 2.08 28 措施井 25.980 180.990 540.080 59.540 5.270 1 765.100 220.610 7.90 2.82 29 措施井 17.730 170.000 604.600 88.450 5.270 1 948.100 245.120 6.90 3.10 30 措施井 29.100 281.900 542.400 44.180 28.130 1 979.220 109.360 7.50 3.03 31 措施井 20.090 233.000 430.000 36.440 22.540 1 612.000 89.090 7.50 2.48 32 回风井 12.730 51.410 599.100 63.810 3.520 1 649.350 175.350 7.60 2.57 33 回风井 48.750 376.900 393.900 16.650 37.840 1 798.200 93.820 7.44 2.72 34 回风井 15.780 74.000 564.000 26.100 6.930 1 553.000 110.500 7.40 2.38 35 ZK916 砖桥组潜水 3.200 55.400 23.450 15.810 3.300 12.970 246.620 8.00 0.33 36 ZK19 9.200 30.000 28.660 0.020 3.190 22.260 177.570 7.50 0.25 37 副井 1.000 218.000 21.620 3.170 22.230 243.130 303.090 7.80 0.70 38 废石井 5.000 91.200 65.650 14.920 17.340 114.410 345.800 8.00 0.60 39 QK1 双庙组潜水 5.400 91.250 30.060 9.240 5.320 61.440 288.010 7.30 0.49 40 QK3 5.600 30.300 32.700 0.370 7.700 14.610 178.790 7.80 0.18 41 包山 松散层潜水 3.800 9.800 20.840 10.210 8.860 12.010 109.220 7.40 0.13 42 李院子 3.000 8.200 51.300 10.820 7.800 12.970 199.500 7.60 0.21 43 曹庄 0.300 8.800 15.630 6.930 10.280 13.920 67.120 7.50 0.12 44 白棵树 0.400 13.700 24.050 17.270 10.280 12.000 170.850 7.50 0.17 注：离子浓度单位为mg/L，TDS(固体溶解总量)单位为g/L. 
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表 2 砖桥组地下水水化学离子比例系数
Table 2. Proportionality coefficients of groundwater hydrochemical ion of Zhuanqiao Formation
地下水类型 潜水 承压水 离子比例系数 最大值 最小值 平均值 最大值 最小值 平均值 γCa2+/γNa+ 1.10 0.11 0.64 17.26 1.20 6.47 γMg2+/γCa2+ 1.12 0.13 0.47 0.28 0.05 0.11 γNa+/γCl- 24.51 8.12 15.57 89.48 3.28 34.15 γCa2+/γSO42- 4.34 0.21 2.25 1.06 0.53 0.82 γCa2+/γHCO3- 0.58 0.22 0.39 15.57 5.67 9.78 γSO42-/γCl- 8.09 2.91 5.26 1 095.83 31.04 224.47 γHCO3-/γCl- 43.49 7.93 23.86 104.86 1.44 20.38 γSO42-/γHCO3- 1.02 0.07 0.42 24.36 6.16 12.29
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表 3 砖桥组承压水相关矩阵系数之间的比值
Table 3. Pearson coefficient of correlation matrix of confined groundwater of Zhuanqiao Formation
水化学参数 K+ Na+ Ca2+ Mg2+ Cl- SO42- HCO3- pH TDS TDS 1.000 K+ 1.000 0.189 0.075 -0.027 0.027 0.221 -0.218 0.142 0.244 Na+ 1.000 -0.008 0.009 0.425 0.762 0.330 -0.081 0.593 Ca2+ 1.000 0.013 -0.661 0.582 0.593 -0.308 0.537 Mg2+ 1.000 -0.084 0.046 0.251 0.203 0.126 Cl- 1.000 -0.072 -0.368 0.241 -0.144 SO42- 1.000 0.376 -0.206 0.801 HCO3- 1.000 -0.282 0.431 pH 1.000 -0.202 注：以上离子比例系数为mEq/L.
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表 4 水文地球化学模拟点水化学测试结果
Table 4. Chemical test data of hydrogeochemical simulation points
水样编号 水温 pH K+ Na+ Ca2+ Mg2+ Cl- SO42- HCO3- SiO2 Fe3+ 35 24.5 8.0 3.20 52.40 23.45 15.81 3.30 12.97 246.62 26.40 0.08 12 26.3 6.9 12.00 70.00 476.15 24.19 3.10 1 321.00 113.50 30.00 0.20 注：水温单位为℃，离子浓度单位mg/L.
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表 5 模拟点主要离子组分存在形式及其含量(mol/kg)
Table 5. Major iron form and contents of simulation points
组分 存在形式 初始水 终态水 组分 存在形式 初始水 终态水 C(4) HCO3- 4.77×10-3 2.14×10-3 Cl- Cl- 9.31×10-5 8.76×10-5 CO2 9.93×10-5 4.97×10-4 K K+ 8.18×10-5 2.96×10-4 CaHCO3+ 2.36×10-5 1.12×10-4 Mg2+ Mg2+ 6.09×10-4 6.26×10-4 MgHCO3+ 2.46×10-5 8.13×10-6 MgSO42- 8.72×10-6 3.63×10-4 CO32- 2.82×10-5 1.37×10-6 MgHCO3+ 2.46×10-5 8.13×10-6 CaCO3 1.33×10-5 4.73×10-6 Na+ Na+ 2.26×10-3 2.98×10-3 Ca2+ Ca2+ 5.42×10-4 8.00×10-3 NaHCO3 5.13×10-6 2.50×10-6 CaSO42- 6.64×10-6 3.79×10-3 NaSO4- 9.66×10-7 7.11×10-5 CaHCO3+ 2.36×10-5 1.12×10-6 S(6) SO42- 1.19×10-4 9.54×10-3 CaCO3 1.33×10-5 4.73×10-6 CaSO42- 6.64×10-6 3.79×10-3 Fe Fe(OH)3 1.21×10-6 1.69×10-6 MgSO42- 8.72×10-6 3.63×10-4 Fe(OH)2+ 1.05×10-7 1.88×10-6 Si H4SiO4 4.33×10-4 5.00×10-4
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表 6 砖桥组次生石英岩矿物饱和指数(SI)计算
Table 6. Saturation index calculation of minerals of secondary quartzite of Zhuanqiao Formation
饱和指数(SI) 初始水 终态水 硬石膏 -3.12 -0.36 方解石 0.38 -0.07 CO2(g) -2.54 -1.82 白云石 0.94 -1.09 O2(g) -35.36 -39.15 石英 0.62 0.66
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表 7 砖桥组承压水水-岩相互作用矿物相的转移量
Table 7. Transfer amount of mineral phases in water-rock interaction of confined groundwater of Zhuanqiao Formation
矿物 硬石膏 石英 绿泥石 方解石 转移量 1.33×10-2 4.20×10-5 -4.33×10-4 -4.06×10-3 矿物 水云母 黄铁矿 Ca2+交换 Na+交换 转移量 3.76×10-4 2.16×10-6 -3.35×10-4 6.71×10-4 注：单位为mol/kg(H2O)，矿物质量转移为正数表示溶解，负数表示沉淀；对Ca2+-Na+交换而言，正值表示Ca2+的降低以及溶液中Na+的升高；负值表示Ca2+的升高以及溶液中Na+的降低.
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