Origin and Evolution of Deep-Seated K-Rich Brine in Paleogene of Qianjiang Depression, Hubei Province
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摘要:
地下深层富钾卤水是非常重要的钾盐资源，目前很少从区域尺度系统研究沉积盆地中富钾卤水水化学特征及成因. 对潜江凹陷深层富钾卤水进行了主、微量元素分析. 研究区卤水矿化度为125.70~347.00 g/L，K含量为0.32~6.83 g/L；富集Li、B、I、Na、Cl，亏损Mg、Br，Ca、SO4有富集也有亏损. 储层岩石矿物学特征、Nadeficit与Caexcess值以及Na/Cl摩尔比（0.83~1.32）和Cl/Br质量比（212~2 017），表明了多种水岩反应过程. 盆地卤水主要经历两个阶段的演化：盐湖含盐系地层沉积期，石膏、钙芒硝、含钾或镁硫酸盐等盐类矿物沉淀后，卤水中K初步富集，储层中硬石膏、方解石胶结作用和白云石化等成岩作用改变了卤水的成分；构造变形和剥蚀期，石盐及含钾盐类矿物被溶滤，导致卤水中K进一步富集.
Abstract:Deep-seated K-rich brine is a very important potash resource. However, there are few systematic studies on the chemical characteristics and genesis of K-rich brine in sedimentary basins on a regional scale. The major and trace element analyses of the deep-seated K-rich brine in Qianjiang Depression were carried out. The brine salinity in the study area is 125.70-347.00 g/L, and the K content is 0.32-6.83 g/L; Li, B, I, Na, Cl are enriched, Mg and Br are depleted, and Ca and SO4 are either enriched or depleted. Mineralogical features of reservoir rocks, the Nadeficit and Caexcess values as well as the molar ratio of Na/Cl (0.83-1.32) and the mass ratio of Cl/Br (212-2 017) indicate multiple water-rock reaction processes. The brine in the basin has undergone two main stages of evolution: during the depositional period of the salt-bearing strata in the salt lake, the precipitation of salt minerals such as gypsum, glauberite, potassium- and magnesium-bearing sulfate led to the initial enrichment of K, and the diagenesis processes such as anhydrite and calcite cementation and dolomitization in the reservoir caused a change in the composition of the brine; during the tectonic deformation and erosion period, the halite and potassium-containing salt minerals were dissolved by shallow or surface waters, leading to the further enrichment of K.
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Key words:
- K-rich brine /
- water-rock interaction /
- water chemistry /
- genetic model /
- Qianjiang Depression /
- mineral deposit
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图 1 潜江凹陷潜江组砂岩等厚图（据胡辉，2005）
Fig. 1. Contour map of sandstone thickness of the Qianjiang Formation in Qianijang Depression (from Hu, 2005)
图 2 潜江凹陷白垩系至古近系地层柱状图（据张永生等，2003）
Fig. 2. Stratigraphic column of the Cretaceous to Paleogene in Qianjiang Depression (from Zhang et al., 2003)
图 3 潜江凹陷卤水元素浓度和矿化度分布特征
红点为城镇或地级市；黑点为采样钻孔
Fig. 3. Distribution characteristics of element concentration and salinity of brine in Qianjiang Depression
图 4 卤水样品离子浓度与蒸发海水对应离子浓度对比
蒸发海水Cl、Na、SO4、Mg和K的变化轨迹来自Carpenter（1978），其他离子轨迹来自周训和李慈君（1995）
Fig. 4. Comparison of ion concentrations of the brine samples with the evaporated seawater
图 5 卤水样品与蒸发海水对应离子比值的对比（据Zhou and Li，1992）
Fig. 5. Comparison of ion ratios of the brine samples with the evaporated seawater (from Zhou and Li, 1992)
图 6 潜江凹陷潜江组卤水Nadeficit和Caexcess的关系
据Lee Davisson and Criss（1996）
Fig. 6. Nadeficit and Caexcess plot of brine in the Qianjiang Formation of Qianjiang Depression
图 7 潜江凹陷潜江组储层砂岩矿物学特征
a. 硬石膏和方解石胶结，正交偏光显微镜照片，Z76井，3 356.8 m；b. 硬石膏胶结，正交偏光显微镜下照片，G70井，3 094.5 m；c. 石英晶间碳酸盐岩胶结，扫描电子显微镜照片，Z76井，3 360.2 m；d. 长石晶间充填白云石，扫描电子显微镜照片，G70井，3 103.2 m. Qtz.石英；Pl.斜长石；Anh.硬石膏；Cal.方解石；Dol.白云石
Fig. 7. Mineralogical features of reservoir sandstone in the Qianjiang Formation of Qianijang Depression
图 8 潜江凹陷潜江组卤水的Na/Cl摩尔比（a）和Cl/Br质量比（b）
Fig. 8. Na/Cl molar ratios(a)and Cl/Br mass ratios(b)of brine in the Qiangjiang Formation of Qianjiang Depression
图 9 潜江凹陷潜江组富钾卤水成因模式简图（改自卢林，2005）
Fig. 9. Schematic diagrams illustrating the hypothesis for the evolution of the K-rich brines in the Qianjiang Formation of Qianjiang Depression (modified from Lu, 2005)
表 1 潜江凹陷潜江组卤水化学成分
Table 1. Chemical compositions of brine in the Qianjiang Formation of Qianjiang Depression
井号 K Na Mg Ca SO4 Cl HCO3 矿化度 I Br B Li g/L mg/L 浩5 3.50 124.73 0.05 0.33 13.15 186.40 0.47 328.70 8.08 602.55 300.17 26.67 浩28 1.12 118.02 0.07 0.38 9.98 177.44 0.40 308.00 ‒ ‒ ‒ ‒ 王45 1.60 129.87 0.05 0.14 22.48 185.18 0.57 339.30 ‒ ‒ ‒ ‒ 王1‒34‒11 0.75 113.15 0.08 0.10 28.48 153.97 0.68 297.10 ‒ ‒ ‒ ‒ 王30‒5 0.78 107.22 0.02 0.20 30.43 143.60 0.67 282.00 ‒ ‒ ‒ ‒ 钟27 0.72 102.98 0.09 0.48 8.77 154.93 0.43 269.00 10.90 463.40 73.80 55.00 钟20 1.00 109.00 0.05 0.12 14.63 158.31 0.89 284.00 10.38 268.74 85.00 60.00 钟19 1.08 110.83 0.05 0.39 9.71 165.22 0.53 288.00 9.58 242.96 127.00 55.50 钟17 0.98 106.29 0.11 1.28 9.17 158.74 0.34 276.40 9.92 290.84 175.20 60.00 钟22 0.85 124.01 0.22 0.85 1.78 193.34 0.44 321.60 ‒ ‒ ‒ ‒ 钟22 1.75 126.35 0.23 1.27 1.75 197.80 0.40 330.00 12.24 539.36 170.00 80.00 钟21 0.84 98.66 0.26 0.13 9.37 147.86 0.67 259.00 6.46 73.29 78.00 40.00 潭22 0.52 87.32 0.02 0.45 6.98 128.60 2.84 226.30 ‒ ‒ ‒ ‒ 潭22 1.06 123.80 0.09 0.61 5.36 189.00 0.41 320.50 12.90 375.50 208.00 75.00 潭7 0.65 103.17 0.13 0.01 7.65 155.00 0.65 267.50 14.80 308.20 123.00 68.00 潭7 0.88 106.92 0.13 0.37 6.18 162.00 0.27 277.00 11.57 340.67 164.00 55.00 潭2 0.44 61.93 0.01 0.18 10.40 83.40 4.94 158.80 6.47 127.00 100.36 30.30 潭132 0.75 95.60 0.11 0.18 7.17 142.60 1.41 247.50 ‒ ‒ ‒ ‒ 王22 1.85 128.21 0.02 0.21 20.80 184.00 0.77 336.00 8.70 280.00 171.82 50.60 广7 2.13 120.47 0.35 1.24 5.29 186.76 0.43 315.80 12.60 509.00 165.00 47.50 广15 3.70 126.06 0.06 0.29 10.08 190.46 0.94 330.10 9.98 369.65 124.31 25.53 广3 2.49 125.42 0.05 0.26 13.02 186.09 1.04 327.40 ‒ ‒ ‒ ‒ 王37 1.15 113.75 0.15 0.15 19.34 162.60 0.56 297.30 ‒ ‒ ‒ ‒ 丫4 0.38 62.88 0.22 0.86 3.79 96.15 0.90 165.80 ‒ ‒ ‒ ‒ 丫4 0.51 79.72 0.54 2.19 3.37 125.88 0.81 213.00 ‒ ‒ ‒ ‒ 丫14 0.39 73.02 0.40 1.67 3.34 114.00 1.02 193.80 ‒ ‒ ‒ ‒ 丫14 0.58 94.56 0.26 0.69 4.16 145.00 0.43 245.80 14.20 402.00 64.20 81.00 丫10 0.48 63.36 0.10 0.19 3.37 95.98 0.51 163.80 12.00 282.00 28.00 50.00 潜深6 1.22 70.02 0.82 1.80 17.10 100.40 2.83 194.20 ‒ ‒ ‒ ‒ 潜6 1.66 120.33 0.08 0.45 7.35 181.52 1.96 321.70 ‒ ‒ ‒ ‒ 熊2 1.09 132.90 0.04 0.18 21.08 190.25 0.96 347.00 16.04 701.70 102.00 60.00 张23 0.32 75.27 0.03 0.16 36.72 87.98 2.91 203.40 ‒ ‒ ‒ ‒ 浩10 1.05 118.09 0.04 0.29 14.03 174.51 0.37 309.10 11.30 492.00 108.00 71.00 浩29 1.15 117.10 0.12 0.38 7.34 176.89 0.58 303.10 10.60 379.40 126.00 59.20 浩29 1.93 125.13 0.06 0.29 6.84 190.05 0.58 324.30 13.60 585.80 158.00 54.50 浩29 1.89 118.76 0.15 0.92 4.38 183.19 0.82 309.40 ‒ ‒ ‒ ‒ 浩6 2.99 122.79 0.16 0.71 3.08 191.27 0.38 320.20 16.93 607.17 238.00 60.00 浩6 2.92 123.25 0.24 0.73 3.94 191.55 0.40 321.90 14.10 650.48 220.00 57.00 浩252 1.93 121.02 0.23 0.72 6.31 185.11 1.02 315.60 15.00 437.20 142.00 57.50 浩52 0.93 118.66 0.10 0.37 7.17 179.08 0.69 306.70 10.80 396.80 144.00 65.00 明4 1.91 123.56 0.09 1.52 1.79 193.70 0.36 322.70 20.70 913.00 100.00 51.00 高1 1.58 125.40 0.05 0.51 10.00 188.00 0.77 326.00 13.75 484.68 144.00 55.00 浩23 2.62 124.08 0.09 0.66 4.30 191.74 0.40 323.50 9.63 582.75 295.00 150.00 浩26 2.83 117.57 0.37 1.96 3.49 185.00 1.42 312.00 ‒ ‒ ‒ ‒ 浩92 2.41 94.11 2.33 13.55 1.53 175.51 2.43 290.90 ‒ ‒ ‒ ‒ 浩9‒1 5.50 119.46 0.07 0.43 6.14 185.49 0.22 314.70 13.76 541.24 253.48 49.00 浩17 2.77 121.84 0.38 2.61 1.90 194.16 0.94 323.50 16.00 354.80 390.00 66.70 浩17 5.09 116.62 0.20 2.32 1.08 188.12 0.36 313.79 16.00 354.80 390.00 66.70 钟38 1.72 117.09 0.14 0.91 2.46 182.00 0.52 305.00 16.50 435.50 272.00 97.00 王23 2.20 116.63 0.12 0.15 28.76 158.63 4.49 310.20 ‒ ‒ ‒ ‒ 王北13‒6 2.25 123.60 0.34 1.52 2.98 193.16 1.62 324.60 ‒ ‒ ‒ ‒ 王8 2.31 124.93 0.07 0.52 4.82 192.00 0.51 325.00 12.70 489.70 176.00 108.00 王8 6.83 70.36 0.73 6.83 1.27 127.00 1.65 211.00 ‒ ‒ ‒ ‒ 钟57 1.78 117.87 0.22 1.57 2.13 184.81 0.58 308.30 ‒ ‒ ‒ ‒ 广4 0.93 47.67 0.02 0.79 1.61 74.56 0.19 125.70 ‒ ‒ ‒ ‒ 丫2 0.63 87.06 0.51 1.89 3.83 136.31 0.89 230.90 ‒ ‒ ‒ ‒ 丫41 1.18 84.62 0.13 0.70 4.34 129.87 0.15 220.70 10.11 347.57 140.35 106.25 丫47 1.44 85.80 0.24 1.24 4.62 132.91 0.31 226.30 11.35 371.43 136.15 118.75 黄12 0.79 121.21 0.02 0.16 28.34 166.70 0.62 318.00 9.50 276.70 114.00 59.00 黄30 1.58 71.33 0.95 1.25 2.82 113.81 0.87 192.00 ‒ ‒ ‒ ‒ 浩192 3.59 126.33 0.10 0.53 7.24 193.97 0.75 332.60 ‒ ‒ ‒ ‒ 王46 3.67 121.05 0.17 1.55 1.31 192.08 0.26 320.00 ‒ ‒ ‒ ‒ 王36 3.36 125.36 0.07 0.34 9.19 190.00 0.65 333.00 11.40 322.70 238.00 65.00 王16 3.39 119.05 0.18 1.42 2.03 188.00 0.31 315.00 ‒ ‒ ‒ ‒ 王北10‒6 3.18 110.37 0.15 1.34 1.15 174.96 0.13 290.10 ‒ ‒ ‒ ‒ 潭17 0.51 82.26 0.07 0.22 10.40 120.00 0.54 214.00 8.50 201.50 47.70 81.00 潭10 0.37 62.84 0.21 0.47 4.80 94.89 0.42 163.90 7.60 162.00 28.00 40.00 广6 4.48 124.58 0.11 0.69 4.70 194.00 0.43 328.00 ‒ ‒ ‒ ‒ 广14 5.93 120.43 0.45 4.09 0.79 198.83 0.36 328.50 27.00 508.70 395.00 45.00 王新四3‒11 3.58 119.71 0.25 3.40 1.57 193.16 0.45 324.10 15.29 503.80 415.31 182.00 王49 3.68 79.14 1.05 0.78 1.76 128.44 0.12 215.00 ‒ ‒ ‒ ‒ 高8 3.11 123.26 0.13 0.66 4.21 191.14 0.48 322.90 ‒ ‒ ‒ ‒ 
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表 2 潜江凹陷卤水元素含量相关系数
Table 2. Correlation coefficient of element concentration of brine in Qianjiang Depression
K Na Mg Ca SO4 Cl HCO3 I Br B Li K 1.00 Na 0.35 1.00 Mg 0.18 ‒0.30 1.00 Ca 0.36 ‒0.14 0.84 1.00 SO4 ‒0.33 0.09 ‒0.29 ‒0.34 1.00 Cl 0.48 0.96 ‒0.13 0.05 ‒0.15 1.00 HCO3 ‒0.15 ‒0.28 0.18 0.16 0.35 ‒0.35 1.00 I 0.53 0.39 0.49 0.68 ‒0.44 0.51 ‒0.26 1.00 Br 0.40 0.61 0.05 0.25 ‒0.22 0.65 ‒0.32 0.60 1.00 B 0.79 0.50 0.41 0.73 ‒0.38 0.61 ‒0.15 0.49 0.30 1.00 Li 0.04 0.06 0.13 0.33 ‒0.30 0.13 ‒0.26 0.09 0.15 0.34 1.00
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