Geochemical Characteristics of Niutitang Formation in Zoumazhen Area, Hefeng, Hubei Province: Provenance, Paleoweathering, Sedimentary Environment and Tectonic Setting
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摘要: 鹤峰地区位于湘西‒鄂西地区层控铅锌多金属成矿带内，不仅是我国“扬子型”铅锌矿床重要产区之一，也是我国页岩气资源重要的远景区，为了探讨区内分布的寒武系下统牛蹄塘组黑色岩系沉积物物质来源及其成熟度、古风化特征、沉积环境以及岩石形成的构造环境，对产于鹤峰县走马镇地区下寒武统牛蹄塘组中下部的黑色岩系开展了岩石学和岩石化学成分分析，结果显示：走马镇地区牛蹄塘组岩石的主量元素含量变化比较大，上下不同层位样品化学成分相差较大，其中下部地层除了SiO2和P2O5含量高于PAAS值外，其他组分均低于PAAS值.强烈富集U、Cr，而亏损Th，具有较高的Ni/Co值和较低的V/Cr值.REE总量略高于PAAS，具有明显的Ce负异常和弱‒微弱的Eu负异常以及略偏大的Y/Ho比值.而上部地层中Al2O3含量明显高于下部地层，与PAAS相比，除了SiO2和Na2O略微富集外，其他组分全部亏损.强烈富集V、U和Ba，明显亏损Zn、Th、Ni和Rb，Ni/Co比值低而V/Cr比值高且变化范围大.REE总量与下部地层相差不大，弱‒微弱的Ce和Eu的负异常，Y/Ho比值比下部地层更接近火成岩和陆源碎屑岩值.结果表明该套岩石为陆源碎屑岩和中性火山岩，在潮湿‒半干旱的气候条件下经过强烈的风化作用，沉积于被动大陆边缘构造环境下的缺氧‒贫氧、局部贫氧‒次氧化的海水中，有热水沉积物的参与.Abstract: The Hefeng area is located in the stratabound-type Pb-Zn polymetallic metallogenic belt in the junctional zone between western Hunan and western Hubei. It is not only one of the important producers of "Yangtze-type" Pb-Zn deposits, but also an important prospecting area of shale gas resources in China. In order to discuss the provenance, paleoweathering, sedimentary environment and tectonic setting of the Niutitang Formation, the petrology and petrochemistry of the black rock series in the middle and lower part of the Niutitang Formation in Zouma Town of Hefeng County are analyzed. The contents of major elements in the rock vary significantly, and the chemical composition of the samples from different layers is quite different. Except for SiO2 and P2O5, most of the compositions in the lower layer are lower than the PAAS value. The rocks are strongly enriched in U and Cr, but depleted in Th. They have high Ni/Co ratios and low V/Cr ratios. The total amount of REE is slightly higher than that of PAAS, with obvious Ce negative anomaly, weak Eu negative anomaly, and slightly larger Y/Ho ratio. The content of Al2O3 in the upper stratum is significantly higher than that in the lower strata. Compared with PAAS, most of the components are depleted except SiO2 and Na2O. The rocks are strongly enriched in V, U, and Ba, obviously depleted in Zn, Th, Ni, and Rb, with low Ni/Co ratios and high V/Cr ratios. The content of the total amount of REE is similar to that of the lower strata with the weak negative anomalies of Ce and Eu, and the Y/Ho ratios are similar to the values of igneous and terrigenous clastic rocks. It is considered that the Niutitang Formation were originated from terrigenous clastic rocks and neutral volcanic rocks, which have undergone strong weathering under humid to semi-arid climatic conditions, and were deposited in the palaeogeographic anoxic/dysoxic environment in the passive continental margin setting.
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Key words:
- Niutitang Formation /
- petrology /
- geochemistry /
- provenance /
- sedimentary environment /
- tectonic setting /
- Hefeng County
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图 1 区域构造纲要图（a）及采样位置（b）
①麻泥山背斜，②来凤‒鹤峰向斜，③长岭向斜，④铁家岭向斜，⑤二坪背斜，⑥雉鸡坪向斜，⑦走马‒东山峰背斜，⑧增壁台背斜. F100为燕家河断裂；F101为八方界断裂；F102为孟家沟‒清官渡断裂；F103为自生桥断裂；F104为碑垭‒官屋场断裂；F105为南里坪断裂. 图b据湖北省地质局第二地质大队，2015，湖北省鹤峰县走马地区铅锌多金属矿调查评价
Fig. 1. Regional structure outline map (a) and sampling location (b)
图 3 岩石主量元素PAAS标准化分布
Fig. 3. Distribution of PAAS normalized abundances of major for the study samples
图 5 牛蹄塘组黑色岩系稀土元素PAAS标准化配分模式
PAAS数据来源于McLennan et al.（1989）
Fig. 5. PAAS-normalized REE patterns for the study samples
图 6 页岩SiO2/Al2O3-K2O/Na2O年龄判别图
底图据Wronkiewicz and Condie（1987）
Fig. 6. Bivariate SiO2/Al2O3 vs. K2O/Na2O age discrimination diagram for shales
图 9 页岩A-CN-K图
底图据Fedo et al.（1995）、Nesbitt et al.（1984）；A. Al2O3；CN. CaO*+Na2O；K. K2O
Fig. 9. A-CN-K ternary diagram showing weathering trend
图 10 SiO2-(Al2O3+K2O+Na2O)古气候判别图
Fig. 10. Bivariate SiO2 vs. (Al2O3+K2O+Na2O) palaeoclimate discrimination diagram
图 11 Ni/Co-V/(V+Ni)古氧化还原条件判别图
Fig. 11. Paleo redox conditions by Ni/Co vs. V/(V+Ni)
图 12 主量元素构造背景判别图解
a. K2O/Na2O-SiO2图解，底图据Roser and Korsch（1986）；b. Na2O-CaO-K2O图解，底图据Bhatia and Crook（1986）；CIA. 大陆岛弧；OIA. 大洋岛弧；PCM. 被动大陆边缘；ACM. 活动大陆边缘
Fig. 12. Tectonic discrimination plots using major elements
表 1 岩石主量元素含量（%）
Table 1. Major elements compositions for the study samples (%)
成分 导线1 导线2+3 PAAS BGP-1-1 BGP-1-2 BGP-1-3 BGP-1-4 BGP-1-5 BGP-1-6 BGP-1-7 BGP-1-8 平均值 BGP-3-1 BGP-3-2 BGP-3-3 BGP-4-1 BGP-4-2 BGP-4-3 BGP-4-4 BGP-4-5 BGP-4-6 平均值 SiO2 69.46 64.94 68.26 69.29 69.36 60.21 66.94 73.59 67.76 63.48 65.26 68.6 68.83 73.14 72.31 70.60 66.86 65.44 68.28 62.8 Al2O3 6.01 6.45 6.59 6.77 6.86 9.38 8.10 6.57 7.09 11.92 12.83 11.59 12.47 11.59 12.44 11.28 14.46 14.63 12.58 18.9 TiO2 0.32 0.34 0.37 0.38 0.42 0.54 0.56 0.37 0.41 0.90 0.64 0.56 0.78 0.68 0.70 0.64 0.75 0.79 0.72 1.00 Fe2O3T 3.59 3.94 3.23 3.43 3.29 5.42 3.67 3.14 3.71 1.82 1.59 2.66 1.17 1.51 1.28 3.57 5.71 3.48 2.53 7.22 MnO 0.020 0.016 0.004 0.006 0.005 0.016 0.004 0.007 0.010 0.003 0.006 0.006 0.005 0.004 0.004 0.005 0.010 0.010 0.01 0.11 CaO 1.97 4.43 0.45 0.37 0.37 0.57 0.19 0.41 1.10 0.11 0.04 0.04 0.06 0.08 0.05 0.04 0.04 0.04 0.06 1.3 MgO 1.30 0.91 1.16 1.12 0.88 1.35 0.63 0.62 1.00 0.79 1.29 1.28 1.33 0.99 1.05 1.03 1.23 1.85 1.20 2.2 Na2O 0.41 0.58 0.05 0.11 0.54 0.82 1.19 0.79 0.56 2.16 1.09 0.76 1.28 1.16 1.26 1.47 1.15 1.67 1.33 1.2 K2O 1.74 1.91 2.13 2.15 2.01 2.61 2.16 1.71 2.05 2.99 3.44 3.08 3.11 2.84 3.08 2.60 3.49 3.25 3.10 3.7 P2O5 0.55 2.76 0.35 0.25 0.13 0.16 0.04 0.14 0.55 0.12 0.05 0.11 0.04 0.04 0.03 0.05 0.06 0.06 0.06 0.16 H2O+ 2.09 2.15 2.97 2.90 3.50 2.95 2.50 1.98 2.63 3.16 3.60 3.63 3.71 2.74 3.11 2.82 2.91 2.89 3.17 CO2 1.15 0.69 0.07 0.09 0.07 0.23 0.05 0.14 0.31 0.05 0.05 0.05 0.02 0.02 0.02 0.05 0.02 0.02 0.03 LOST 14.38 13.46 15.66 14.83 15.46 18.43 15.99 12.10 15.04 15.28 13.03 10.44 10.40 7.34 7.41 8.39 5.68 8.45 9.60 6.00 Total 103.0 102.6 101.3 101.7 102.9 102.7 102.0 101.6 102.2 102.8 102.9 102.8 103.2 102.1 102.7 102.5 102.4 102.6 102.67 104.59 Al2O3/TiO2 18.53 19.03 17.99 17.97 16.48 17.39 14.52 17.61 17.44 13.28 20.20 20.59 15.98 17.02 17.74 17.73 19.24 18.63 17.82 Al/Ti 16.35 16.79 15.88 15.86 14.54 15.35 12.81 15.54 15.39 11.72 17.82 18.17 14.10 15.02 15.66 15.64 16.98 16.44 15.73 SiO2/Al2O3 11.56 10.06 10.36 10.23 10.12 6.42 8.26 11.20 9.78 5.32 5.09 5.92 5.52 6.31 5.82 6.26 4.62 4.47 5.48 K2O/Na2O 4.29 3.28 40.00 20.20 3.73 3.19 1.81 2.16 9.83 1.38 3.15 4.03 2.42 2.44 2.45 1.78 3.04 1.94 2.51 K2O/Al2O3 0.29 0.30 0.32 0.32 0.29 0.28 0.27 0.26 0.29 0.25 0.27 0.27 0.25 0.25 0.25 0.23 0.24 0.22 0.25 ICV 1.50 1.83 1.07 1.06 1.04 1.15 0.97 1.02 1.21 0.66 0.58 0.68 0.56 0.57 0.54 0.77 0.80 0.70 0.65 Al2O3 0.058 9 0.063 3 0.064 6 0.066 4 0.067 2 0.092 0 0.079 5 0.064 4 0.070 0 0.116 9 0.125 8 0.113 6 0.122 2 0.113 7 0.121 9 0.110 5 0.141 8 0.143 4 0.12 CaO* 0.006 5 0.009 4 0.000 9 0.001 7 0.005 7 0.009 0 0.003 0 0.006 4 0.010 0 0.001 1 0.000 4 0.012 3 0.000 8 0.001 1 0.000 7 0.000 4 0.000 3 0.000 3 0.00 Na2O 0.006 5 0.009 4 0.000 9 0.001 7 0.008 7 0.013 2 0.019 2 0.012 8 0.010 0 0.034 8 0.017 6 0.012 3 0.020 7 0.018 8 0.020 3 0.023 7 0.018 5 0.027 0 0.02 K2O 0.018 5 0.020 3 0.022 7 0.022 9 0.021 4 0.027 8 0.023 0 0.018 2 0.020 0 0.031 8 0.036 6 0.032 8 0.033 0 0.030 2 0.032 8 0.027 7 0.037 1 0.034 6 0.03 CIA 65.12 61.78 72.58 71.58 65.19 64.80 63.74 63.31 66.01 63.32 69.75 66.43 69.16 69.40 69.41 68.14 71.71 69.85 68.57 PIA 75.57 69.54 96.06 92.67 75.99 74.33 71.75 70.73 78.33 70.32 83.23 76.65 80.61 80.74 80.97 77.54 84.76 79.94 79.42 CIW 81.84 77.09 97.41 95.07 82.29 80.58 78.14 77.10 83.69 76.49 87.49 82.18 85.07 85.10 85.33 82.16 88.29 84.01 84.01 CIW' 90.02 87.06 98.69 97.47 88.52 87.44 80.54 83.45 89.15 77.04 87.71 90.21 85.53 85.82 85.73 82.38 88.44 84.15 85.22 注：Al2O3、CaO*、Na2O、K2O的单位为moles；ICV（index of compositional variation）和CIA（chemical index of alteration）据Nesbitt and Young（1982）；PIA（plagioclase index of alteration）据 Fedo et al.（1995） ；CIW（chemical index of weathering）据Harnois（1988）；CIW'据Cullers（2000）.
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表 2 牛蹄塘组黑色岩系微量元素含量（10‒6）
Table 2. Trace elements compositions for the study samples (10‒6)
元素 导线1 导线2+3 BGP-
1-1BGP-
1-2BGP-
1-3BGP-
1-4BGP-
1-5BGP-
1-6BGP-
1-7BGP-
1-8平均值 BGP-
3-1BGP-3-2 BGP-
3-3BGP-4-1 BGP-4-2 BGP-
4-3BGP-
4-4BGP-4-5 BGP-
4-6平均数 Cu 228.71 261.53 534.30 433.16 66.72 73.11 19.67 31.14 206.04 22.76 15.42 15.46 8.54 8.91 11.60 12.57 55.74 14.06 18.34 Zn 310.24 358.85 1 134.03 1 009.30 206.00 446.09 22.66 89.12 447.04 16.29 21.14 83.08 26.33 44.68 33.50 78.01 245.55 198.79 83.04 Pb 20.01 19.43 23.66 26.51 18.93 17.32 17.44 16.45 19.97 12.34 16.84 20.54 14.81 10.38 23.44 20.69 17.13 14.89 16.78 U 19.20 27.20 55.60 54.30 66.40 93.90 32.60 27.00 47.03 71.50 19.25 25.00 18.40 15.30 12.10 10.95 11.60 13.50 21.96 Th 4.84 5.24 6.06 6.03 6.06 8.66 6.94 6.35 6.27 13.35 10.65 10.85 14.50 13.25 10.00 8.55 13.75 11.45 11.82 V 1 220 1 050 9 860 7 650 3 440 2 580 1 060 940 3 475 547 1 040 1 440 319 250 224 225 230 293 507.56 Cr 870 750 2 390 2 030 260 190 100 80 833.75 130 130 140 120 100 100 90 120 120 116.67 Ni 129.00 146.40 390.90 333.70 215.00 322.60 179.10 137.50 231.78 47.66 54.64 53.18 26.67 31.41 16.47 86.06 95.61 68.57 53.36 Co 15.95 31.16 31.76 36.75 45.29 33.34 309.30 36.32 67.48 367.10 72.87 77.57 25.22 28.86 39.04 87.23 39.30 44.41 86.84 Ag 0.35 0.29 0.31 0.24 0.37 0.26 0.29 0.27 0.30 0.25 0.54 0.61 0.95 0.91 2.33 2.04 2.68 6.36 1.85 V 317 379 250 293 230 225 224 250 271 319 1 440 1 040 547 940 1 060 2 580 3 440 7 650 2 113 Mo 28.70 48.80 33.28 28.52 27.27 31.18 24.67 41.44 32.98 64.05 133.00 92.18 51.63 37.16 140.90 177.50 164.10 92.09 105.85 Rb 121.00 126.00 126.00 138.00 147.50 107.50 129.50 117.50 126.63 129.00 121.50 130.00 96.00 55.20 71.60 91.20 72.20 93.60 95.59 Ba 2 040 2 130 1 845 2 100 3 890 2 400 3 860 4 560 2 853.13 4 640 6 600 7 470 10 000 3 620 4 540 5 200 3 780 3 430 5 475.56 Hf 3.60 4.10 3.90 4.40 3.90 3.30 3.80 3.60 3.83 4.60 3.50 3.70 6.40 2.30 3.40 3.30 2.60 2.30 3.57 Zr 138 153 141 161 146 124 140 141 143 173 130 146 246 90 130 131 101 89 137.33 Ta 1.00 1.10 1.10 1.20 1.10 1.00 1.10 1.10 1.09 1.20 0.80 0.90 1.10 0.80 0.80 0.70 0.70 0.70 0.86 Ni/Co 8.09 4.70 12.31 9.08 4.75 9.68 0.58 3.79 6.62 0.13 0.75 0.69 1.06 1.09 0.42 0.99 2.43 1.54 1.01 Cu/Zn 0.74 0.73 0.47 0.43 0.32 0.16 0.87 0.35 0.51 1.40 0.73 0.19 0.32 0.20 0.35 0.16 0.23 0.07 0.40 V/（V+Ni） 0.71 0.72 0.39 0.47 0.52 0.41 0.56 0.65 0.55 0.87 0.96 0.95 0.95 0.97 0.98 0.97 0.97 0.99 0.96 V/Cr 0.36 0.51 0.10 0.14 0.88 1.18 2.24 3.13 1.07 2.45 11.08 7.43 4.56 9.40 10.60 28.67 28.67 63.75 18.51 U/Th 3.97 5.19 9.17 9.00 10.96 10.84 4.70 4.25 7.26 5.36 1.81 2.30 1.27 1.15 1.21 1.28 0.84 1.18 1.82
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表 3 牛蹄塘组黑色岩系稀土元素分析结果（10-6）
Table 3. Rare earth elements compositions for the study samples (10-6)
导线号 样品号 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y ΣREE LREE HREE Y/ Ho LaN/YbN δEu δCe 导线1 BGP-1-1 26.2 27.4 5.69 22.8 4.40 0.88 5.52 0.88 5.84 1.46 4.43 0.62 3.65 0.57 57 167.34 87.37 79.97 39 4.84 0.55 0.52 BGP-1-2 40.9 43.6 10.00 44.4 9.85 2.34 12.55 1.84 10.75 2.49 7.09 0.91 5.42 0.81 95 287.55 151.09 136.46 38 5.09 0.64 0.50 BGP-1-3 45.3 43.3 10.40 44.3 8.86 1.88 11.50 1.86 12.15 3.02 9.13 1.23 7.29 1.08 121 321.80 154.04 167.76 40 4.19 0.57 0.46 BGP-1-4 36.5 39.2 8.95 36.4 7.42 1.53 8.96 1.39 9.06 2.21 6.49 0.96 5.44 0.83 87 252.35 130.00 122.35 39 4.52 0.57 0.51 BGP-1-5 26.2 38.6 5.37 20.0 3.58 0.68 3.63 0.59 3.76 0.94 2.69 0.40 2.39 0.37 34 142.80 94.43 48.37 36 7.39 0.57 0.74 BGP-1-6 31.8 50.6 6.93 27.1 5.04 1.09 5.13 0.80 5.02 1.20 3.54 0.51 3.22 0.49 40 181.97 122.56 59.41 33 6.66 0.65 0.79 BGP-1-7 31.4 52.2 6.69 24.6 3.87 0.72 3.20 0.49 3.15 0.74 2.27 0.33 2.02 0.30 29 160.78 119.48 41.30 39 10.48 0.61 0.83 BGP-1-8 21.0 36.8 4.51 17.5 3.24 0.60 3.54 0.54 3.29 0.74 2.06 0.29 1.77 0.27 26 121.65 83.65 38.00 34 8.00 0.54 0.87 平均值 32.41 41.46 7.32 29.64 5.78 1.22 6.75 1.05 6.63 1.60 4.71 0.66 3.90 0.59 60.81 204.53 117.83 86.70 37.29 6.40 0.59 0.65 导线2+3 BGP-3-1 51.8 85.7 9.74 34.3 5.71 0.82 5.50 0.94 5.96 1.40 4.29 0.59 3.60 0.54 51 262.19 188.07 74.12 37 9.70 0.44 0.86 BGP-3-2 32.2 61.6 7.01 24.8 4.14 0.59 3.27 0.53 3.30 0.77 2.41 0.39 2.37 0.37 25 168.75 130.34 38.41 32 9.16 0.47 0.95 BGP-3-3 28.3 51.8 6.20 21.1 3.55 0.59 2.78 0.51 3.13 0.74 2.26 0.36 2.32 0.36 22 145.80 111.54 34.26 29 8.22 0.55 0.90 BGP-4-1 42.9 81.2 8.87 31.0 4.52 0.72 3.58 0.58 3.67 0.84 2.41 0.38 2.28 0.33 24 207.38 169.21 38.17 29 12.69 0.53 0.95 BGP-4-2 37.3 70.7 7.73 26.5 4.20 0.66 3.20 0.55 3.41 0.77 2.22 0.33 2.08 0.32 23 182.77 147.09 35.68 30 12.09 0.53 0.95 BGP-4-3 39.9 74.2 8.07 27.6 4.22 0.61 3.19 0.57 3.52 0.76 2.24 0.35 2.03 0.31 22 189.87 154.60 35.27 29 13.25 0.49 0.94 BGP-4-4 32.2 62.1 6.82 24.1 3.81 0.64 3.34 0.55 3.33 0.78 2.29 0.33 1.98 0.30 22 164.77 129.67 35.10 28 10.96 0.54 0.96 BGP-4-5 44.0 89.1 10.20 40.6 8.63 1.86 8.45 1.28 7.39 1.55 4.23 0.62 3.74 0.55 45 267.40 194.39 73.01 29 7.93 0.66 0.98 BGP-4-6 43.4 83.0 9.58 35.4 6.17 1.03 4.74 0.74 4.17 0.92 2.62 0.38 2.45 0.34 25 219.94 178.58 41.36 27 11.94 0.56 0.94 平均值 39.11 73.27 8.25 29.49 4.99 0.84 4.23 0.69 4.21 0.95 2.77 0.41 2.54 0.38 28.86 200.99 155.94 45.04 30.11 10.66 0.53 0.94
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