Geochemical records of hydrothermal fluids in corals: Evidence of rare earth elements from coral reefs in the Yongxing Island, Xisha, South China Sea
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摘要:
碳酸盐岩中稀土元素的含量、配分模式及元素异常记录了周围沉积水体的特征，能够很好地指示古海洋及沉积环境。珊瑚具有的高分辨率和稀土元素的高稳定性的特点，能够忠实地记录周围海水的地球化学特征。本文以南海西沙宣德环礁永兴岛142～84 ka发育的珊瑚礁为研究对象，通过主微量元素含量，尤其是稀土元素含量及其配分图解，判断珊瑚礁形成时周围水体的特征。结果表明自142 ka以来，永兴岛大部分珊瑚礁具有正常海相碳酸盐岩的稀土配分特征，表现为LREE亏损，Ce负异常及高的Y/Ho比值，表明周围水体属于开阔的浅海，但是位于23 m处（年龄为114 ka）的滨珊瑚骨骼格架除了有正常海相碳酸盐岩的特征外，还具有明显的Eu正异常，这表明其形成时有热液流体的加入。经过模型计算，认为在滨珊瑚骨骼格架的生长阶段，至少有0.1%的热液加入周围的海水中。通过资料查询和年龄对比，认为这些热液可能与高尖石岛或海南岛火山活动有关。
Abstract:The contents, distribution pattern and elemental anomalies of rare earth elements in carbonates are the records of surrounding water. Corals are characterized by high resolution and high stability of rare earth elements and may faithfully record the geochemical characteristics of the surrounding seawater. In this paper, we analyzed the coral reefs from 142 to 84 ka collected from the Yongxing Island of the Xuande Atoll of Xisha Islands, South China Sea. Trace element contents, especially the rare earth element contents and their distribution patterns are used in this paper to determine the characteristics of the sea water, in which the coral reefs grew. Results show that, since 142 ka, most of the coral reefs in the Yongxing Island has a normal rare earth element distribution pattern of marine carbonates, characterized by LREE depletion, negative Ce anomalies and high Y/Ho ratios, indicating an environment of open shallow sea. In contrast, the coral skeletons in depth of 23 m 114 ka have similar LREE depletion, negative Ce anomalies and high Y/Ho ratios, but positive Eu anomalies. This suggests that certain amount of hydrothermal fluid has been input during the growth of corals. Based on the model calculations, it is inferred that at least 0.1% of hydrothermal fluid has been added to the open seawater during that time. The hydrothermal fluids may be related to the volcanic activities observed at Gaojianshi island or Hainan island.
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Key words:
- coral /
- rare earth element /
- Eu anomaly /
- hydrothermal solution /
- South China Sea
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表 1 珊瑚礁样品矿物物相组成
Table 1. Mineral phase composition of coral reef samples
样品号 深度/m 文石/% 方解石/% 18.40 18.40 76.4 23.6 22.80 22.80 100 − 23 23 76.3 23.7 27.75 27.75 43.6 56.4 31.20 31.20 − 100 41.80 41.80 − 100 注：−表示未检出。 
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表 2 岩心柱中部分珊瑚（包括滨珊瑚骨骼化石）238U-232Th测年结果
Table 2. 238U-232Th dating results of some corals （including
Porites skeleton fossil） in core column 样品号 238U（×10−9） 232Th（×10−12） δ234U*（测量值） 230Th/238U δ234UInitial**（校正后） 年龄/ka 校正后年龄/kaBP YL-1835 1 670±1.1 24 128±52 114±1.1 0.606 4±0.000 745 144±1.4 84.18±0.206 83.82±0.277 YL-1890 2 766±1.8 1 417±44 109±1.0 0.723 8±0.000 900 150±1.3 112.40±0.305 112.38±0.305 YL-2175 2 400±1.3 741±37 109±1.8 0.743 1±0.001 038 151±2.5 117.74±0.473 117.73±0.473 YL-2300 2 480±1.3 398±41 113±1.0 0.734 2±0.000 812 156±1.4 114.36±0.299 114.35±0.30 YL-2495 1 222±0.9 942±46 107±1.2 0.821 4±0.001 177 160±1.8 142.49±0.540 142.47±0.540 YL-3011 3 108±2.2 111 312±143 104±1.0 0.795 9±0.000 981 152±1.4 134.64±0.412 133.73±0.615 YL-3650 1 888±1.2 14 549±45 85±1.1 1.063 0±0.001 193 220±3.8 337.10±3.71 336.92±3.71 YL-4285 924±0.7 6 890±47 89±1.2 1.007 3±0.001 333 183±2.6 255.73±1.837 255.54±1.839 YL-4605 951±0.7 594±40 88±1.1 0.982 6±0.001 357 171±2.2 234.82±1.47 234.80±1.47 YL-4850 963±0.7 579±48 82±1.0 0.986 6±0.001 279 163±2.2 243.85±1.53 243.84±1.53 YL-5015 509±0.4 184±40 92±1.3 0.894 8±0.001 208 152±2.2 177.96±0.848 177.95±0.848 YL-5530 1 816±1.1 158±47 88±1.0 0.962 6±0.001 209 163±1.9 220.19±1.135 220.19±1.135 注：234U、238U和230Th的衰变常数 
、
和
；
；校正的230Th年龄是假定初始的230Th/232Th原子比为（4.4±2.2）×10−6。年龄均相对于1 950 a。
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表 3 主量元素测试结果（单位：%）
Table 3. Major element test results（unit: %）
样品名称 Al2O3 CaO K2O MgO Na2O P2O5 样品名称 SiO2 2-6 0.03 48.62 0.02 0.15 0.53 – 000-1 0.034 2-16 0.03 42.2 0.01 0.12 0.44 0.01 000-2 0.016 5-1 0.01 43.88 0.01 0.17 0.59 – 000-3 0.078 5-8 0.01 43.24 0.01 0.17 0.59 – 000-4 0.031 9-1 0.01 43.6 0.01 0.25 0.59 – 000-5 0.044 9-8 0.01 45.2 0.01 0.24 0.67 – 000-6 0.020 15-1 0.01 43.62 0.01 0.24 0.6 – 001-1 – 15-8 0.01 42.97 0.01 0.24 0.6 – 001-2 0.011 19-1 0.01 52.1 0.02 0.33 0.81 – 001-3 0.057 19-11 0.01 52.4 0.02 0.3 0.99 – 010-1 – 18.75-2 0.01 54.05 – 0.66 0.21 0.08 010-2 – 20.00-1 0.02 53.79 0.01 0.46 0.32 0.05 010-3 – 20.00-2 0.02 53.83 0.01 0.15 0.51 0.01 021-1 – 20.25-1 0.02 63.04 0.01 0.27 0.58 0.01 021-2 0.033 20.25-2 0.01 55.06 0.01 0.45 0.32 0.03 021-3 0.008 21.05-1 0.01 53.09 0.01 0.16 0.53 0.01 034-1 0.004 21.90-2 0.03 57.59 0.01 0.33 0.43 0.04 034-2 0.011 22.75-2 0.01 54.21 – 0.82 0.36 0.05 034-3 0.020 23.40 0.01 54.16 – 0.25 0.27 0.05 039-1 0.015 24.00-1 0.01 53.17 0.01 0.5 0.4 0.02 039-2 0.018 24.00-2 0.01 53.05 – 0.82 0.17 0.04 039-3 – 25.25-1 0.02 53.61 0.01 0.56 0.38 0.05 054-1 0.028 25.25-2 0.02 54.85 – 0.64 0.16 0.04 054-2 0.011 26.55-1 0.01 54.68 – 0.3 0.25 0.02 26.55-2 0.01 54.06 0.01 0.13 0.36 0.01 注：−表示未检出，SiO2为电子探针测试数据。
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表 4 稀土元素含量（×10-6）及其相关指标
Table 4. Rare earth element content （×10-6） and related indicators
样品名称 Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ΣREY ΣREE ΣLREE/ΣHREE Y/Ho La/La* Ce/Ce* Eu/Eu* BLANK-1 0.000 0.001 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.002 13.301 51.776 2.496 0.914 1.549 BLANK-2 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.001 13.654 259.538 1.743 0.990 1.161 GSR-12 1.311 0.909 2.776 0.257 0.909 0.187 0.039 0.200 0.029 0.168 0.034 0.092 0.012 0.070 0.010 7.003 5.692 8.244 38.690 0.691 1.318 0.952 JDO-1 12.412 7.272 1.890 0.917 3.503 0.611 0.138 0.779 0.106 0.650 0.148 0.420 0.050 0.273 0.038 29.206 16.794 5.815 83.682 1.817 0.161 0.920 2-1 0.096 0.011 0.013 0.002 0.009 0.002 0.001 0.004 0.001 0.004 0.001 0.004 0.001 0.004 0.001 0.153 0.057 2.065 86.474 1.435 0.650 1.928 2-10 0.101 0.011 0.012 0.002 0.008 0.002 0.001 0.004 0.001 0.005 0.001 0.004 0.001 0.004 0.001 0.157 0.055 1.916 89.482 1.574 0.607 1.875 5-8 0.048 0.005 0.010 0.001 0.005 0.001 0.000 0.001 0.000 0.002 0.000 0.002 0.000 0.002 0.000 0.078 0.031 2.699 97.139 1.694 0.972 1.529 9-1 0.064 0.007 0.014 0.001 0.006 0.002 0.001 0.003 0.000 0.003 0.001 0.003 0.000 0.003 0.001 0.109 0.044 2.321 81.114 1.415 1.017 1.336 12-1 0.057 0.006 0.011 0.001 0.005 0.002 0.001 0.002 0.000 0.003 0.001 0.002 0.000 0.002 0.000 0.092 0.035 2.373 96.235 1.168 0.966 2.581 12-7 0.057 0.005 0.011 0.001 0.005 0.001 0.001 0.002 0.000 0.002 0.001 0.002 0.000 0.002 0.000 0.091 0.034 2.538 104.135 1.244 1.010 2.940 22-1 0.059 0.008 0.016 0.002 0.007 0.002 0.001 0.003 0.000 0.002 0.001 0.002 0.000 0.002 0.000 0.106 0.047 3.222 96.631 1.189 0.937 2.347 22-12 0.061 0.006 0.014 0.001 0.006 0.002 0.001 0.002 0.000 0.002 0.001 0.002 0.000 0.002 0.000 0.101 0.040 2.972 105.648 1.163 1.071 2.688 18.60-1 1.306 0.245 0.159 0.047 0.209 0.058 0.015 0.081 0.013 0.092 0.021 0.065 0.009 0.055 0.009 2.383 1.076 2.135 61.970 1.628 0.340 1.021 18.75-2 1.675 0.276 0.189 0.058 0.250 0.071 0.019 0.103 0.016 0.108 0.027 0.082 0.011 0.074 0.012 2.969 1.295 1.992 62.717 1.411 0.346 0.988 18.95-2 2.125 0.327 0.193 0.067 0.305 0.086 0.023 0.125 0.021 0.150 0.035 0.107 0.015 0.090 0.014 3.682 1.557 1.798 60.146 1.571 0.300 1.001 19.25-2 0.240 0.038 0.036 0.008 0.034 0.009 0.003 0.012 0.002 0.013 0.003 0.010 0.001 0.009 0.001 0.419 0.179 2.488 78.458 1.314 0.475 1.348 19.70-1 1.235 0.330 0.277 0.067 0.281 0.070 0.018 0.090 0.014 0.090 0.020 0.061 0.008 0.050 0.008 2.618 1.383 3.064 61.976 1.378 0.429 1.033 19.70-2 1.268 0.366 0.469 0.075 0.309 0.076 0.020 0.096 0.016 0.100 0.022 0.066 0.009 0.057 0.009 2.957 1.690 3.503 56.963 1.278 0.651 1.105 20.00-1 1.159 0.364 0.442 0.074 0.301 0.075 0.022 0.100 0.015 0.093 0.021 0.063 0.009 0.051 0.008 2.798 1.639 3.559 55.897 1.283 0.621 1.191 20.25-1 0.300 0.072 0.053 0.014 0.063 0.017 0.005 0.021 0.003 0.020 0.004 0.013 0.002 0.010 0.002 0.598 0.298 2.958 70.121 1.736 0.387 1.235 20.25-2 0.903 0.204 0.146 0.040 0.179 0.049 0.013 0.064 0.010 0.068 0.015 0.044 0.006 0.035 0.006 1.782 0.879 2.539 59.751 1.609 0.372 1.092 21.05-1 0.127 0.029 0.025 0.004 0.020 0.005 0.002 0.008 0.001 0.008 0.003 0.006 0.001 0.005 0.001 0.246 0.118 2.649 46.176 2.157 0.494 1.300 21.05-2 0.885 0.196 0.140 0.038 0.166 0.045 0.012 0.061 0.010 0.066 0.015 0.043 0.006 0.035 0.005 1.722 0.837 2.484 60.907 1.545 0.372 1.058 21.90-1 0.192 0.055 0.067 0.009 0.036 0.008 0.003 0.011 0.002 0.011 0.002 0.007 0.001 0.006 0.001 0.412 0.219 4.326 78.490 1.357 0.673 1.342 21.90-2 1.202 0.571 0.348 0.093 0.413 0.101 0.025 0.126 0.017 0.111 0.025 0.071 0.010 0.058 0.009 3.179 1.977 3.644 48.811 1.896 0.343 1.029 22.75-2 1.589 0.382 0.252 0.075 0.330 0.088 0.023 0.119 0.018 0.122 0.027 0.078 0.010 0.064 0.010 3.188 1.599 2.565 58.486 1.569 0.343 1.017 23.40 0.681 0.160 0.114 0.033 0.149 0.040 0.011 0.052 0.008 0.050 0.012 0.034 0.005 0.026 0.004 1.379 0.699 2.672 58.194 1.557 0.362 1.068 23.50 0.466 0.131 0.093 0.027 0.126 0.032 0.009 0.041 0.006 0.038 0.009 0.025 0.003 0.019 0.003 1.028 0.562 2.912 54.056 1.657 0.360 1.137 24.00-1 0.760 0.155 0.117 0.030 0.137 0.037 0.010 0.049 0.008 0.053 0.012 0.037 0.005 0.031 0.005 1.446 0.686 2.424 61.510 1.625 0.394 1.067 24.00-2 1.226 0.290 0.208 0.055 0.250 0.068 0.017 0.090 0.014 0.095 0.021 0.063 0.009 0.052 0.008 2.467 1.241 2.527 57.182 1.677 0.378 1.009 25.25-1 1.322 0.303 0.212 0.059 0.263 0.069 0.018 0.092 0.015 0.099 0.023 0.068 0.009 0.055 0.008 2.614 1.292 2.506 58.185 1.560 0.363 1.036 25.25-2 1.160 0.321 0.227 0.064 0.278 0.071 0.018 0.092 0.014 0.094 0.021 0.062 0.008 0.049 0.008 2.487 1.327 2.810 54.668 1.486 0.365 1.017 25.76-1 0.548 0.135 0.093 0.029 0.137 0.038 0.010 0.052 0.008 0.049 0.010 0.029 0.004 0.021 0.003 1.165 0.617 2.508 52.469 1.600 0.341 1.012 25.76-2 1.778 0.339 0.243 0.069 0.305 0.082 0.021 0.110 0.018 0.122 0.029 0.085 0.012 0.070 0.011 3.294 1.516 2.313 62.053 1.502 0.366 1.031 26.55-1 0.376 0.115 0.093 0.024 0.111 0.029 0.009 0.035 0.005 0.033 0.007 0.020 0.003 0.016 0.002 0.880 0.504 3.111 51.114 1.558 0.405 1.350 26.55-2 0.085 0.013 0.016 0.002 0.010 0.003 0.001 0.005 0.001 0.005 0.001 0.003 0.001 0.003 0.000 0.149 0.063 2.560 73.292 2.090 0.717 1.354 27.55-1 2.271 0.718 0.381 0.107 0.485 0.130 0.033 0.174 0.029 0.191 0.043 0.128 0.018 0.101 0.016 4.822 2.551 2.653 52.835 2.161 0.309 1.008 27.55-2 1.549 0.286 0.191 0.056 0.258 0.068 0.018 0.092 0.015 0.105 0.025 0.077 0.011 0.062 0.010 2.822 1.273 2.209 62.010 1.664 0.345 1.032
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表 5 微量元素含量（单位：×10−6）
Table 5. Trace element content （unit: ×10−6）
样品名称 Tm Yb Lu Sc Mn Fe Ni Cu Zr Pb U BLANK-1 0.000 0.000 0.000 0.000 0.001 0.179 0.017 0.029 0.006 0.005 0.002 BLANK-2 0.000 0.000 0.000 ＜LOD 0.002 0.294 0.010 0.013 0.005 ＜LOD 0.001 GSR-12 0.012 0.070 0.010 0.064 62.169 619.126 74.563 7.958 0.096 1.289 0.074 JDO-1 0.050 0.273 0.038 0.180 51.294 76.914 2.340 0.443 0.118 0.319 0.549 2-1 0.001 0.004 0.001 0.030 2.493 73.733 51.168 82.984 0.029 0.134 1.747 2-10 0.001 0.004 0.001 0.034 0.728 33.919 64.113 3.305 0.022 0.058 1.969 5-8 0.000 0.002 0.000 0.026 0.707 – 1.639 1.041 0.015 0.266 1.804 9-1 0.000 0.003 0.001 0.034 1.765 – 1.553 2.762 0.015 0.262 2.203 12-1 0.000 0.002 0.000 0.038 1.292 1.980 1.149 2.666 0.017 0.084 1.658 12-7 0.000 0.002 0.000 0.039 0.988 1.711 1.100 1.584 0.017 0.119 1.861 22-1 0.000 0.002 0.000 0.033 1.118 2.367 1.049 1.606 0.022 0.114 1.783 22-12 0.000 0.002 0.000 0.032 1.266 3.013 1.533 2.040 0.024 0.112 1.918 18.60-1 0.009 0.055 0.009 0.075 35.654 6.444 9.838 1.059 0.099 0.331 1.725 18.75-2 0.011 0.074 0.012 0.084 23.330 – 3.154 4.937 0.080 0.511 2.285 18.95-2 0.015 0.090 0.014 0.099 30.505 9.423 2.182 0.604 0.139 0.372 1.015 19.25-2 0.001 0.009 0.001 0.051 3.023 2.456 0.796 1.325 0.038 0.065 2.054 19.70-1 0.008 0.050 0.008 0.089 12.991 6.245 3.862 1.797 0.174 0.261 1.383 19.70-2 0.009 0.057 0.009 0.126 12.201 15.666 7.191 2.555 0.651 0.293 1.783 20.00-1 0.009 0.051 0.008 0.112 13.065 – 9.656 0.917 0.582 0.363 2.161 20.25-1 0.002 0.010 0.002 0.045 5.453 3.263 3.261 8.437 0.039 0.155 2.224 20.25-2 0.006 0.035 0.006 0.075 24.240 8.048 1.443 5.293 0.098 0.258 2.112 21.05-1 0.001 0.005 0.001 0.033 2.548 – 5.812 13.849 0.019 0.160 2.780 21.05-2 0.006 0.035 0.005 0.078 13.212 4.427 2.597 13.135 0.057 0.230 1.641 21.90-1 0.001 0.006 0.001 0.046 1.020 4.089 1.174 1.839 0.020 0.042 1.784 21.90-2 0.010 0.058 0.009 0.061 10.913 – 0.688 1.520 0.150 0.788 2.708 22.75-2 0.010 0.064 0.010 0.107 17.480 5.726 0.725 4.369 0.101 0.396 1.723 23.40 0.005 0.026 0.004 0.045 3.529 2.209 0.905 0.478 0.070 0.200 1.974 23.50 0.003 0.019 0.003 0.040 2.536 1.934 0.459 0.630 0.064 0.181 1.964 24.00-1 0.005 0.031 0.005 0.054 5.503 4.197 0.595 3.818 0.065 0.207 1.639 24.00-2 0.009 0.052 0.008 0.072 9.951 5.948 0.720 3.302 0.090 0.343 1.173 25.25-1 0.009 0.055 0.008 0.074 7.101 4.257 2.776 15.709 0.108 0.319 1.627 25.25-2 0.008 0.049 0.008 0.067 8.883 4.157 1.359 16.578 0.102 0.342 1.151 25.76-1 0.004 0.021 0.003 0.050 4.696 2.398 0.536 0.488 0.042 0.146 2.683 25.76-2 0.012 0.070 0.011 0.085 8.654 5.156 0.712 0.768 0.134 0.408 1.966 26.55-1 0.003 0.016 0.002 0.048 3.130 4.850 0.666 0.947 0.048 0.116 1.594 26.55-2 0.001 0.003 0.000 0.028 1.165 – 1.181 0.539 0.039 0.110 2.590 27.55-1 0.018 0.101 0.016 0.109 14.908 5.549 0.726 0.695 0.148 0.514 1.299 27.55-2 0.011 0.062 0.010 0.091 10.275 4.326 0.646 0.883 0.108 0.427 2.101 注：−表示未检测。
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