Geochemical characteristics and genesis of detrital apatites from the surrounding rivers into the Bohai Sea
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摘要:
渤海的碎屑物质详细记录了源区的地质信息，对其进行物源示踪研究有助于提高我们对周围造山带及黄河的演化、中国东部陆架海碎屑物质扩散等的认识。本文利用激光剥蚀电感耦合等离子质谱分别对辽东湾、渤海湾及莱州湾周围主要汇入河流的碎屑磷灰石进行原位微量元素分析，结合Kolmogorov-Smirnov统计方法的多维判别图与反向传播神经网络等方法，分析渤海主要汇入河流碎屑磷灰石的微量元素与稀土元素。结果表明在汇入渤海的主要河流中，碎屑磷灰石的微量元素主要以Sr元素与Y元素为主，且都出现较为明显的HREE富集，但在不同河流之间的碎屑磷灰石Sr元素与REE也存在一定差异，这可能与其母岩不同相关。
Abstract:To trace where the detrital deposits of the Bohai Sea come from is important for better understanding the basin-mountain coupling and the formation of the Yellow River, in addition to the distribution of the detrital sediments around the Bohai Sea. In this paper, the laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is applied to analyze the composition of trace elements of the detrital apatite grains from the main rivers pouring into Liaodong Bay, Bohai Bay, and Laizhou Bay, combining with Kolmogorov-Smirnov multi-dimensional discrimination diagram (MDS) and Back Propagation(BP) neural network to perform sediment provenance discrimination. Results show that they are all characterized by high Sr, Y and light rare earth elements(LREE). However, there are some differences in the sediments from different rivers, which may be related to the source rocks of apatite.
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Key words:
- apatite /
- trace element /
- provenance tracing /
- Bohai Sea
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表 1 渤海主要汇入河流的水文特征
Table 1. Hydrological characteristics of the main rivers flowing into the Bohai Sea
河流 发源山区 总长度/km 流域总面积/104 km2 输沙量/104 t 径流量/108 m3 入海海湾 辽河 燕山、大兴安岭 1345 21.96 173（2009—2019年） 26.12（2009—2019年） 辽东湾* 滦河 燕山 877 4.4 1739（1950—1984年） 46.5（1950—1984年） 辽东湾[16] 黄河 青藏高原 5500 75 17200（2009—2019年） 282.3（2009—2019年） 渤海湾* 滹沱河 太行山 587 2.7 – 9.46（1956—2000年） 渤海湾[42] 漳河 太行山 412 1.8 728（1951—2015年） 8.59（1951—2015年） 渤海湾* 弥河 鲁中山区 206 0.38 84.1（多年平均） 4.27（多年平均） 莱州湾[24] 注：*数据来源于《2019中国河流泥沙公报》。 
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表 2 渤海主要汇入河流碎屑磷灰石微量元素游程检验
Table 2. Runs test of trace elements in main rivers of Bohai Sea
辽河 滦河 漳河 滹沱河 黄河 弥河 Li 0.76 0.514 0.625 0.97 0.739 0.328 B 0.096 0.888 0.801 0.412 0.713 0.801 Sc 0.571 0.574 0.803 0.838 0.675 0.379 V 0.982 0.576 0.092 0.246 0.637 0.317 Cr 0.466 0.33 0.468 0.502 0.071 0.201 Co 0.329 0.706 0.125 0.653 0.036 0.6 Ni 0.896 0.964 0.626 0.158 0.54 0.54 Cu 0.827 0.36 0.37 0.906 0.488 0.002 Zn 0.76 0.328 0.803 0.54 0.86 0.283 Ga 0.088 0.178 0.919 0.013 0.749 0.801 Rb 0.756 0.502 0.317 0.861 0.899 0.758 Sr 0.173 0.061 0.118 0.05 0.112 0.795 Y 0.492 0.088 0.695 0.818 0.637 0.514 Zr 0.851 0.845 0.861 0.054 0.772 0.046 Nb 0.466 0.709 0.246 0.54 0.861 0.302 Mo 0.894 0.125 0.656 0.828 0.245 0.602 Ag 0.398 0.434 0.75 0.755 0.772 0.349 Cd 0.163 0.577 0.067 0.201 0.016 0.477 Sn 0.695 0.902 0.195 0.28 0.938 0.412 Sb 0.078 0.845 0.125 0.545 0.686 0.6 Cs 0.87 0.328 0.289 0.493 0.329 0.16 Ba 0.063 0.656 0.22 0.32 0.47 0.555 Hf 0.851 0.803 0.435 0.606 0.772 0.046 Ta 0.386 0.795 0.801 0.755 0.772 0.036 W 0.517 0.204 0.353 0.468 0.049 0.876 Tl 0.576 0.709 0.434 0.071 0.179 0.732 Bi 0.334 0.205 0.076 0.576 0.464 0.992 Pb 0.236 0.97 0.577 0.033 0.153 0.193 Th 0.659 0.814 0.222 0.04 0.416 0.05 U 0.571 0.449 0.599 0.768 0.223 0.732 La 0.002 0.379 0.069 0.964 0.25 0.625 Ce 0.238 0.246 0.246 0.172 0.494 0.193 Pr 0.088 0.178 0.195 0.134 0.749 0.821 Nd 0.276 0.223 0.782 0.235 0.863 0.602 Sm 0.96 0.773 0.574 0.33 0.722 0.655 Eu 0.695 0.803 0.258 0.007 0.22 0.828 Gd 0.982 0.106 0.081 0.119 0.829 0.919 Tb 0.692 0.371 0.514 0.838 0.954 0.919 Dy 0.576 0.625 0.709 0.95 0.829 0.919 Ho 0.692 0.755 0.97 0.95 0.452 0.97 Er 0.626 0.493 0.695 0.66 0.546 0.514 Tm 0.96 0.75 0.695 0.383 0.723 0.278 Yb 0.886 0.178 0.54 0.845 0.954 0.344 Lu 0.768 0.022 0.54 0.858 0.749 0.344
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表 3 辽东湾、渤海湾及莱州湾主要汇入河流微量元素数据统计
Table 3. The value of the trace elements of apatite from the main rivers around Liaodong Bay, Bohai Bay and Laizhou Bay
μg/g 辽河（n=60） 滦河（n=60） 漳河（n=60） 滹沱河（n=60） 黄河（n=67） 弥河（n=60） 最大值 最小值 平均值 最大值 最小值 平均值 最大值 最小值 平均值 最大值 最小值 平均值 最大值 最小值 平均值 最大值 最小值 平均值 Li 5.4 0 0.5 2.0 0 0.4 2.9 0 0.4 4.5 0 0.4 10.4 0 0.8 5.5 0.2 1.4 B 3.7 0 2.4 3.8 0.4 1.8 3.9 0.4 2.0 5.9 0.6 2.2 6.6 0 1.3 4.2 0 2.1 Sc 2.6 0 0.3 11.6 0 0.7 1.9 0 0.2 1.4 0 0.2 66.9 0 1.2 0.9 0 0.3 V 15.6 0.1 4.2 186.2 0 7.8 40.6 0 5.2 8.3 0 2.2 32.1 0 6.0 12.5 0.9 5.6 Cr 2.2 0 0.5 2.1 0 0.6 3.6 0 0.7 2.4 0 0.5 6.7 0 0.3 3.0 0 0.7 Co 0.5 0 0 0.2 0 0 2.2 0 0.1 0.1 0 0 7.3 0 0.2 0.6 0 0 Ni 11.9 0 0.3 0.8 0 0.2 3.6 0 0.3 0.9 0 0.2 12.7 0 0.5 1.6 0 0.2 Cu 4.5 0 0.2 2.5 0 0.3 9.5 0 0.2 1.4 0 0.1 89.9 0 2.8 1.2 0 0.2 Zn 1.8 0 0.2 1.3 0 0.2 2.5 0 0.3 1.8 0 0.2 21.3 0 0.6 7.0 0 0.2 Ga 23.9 0.8 8.3 30.1 0.3 9.7 47.9 0.5 9.7 29.5 0.7 6.5 39.0 0.3 10.5 20.3 1.3 9.6 Rb 14.0 0 0.3 0.6 0 0.1 0.3 0 0.1 0.7 0 0.1 2.3 0 0.1 19.1 0 0.4 Sr 1049.6 252.7 534.9 6083.4 87.9 990.3 8672.2 123.6 911.8 1709.9 76.3 370.7 5526.5 95.0 717.2 537.1 165.8 303.2 Y 1683.4 17.5 472.0 3136.1 74.6 919.0 2914.4 38.2 550.3 3717.5 0.7 521.9 2876.5 27.0 631.7 2897.1 119.0 609.6 Zr 3126.7 0 53.6 9.3 0 0.5 3.6 0 0.6 333.9 0 6.5 131785.6 0 2052.0 122.2 0 3.4 Nb 0.1 0 0 0.2 0 0 0.2 0 0 0.1 0 0 31.5 0 0.5 0.1 0 0 Mo 0.4 0 0 0.5 0 0 11.2 0 0.2 0.2 0 0 0.7 0 0.1 0.1 0 0 Ag 0.1 0 0 0 0 0 0 0 0 0 0 0 4.9 0 0.1 0 0 0 Cd 1.1 0 0.2 13.2 0 3.6 1.1 0 0.3 0.5 0 0.1 4.2 0 0.2 0.6 0 0.2 Sn 1.3 0 0.6 1.8 0 0.9 1.1 0 0.6 1.4 0 0.6 1.5 0 0.4 1.2 0.1 0.6 Sb 0.1 0 0 0.6 0 0.1 0.2 0 0 0.2 0 0 0.1 0 0 0.3 0 0 Cs 0.1 0 0 0.1 0 0 0.1 0 0 0.1 0 0 0.2 0 0 0.4 0 0 Ba 6.1 0 0.7 74.7 0 2.4 13.0 0 1.2 2.7 0 0.4 43.3 0 1.5 10.7 0 0.3 Hf 78.0 0 1.3 0.1 0 0 0.1 0 0 8.2 0 0.2 2775.4 0 43.3 3.5 0 0.1 Ta 0.1 0 0 0 0 0 0 0 0 0 0 0 2.5 0 0 0 0 0 W 16.6 0 0.8 6.5 0 0.8 2.0 0 0.2 2.7 0 0.6 10.8 0 1.1 2.3 0 0.2 Hg 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Tl 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.1 0 0 Bi 0.1 0 0 0.6 0 0 0.3 0 0 0.3 0 0 5.1 0 0.4 0.2 0 0 Pb 6.6 1.1 3.2 26.4 0.6 6.6 10.9 0.6 3.0 10.4 0.9 3.3 17.8 1.0 4.3 29.9 4.5 11.5 Th 165.2 0 15.2 174.2 0.1 18.5 53.8 0 11.7 103.9 0 7.3 161.6 0 17.8 145.2 5.7 43.4 U 110.9 0.5 14.6 58.1 1.7 14.8 71.6 0.2 10.6 60.7 0 12.5 46.4 0.2 11.5 62.5 8.1 31.4
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表 4 辽东湾、渤海湾及莱州湾主要汇入河流碎屑磷灰石REE含量
Table 4. The average value of the rare earth elements of apatite from the main rivers around Bohai Bay Basin
μg/g La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 辽河（n=60） 最大值 1407.1 2132.7 252.3 1179.8 396.3 63.6 377.4 56.3 318.6 51.5 134.9 17.5 106.4 18.2 最小值 1.5 8.4 1.9 14.4 5.9 1.4 4.8 0.7 3.0 0.5 1.3 0.2 1.4 0.3 平均值 221.1 593.0 88.9 464.6 119.1 21.5 113.7 15.7 83.0 15.1 42.2 5.3 32.0 4.8 滦河（n=60） 最大值 1082.7 2664.6 327.7 1541.2 361.8 84.6 642.7 110.4 842.3 201.4 670.4 111.7 734.8 100.2 最小值 0.1 0.5 0.1 1.5 1.4 0.6 6.7 1.6 13.7 2.2 6.1 0.7 2.8 0.3 平均值 218.2 666.4 104.5 522.1 132.9 21.8 169.3 27.4 168.8 33.7 89.7 12.2 70.8 9.4 漳河（n=60） 最大值 1626.7 3794.5 575.9 1172.0 265.7 69.7 576.8 78.9 525.3 100.6 289.5 38.4 230.1 34.9 最小值 1.2 4.7 0.9 4.9 2.4 0.3 4.3 0.8 7.2 1.2 3.3 0.4 1.8 0.4 平均值 348.6 779.2 107.4 461.9 109.1 20.7 127.8 16.2 98.9 18.4 50.3 6.4 37.4 5.4 滹沱河（n=60） 最大值 887.7 1977.9 372.0 1082.4 279.0 98.2 326.8 182.6 1174.6 235.5 645.1 80.7 463.8 58.5 最小值 0.3 1.1 0.2 1.4 0.4 0.1 0.2 0.0 0.2 0.0 0.0 0.0 0.0 0.0 平均值 166.4 458.7 69.5 298.4 78.6 12.4 81.9 16.0 99.5 20.8 58.9 7.3 42.4 6.0 黄河（n=67） 最大值 5126.7 7593.3 794.5 3656.9 822.0 87.6 776.2 101.9 561.5 100.5 277.2 38.0 246.9 31.3 最小值 3.5 13.1 3.0 21.0 10.7 2.8 10.3 1.0 5.2 0.8 2.0 0.2 1.2 0.2 平均值 578.1 1502.4 210.4 973.3 200.2 23.6 183.1 22.4 119.5 21.5 55.6 6.8 41.3 5.7 弥河（n=60） 最大值 1079.7 2199.5 242.5 1062.1 308.0 48.2 430.0 67.6 376.1 68.6 236.0 37.7 326.7 53.2 最小值 15.8 53.3 7.9 38.3 8.7 5.2 10.5 1.7 11.3 3.0 12.2 2.2 18.7 2.9 平均值 251.6 745.0 107.7 491.8 115.9 21.3 119.7 16.6 90.2 17.6 55.1 7.6 57.9 8.8
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