Trace rare earth elements in the Pinghu Formation of Xihu Sag and its implications for paleo-production environment
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摘要:
西湖凹陷是中国东海已证实的富烃凹陷，始新统平湖组是该凹陷主力烃源岩层系。通过对西湖凹陷30口井433个样品的地球化学及微量元素分析测试，从平湖组下段、中段、上段3个层段分析了有机碳、微量元素、稀土元素的特征及其垂向变化规律，从纵向上分析平湖组的古盐度、古气候、古氧化还原环境、古水深、古水温、古生产力等古生产环境。结果表明：微量元素Rb、Ba、Zr富集，均表现出明显的正异常，而Co、Mo、Sc、Hf相对亏损。Sr/Ba、Sr/Cu、古气候C值、V/Cr、Ni/Co、U/Th、V/(V+Ni)、V/Sc、Mn/Fe、Co、Sr、Sr/Cu、生源Ba等参数表明平湖组为温暖气候下的陆相淡水沉积，属于半干旱-半潮湿气候环境，具有较高的古生产力，生烃潜力好。
Abstract:The Xihu Sag has been proved as a hydrocarbon-rich basin in the East China Sea with the Pinghu Formation of Eocene as the main source rock. Based on the analysis data of 433 samples from 30 wells in the sag for geochemistry and micronutrients, the characteristics and vertical distribution patterns of organic carbon, micronutrients and rare earth elements are studied for the lower, middle and upper members of the Pinghu Formation respectively. The vertical patterns of palaeosalinities, palaeoclimate, palaeooxidation-reduction environment, palaeowater depth, palaeotemperature and palaeoproductivities of the Pinghu Formation suggest that Rb, Ba and Zr are enriched in micronutrients, shown as significant positive anomalies, while Co, Mo, Sc and Hf are deficient relatively. Sr/Ba、Sr/Cu、paleoclimate value C、V/Cr、Ni/Co、U/Th、V/(V+Ni)、V/Sc、Mn/Fe、Co、Sr、Sr/Cu、Baxs indicate that Pinghu Formation is formed in a terrestrial fresh water environment under warm, semi-arid to semi-humid climate with high paleoproductivity and high potential for hydrocarbon generation.
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Key words:
- trace elements /
- rare earth elements /
- ancient productivity /
- hydrocarbon potential /
- Pinghu Formation /
- Xihu Sag
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表 1 西湖凹陷平湖组烃源岩丰度统计
Table 1. Organic matter abundance in source rocks of Pinghu Formation in Xihu Sag
岩性 层位 TOC/
%（S1+S2）/
（mg/g）HI
（mgHC/gTOC）Tmax/
℃泥岩 平上段 0.5～5.98 1.59（367） 0.22～59.83 5.76（367） 31.43～913.82 279.61（346） 321～484.3 444.01（346） 平中段 0.5～5.97 1.68（543） 0.21～54.29 6.18（543） 21.65～893.89 253.03（539） 260～496 428.61（539） 平下段 0.5～5.52 1.36（191） 0.34～54.08 6.12（191） 30.82～891.77 255.36（191） 355～490 442.32（191） 碳质泥岩 平上段 6.45～19.64 11.38（39） 5.81～184 31.78（39） 80.4～921.72 249.1（39） 422～461 441.9（39） 平中段 6.06～19.63 10.95（89） 1.43～143.8 46.91（89） 8.31～900.06 383.02（89） 344～506 444.97（89） 平下段 6.59～14.9 10.365（8） 9.79～62.12 31.27（8） 85.5～763.77 275.31（8） 431～479 451（8） 煤 平上段 20.55～72.95 51.47（32） 56.32～219.15 137.05（32） 180.26～663.58 284.35（19） 421～457 444.63（19） 平中段 20.2～69.2 35.32（41） 51.36～421.85 159.16（41） 192.92～976.14 412.14（41） 417～469 442（41） 平下段 21.99～61.9 43.586（5） 56.14～193.8 98.1（5） 92.27～326.01 225.86（5） 432～489 454（5） 注： 
。
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表 2 平湖组微量元素分布范围
Table 2. The distribution of trace elements in Pinghu Formation
μg/g 元素 平上段 平中段 平下段 Rb 0.063～231.021
118.637（72）0.074～234.798
117.107（122）5.22～337.659
134.726（66）Ba 165.969～18 866
2 154.651（135）180～32 697
2 989.647（189）230.7～29 319.518
3 488.624（109）Zr 38.5～437.515
269.44（72）42.2～433.044
247.493（122）45.32～400.232
215.673（66）Co 2.61～42.511
19.34（135）4.52～33.146
17.226（187）3.24～40.384
15.439 （107）Mo 0.38～14.369
1.998（91）0.38～89.894
2.061（134）0.15～66.7
2.198（67）Sc 0.005～25.65
14.372（94）0.007～24.36
14.022（137）2.638～27.52
14.514（66）Hf 0.74～12.883
7.622（72）0.52～12.331
6.984（122）0.74～11.691
6.217（66）注： 
。
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表 3 西湖凹陷平湖组烃源岩稀土元素含量
Table 3. ΣREE analytical data of source rocks of Pinghu Formation in Xihu Sag
层位 井名 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ΣREE/
（μg/g）ΣLREE/
（μg/g）ΣHREE/
（μg/g）ΣLREE/
ΣHREELaN/
YbNδEu δCe /（μg/g） 平上段 C-22 61.0 130 14.6 55.0 11.0 2.23 10.6 1.43 9.45 1.55 4.70 0.65 4.47 0.75 306.94 273.35 33.60 8.14 1.32 0.91 0.95 C-1 34.8 90.3 8.54 30.5 6.41 1.49 6.28 0.90 6.14 1.01 2.75 0.44 2.70 0.73 193.09 172.14 20.95 8.22 1.25 1.03 1.14 C-2 51.4 111 12.1 44.6 9.19 2.16 8.22 1.11 7.65 1.23 3.61 0.52 3.58 0.60 256.93 230.42 26.51 8.69 1.39 1.09 0.97 C-3 44.6 88.0 10.3 37.8 7.74 1.63 7.07 1.02 7.30 1.18 3.50 0.48 3.30 0.57 214.47 190.05 24.42 7.78 1.31 0.97 0.90 C-4 45.7 89.0 9.92 36.5 7.38 1.59 6.57 0.94 7.04 1.15 3.43 0.48 3.39 0.60 213.69 190.10 23.59 8.06 1.31 1.00 0.91 B-1 48.5 97.3 11.4 42.5 8.89 1.98 8.46 1.18 8.17 1.30 3.74 0.51 3.51 0.60 238.07 210.59 27.47 7.67 1.34 1.00 0.90 C-5 41.7 103 8.83 31.8 6.83 1.85 5.57 0.76 5.80 0.89 2.81 0.39 2.89 0.50 213.93 194.34 19.59 9.92 1.40 1.32 1.17 A-3 35.4 90.8 9.22 31.2 6.88 1.79 6.72 1.37 6.69 1.48 3.15 0.86 3.07 1.16 199.74 175.24 24.50 7.15 1.12 1.16 1.09 B-2 40.7 98.7 9.59 35.9 7.52 1.75 6.53 0.92 6.44 1.03 3.01 0.43 3.08 0.53 216.06 194.09 21.97 8.84 1.28 1.10 1.09 B-3 47.8 115 11.0 40.5 10.4 3.17 7.91 1.10 7.72 1.25 3.71 0.53 3.53 0.64 254.34 227.94 26.39 8.64 1.31 1.54 1.09 C-6 68.92 33.81 12.64 12.86 2.3 1 1.6 0.57 0.45 0.32 0.42 0.41 0.65 0.09 136.04 131.53 4.51 29.16 10.27 2.29 0.25 C-12 28.3 66.7 2.45 24.7 21.1 8.39 6.64 3.07 1.82 4.13 167.30 151.64 15.66 9.68 0.66 3.11 1.74 C-23 21.4 39.9 4.33 16.4 5.73 2.4 3.32 0.36 2.46 0.4 1.3 0.15 1.24 0.14 99.53 90.16 9.37 9.62 1.67 2.42 0.90 C-13 27.2 53.4 6.09 23.3 6.48 2.19 5.22 0.59 3.68 0.61 1.83 0.22 1.69 0.21 132.71 118.66 14.05 8.45 1.56 1.65 0.90 C-14 27.1 51.5 6 22.7 5.32 1.46 5.2 0.65 3.67 0.67 1.89 0.28 1.81 0.28 128.53 114.08 14.45 7.89 1.45 1.22 0.88 C-15 41.86 81.31 8.74 31.78 8.62 3.24 5.94 0.86 4.75 0.83 2.26 0.29 2.10 0.35 192.94 175.56 17.38 10.10 1.93 1.99 0.93 C-16 57.20 114.28 13.31 53.51 11.94 2.74 11.64 1.62 9.32 1.77 5.18 0.82 5.00 0.82 289.15 252.98 36.17 6.99 1.11 1.02 0.90 平中段 C-22 40.3 97.6 9.84 37.3 7.69 1.60 7.23 1.03 7.62 1.24 3.69 0.50 3.62 0.63 219.85 194.29 25.56 7.60 1.08 0.94 1.07 C-3 38.8 77.0 8.82 32.2 7.32 1.95 5.83 0.84 6.10 0.95 2.85 0.39 2.88 0.49 186.50 166.16 20.34 8.17 1.30 1.31 0.91 C-12 22.4 44.4 0.29 18.3 57.7 34.5 4.57 1.9 1.46 4.04 189.56 177.59 11.97 14.84 0.54 9.33 3.79 C-14 28.2 55.5 6.29 24.5 5.6 1.36 5.62 0.67 4.01 0.67 2.02 0.27 2 0.26 136.97 121.45 15.52 7.83 1.37 1.06 0.91 C-16 45.06 89.62 10.51 42.79 9.40 2.20 9.06 1.27 7.03 1.30 3.76 0.63 3.52 0.64 226.81 199.58 27.22 7.33 1.24 1.05 0.90 C-2 50.6 113 11.6 43.4 13.4 5.00 8.52 1.15 8.10 1.29 3.76 0.49 3.50 0.61 264.37 236.95 27.42 8.64 1.40 2.06 1.01 C-4 40.5 79.8 9.23 35.0 7.49 1.73 6.61 0.94 6.65 1.04 3.00 0.41 2.89 0.51 195.88 173.83 22.05 7.88 1.36 1.08 0.90 B-1 41.4 82.6 9.83 37.5 8.11 1.83 7.27 1.02 7.33 1.16 3.39 0.45 3.24 0.57 205.62 181.19 24.43 7.42 1.24 1.05 0.89 C-5 37.5 118 8.56 31.3 7.18 1.90 5.84 0.82 6.21 0.95 2.92 0.42 3.14 0.54 224.94 204.09 20.85 9.79 1.16 1.29 1.43 C-6 54.32 49.18 10 10.96 2.47 0.84 3.01 0.78 0.86 0.44 0.91 0.53 0.57 0.12 134.99 127.77 7.22 17.70 9.23 1.35 0.46 C-1 31.69 57.94 7.13 26.95 4.89 1.15 4.58 0.70 3.83 0.77 2.17 0.31 2.01 0.29 144.41 129.74 14.67 8.84 1.52 1.06 0.84 C-23 27.9 53.6 6.15 22.8 6.2 2.14 4.71 0.61 3.38 0.62 1.74 0.25 1.6 0.26 131.96 118.79 13.17 9.02 1.69 1.74 0.89 C-13 25.8 48.9 5.56 20.9 9.98 4.8 4.17 0.47 2.74 0.43 1.26 0.16 1.13 0.16 126.46 115.94 10.52 11.02 2.21 3.27 0.89 C-15 33.92 66.58 7.61 27.89 5.70 1.58 5.32 0.86 4.49 0.86 2.32 0.39 2.36 0.45 160.33 143.28 17.05 8.40 1.39 1.26 0.90 C-18 48.09 95.27 9.96 43.01 9.52 2.68 7.93 1.20 6.63 1.24 3.42 0.54 3.19 0.53 233.23 208.54 24.69 8.45 1.46 1.35 0.95 C-19 41.77 84.72 9.82 38.49 8.06 1.77 7.35 1.08 6.04 1.18 3.32 0.59 3.30 0.59 208.07 184.63 23.44 7.88 1.23 1.01 0.91 平下段 C-23 45.2 72.9 9.72 34.8 7.15 1.60 6.15 0.96 7.35 1.26 3.96 0.56 4.00 0.68 196.31 171.40 24.90 6.88 1.10 1.06 0.76 C-22 54.7 120 12.4 46.1 9.97 2.43 9.37 1.27 8.67 1.45 4.22 0.58 4.06 0.69 275.94 245.62 30.31 8.10 1.31 1.11 1.00 平下段 C-1 35.0 87.3 8.22 31.2 5.85 1.42 6.05 0.71 6.61 0.67 2.62 0.66 1.99 1.45 189.76 169.00 20.77 8.14 1.71 1.05 1.12 C-4 50.9 101 11.7 43.7 9.22 2.07 8.50 1.19 8.11 1.30 3.77 0.52 3.79 0.63 246.50 218.69 27.81 7.86 1.30 1.03 0.90 C-6 65.24 40.32 11.23 8.56 2.35 0.78 0.45 0.78 0.41 0.56 0.56 0.54 0.5 0.05 132.33 128.48 3.85 33.37 12.64 3.33 0.32 C-20 50.9 98.3 10.7 40.7 7.13 1.49 5.84 0.949 5.09 1 2.91 0.475 3.14 0.442 229.07 209.22 19.85 10.54 1.57 1.01 0.92 C-21 39.4 75.2 8.22 31.1 5.11 1.06 4.19 0.7 3.87 0.755 2.63 0.401 2.69 0.444 175.77 160.09 15.68 10.21 1.42 1.01 0.91 C-8 16.17 30.21 3.58 13.14 2.22 0.74 2.02 0.28 1.53 0.30 0.82 0.13 0.78 0.11 72.03 66.05 5.97 11.06 2.01 1.54 0.87 C-13 25.7 50.7 5.74 21.9 6.69 2.48 4.66 0.52 3.16 0.5 1.52 0.19 1.45 0.18 125.39 113.21 12.18 9.29 1.72 1.95 0.91 C-2 30.99 59.76 7.06 25.54 7.03 2.78 4.68 0.79 3.74 0.75 1.88 0.39 1.84 0.44 147.67 133.16 14.50 9.18 1.64 2.13 0.88 C-15 45.36 89.47 10.20 37.14 7.21 1.73 7.59 1.12 6.46 1.12 3.04 0.43 3.22 0.50 214.58 191.11 23.47 8.14 1.37 1.03 0.91 C-18 50.71 98.86 10.33 44.64 8.32 1.87 6.96 0.91 4.71 0.86 2.41 0.41 2.62 0.43 234.03 214.72 19.31 11.12 1.87 1.08 0.94
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表 4 氧化还原环境的元素判别指标
Table 4. Element parameters for redox condition
元素 氧化 氧化还原 还原 V/Cr ＜2 2～4.25 ＞4.25 Ni/Co ＜5 5～7 ＞7 U/Th ＜2 2～4.25 ＞4.25 V/（V+Ni） ＜0.6 0.6～0.84 ＞0.84 V/Sc ＜9 9～30 ＞30
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表 5 平湖组氧化还原环境判识结果
Table 5. The REDOX environment of Pinghu Formation
元素 平上段 平中段 平下段 V/Cr 0.21～5.01
0.88（135）0.2～5.17
0.9（189）0.12～39.71
1.87（85）Ni/Co 0.41～4.15
2.23（135）0.75～28.14
2.4（187）0.15～12.96
3.39（107）U/Th 0.08～0.76
0.27（93）0.06～0.93
0.25（130）0.15～1.41
0.29（69）环境 富氧氧化 V/（V+Ni） 0.4～0.91
0.76（85）0.16～0.93
0.79（189）0.55～0.92
0.79（135）V/Sc 2.57～27.23
10.1（91）1.82～24.65
9.8（135）0.5～50.79
9.24（67）环境 氧化-还原 注： 
。
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表 6 平湖组不同层段水深微量元素含量
Table 6. Trace element contents in different layers of water depth for Pinghu Formation
元素 平湖组上段 平湖组中段 平湖组下段 Co/(μg/g) 2.61～42.51
19.34（135）4.52～33.15
17.23（187）3.24～40.384
15.44（107）Cu/(μg/g) 5.29～124
33.01（135）2.19～91.78
26.77（189）4.59～56.07
24.28（87）Ni/(μg/g) 5.7～88.5
41（13）6～730.9
40.9（190）1.8～129.2
38.2（110）Mn/Ti 0.01～0.86
0.18（132）0.01～1.97
0.19（186）0.03～1.18
0.15（104）Mn/Fe 0.01～0.05
0.01（84）0.01～0.04
0.01（116）0.01～0.05
0.01（69）注： 
。
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