Geochemical Characteristics and Signatures of Siltstones from Laiyang Group at Lingshan Island, Qingdao, Shandong
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摘要: 灵山岛下部莱阳群重力流沉积地层以其巨厚的沉积规模，独特的沉积特征受到国内外地质学界越来越多的重视.但目前，该套地层的源区风化程度、物源性质、物源区构造背景及沉积环境尚不明确，通过对灵山岛下部莱阳群粉砂岩进行岩相学分析、主量元素XRF测试、稀土及微量元素ICP-MS测试，结果显示：粉砂岩SiO2含量较低 (平均51.78%)，Fe2O3T含量较高 (平均5.73%)，Na2O平均含量为2.74%，K2O平均含量为2.79%；通过主量元素投图分析，样品归类为杂砂岩及岩屑砂岩；样品ΣREE为153.00×10-6~254.38×10-6，平均为201.65×10-6，高于PAAS及UCC，富集轻稀土元素，贫重稀土元素，具有中等程度Eu负异常，弱Ce负异常；相对于UCC，样品富集大离子亲石元素，弱富集高场强元素，亏损过渡组元素.样品ICV值高 (＞0.84)、为初次循环沉积，CIA值低 (＜65) 表明源区风化强度低，物源为长英质物质及少量古地壳再旋回物质，物源区大地构造背景为大陆岛弧与活动大陆边缘，沉积环境为海相还原环境且莱阳期为干热气候.此外，应用对REE元素进行归类统计的方法来推测物源区，分析表明样品物源区最有可能为胶南群与蓬莱群地层.Abstract: Gravity flow deposits of Laiyang Group at the lower part of Lingshan island attract an increasing attention of geologists at home and abroad because of its huge thickness and unique sedimentary features. However, its weathering degree, characteristics and structural setting of provenance, and depositional environment stillremain in dispute. In this study, major elements, rare earth elements and trace elements contents of the siltstones from Laiyang Group at Lingshan Island were examined by XRF and ICP-MS. It is found that siltstones are characterized by relatively low contents of SiO2 (avg. 51.78%) and high contents of Fe2O3T (avg. 51.78%); average contents of Na2O and K2O of siltstones are 2.74% and 2.79%, respectively, the siltstones are classified as litharenites and greywackes; ΣREE contents of the samples are 153.00×10-6-254.38×10-6 (avg. 201.65×10-6), which are higher than those of UCC and PAAS; the pattern of REE is characterized by LREE enrichment, HREE depletion, moderately negative Eu abnormity and weakly negative Ce abnormity; compared with UCC, samples are enriched in LILEs, weakly enriched in HFSEs and depleted in transitional elements. Index of Compositional Variability (ICV) values of siltstones in Lingshan Island are high, which indicates the source materials are mainly primary cycle sediments, Chemical Index of Alteration (CIA) values are relatively low, which suggests that the weathering intensity of provenance is low. Element analysis indicates that felsic rocks serve as the main source rocks, including small amounts of contributions from recycled orogenic belt materials; tectonic settings of provenance belong to active continental margin and continental island arc; sedimentary environment is reducing marine environment and paleoclimate of Laiyang Period was arid. It is original for the authors to apply the statistical analysis method to determine the provenance regions more precisely according to the features of REEs, and it is concluded that the source rocks are most likely from Jiaonan Group and Penglai Group.
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Key words:
- Lingshan island /
- Laiyang Group /
- geochemistry /
- sedimentary environment
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图 1 灵山岛大地构造位置及地质简图
1.下白垩统青山群；2.下白垩统莱阳群；3.白色流纹质熔岩；4.断层；5.地层产状；6.地形等高线；据栾光忠等修改 (2010)
Fig. 1. The sketch showing geotectonic position and geologic framework of Lingshan island
图 3 灵山岛莱阳群粉砂岩镜下特征
a.灯塔剖面典型粉砂岩镜下照片 (正交光)；b.千层崖剖面典型粉砂岩镜下照片 (正交光)；c.船厂剖面典型粉砂岩镜下照片 (正交光)；d.钓鱼台剖面典型粉砂岩镜下照片 (单偏光)
Fig. 3. The micrograph feature of siltstones in Lingshan island
图 4 主量元素上地壳标准化蛛网图及砂岩化学成分分类
图a.UCC数据据Rudnick and Gao (2003)；PAAS数据Taylor and McLennan (1985)；图b底图据Prettijohn and Potter (1972)
Fig. 4. Normalization of major elements to upper continental crust and chemical classification diagrams discriminating sediments
图 5 微量元素上地壳标准化蛛网图
Fig. 5. Trace elements spider-diagram normalized to average upper continental crustal values
图 6 灵山岛莱阳群粉砂岩REE分布模式
标准化值据Taylor and Mclennan (1985)
Fig. 6. Chondrite-normalized REE diagrams of the Laiyang Group siltstones in Lingshan island
图 7 灵山岛莱阳群粉砂岩Al2O3-(CaO+Na2O)-K2O关系
Fig. 7. Al2O3-(CaO+Na2O)-K2O molecular proportion for siltstone from Laiyang Group at Lingshan island
图 8 主量元素源区判别
F1=(-1.773TiO2)+(0.607Al2O3)+(0.760Fe2O3T)+(-1.500MgO)+(0.616CaO)+(0.509Na2O)+(-1.224K2O)+(-9.090)；F2=(0.445TiO2)+(0.070Al2O3)+(-0.250Fe2O3T)+(-1.142MgO)+(0.438CaO)+(1.475Na2O)+(1.426K2O)+(-6.861)；底图据Roser and Korsch (1988)
Fig. 8. Major element provenance discriminant plot
图 9 灵山岛莱阳群粉砂岩La/Th-Hf图解
Fig. 9. La/Th-Hf plot for the provenance of the siltstone from Laiyang Group in Lingshan
图 10 灵山岛莱阳群粉砂岩Co/Th-La/Sc图解
Fig. 10. Co/Th-La/Sc plot for the provenance of the siltstone from Laiyang Group in Lingshan island
图 11 主量元素构造环境判别图解
ACM.活动大陆边缘；PM.被动大陆边缘；CIA.大陆岛弧；OIA.大洋岛弧；A1.具长英质源区演化弧；A2.源区为玄武质和安山质的弧；图a据Maynard et al.(1982)；图b据Bhatia (1983)
Fig. 11. Major elements discrimination diagram to indicate the tectonic setting
图 12 灵山岛莱阳群粉砂岩源岩构造背景判别图
PAAS.后台古代澳大利亚页岩；MA.理想安山岩；MAR.岩浆弧；A.大洋岛弧；B.大陆岛弧；C.活动大陆边缘；D.被动大陆边缘；图a据Girty et al.(1993)；图b~d据Bhatia and Crook (1986)
Fig. 12. Trace element plots of siltstones from Laiyang Group in Lingshan island for tectonic discrimination
图 14 SiO2-(Al2O3+K2O+Na2O) 古气候判别图
Fig. 14. Bivariate SiO2 wt.% versus (Al2O3+K2O+Na2O) wt.% palaeoclimate discrimination diagram
表 1 灵山岛莱阳群粉砂岩主量元素分析结果 (%)
Table 1. Major element contents (%) of siltstones from Laiyang Group at Lingshan island
样品号 船厂剖面 千层崖剖面 灯塔剖面 钓鱼台剖面 平均值 CC-1 CC-2 CC-3 QCY-1 QCY-2 QCY-3 DT-1 DT-2 DT-5 DYT-1 DYT-2 DYT-3 SiO2 55.55 55.98 54.72 46.48 49.54 50.59 53.82 52.73 59.92 46.56 48.57 46.85 51.78 Al2O3 13.60 13.34 14.77 13.44 13.29 13.78 14.46 15.31 17.73 12.11 11.56 11.82 13.77 FeO 3.35 2.55 3.73 3.93 3.89 3.98 3.30 3.46 3.20 4.31 4.20 4.42 3.69 Fe2O3 0.83 1.72 1.30 3.02 3.16 1.31 1.99 2.23 1.21 0.90 0.78 1.03 1.62 Fe2O3T 4.55 4.56 5.45 7.39 7.48 5.74 5.66 6.07 4.77 5.69 5.45 5.95 5.73 MgO 2.63 2.69 4.13 3.81 3.80 3.99 3.65 3.84 2.91 4.20 4.04 4.25 3.66 CaO 6.13 6.36 5.56 6.70 6.51 7.60 5.26 5.98 1.57 10.70 10.32 10.71 6.95 Na2O 3.10 3.29 2.22 2.78 3.05 3.14 2.18 2.54 2.33 2.62 2.77 2.83 2.74 K2O 2.52 2.52 3.41 2.58 2.58 2.70 3.06 3.22 4.19 2.28 2.19 2.28 2.79 MnO 0.08 0.06 0.05 0.09 0.06 0.07 0.06 0.05 0.02 0.17 0.13 0.13 0.08 TiO2 0.68 0.37 0.39 0.65 0.37 0.37 0.71 0.41 0.48 0.63 0.32 0.34 0.48 P2O5 0.24 0.12 0.10 0.20 0.10 0.10 0.46 0.25 0.09 0.22 0.10 0.11 0.17 LOI 10.21 10.53 8.97 10.83 11.20 11.45 10.27 9.53 5.89 13.62 14.17 14.22 10.91 Total 98.92 99.52 99.36 94.50 97.54 99.08 99.23 99.55 99.55 98.31 99.14 98.99 98.64 ICV 1.45 1.49 1.44 1.79 1.79 1.71 1.42 1.44 0.92 2.17 2.18 2.24 1.67 CIA 51.25 49.61 57.32 52.94 50.85 50.99 57.95 56.40 61.21 52.19 50.17 50.08 53.41 F1 -0.26 0.29 -2.50 0.21 0.73 -0.04 -2.15 -0.64 -2.91 0.31 0.53 0.87 -0.46 F2 1.10 1.25 -1.17 -1.12 -0.94 0.08 -1.23 -0.57 0.18 -0.15 -0.16 -0.11 -0.24 注：Fe2O3T= Fe2O3+1.111 3×FeO，总和不包括Fe2O3T含量；F1，F2函数系数据Roser and Korsch (1988)；ICV=Fe2O3+K2O+Na2O+CaO+MgO+MnO+TiO2)/Al2O3(百分含量)；CIA=[(Al2O3/(Al2O3+CaO*+Na2O+K2O)]×100(摩尔量)，CaO*为硅酸盐矿物中的CaO含量，不包含碳酸盐与磷灰石中的CaO. 
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表 2 灵山岛莱阳群粉砂岩微量及稀土元素分析结果 (10-6)
Table 2. Trace elements contents of siltstones from Laiyang Group at Lingshan island
样品号 船厂剖面 千层崖剖面 灯塔剖面 钓鱼台剖面 平均值 CC-1 CC-2 CC-3 QCY-1 QCY-2 QCY-3 DT-1 DT-2 DT-5 DYT-1 DYT-2 DYT-3 Li 34.47 32.17 78.12 56.98 54.28 58.03 61.22 58.45 66.57 41.75 41.45 44.65 52.35 Be 2.09 2.10 2.56 2.64 2.58 2.31 3.35 3.22 4.11 1.94 1.88 1.70 2.54 Sc 11.57 8.90 10.17 11.54 10.96 10.34 14.45 14.94 14.47 14.56 10.32 10.53 11.90 V 74.14 80.88 87.42 94.91 94.47 91.10 128.24 130.07 124.54 60.93 62.93 65.87 91.29 Cr 52.29 56.46 67.39 99.58 102.51 81.04 95.33 101.83 90.46 52.13 56.46 64.05 76.63 Co 12.66 11.95 19.83 32.64 31.60 25.05 11.77 11.58 12.16 18.32 18.82 22.50 19.07 Ni 19.51 21.47 29.83 87.09 91.11 32.39 25.12 27.16 30.13 25.32 27.29 29.08 37.13 Cu 19.24 21.57 26.41 30.83 33.00 30.95 26.16 28.21 36.07 25.43 27.61 32.33 28.15 Zn 80.40 75.62 75.70 94.20 97.42 89.18 80.14 84.96 116.03 102.00 107.50 106.84 92.50 Ga 17.86 17.95 20.30 25.42 27.66 21.00 23.68 26.33 31.10 19.04 21.40 16.94 22.39 Rb 97.84 94.68 117.24 118.61 114.76 93.16 132.86 128.33 156.04 88.83 86.10 73.95 108.53 Sr 438.14 429.52 285.55 528.90 528.69 503.00 315.10 311.85 151.55 825.92 830.07 736.54 490.40 Y 21.89 21.63 24.23 25.10 27.77 26.36 32.48 31.64 25.83 32.43 29.37 28.06 27.23 Cs 7.85 8.27 14.13 7.34 8.05 8.03 11.17 11.77 11.82 4.95 4.90 5.72 8.67 Ba 620.59 628.52 625.97 987.70 984.03 839.13 837.46 831.57 1021.56 730.52 733.87 679.20 793.34 La 40.55 32.60 36.87 49.43 38.88 35.74 46.98 50.72 54.28 46.01 46.03 41.56 43.31 Ce 70.87 65.25 75.92 82.79 79.98 71.32 96.31 106.05 104.02 89.05 87.88 81.64 84.26 Pr 8.37 8.51 9.16 9.95 9.85 9.10 12.17 13.59 12.39 10.66 11.40 10.09 10.44 Nd 31.96 27.82 32.51 38.48 33.71 30.50 48.47 48.76 41.93 39.96 38.98 35.53 37.38 Sm 6.17 4.81 5.90 6.70 6.06 5.99 8.67 8.91 7.19 7.04 6.94 6.36 6.73 Eu 1.12 1.05 1.12 1.40 1.40 1.29 1.93 2.03 1.35 1.63 1.73 1.59 1.47 Gd 4.51 4.34 4.97 5.69 5.45 5.07 7.47 8.13 5.70 6.05 6.32 5.63 5.78 Tb 0.73 0.71 0.79 0.92 0.90 0.82 1.19 1.30 0.89 0.98 1.04 0.93 0.93 Dy 3.63 3.44 3.81 4.66 4.24 3.95 5.86 6.16 4.24 4.89 4.99 4.55 4.53 Ho 0.71 0.65 0.79 0.90 0.80 0.82 1.11 1.15 0.82 0.96 0.98 0.87 0.88 Er 2.06 2.01 2.22 2.59 2.45 2.30 3.13 3.35 2.60 2.79 2.84 2.69 2.59 Tm 0.31 0.34 0.37 0.39 0.39 0.36 0.47 0.53 0.43 0.41 0.47 0.44 0.41 Yb 1.94 2.05 2.28 2.43 2.54 2.36 2.93 3.18 2.86 2.48 2.70 2.73 2.54 Lu 0.32 0.33 0.35 0.39 0.38 0.35 0.46 0.53 0.43 0.40 0.47 0.44 0.40 Tl 0.62 0.58 0.78 0.83 0.83 0.66 0.74 0.81 0.93 0.61 0.69 0.60 0.72 Pb 16.49 17.36 25.99 25.85 27.97 31.83 12.82 14.64 23.87 20.38 22.09 23.20 21.87 Bi 0.33 0.31 0.34 0.36 0.36 0.36 0.38 0.37 0.42 0.28 0.28 0.31 0.34 Th 13.85 14.06 16.13 16.36 16.31 17.28 15.50 16.88 22.14 13.72 14.46 15.51 16.02 U 6.42 5.80 3.51 6.11 5.69 5.82 8.08 7.84 3.21 5.18 5.17 5.14 5.66 Nb 14.22 13.44 13.82 16.99 16.90 11.47 15.04 15.34 17.81 13.04 13.84 10.41 14.36 Ta 1.21 1.11 1.01 1.14 1.00 0.80 0.99 1.05 1.25 1.08 1.07 0.73 1.04 Zr 231.08 219.41 212.95 213.05 204.59 220.96 202.09 221.79 200.12 217.67 210.04 179.22 211.08 Hf 7.69 6.39 5.40 6.84 6.23 5.13 6.51 6.60 5.69 6.78 6.30 4.90 6.20 B 158.00 199.00 149.00 151.00 125.00 141.00 169.00 149.00 175.00 157.00 103.00 122.00 149.83 Zr/Hf 30.05 34.34 39.46 31.16 32.86 43.11 31.06 33.61 35.18 32.10 33.35 36.56 34.40 Zr/Th 16.68 15.61 13.20 13.02 12.54 12.79 13.04 13.14 9.04 15.86 14.53 11.56 13.42 La/Th 2.93 2.32 2.29 3.02 2.38 2.07 3.03 3.00 2.45 3.35 3.18 2.68 2.73 La/Y 1.85 1.51 1.52 1.97 1.40 1.36 1.45 1.60 2.10 1.42 1.57 1.48 1.60 Th/Sc 1.20 1.58 1.59 1.42 1.49 1.67 1.07 1.13 1.53 0.94 1.40 1.47 1.37 Sc/Ni 0.59 0.41 0.34 0.13 0.12 0.32 0.58 0.55 0.48 0.57 0.38 0.36 0.40 Sc/Cr 0.22 0.16 0.15 0.12 0.11 0.13 0.15 0.15 0.16 0.28 0.18 0.16 0.16 Cr/Ni 2.68 2.63 2.26 1.14 1.13 2.50 3.79 3.75 3.00 2.06 2.07 2.20 2.43 Ni/Co 1.54 1.80 1.50 2.67 2.88 1.29 2.14 2.35 2.48 1.38 1.45 1.29 1.90 La/Yb 20.86 15.88 16.20 20.34 15.29 15.17 16.03 15.93 18.99 18.54 17.03 15.23 17.12 Rb/Sr 0.22 0.22 0.41 0.22 0.22 0.19 0.42 0.41 1.03 0.11 0.10 0.10 0.30 Th/U 2.16 2.42 4.60 2.68 2.87 2.97 1.92 2.15 6.90 2.65 2.80 3.02 3.09 La/Sc 3.50 3.66 3.62 4.28 3.55 3.46 3.25 3.39 3.75 3.16 4.46 3.95 3.67 Co/Th 0.91 0.85 1.23 2.00 1.94 1.45 0.76 0.69 0.55 1.33 1.30 1.45 1.20 Zr/Y 10.55 10.15 8.79 8.49 7.37 8.38 6.22 7.01 7.75 6.71 7.15 6.39 7.91 B/Ga 8.85 11.08 7.34 5.94 4.52 6.71 7.14 5.66 5.63 8.25 4.81 7.20 6.93 Ga/Rb 0.18 0.19 0.17 0.21 0.24 0.23 0.18 0.21 0.20 0.21 0.25 0.23 0.21 ΣREE 173.26 153.91 177.04 206.71 187.04 169.97 237.16 254.38 239.13 213.31 212.77 195.08 201.65 LREE 159.05 140.04 161.48 188.74 169.88 153.93 214.53 230.06 221.17 194.35 192.96 176.78 183.58 HREE 14.22 13.87 15.56 17.96 17.16 16.03 22.63 24.33 17.97 18.96 19.81 18.29 18.07 L/H 11.19 10.10 10.38 10.51 9.90 9.60 9.48 9.46 12.31 10.25 9.74 9.66 10.21 (La/Yb)N 1.54 1.17 1.20 1.50 1.13 1.12 1.18 1.18 1.40 1.37 1.26 1.12 1.26 (La/Sm)N 0.95 0.98 0.91 1.07 0.93 0.87 0.79 0.83 1.10 0.95 0.96 0.95 0.94 (Gd/Yb)N 1.40 1.28 1.32 1.42 1.30 1.30 1.54 1.54 1.21 1.48 1.41 1.25 1.38 δEu 1.00 1.08 0.97 1.07 1.15 1.10 1.13 1.12 1.00 1.18 1.23 1.25 1.11 δCe 0.89 0.90 0.95 0.86 0.94 0.91 0.93 0.93 0.93 0.93 0.88 0.92 0.91 Ceanom －0.06 －0.01 －0.01 －0.08 0.00 －0.01 －0.03 －0.01 －0.02 －0.03 －0.03 －0.02 －0.03 注：L/H为轻重稀土比值；下标N表示元素相对于PAAS标准化，下标anom表示元素相对于北美页岩标准化；δEu=2×EuN/(SmN+GdN)，δCe=2×CeN/(LaN+NdN)，该式中N为PAAS标准化，球粒陨石值参考Taylor and Mclennan (1985)；Ceanom=lg[3CeN/(2LaN+NdN)]，该式中N为北美页岩标准化，北美页岩值参考 Gromet et al.(1984) .
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表 3 灵山岛粉砂岩与不同构造环境砂岩稀土元素特征参数的对比
Table 3. Comparison REE characteristics of siltsones in Lingshan island with sandstones in different tectonic settings
构造环境 大洋岛弧 大陆岛弧 安第斯型大陆边缘 被动大陆边缘 灵山岛粉砂岩 物源类型 未切割的岩浆弧 (10-6) 切割岩浆弧 (10-6) 隆升的基底 (10-6) 克拉通内部构造高地 (10-6) 平均值 (10-6) La 8±1.7 27±4.5 37 39 43.31 Ce 19±3.7 59±8.2 78 85 84.26 δEu 1.04±0.11 0.79±0.1 0.6 0.56 0.70 ΣREE 58±10 146±20 186 210 201.65 LREE/HREE 3.8±0.9 7.7±1.7 9.1 8.5 10.21 La/Yb 4.2±1.3 11.0±3.6 12.5 15.9 17.12 (La/Yb)N 2.8±0.9 7.5±2.5 8.5 10.8 12.28 注：大洋岛弧、大陆岛弧、安第斯型大陆边缘、被动大陆边缘数据据Bhatia (1985)；Bhatia and Crook (1986).
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表 4 Bayes判别函数的标准化系数
Table 4. Standardized coefficients of Bayes discriminant function
荆山群 胶南群 粉子山群 海州群 中生代岩浆岩 TTG岩系 五莲群 蓬莱群 La 0.055 0.069 0.078 0.024 0.014 0.042 0.082 -0.003 Ce 0.071 0.040 0.023 -0.022 0.070 0.088 -0.045 -0.016 Pr -1.854 -0.324 0.562 0.886 0.203 -1.217 2.049 1.059 Nd 0.362 -0.053 -0.166 -0.276 -0.130 0.139 -0.568 -0.325 Sm -1.646 -1.691 -2.095 0.178 -1.003 -2.895 0.589 0.311 Eu 0.988 1.341 3.738 0.929 2.684 2.724 0.548 0.416 Gd 1.699 2.121 0.073 -0.354 0.265 1.597 -0.475 0.186 Tb 3.131 6.572 0.637 1.209 0.973 5.615 3.014 4.752 Dy -0.734 3.624 2.542 1.649 1.715 4.939 4.972 3.297 Ho -9.315 -23.509 -5.786 -6.086 -4.370 -16.735 -18.924 -20.573 Er 4.830 -2.937 -3.630 -3.069 -2.637 -4.343 -8.198 -4.416 Tm 13.327 27.889 29.701 11.097 25.040 27.184 27.649 26.890 Yb -3.148 -1.168 1.608 2.561 -0.055 -0.566 2.885 1.530 Lu -2.148 2.083 -18.650 -2.750 -14.854 -4.873 -1.694 -1.339 常数 -4.104 -5.124 -4.088 -4.824 -5.104 -6.668 -5.868 -3.498
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表 5 Bayes判别系数
Table 5. Bayes discriminant coefficients
荆山群 胶南群 粉子山群 海州群 中生代岩浆岩 TTG岩系 五莲群 蓬莱群 DYT-1 -3.59 -3.31 -5.21 -6.80 -5.37 -8.02 -6.73 -3.38 DYT-2 -3.24 -1.47 -5.88 -6.30 -5.23 -6.51 -5.49 -1.83 DYT-3 -7.26 -5.48 -5.63 -5.71 -6.41 -10.98 -5.02 -2.51 QCY-1 -6.17 -5.00 -5.93 -6.33 -6.40 -10.36 -5.72 -2.74 QCY-2 -4.57 -1.69 -3.56 -4.91 -4.88 -7.06 -3.35 -0.54 QCY-3 -6.04 -2.90 -4.58 -4.65 -5.20 -10.19 -1.79 -0.22 DT-1 -1.18 3.08 0.12 -0.23 0.01 -0.94 2.62 3.00 DT-2 -2.24 1.56 -0.35 -0.81 -0.89 -2.43 1.92 2.24 DT-5 -1.93 2.22 -0.49 0.17 -0.10 -3.53 4.08 3.28 CC-1 -1.82 -0.84 -3.68 -2.42 -2.58 -4.94 -0.95 -0.29 CC-2 0.28 1.95 -1.50 -1.93 -1.10 -1.37 -0.29 0.20 CC-3 -1.82 -0.84 -3.68 -2.42 -2.58 -4.94 -0.95 -0.29
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