Metallogenic Age and Metallogenic Environment of Yuanjiacun Iron Deposit in Shanxi Province
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摘要: 为了进一步约束袁家村铁矿成矿年龄和成矿作用，揭示其对古海洋环境的指示，对采集自袁家村铁矿的BIFs样品进行碎屑锆石U-Pb年龄测定、全岩主微量元素分析及赤铁矿原位微量元素分析.其碎屑锆石U-Pb年龄可将袁家村铁矿沉积时代约束在2 200~2 235 Ma.主微量元素特征表明其受陆源碎屑干扰较小，成矿物质主要来源于海水与热液的混合，并且沉积过程中存在河流输入铁源的可能性.袁家村铁矿沉积在大氧化事件末期，其稀土配分模式特征存在明显的分组，同时存在负Ce异常和微弱的正Ce异常指示一个还原和氧化并存的环境，表明当时的古海洋环境特征为氧化还原分层的状态.说明大氧化事件后古海洋环境发生巨变，海水发生了一定程度的氧化，从原先单一的还原环境转变成了氧化还原分层的状态.Abstract: In order to restrict the age and mineralization of the Yuanjiacun iron deposit and reveal its implications for the paleomarine environment, it determined the detrital zircon U-Pb chronology, major and trace elements of whole rock and trace elements of hematite for BIFs samples which collected from the Yuanjiacun iron deposit. Its detrital zircon U-Pb age constrains the sedimentary age of Yuanjiacun iron ore between 2 200 and 2 235 Ma. The characteristics of major and trace elements indicate that it is a relatively pure sediment and formed by the mixing of seawater and high temperature hydrothermal fluid. And the river input may be one of iron sources during the deposition process. Yuanjiacun iron deposit was formed at the end of the GOE. There are obvious grouping of REE distribution pattern characteristics in Yuanjiacun iron deposit, as well as negative Ce anomaly and slight positive Ce anomaly. This agrees with a reductive and oxidative environment, indicating that the paleomarine environment at that time was characterized by redox stratification. These features suggest a dramatic change in the paleo-marine environment after the GOE, with some degree of oxidation occurring in seawater and shifting from the original single reducing environment to a redox stratified state.
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图 1 山西吕梁区域地质简图(a)及其大地构造位置(b)
a. 改编自万渝生（2000）；b.据Wilde and Zhao（2005）
Fig. 1. Geological sketch map of Lüliang area in Shanxi Province (a) and its tectonic location (b)
图 3 样品野外及镜下照片
a.袁家村铁矿采矿场，主要以赤铁矿相为主；b.袁家村铁矿赋存于吕梁群中，围岩主要为绢云母片岩；c.赤铁矿样品，可见有条带；d.富铁条带与富硅条带互层，单偏光；e.赤铁矿交代磁铁矿（Mt）假象分布，仍残存部分磁铁矿，反射光；f.赤赤铁矿（Hem）与石英（Qtz）构成主要矿物，可见有少量角闪石（Amp）与铁闪石（Gru），正交光；g.富铁条带中的赤铁矿交代磁铁矿，反射光；h.赤铁矿在石英边缘或被石英包裹，呈鲕状分布，可见有少量铁闪石（Gru）；矿物缩写：Mt.磁铁矿；Hem.赤铁矿；Q.石英；Gru.铁滑石；Amp.角闪石
Fig. 3. Field photos and microscopic photos of samples
图 4 袁家村样品碎屑锆石阴极发光图像
Fig. 4. Cathodoluminescence (CL) images for detrital zircons in the Yuanjiacun samples
图 5 袁家村BIFs碎屑锆石年龄谱，年龄谱剔除了Th/U小于0.4及谐和度低于90%的数据点
Fig. 5. Binned frequency histogram of detrital zircon age for the Yuanjiacun BIFs, Th/U greater than 0.4 and the consistency higher than 90% of all data
图 6 袁家村组碎屑锆石年龄谱，年龄谱剔除了Th/U小于0.4及谐和度低于90%的数据点
其中n1采自变质砂岩，数据来源Wang et al.（2014a）；n2原岩采自石英绢云母片岩，n3采自炭质板岩，n4采自长石石英岩，数据来源Liu et al.（2014）
Fig. 6. Binned frequency histogram of detrital zircon age for the Yuanjiacun Group, Th/U greater than 0.4 and the consistency higher than 90% of all data
图 7 岩浆锆石与热液锆石微量元素判别图解
a~d为4组年龄峰的碎屑锆石稀土元素，其中~2 520 Ma的数据包括 > 2 200 Ma的所有碎屑锆石（a），b~d分别为~1 908 Ma、~805 Ma、~261 Ma 3组年龄峰值的锆石数据，数据范围为1 200~2 200 Ma、600~1 200 Ma、 < 600 Ma，由于数据较多，图中只选取部分
Fig. 7. Discrimination diagrams for magmatic and hydrothermal zircons
图 8 袁家村样品碎屑锆石稀土配分模式图(据Li，2005)
Fig. 8. Diagrams of REE distribution pattern of detrital zircon from Yuanjiacun sample (modified from Li, 2005)
图 9 海水、热液及样品的REY配分模式图
a.实心符号为氧化水体，空心为缺氧水体；NPDW.北太平洋2 400 m深度的海水样品（Alibo and Nozaki, 1999）；Southern Ocean.南大西洋418 m、916 m和1 466 m深度海水的平均值（German et al., 1995），Black sea100 m、130 m和2 153 m深度的平均值（German，1991），Saanic Inlet萨尼奇湾深度215 m的海水（German，1989）；b.高温热液与低温热液的稀土特征，数据来自Bau and Dulski（1996）；Wheat（2002）；Bolhar et al.（2004）；c.袁家村稀土特征图，轻重稀土分异较大；d.袁家村稀土特征图，轻重稀土分异较小，曲线平缓；除了本文数据外，还加入了Wang et al.（2014b）一起讨论，图中用绿色线条表示，页岩标准化（PAAS）数值均为McLennan（1989）中的Post-Archean Australian Shale（PAAS）数值
Fig. 9. REY distribution patterns of seawater, hydrothermal solution and samples
图 10 袁家村BIFs微量元素三端元混合模拟图
a.Zr-Y/Ho判别图，区别碎屑物质对BIFs的干扰，来自Bolhar et al.（2004）；b.Eu/Sm-Y/Ho判别图，大部分样品落在上陆壳、海水、热液三端元控制的区域，同时0.1%的热液参与就可以解释袁家村样品的Eu/Sm值；c.Eu/Sm-Sm/Yb判别图，用海水与热液两个端元的混合来限制样品，样品未落在曲线上表明存在其他的REY来源，可能为上陆壳；d.Sm/Yb-Y/Ho判别图，上陆壳端元未能较好的约束袁家村样品，这可能与陆源输入的方式有关.图据Alexander et al.（2008），高T流体、NPDW和上陆壳数据参考Bau and Dulski（1996）和Alibo and Nozaki（1999），数据包括本文工作、Hou et al.（2014）、Li et al.（2014）、Wang et al.（2014b）
Fig. 10. Simulation diagrams of ternary mixing of trace elements in BIFS of the Yuanjiacun
图 11 袁家村铁矿Pr-Ce判别图解
数据来源除了本文数据外，还包括Hou et al.（2014）、Li et al.（2014）、Wang et al.（2014b）；图据Bau and Dulski（1996）
Fig. 11. Pr-Ce discrimination diagram of the Yuanjiacun BIFs
图 12 苏必利尔型铁建造REE+Y特征的时间变化趋势图解
a.Pr异常（PrPAAS/（0.5（CePAAS+NdPAAS）））；b.Ce异常（CePAAS/（0.5（PrPAAS+LaPAAS）））；c.轻稀土与重稀土之比（Pr/Yb）PAAS；d.Y/Ho比率，灰色条条表示PAAS页岩数值范围，数据取自Planavsky et al.（2010）中的2.48 Ga（W-18-740A、KOEN-2、KU-9-537）与2.47 Ga（DDH75/1-466、RM8、RM9、DDH75/1），2.0 Ga为Frei et al.（2009）的19600-2845-3、19600-2845-1、19600-2960-4、19600-2960-2、19600-2964、25L88-13-3020-B、25L88-13-3020-A，2.3 Ga的样品为本文工作和Wang et al.（2014b）
Fig. 12. Diagrams of the temporal trend on superior-type iron formation
表 1 袁家村铁矿BIF主微量元素分析结果(主量单位为%，微量为10-6)
Table 1. Major element (%) and rare earth element (10-6) compositions of the samples obtained from Yuanjiacun BIFs
样品 15YJC3 15YJC5 15YJC6 15YJC7 15YJC9 15YJC11 15YJC12 15YJC13 15YJC15 15YJC17 15YJC18 Rock-type BIF Specularite BIF Specularite BIF BIF Specularite Specularite BIF BIF BIF Location 10 10 10 10 10 10 10 10 2 2 2 SiO2 54.1 63.0 47.7 42.4 37.3 43.8 50.9 45.5 56.2 48.0 58.6 Al2O3 0.07 0.99 0.13 0.10 0.39 0.04 0.06 0.07 0.41 0.33 0.10 Fe2O3 45.4 34.6 51.9 57.3 61.9 53.5 49.3 54.2 41.7 49.6 40.9 MnO - 0.01 0.02 0.01 0.01 0.04 - - 0.02 0.01 0.01 MgO 0.04 0.07 0.05 0.04 0.17 1.51 0.03 0.04 0.49 0.13 0.07 CaO 0.09 0.16 0.03 0.05 0.04 1.92 0.02 0.03 0.07 0.64 0.03 Na2O 0.02 0.02 0.02 0.02 0.01 0.03 0.01 0.02 0.04 0.03 0.02 K2O - 0.02 - 0.01 - 0.01 - - 0.13 0.01 0.01 TiO2 - 0.01 - - 0.01 - - - 0.01 0.01 - P2O5 0.02 0.09 0.01 0.04 0.06 0.13 0.02 0.02 0.02 0.48 0.04 LOI 0.28 0.66 0.25 0.25 0.35 -1.02 0.08 0.08 0.82 0.98 0.29 Total 100 99.7 100 100 100 100 100 100 99.9 100 100 Ba 6.80 5.80 8.20 5.50 5.00 7.50 2.50 2.60 5.00 26.9 4.90 Ce 3.50 14.5 3.30 2.50 4.30 2.70 2.00 2.50 2.60 9.90 1.10 Cr 80.0 90.0 70.0 80.0 90.0 50.0 90.0 50.0 90.0 30.0 80.0 Cs 0.08 0.11 0.01 0.04 0.08 0.17 - - 1.87 0.60 0.04 Dy 1.20 1.98 0.58 0.45 1.28 0.45 0.50 0.54 0.22 2.27 0.58 Er 0.91 1.19 0.31 0.32 1.08 0.34 0.43 0.35 0.17 1.46 0.45 Eu 0.43 0.70 0.12 0.17 0.33 0.16 0.17 0.15 0.05 0.64 0.11 Ga 1.10 2.40 0.60 1.00 1.10 0.60 1.00 1.10 1.50 1.10 1.20 Gd 1.09 2.07 0.51 0.41 1.04 0.43 0.46 0.49 0.21 1.74 0.45 Ho 0.30 0.39 0.11 0.11 0.32 0.13 0.12 0.16 0.05 0.51 0.13 La 2.00 7.50 1.90 1.40 2.30 1.60 1.10 1.40 1.40 4.60 0.60 Lu 0.14 0.14 0.06 0.05 0.18 0.06 0.07 0.08 0.06 0.17 0.06 Nb 0.30 0.30 0.20 0.20 0.20 0.20 - - 0.20 0.40 0.20 Nd 2.00 7.30 1.40 1.40 2.10 1.40 1.20 1.30 1.30 6.00 0.70 Pr 0.41 1.91 0.35 0.36 0.54 0.34 0.23 0.30 0.32 1.34 0.14 Rb 0.40 1.30 0.20 0.50 0.60 0.80 0.20 0.30 9.30 1.30 0.30 Sm 0.51 1.64 0.31 0.31 0.62 0.31 0.27 0.31 0.17 1.34 0.31 Sr 2.70 3.50 4.10 3.80 2.40 11.9 1.30 1.20 8.10 12.5 2.30 Tb 0.22 0.31 0.10 0.07 0.19 0.08 0.07 0.06 0.03 0.28 0.09 Th 0.10 0.21 - 0.06 0.18 - 0.05 0.06 0.22 0.10 0.07 Tm 0.12 0.19 0.05 0.05 0.18 0.06 0.07 0.08 0.04 0.21 0.06 U 0.72 0.69 0.25 0.62 0.28 - 0.55 0.90 0.07 0.10 0.21 V 11.00 29.00 - 7.00 10.00 - 5.00 6.00 8.00 9.00 7.00 W - 1.00 1.00 1.00 2.00 - 1.00 1.00 - 1.00 1.00 Y 10.50 14.00 4.40 3.40 11.30 4.70 4.90 5.30 1.70 16.5 4.50 Yb 0.77 1.09 0.31 0.24 0.93 0.35 0.41 0.47 0.22 0.95 0.45 Zr 5.00 5.00 3.00 3.00 5.00 - 2.00 2.00 7.00 4.00 3.00 Y/Ho 35.0 35.9 40.0 30.9 35.3 36.2 40.8 33.1 34.0 32.4 34.6 Eu/Sm 0.84 0.43 0.39 0.55 0.53 0.52 0.63 0.48 0.29 0.48 0.35 Sm/Yb 0.66 1.50 1.00 1.29 0.67 0.89 0.66 0.66 0.77 1.41 0.69 (Y/Y*)PAAS 1.39 1.27 1.39 1.22 1.40 1.53 1.59 1.42 1.29 0.93 1.22 (La/La*)PAAS 2.46 0.90 1.37 0.92 1.01 1.27 3.92 1.45 1.14 1.19 1.19 (Ce/Ce*)PAAS 0.89 0.88 0.93 0.81 0.89 0.84 0.92 0.89 0.90 0.93 0.91 (Pr/Pr*)PAAS 0.90 1.09 0.96 1.12 1.05 1.02 0.86 0.97 1.02 1.00 1.01 (Eu/Eu*)PAAS 1.75 2.19 2.14 1.73 2.00 1.34 2.44 1.82 1.22 1.93 1.34 (Gd/Gd*)PAAS 0.75 1.18 0.81 1.04 1.03 0.83 1.33 2.65 1.48 0.96 1.57 (Sm/Yb)PAAS 0.34 0.76 0.51 0.66 0.34 0.45 0.33 0.34 0.39 0.64 0.72 (Pr/Yb)PAAS 0.17 0.56 0.36 0.48 0.19 0.31 0.18 0.20 0.46 0.31 0.45 (La/Yb)PAAS 0.19 0.51 0.45 0.43 0.18 0.34 0.20 0.22 0.47 0.20 0.36 注：(La/La*)PAAS=(La)PAAS/(3×PrPAAS-2×NdPAAS); (Pr/Pr*)PAAS=2×(Pr)PAAS/(CePAAS+NdPAAS); (Ce/Ce*)PAAS=2×(Ce)PAAS/(LaPAAS+PrPAAS); (Y/Y*)PAAS=2×(Y)PAAS/(DyPAAS+HoPAAS)，据 Bolhar et al.(2004) ; (Eu/Eu*)PAAS=EuPAAS/SQRT(Sm×Gd)PAAS, 据Bau and Dulski(1996)；所有页岩标准化(PAAS)数值均为McLennan(1989)中的Post-Archean Australian Shale(PAAS)数值.
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表 2 袁家村铁矿赤铁矿微量元素分析结果(10-6)
Table 2. Trace element (10-6) compositions of the hematite in Yuanjiacun BIFs
Element Mg Mn Al Ti V Cr Co Ga 15YJC3-1 111 2.06 3 396 39.7 13.7 17.9 0.88 1.03 15YJC3-2 157 4.71 162 32.4 14.0 19.8 1.71 0.69 15YJC3-3 106 14.7 280 36.9 18.1 19.0 3.18 0.71 15YJC3-5 123 2.01 88.6 36.9 15.0 3.60 1.43 0.55 15YJC3-6 168 3.42 115 38.0 13.5 4.50 1.44 0.62 15YJC3-7 130 5.20 95.9 34.1 13.3 5.04 1.28 0.63 15YJC3-8 188 0.80 183 11.9 4.03 5.20 0.90 0.47 15YJC3-9 112 2.01 260 16.8 5.07 4.47 0.97 0.63 15YJC3-10 101 0.88 87.9 24.1 7.57 2.80 1.21 0.77 15YJC9-1 338 25.2 97.3 49.0 6.37 2.50 0.40 0.48 15YJC9-2 302 7.05 1658 30.5 5.23 23.1 1.08 0.64 15YJC9-3 258 7.42 72.3 29.4 4.01 4.10 0.70 0.73 15YJC9-4 396 10.3 328 33.5 4.11 7.73 2.03 0.20 15YJC9-5 315 11.4 149 27.9 4.20 4.95 1.59 0.78 15YJC9-6 473 6.51 145 27.5 4.06 21.0 1.15 0.68 15YJC9-7 420 6.69 294 50.0 6.85 31.3 1.63 0.43 15YJC9-8 483 19.4 78.1 34.1 5.21 13.2 1.28 0.45 15YJC9-9 885 158 2538 52.6 7.37 31.5 9.55 0.47 15YJC9-10 399 12.0 1081 39.7 5.89 59.4 2.09 0.60 15YJC6-1 96.7 7.27 27.4 2.70 1.30 3.00 0.50 0.20 15YJC6-2 100 15.4 21.6 3.81 1.39 5.00 0.87 0.28 15YJC6-3 466 2.74 43.9 6.02 1.81 57.3 0.60 0.20 15YJC6-4 936 3.43 179 9.61 1.82 11.0 0.94 0.30 15YJC6-5 172 5.25 471 29.5 2.50 43.2 0.80 0.39 15YJC6-6 47.2 7.24 71.1 2.15 0.85 8.88 0.59 0.17 15YJC6-7 124 3.29 271 4.01 1.73 74.3 1.18 0.20 15YJC6-8 349 0.82 73.9 4.75 1.58 7.64 0.50 0.20 15YJC6-9 132 15.5 41.5 2.60 1.46 4.57 0.60 0.20 15YJC6-10 149 7.27 115 2.90 1.75 24.4 0.70 0.20 15YJC6-11 151 1.05 150 2.90 1.76 3.90 0.70 0.30 15YJC6-12 153 90.8 498 2.90 1.50 36.2 1.22 0.36 15YJC6-13 158 0.67 570 3.20 1.33 13.7 0.80 0.30 15YJC6-14 140 2.85 36.2 2.80 1.39 7.57 0.60 0.20 15YJC6-15 148 3.98 50.4 3.84 1.36 6.61 0.77 0.20 15YJC6-16 113 25.6 135 6.51 1.61 5.74 0.62 0.20 15YJC6-17 765 2.97 34.6 3.20 2.07 4.10 0.76 0.30
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