鄂西晚泥盆世含磷鲕状铁矿石中磷的赋存状态与形成

柴辛娜; 李明; 金振民; 高山

doi:10.3799/dqkx.2011.047

鄂西晚泥盆世含磷鲕状铁矿石中磷的赋存状态与形成

doi: 10.3799/dqkx.2011.047

柴辛娜^{1, 2,},
李明^{1, 2, 3},
金振民^{1, 2, 3},
高山^{1, 2, 3, ,}

1.
中国地质大学地质过程与矿产资源国家重点实验室, 湖北武汉 430074
2.
中国地质大学地球科学学院, 湖北武汉 430074
3.
中国地质大学地球物质与区域资源和环境湖北省重点实验室, 湖北武汉 430074

基金项目:

国家自然科学基金 40821061

教育部高等学校学科创新引智计划 B07039

地质过程与矿产资源国家重点实验室科技部专项基金 MSFGPMR201009

中央高校基本科研业务费专项资金 CUG090105

详细信息

作者简介:
柴辛娜(1980-), 女, 博士研究生, 主要从事分析地球化学的研究.E-mail: chaixinna2233@163.com

通讯作者:
高山, sgao@263.net

中图分类号: P596
计量
- 文章访问数: 3270
- HTML全文浏览量: 181
- PDF下载量: 63
- 被引次数: 0
出版历程
- 收稿日期: 2011-02-05
- 刊出日期: 2011-05-01

Occurrence and Formation of Phosphorus in Late Devonian Phosphate-Bearing Ooidal Ironstones from Western Hubei, China

CHAI Xin-na^{1, 2
,},
LI Ming^{1, 2, 3},
JIN Zhen-min^{1, 2, 3},
GAO Shan^{1, 2, 3
, ,}

1.
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China
2.
Faculty of Earth Science, China University of Geosciences, Wuhan 430074, China
3.
Key Laboratory of Earth Material and Regional Resources and Environment, China University of Geosciences, Wuhan 430074, China

摘要

摘要: 广泛分布于我国南方泥盆纪地层的"宁乡式"铁矿储量巨大, 然而含磷高严重制约了该类型铁矿的开发利用.铁矿石中磷的赋存状态是设计该类型铁矿"提铁降磷"方案的理论基础, 是开发该铁矿首先要了解的问题.充分利用湿化学全岩分析、电感耦合等离子体质谱分析等全岩元素分析, 扫描电子显微镜、X射线衍射等物相分析, 电子探针微分析、激光剥蚀电感耦合等离子体质谱分析等微区分析技术, 对鄂西晚泥盆世含磷鲕状铁矿石中磷的赋存状态、物质来源与磷矿物形成过程进行了初步探讨.铁矿石中的含磷矿物主要为碳氟磷灰石, 分别以短柱状磷灰石晶体颗粒(65%以上粒径小于20 μm)、磷灰石内碎屑(粗砂至极粗砂级, 集中形成透镜状或带状层理)以及鲕粒中与赤铁矿相互包裹的凝胶状磷灰石(层厚度10~50 μm)3种形式存在.磷灰石晶体是在孔隙水中重结晶而生成, 磷质可能来源于晚震旦世地层的磷块岩; 磷灰石内碎屑是古海水体中原位化学沉积的产物, 磷质可能来源于古海周边的大陆; 鲕粒中凝胶状磷灰石也是原位化学沉积的产物, 但与铁质沉积位置相同, 并与富铁的鲕绿泥石混合或相互包裹形成鲕粒.
- 鲕状铁矿石 /
- 磷 /
- 赋存状态 /
- 晚泥盆世 /
- 鄂西 /
- 地球化学
Abstract: Ningxiang-type iron deposits are widely distributed in Devonian strata in southern China with huge reserves, but exploitation of this type iron deposits have been severely circumscribed due to their high phosphorus content. Occurrences of phosphorus are theoretical foundations for dephosphorization researches, which should be solved first. Preliminary researches of occurrence, formation and origin of phosphorus in Late Devonian phosphate-bearing ooidal ironstones from Western Hubei in China have been done in this study by means of whole-rock element analysis (wet chemical whole-rock analysis, inductively coupled plasma mass spectrometry), mineral phase analysis (scanning electron microscopy, X-ray diffraction analysis) and in-situ element analysis (electron microprobe analysis, laser ablation inductively coupled plasma mass spectrometry). Phosphorous-bearing minerals are mainly carbonate fluorapatite in ironstone and there are three formations, including prismatic apatite crystal particles (more than 65% particle sizes < 20 μm), apatite intraclasts (very coarse and coarse sand size level particles concentrate in lenticular and banded beddings), and layered gelatinous apatite entangled by hematite in ooids (layer thickness are of 10-50 μm). Apatite crystals recrystallized from pore water, and might have originated from phosphorite in late Sinian strata. Apatite intraclasts were the product of in-situ chemical deposition in seawater, and might have come from land around paleo-ocean. Gelatinous apatite also was in-situ chemical deposition product, but formed at iron deposition position and mixed or mutual parcel with chamosite and formed ooids.
- ooidal ironstones /
- phosphorus /
- occurrence /
- Late Devonian /
- western Hubei /
- geochemistry

HTML全文

图 1 (a) 湖北泥盆-石炭纪地层混层及鄂西鲕状铁矿石分布简图；(b)采样点

Fig. 1. (a) Devonian-Carboniferous strata in Hubei and distribution of ooidal ironstone deposits in western Hubei; (b) Sampling point

下载: 全尺寸图片幻灯片

图 2 铁矿石样品剖面

(a)铁矿石BY-1剖面颜色均匀，局部石英碎屑集中而颜色略浅；(b)铁矿石BY-3剖面存在黄白或黑灰色碎屑颗粒，并形成水平或透镜状层理

Fig. 2. Ironstone profiles

下载: 全尺寸图片幻灯片

图 3 铁矿石样品(a)稀土元素页岩(PAAS)标准化曲线和(b)微量元素页岩(PAAS)标准化曲线

Fig. 3. Post-Archean Australian shale (PAAS) normalized (a) REE and (b) trace elements patterns of ironstones

下载: 全尺寸图片幻灯片

图 4 铁矿石BY-3中碎屑层与铁矿层XRD图样

Fig. 4. XRD patterns of debris layer and ironstone layer in ironstone BY-3

下载: 全尺寸图片幻灯片

图 5 铁矿石光片扫描电子显微镜背散射电子成像及铁矿石新鲜断面扫描电子显微镜二次电子成像

(a)孔隙式胶结鲕粒构造；(b)赤铁矿基质中的磷灰石晶体；(c)鲕绿泥石片层中的磷灰石晶体；(d)放射状磷灰石微晶集合体；(e)镶嵌式胶结鲕粒构造；(f)鲕粒和半塑性磷灰石内碎屑；(g)鲕粒中的凝胶状磷灰石；(h)鲕粒外磷灰石内碎屑(微晶集合体)；Hem.赤铁矿；Ap.磷灰石；Qz.石英；Cha.鲕绿泥石

Fig. 5. SEM-BSE imaging of ironstone published sections and SEI of fresh fractured ironstone surfaces

下载: 全尺寸图片幻灯片

图 6 激光剥蚀样品表面扫描电子显微镜背散射电子成像

(a)由鲕粒外层向内依次为：磷灰石、鲕绿泥石、赤铁矿，核心为鲕绿泥石(外侧混有磷灰石)；(b)赤铁矿与鲕绿泥石混层鲕粒，核心为被磷灰石交代的碎屑石英颗粒，鲕绿泥石层中混有磷灰石；(c)由鲕粒外层向内依次为：赤铁矿(在鲕粒长轴两端混有若干层鲕绿泥石)、磷灰石、鲕绿泥石，核部为3~4层磷灰石构成的球粒；Hem.赤铁矿；Ap.磷灰石；Qz.石英；Cha.鲕绿泥石；●.激光剥蚀点

Fig. 6. SEM-BSE imaging of published sections used for LA-ICP-MS analysis

下载: 全尺寸图片幻灯片

图 7 铁矿石样品LA-ICP-MS微区各主量元素对P₂O₅的变化趋势

Fig. 7. Relationship between P₂O₅ and major elements of ironstones

下载: 全尺寸图片幻灯片

图 8 矿石样品LA-ICP-MS微区代表性微量元素对P₂O₅的变化趋势

Fig. 8. Relationship between P₂O₅ and trace elements of ironstones

下载: 全尺寸图片幻灯片

图 9 铁矿石样品微区稀土元素页岩标准化

a.磷灰石晶体；b.磷灰石内碎屑；c.鲕粒中较纯净的磷灰石层；c.鲕粒中较纯净的赤铁矿层

Fig. 9. PAAS normalized REE patterns of ironstones

下载: 全尺寸图片幻灯片

表 1 铁矿石样品全岩主、微量元素分析结果

Table 1. Whole-rock major and trace element analysis of ironstones

	BY-1	BY-2	BY-3	BY-4	BY-5	铁矿层	碎屑层
%
Na₂O	0.05	0.12	0.05	0.03	0.11	1.72	17.27
MgO	0.55	0.16	0.22	0.20	0.27
Al₂O₃	4.60	2.66	3.44	4.24	3.07
SiO₂	14.06	28.51	12.83	15.11	13.14
K₂O	0.03	0.03	0.02	0.03	0.03
CaO	3.99	3.36	6.55	3.64	6.20
TiO₂	0.24	0.18	0.19	0.22	0.16
MnO	0.01	0.01	0.02	0.01	0.02
P₂O₅	3.40	2.68	5.01	2.77	4.56
Fe₂O₃	63.50	59.73	65.50	70.16	63.96
FeO	4.62	0.54	3.33	0.67	4.45
CO₂	0.10	0.10	0.13	0.13	0.13
H₂O⁺	3.85	1.76	2.17	2.45	3.51
Total	99.00	99.84	99.46	99.66	99.61
TFe	48.00	42.20	48.40	49.59	48.19	53.32	24.82
μg·g^-1
Be	48.0	9.0	19.6	14.5	18.8	12.1	41.0
B	18.4	16.6	22.0	14.6	18.2	21.0	22.0
Sc	44.0	21.0	24.0	24.0	27.0	16.8	52.0
V	823	373	436	473	423	510	239
Cr	84	61	59	62	59	58	33
Co	39	37	47	51	100	44	38
Ni	52	35	44	49	48	39	33
Cu	1.0	2.5	2.5	2.2	1.9	1.8	9.1
Zn	139	79	124	105	150	113	114
Ga	22.0	8.5	9.6	12.1	11.5	9.3	8.1
Rb	0.43	0.28	0.22	0.30	0.89	0.16	0.13
Sr	104	146	285	151	235	130	897
Y	286	86	114	73	127	39	389
Zr	61	84	76	90	79	55	104
Nb	4.2	1.9	2.2	2.7	2.3	2.0	1.0
Mo	2.4	4.8	5.4	6.8	5.3	6.8	4.0
Cd	0.086	0.050	0.150	0.041	0.050	0.059	0.110
Sn	2.00	1.50	1.20	1.40	1.40	1.30	0.52
Cs	0.560	0.140	0.180	0.180	0.900	0.150	0.069
Ba	45	28	43	30	45	24	104
La	206.0	11.6	14.4	13.0	14.4	11.4	20.0
Ce	521	36	44	36	45	34	83
Pr	79.0	6.5	8.1	6.2	8.5	5.4	16.7
Nd	357	38	47	34	50	27	105
Sm	81.0	11.7	14.4	10.4	16.6	6.4	46.0
Eu	15.8	2.4	3.1	2.1	3.6	1.2	11.0
Gd	75.0	13.2	16.8	11.5	19.2	6.2	56.0
Tb	11.5	2.3	2.9	2.1	3.4	1.1	9.9
Dy	62.0	14.1	18.5	13.0	21.0	8.2	74.0
Ho	10.8	2.8	3.8	2.6	4.2	1.3	11.2
Er	24.0	7.1	9.7	6.8	10.9	4.1	34.0
Tm	3.20	1.10	1.50	1.00	1.60	0.59	4.70
Yb	17.1	6.2	8.5	6.3	9.5	3.9	28.0
Lu	2.20	0.86	1.20	0.87	1.30	0.56	3.60
Hf	1.6	2.1	2.1	2.3	2.1	1.4	2.6
Ta	0.21	0.14	0.16	0.20	0.16	0.10	0.14
W	5.1	1.6	2.0	2.3	2.6	2.5	1.1
Pb	16.3	9.2	19.2	13.0	14.7	10.8	21.0
Th	25.0	10.8	12.9	13.1	12.1	10.4	8.1
U	4.1	4.8	6.1	6.4	6.4	3.3	13.4
∑REE	1467	153	194	146	210	112	503
(La/Nd)_SN	0.51	0.27	0.27	0.34	0.25	0.37	0.17
(Er/Lu)_SN	1.71	1.26	1.28	1.18	1.28	1.11	1.45
(La/Yb)_SN	0.89	0.14	0.13	0.15	0.11	0.21	0.05

下载: 导出CSV

表 2 铁矿石样品较纯净矿物相EMPA微区主量元素分析结果(%)

Table 2. EMPA data of major elements of single minerals in thin section of ironstones

	CaO	P₂O₅	Fe₂O₃	SiO₂	Al₂O₃	F	Cr₂O₃	MgO	TiO₂	MnO	K₂O
磷灰石	56.00	39.0	1.1	0.3	0.6	2.1	0.10	0.03	0.030	0.080	0.020
赤铁矿	0.07	0.2	97.0	1.5	1.3	n.d.	0.15	0.06	0.120	0.020	0.013
鲕绿泥石	0.50	0.3	41.0	27.0	22.0	n.d.	1.00	1.80	0.036	0.045	0.200

下载: 导出CSV

参考文献(71)

[1]	Baioumy, H.M., 2007. Iron-phosphorus relationship in the iron and phosphorite ores of Egypt. Chemie der Erde-Geochemistry, 67: 229-239. doi: 10.1016/j.chemer.2004.10.002
[2]	Becker, J.S., Matusch, A., Depboylu, C., et al., 2007. Quantitative imaging of selenium, copper, and zinc in thin sections of biological tissues (slugs-genus arion) measured by laser ablation inductively coupled plasma mass spectrometry. Analytical Chemistry, 79: 6074-6080. doi: 10.1021/ac0700528
[3]	Bhattacharyya, D.P., 1989. Concentrated and lean oolites: examples from the Nubia Formation at Aswan, Egypt, and significance of the oolite types in ironstone genesis. In: Young, T.P., Taylor, W.E.G., eds., Phanerozoic ironstones. Geological Society Special Publication, 46: 93-103.
[4]	Bhattacharyya, D.P., Kakimoto, P., 1982. Origin of ferriferous ooids: an SEM study of ironstone ooids and bauxite pisiods. Joumal of Sedimentary Petrology, 52(3): 849-857. http://www.researchgate.net/publication/282542526_Origin_of_Ferriferous_Ooids_An_Sem_Study_of_Ironstone_Ooids_and_Bauxite_Pisoids
[5]	Cotter, E., 1992. Diagenetic alteration of chamositic clay minerals to ferric oxide in oolitic ironstone. Joumal of Sedimentary Petrology, 62(1): 54-60.
[6]	Franceschelli, M., Puxeddu, M., Carta, M., 2000. Mineralogy and geochemistry of Late Ordovician phosphate-bearing oolitic ironstones from NW Sardinia, Italy. Mineralogy and Petrology, 69: 267-293. doi: 10.1007/s007100070024
[7]	Gagnon, J.E., Fryer, B.J., Samson, I.M., et al., 2008. Quantitative analysis of silicate certified reference materials by LA-ICP-MS with and without an internal standard. Journal of Analytical Atomic Spectrometry, 23: 1529-1537. doi: 10.1039/b801807n
[8]	Garzanti, E., Haas, R., Jadoul, F., 1989. Ironstones in the Mesozoic passive margin sequence of the Tethys Himalaya (Zanskar, northern India): sedimentology and metamorphism. In: Young, T.P., Taylor, W.E.G., eds., Phanerozoic ironstons. Geological Society Special Publication, 46: 229-244.
[9]	Gehring, A.U., 1989. The formation of goethitic ooids in condensed Jurassic deposits in northern Switzerland. In: Young, T.P., Taylor, W.E.G., eds., Phanerozoic ironstons. Geological Society Special Publication, 46: 133-139.
[10]	Guillong, M., Hametner, K., Reusser, E., et al., 2005. Preliminary characterisation of new glass reference materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation inductively coupled plasma mass spectrometry using 193 nm, 213 nm and 266 nm wavelengths. Geostandards and Geoanalytical Research, 29: 315-331. doi: 10.1111/j.1751-908X.2005.tb00903.x
[11]	Gunnars, A., Blomqvist, S., Martinsson, C., 2004. Inorganic formation of apatite in brackish seawater from the Baltic Sea: an experimental approach. Marine Chemistry, 91: 15-26. doi: 10.1016/j.marchem.2004.01.008
[12]	Günther, D., Heinrich, C.A., 1999. Comparison of the ablation behaviour of 266 nm Nd: YAG and 193 nm ArF excimer lasers for LA-ICP-MS analysis. Journal of Analytical Atomic Spectrometry, 14: 1369-1374. doi: 10.1039/A901649J
[13]	Halicz, L., Günther, D., 2004. Quantitative analysis of silicates using LA-ICP-MS with liquid calibration. Journal of Analytical Atomic Spectrometry, 19: 1539-1545. doi: 10.1039/b410132
[14]	Heikoop, J.M., Tsujita, C.J., Risk, M.J., et al., 1996. Modorn iron ooids from a shallow-marine volcanic setting: mahengetang, Indonesia. Geology, 24(8): 759-762. doi: 10.1130/0091-7613(1996)024<0759:MIOFAS>2.3.CO;2
[15]	Hou, H.F., Wang, S.T., 1985. Devonian palaeogeography of China. Acta Palaeontologica, 24(2): 186-193 (in Chinese with English abstract). http://en.cnki.com.cn/Article_en/CJFDTOTAL-GSWX198502005.htm
[16]	Hren, M.T., Lowe, D.R., Tice, M.M., et al., 2006. Stable isotope and rare earth element evidence for recent ironstone pods within the Archean Barberton greenstone belt, South Africa. Geochimica et Cosmochimica Acta, 70: 1457-1470. doi: 10.1016/j.gca.205.11.016
[17]	Hu, N., Xu, A.W., 1998. Horizon, lithofacies and genesis of the Ningxiang-type iron deposit in western Hubei, China. Contributions to Geology and Mineral Resources Research, 13(1): 40-47 (in Chinese with English abstract). http://en.cnki.com.cn/Article_en/CJFDTOTAL-DZZK801.004.htm
[18]	Hu, S.H., Zhang, S.C., Hu, Z.C., et al., 2007. Detection of multiple proteins on one spot by laser ablation inductively coupled plasma mass spectrometry and application to immuno-microarray with element-tagged antibodies. Analytical Chemistry, 79: 923-929. doi: 10.1021/ac061269p
[19]	Hu, Z.C., Gao, S., Liu, Y.S., et al., 2008. Signal enhancement in Laser Ablation ICP-MS by addition of nitrogen in the central channel gas. Journal of Analytical Atomic Spectrometry, 23: 1093-1101. doi: 10.1039/b804760j
[20]	Ilyin, A.V., 1998. Rare-earth geochemistry of 'old' phosphorites and probability of syngenetic precipitation and accumulation of phosphate. Chemical Geology, 144: 243-256. doi: 10.1016/S0009-2541(97)00134-4
[21]	Kearsley, A.T., 1989. Iron-rich ooids, their mineralogy and microfabric: clues to their origin and evolution. In: Young, T.P., Taylor, W.E.G., eds., Phanerozoic ironstons. Geological Society Special Publication, 46: 141-164.
[22]	Leach, A.M., Hieftje, G.M., 2000. Methods for shot-to-shot normalization in laser ablation with an inductively coupled plasma time-of-flight mass spectrometer. Journal of Analytical Atomic Spectrometry, 15: 1121-1124. doi: 10.1039/b001968m
[23]	Leach, A.M., Hieftje, G.M., 2001. Standardless semiquantitative analysis of metals using single-shot laser ablation inductively coupled plasma time-of-flight mass spectrometry. Analytical Chemistry, 73: 2959-2967. doi: 10.1021/ac001272n
[24]	Leach, A.M., Hieftje, G.M., 2002. Identification of alloys using single shot laser ablation inductively coupled plasma time-of-flight mass spectrometry. Journal of Analytical Atomic Spectrometry, 17: 852-857. doi: 10.1039/b203523n
[25]	Lécuyer, C., Grandjean, P., Barrat, J., et al., 1998. δ¹⁸O and REE contents of phosphatic brachiopods: a comparison between modern and Lower Paleozoic populations. Geochimica et Cosmochimica Acta, 62(14): 2429-2436. doi: 10.1016/S0016-7037(98)00170-7
[26]	Lécuyer, P.G., Feist, R., Albarède, F., 1993. Rare earth elements in old biogenic apatites. Geochimica et Cosmochimica Acta, 57: 2507-2514. doi: 10.1016/0016-7037(93)90413Q
[27]	Li, M., Hu, Z.C., Gao, S., et al., 2011. Direct quantitative determination of trace elements in fine-grained whole rocks by laser ablation-inductively coupled plasma-mass spectrometry. Geostandards and Geoanalytical Research, 35: 7-22. doi: 10.1111/j.1751-908X.2010.00028.x
[28]	Liao, S.F., 1993. Phanerozoic oolitic ironstone in China. Sedimentary Geology and Tethyan Geology, 13(3): 1-8 (in Chinese with English abstract). http://en.cnki.com.cn/Article_en/CJFDTOTAL-TTSD199303000.htm
[29]	Liao, S.F., Wei, L.H., Liu, C.D., et al., 1993. Sedimentary environments and origin of the Devonian oolitic ironstones in China. Acta Sedimentologica Sinica, 11(1): 93-102 (in Chinese with English abstract). http://en.cnki.com.cn/Article_en/CJFDTOTAL-CJXB199301010.htm
[30]	Liu, Y.J., Cao, L.M., Li, Z.L., et al., 1984. Elemental Geochemistry. Science Press, Beijing (in Chinese).
[31]	Liu, Y.S., Gao, S., Hu, Z.C., et al., 2010. Continental and oceanic crust recycling-induced melt-peridotite interactions in the Trans-North China Orogen: U-Pb dating, Hf isotopes and trace elements in zircons from mantle xenoliths. Journal of Petrology, 51: 537-571. doi: 10.1093/petrology/egp082
[32]	Liu, Y.S., Hu, Z.C., Gao, S., et al., 2008a. In-situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard. Chemical Geology, 257: 34-43. doi: 10.1016/j.chemgeo.2008.08.004
[33]	Liu, Y.S., Zong, K.Q., Kelemen, P.B., et al., 2008b. Geochemistry and magmatic history of eclogites and ultramafic rocks from the Chinese continental scientific drill hole: subduction and ultrahigh-pressure metamorphism of lower crustal cumulates. Chemical Geology, 247: 133-153. doi: 10.1016/j.chemgeo.2007.10.016
[34]	Liu, Y.X., Ge, D.Y., Zeng, Y.F., et al., 1994. The enrichment characteristics of apatite from phosphorites in East Yunnan. Journal of Mineralogy and Petrology, 14(4): 17-34 (in Chinese with English abstract). http://en.cnki.com.cn/Article_en/CJFDTOTAL-KWYS404.002.htm
[35]	Mclennan, S.M., 1989. Rare earth elements in sedimentary rocks: influence of provenance and sedimentary processes. Reviews in Mineralogy and Geochemistry, 21(1): 169-200. http://www.researchgate.net/publication/313503357_Rare_earth_elements_in_sedimentary_rocks_influence_of_provenance_and_sedimentary_processes
[36]	Mücke, A., 2000. Environmental conditions in the Late Cretaceous African Tethys: conclusions from a microscopic-microchemical study of ooidal ironstones from Egypt, Sudan and Nigeria. Journal of African Earth Sciences, 30(1): 25-46. doi: 10.1016/S0899-5362(00)00006-3
[37]	Mücke, A., 2006. Chamosite, siderite and the environmental conditions of their formation in chamosite-type Phanerozoic ooidal ironstones. Ore Geology Reviews, 28: 235-249. doi: 10.1016/j.oregeorev.2005.03.004
[38]	Mücke, A., Farshad, F., 2005. Whole-rock and mineralogical composition of Phanerozoic ooidal ironstones: comparison and differentiation of types and subtypes. Ore Geology Reviews, 26: 227-262. doi: 10.1016/j.oregeorev.2004.08.001
[39]	Pisonero, J., Kroslakova, I., Günther, D., 2006. Laser ablation inductively coupled plasma mass spectrometry for direct analysis of the spatial distribution of trace elements in metallurgical-grade silicon. Analytical and Bioanalytical Chemistry, 386: 12-20. doi: 10.1007/s00216-006-0658-0
[40]	Reynard, B., Lécuyer, C., Grandjean, P., 1999. Crystal-chemical controls on rare-earth element concentrations in fossil biogenic apatites and implications for paleoenvironmental reconstructions. Chemical Geology, 155: 233-241. doi: 10.1016/S0009-2541(98)00169-7
[41]	Riquier, L., Tribovillard, N., Averbuch, O., et al., 2006. The Late Frasnian Kellwasser horizons of the Harz Mountains (Germany): two oxygen-deficient periods resulting from different mechanisms. Chemical Geology, 233: 137-155. doi: 10.1016/j.chemgeo.2006.02.21
[42]	Rollinson, H.R., 1993. Using Geochemical data: evaluation, presentation, interpretation. Longman Group Ltd., London.
[43]	Sarah, G., Gratuze, B., Barrandon, J.N., 2007. Application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the investigation of ancient silver coins. Journal of Analytical Atomic Spectrometry, 22: 1163-1167. doi: 10.1039/B704879C
[44]	Sha, L.K., Chappell, B.W., 1999. Apatite chemical composition, determined by electron microprobe and laser-ablation inductively coupled plasma mass spectrometry, as a probe into granite petrogenesis. Geochimica et Cosmochimica Acta, 63(22): 3861-3881. doi: 10.1016/S0016-7037(99)00210-0
[45]	Shields, G., Stille, P., 2001. Diagenetic constraints on the use of cerium anomalies as palaeoseawater redox proxies: an isotopic and REE study of Cambrian phosphorites. Chemical Geology, 175: 29-48. doi: 10.1016/S0009-2541(00)00362-4
[46]	Stefánsson, A., Gíslason, S.R., Arnórsson S., 2001. Dissolution of primary minerals in natural waters Ⅱ. Mineral saturation state. Chemical Geology, 172: 251-276. doi: 10.1016/S0009-2541(00)00262-X
[47]	Sturesson, U., 1995. Llanvirnian (Ord. ) iron ooids in Baltoscandia: element mobility, REE distribution patterns, and origin of the REE. Chemical Geology, 125: 45-60. doi: 10.1016/0009-2541(95)00076-X
[48]	Sturesson, U., 2003. Lower Palaeozoic iron oolites and volcanism from a Baltoscandian perspective. Sedimentary Geology, 159: 241-256. doi: 10.1016/S0037-0738(2)00330-5
[49]	Sturesson, U., Dronov, A., Saadre, T., 1999. Lower Ordovician iron ooids and associated oolitic clays in Russia and Estonia: a clue to the origin of iron oolites? Sedimentary Geology, 123: 63-80. doi: 10.1016/S0037-0738(98)00112-2
[50]	Sturesson, U., Heikoop, J.M., Risk, M.J., 2000. Modern and Palaeozoic iron ooids-a similar volcanic origin. Sedimentary Geology, 136: 137-146. doi: 10.1016/S0037-0738(00)00091-9
[51]	Taylor, K.G., Simo, J.A., Yocum, D., et al., 2002. Stratigraphic significance of ooidal ironstones from the Cretaceous western interior seaway: the peace river formation, Alberta, Canada, and the castlegate sandstone, Utah, U.S.A. . Journal of Sedimentary Research, 72: 316-327. doi: 10.1306/060801720316
[52]	Trythall, R.J.B., 1989. The Mid-Ordovician oolitic ironstones of North Wales: a field guide. In: Young, T.P., Taylor, W.E.G., eds., Phanerozoic ironstons. Geological Society Special Publication, 46: 213-220. doi: 10.1144/GSL.SP.1989.046.01.18
[53]	Tucker, M.E., 1991. Sedimentary Petrology. Blackwell, London.
[54]	Yang, J.Z., Mu, E.Z., 1953. The Devonian strata in western Hubei Province. Acta Palaeontologica, 1(2): 58-66 (in Chinese). http://www.researchgate.net/publication/286016970_The_Devonian_strata_in_western_Hubei_Province
[55]	Ye, L.J., Chen, Q.Y., Zhao, D.X., et al., 1989. Chinese Phosporite. Science Press, Beijing (in Chinese).
[56]	Young, T.P., 1989a. Phanerozoic ironstones: an introduction and review. In: Young, T.P., Taylor, W.E.G., eds., Phanerozoic ironstons. Geological Society Special Publication, 46: Ⅸ-ⅩⅩⅤ. doi: 10.1144/GSL.SP.1989.046.01.02
[57]	Young, T.P., 1989b. Ecstatically controlled ooidal ironstone deposition: facies relationships of the Ordovician open-shelf ironstones of western Europe. In: Young, T.P., Taylor, W.E.G., eds., Phanerozoic ironstons. Geological Society Special Publication: 46: 51-63.
[58]	Zhao, Y.M., Bi, C.S., 2000. Time-space distribution and evolution of the Ningxiang type sedimentary iron deposits. Mineral Deposits, 19(4): 350-362 (in Chinese with English abstract). http://en.cnki.com.cn/Article_en/CJFDTOTAL-KCDZ200004007.htm
[59]	Zheng, W. Z, Dongye, M.X., Hu, L.L., 1992. REE geochemistry of phosphorites of the sinian doushantou formation in western Hubei. Geological Review, 38(4): 352-359 (in Chinese with English abstract). http://en.cnki.com.cn/Article_en/CJFDTOTAL-DZLP199204007.htm
[60]	Zhu, X.Q., Wang, Z.G., Huang, Y., et al., 2004. REE content and distribution in apatite and its geological tracing significance. Chinese Rare Earths, 25(5): 41-45 (in Chinese with English abstract). http://www.researchgate.net/publication/309347819_REE_content_and_distribution_in_apatite_and_its_geological_tracing_significance
[61]	候鸿飞, 王士涛, 1985. 中国泥盆纪古地理. 古生物学报, 24(2): 186-193. https://www.cnki.com.cn/Article/CJFDTOTAL-GSWX198502005.htm
[62]	胡宁, 徐安武, 1998. 鄂西宁乡式铁矿分布层位岩相特征与成因探讨. 地质找矿论丛, 13(1): 40-47. https://www.cnki.com.cn/Article/CJFDTOTAL-DZZK801.004.htm
[63]	廖士范, 1993. 我国显生宙鲕铁石. 岩相古地理, 13(3): 1-8. https://www.cnki.com.cn/Article/CJFDTOTAL-TTSD199303000.htm
[64]	廖士范, 魏梁鸿, 刘成德, 等, 1993. 中国泥盆纪鲕铁石沉积环境、成因. 沉积学报, 11(1): 93-102. https://www.cnki.com.cn/Article/CJFDTOTAL-CJXB199301010.htm
[65]	刘英俊, 曹励明, 李兆麟, 等, 1984. 元素地球化学. 北京: 科学出版社.
[66]	刘永先, 戈定夷, 曾允孚, 等, 1994. 滇东磷块岩矿床中磷灰石的富集特征. 矿物岩石, 14(4): 17-34. https://www.cnki.com.cn/Article/CJFDTOTAL-KWYS404.002.htm
[67]	杨敬之, 穆思之, 1953. 鄂西泥盆纪地层. 古生物学报, 1(2): 58-66. https://www.cnki.com.cn/Article/CJFDTOTAL-GSWX195302001.htm
[68]	叶连俊, 陈其英, 赵东旭, 等, 1989. 中国磷块岩. 北京: 科学出版社.
[69]	赵一鸣, 毕承思, 2000. 宁乡式沉积铁矿床的时空分布和演化. 矿床地质, 19(4): 350-362. doi: 10.3969/j.issn.0258-7106.2000.04.008
[70]	郑文忠, 东野脉兴, 胡珞兰, 1992. 鄂西震旦纪陡山沱组磷块岩稀土元素地球化学. 地质论评, 38(4): 352-359. doi: 10.3321/j.issn:0371-5736.1992.04.008
[71]	朱笑青, 王中刚, 黄艳, 等, 2004. 磷灰石的稀土组成及其示踪意义. 稀土, 25(5): 41-45. doi: 10.3969/j.issn.1004-0277.2004.05.013