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
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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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