应用电感耦合等离子体质谱/光谱法研究上扬子区新华磷块岩稀土元素特征及沉积学意义

段凯波; 王登红; 何汉江; 郑国栋; 熊先孝; 袁建国; 贺宝宝; 屈云燕

doi:10.15898/j.cnki.11-2131/td.2015.02.018

应用电感耦合等离子体质谱/光谱法研究上扬子区新华磷块岩稀土元素特征及沉积学意义

1.
中化地质矿山总局化工地质调查总院, 北京 100013

2.
中国地质科学院矿产资源研究所, 北京 100037

3.
中化地质矿山总局地质研究院分析测试中心, 河北涿州 072750

基金项目: 中国地质大调查项目——我国三稀金属资源战略调查计划项目(1212011220803)

详细信息

作者简介: 段凯波, 博士, 高级工程师, 主要从事沉积矿床地质学研究. E-mail:duankaibo@sina.com

中图分类号: O657.34;O657.63;P595

收稿日期: 2014-11-26

修回日期: 2015-02-16

录用日期: 2015-03-05

刊出日期: 2015-02-25

Study on Geochemical Characteristics of Rare Earth Elements of Xinhua Phosphate Rocks in the Upper Yangtze, South China by ICP-MS/AES and Its Sedimentology Implications

1.
General Institute of Chemical Geology Survey, China Chemical Geology and Mine Bureau, Beijing 100013, China

2.
Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China

3.
Analysis and Testing Centre, Geological Institute of China Chemical Geology and Mine Bureau, Zhuozhou 072750, China

Received Date: 26 November 2014

Revised Date: 16 February 2015

Accepted Date: 05 March 2015

Publish Date: 25 February 2015

摘要

摘要:
新华磷矿床是我国重要的富集稀土元素的沉积型含稀土磷块岩矿床, 本文利用电感耦合等离子体质谱/光谱法(ICP-MS/AES), 辅以岩矿鉴定等分析技术, 结合沉积学理论研究了新华磷块岩稀土元素地球化学特征及相关问题。结果表明, 新华磷块岩稀土总量(∑REEs)较高, 集中值介于800×10^-6~1200×10^-6, 其组成属轻稀土+钇型, 稀土元素主要以类质同象形式存在于胶磷矿中; 新华磷块岩和昆阳磷块岩具相似的REEs配分曲线和明显铈负异常, δCe介于0.28~0.36, 表明上扬子区南缘成磷环境为氧化条件, 且为稳定的滨浅海被动大陆边缘沉积环境; 但新华磷块岩与其上覆黑色岩系REEs配分曲线迥异, 后者表现出不明显的铈、铕异常, 说明黑色岩系主要形成于深海-半深海静水还原环境, 从梅树村期早期至晚期经历了海平面升高的过程, 地层层序整体显示向上变深的沉积相变, 磷块岩和黑色岩系之间的接触面可能为三级层序甚至更小层序级别的界面。这些沉积学的认识揭示了上扬子区下寒武统层序地层学意义和海相沉积环境特征, 对华南早寒武世生命大爆发和层序地层学深入研究提供了证据。
- 新华磷块岩 /
- 昆阳磷块岩 /
- 黑色岩系 /
- 稀土元素特征 /
- 沉积环境 /
- 层序地层 /
- 电感耦合等离子体质谱/光谱法(ICP-MS/AES)
Abstract:
Xinhua phosphorus is a sedimentary phosphate deposit in China with strong REEs enrichment. In this study, Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES) as well as rock-mineral identification, major and trace elements analysis together with sedimentology theory have been used to study geochemical characteristics of REEs in Xinhua phosphate rocks. ∑REEs of Xinhua phosphate rocks range from 800×10^-6 to 1200×10^-6 and are dominated by LREEs and Yttrium. REEs occur in collophanite by isomorphism dominantly. REEs pattern curves show remarkably negative Ce anomaies with values ranging from 0.28 to 0.36 in Xinhua phosphate rocks, which are similar to those of Kunyang phosphate rocks, indicating phosphorus in the south of the upper Yangtze was formed in an oxidative environment and precipitated at the stable epicontinental sea of the passive continental margin. However, REEs pattern curves of the upper black shales and weak Ce and Eu anomalies are different from those of Xinhua phosphate rocks, which reflect black shales were formed in a deep and bathyal sea of a reductive environment. The Meishucunian period had a transgression process and the Meishucunian stage had an upward deep regressive sequence, the boundary between phosphate rocks and black shales possibly being a third-order even less scale sequence boundary. All of this sedimentology information is helpful to reveal the sequence of stratigraphy and marine sedimentary environment, which provides evidence for biological outbreak and stratigraphy sequence of early Cambrian in the Yangtze area, South China.
- Xinhua phosphate rock /
- Kunyang phosphate rock /
- black shale /
- REEs /
- sedimentary environment /
- sequence stratigraphy /
- Inductively Coupled Plasma-Mass Spectrometry/Atomic Emission Spectrometry(ICP-MS/AES)

HTML全文

图 1 新华磷块岩显微特征及其产出状态

Figure 1.

下载: 全尺寸图片幻灯片

图 2 磷块岩和黑色岩系稀土元素标准化的REEs配分曲线

Figure 2.

下载: 全尺寸图片幻灯片

表 1 新华磷块岩中稀土元素ICP-MS分析结果

Table 1. ICP-MS analytical results for REEs in Xinhua phosphate rock samples

样品编号	岩性	稀土元素含量(10^-6)
样品编号	岩性	La	Ce	Pr	Nd	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu	Y	∑REEs
S01	灰色磷块岩	214.6	119.9	33.26	142.0	24.21	5.98	26.10	4.12	24.51	5.06	13.54	1.71	8.56	1.30	297.2	921.84
S02	灰色磷块岩	210.9	109.4	31.20	130.4	23.05	5.25	25.69	4.10	24.36	5.26	14.36	1.80	8.85	1.31	317.5	913.35
S03	灰色磷块岩	281.3	142.7	39.15	166.1	28.19	6.45	31.45	5.03	30.33	6.42	17.45	2.19	10.64	1.60	395.7	1164.63
S04	灰色磷块岩	253.9	125.4	35.23	149.2	25.45	5.71	28.32	4.58	27.29	5.90	15.85	2.01	10.32	1.54	364.3	1054.89
S05	灰色磷块岩	313.1	171.2	45.89	193.0	32.26	7.98	34.39	5.22	29.68	6.08	16.30	2.02	10.14	1.51	358.2	1226.91
S06	硅质磷块岩	217.6	115.1	31.48	133.5	22.03	4.91	23.66	3.72	21.62	4.60	12.37	1.52	7.73	1.16	306.4	907.23
S07	硅质磷块岩	106.5	61.9	15.03	65.1	11.04	2.61	12.89	2.11	13.53	2.96	8.07	1.04	5.36	0.80	178.8	487.62
S08	暗红色磷块岩	182.0	107.3	25.18	110.1	18.89	4.67	22.03	3.66	22.79	4.92	13.32	1.66	8.30	1.22	297.5	823.37
S09	灰黑色磷块岩	213.2	113.9	29.83	126.1	21.26	4.95	24.19	3.86	23.23	5.02	13.66	1.67	8.28	1.22	309.2	899.44
S10	灰红色磷块岩	184.7	125.9	33.85	150.8	27.30	8.47	29.39	4.64	26.21	5.19	13.19	1.58	7.50	1.01	300.7	920.30
S11	灰黑色磷块岩	229.4	125.8	33.26	138.7	23.44	5.49	25.65	4.10	23.61	4.96	13.43	1.67	8.22	1.22	310.5	949.32
S12	灰黑色磷块岩	193.2	106.8	28.89	124.5	21.55	5.69	24.75	4.00	23.85	5.04	13.38	1.62	8.10	1.18	308.9	871.29
S13	灰黑色磷块岩	256.9	134.2	36.56	158.3	27.56	6.25	30.59	4.98	29.75	6.30	16.64	2.06	10.06	1.47	385.8	1107.35
S14	灰黑色磷块岩	561.7	275.9	68.78	301.9	53.76	17.56	58.50	8.99	50.80	9.99	26.01	3.12	14.80	2.13	668.3	2122.11
S15	暗红色磷块岩	210.0	131.5	34.69	151.3	26.84	7.98	29.99	4.70	27.46	5.54	14.49	1.74	8.36	1.20	329.6	985.23
S16	黑色岩系	50.9	78.6	10.73	43.1	8.59	2.06	7.86	1.30	7.50	1.44	4.05	0.60	3.81	0.60	52.9	273.95
S17	风化磷块岩	343.7	176.9	47.87	204.6	35.22	9.07	39.04	6.38	37.91	8.03	21.62	2.74	13.78	2.02	578.0	1526.77
S18	风化磷块岩	381.7	204.1	53.78	232.6	41.26	10.39	45.27	7.36	43.87	9.05	24.12	2.99	15.08	2.17	649.6	1723.22
S19	灰色磷块岩	241.3	125.7	34.93	146.7	25.07	5.84	27.38	4.45	25.94	5.46	14.92	1.91	9.56	1.40	338.1	1008.56
S20	灰色磷块岩	254.2	138.6	37.64	159.4	26.83	7.11	29.85	4.67	27.93	5.89	15.99	1.99	9.69	1.48	372.6	1093.74

下载: 导出CSV

表 2 新华磷块岩中稀土元素地球化学特征

Table 2. Geochemistric characteristics of REEs in Xinhua phosphate rock samples

样号	S01	S02	S03	S04	S05	S06	S07	S08	S09	S10	S11	S12	S13	S14	S15	S16	S17	S18	S19	S20	平均值 (除S16外)
La/∑LREEs	0.40	0.41	0.42	0.43	0.41	0.41	0.41	0.41	0.42	0.35	0.41	0.40	0.41	0.44	0.37	0.26	0.42	0.41	0.42	0.41	0.41
Ce/∑LREEs	0.22	0.21	0.21	0.21	0.22	0.22	0.24	0.24	0.22	0.24	0.23	0.22	0.22	0.22	0.23	0.41	0.22	0.22	0.22	0.22	0.22
Nd/∑LREEs	0.26	0.26	0.25	0.25	0.25	0.25	0.25	0.25	0.25	0.28	0.25	0.26	0.26	0.24	0.27	0.22	0.25	0.25	0.25	0.26	0.25
Y/∑HREEs	0.78	0.79	0.79	0.79	0.77	0.80	0.79	0.79	0.79	0.77	0.79	0.79	0.79	0.79	0.78	0.66	0.81	0.81	0.79	0.79	0.79
∑LREEs/∑HREEs	1.41	1.27	1.33	1.29	1.65	1.37	1.16	1.19	1.30	1.36	1.41	1.23	1.27	1.52	1.33	2.42	1.15	1.16	1.35	1.33	1.32
∑LREEs/∑HREEs#	6.30	5.95	6.32	6.21	7.25	6.87	5.60	5.75	6.28	5.99	6.71	5.87	6.09	7.34	6.01	7.13	6.21	6.16	6.37	6.40	6.34
δCe(球粒陨石)	0.31	0.29	0.29	0.28	0.31	0.30	0.33	0.33	0.30	0.36	0.31	0.31	0.29	0.29	0.34	0.77	0.29	0.30	0.29	0.30	0.33
δEu(球粒陨石)	0.72	0.66	0.66	0.65	0.73	0.65	0.67	0.70	0.67	0.91	0.68	0.75	0.66	0.95	0.86	0.75	0.74	0.73	0.68	0.76	0.73
注：“∑HREEs#”为除Y外的重稀土元素含量。

下载: 导出CSV

表 3 碳氟磷灰石单矿物分析结果

Table 3. Analytical results of collophanite single mineral

组分	各样品中磷和稀土元素含量					S21/S22	S22/S23	S23/S24	S24/S25
组分	S21	S22	S23	S24	S25
P₂O₅	S21	S22	S23	S24	S25	32.25	35.37	36.90	33.76	31.12	0.91	0.96	1.09	1.08
La	369.0	389.0	446.5	432.2	316.0	0.95	0.87	1.03	1.37
Ce	194.0	186.0	216.7	222.6	153.3	1.04	0.86	0.97	1.45
Pr	50.80	53.40	61.17	60.97	43.86	0.95	0.87	1.00	1.39
Nd	212.0	225.0	256.6	257.0	187.2	0.94	0.88	1.00	1.37
Sm	35.70	37.80	43.17	42.50	32.06	0.94	0.88	1.02	1.33
Eu	9.02	8.29	9.93	10.32	7.62	1.09	0.83	0.96	1.35
Gd	38.80	41.80	48.68	47.82	37.58	0.93	0.86	1.02	1.27
Tb	6.30	6.90	7.96	7.88	6.25	0.91	0.87	1.01	1.26
Dy	37.00	41.30	45.98	44.91	36.96	0.90	0.90	1.02	1.22
Ho	7.71	8.68	9.56	9.28	7.88	0.89	0.91	1.03	1.18
Er	20.60	23.40	26.13	25.37	22.04	0.88	0.90	1.03	1.15
Tm	2.62	2.99	3.20	3.20	2.88	0.88	0.94	1.00	1.11
Yb	12.80	14.80	15.95	15.41	13.88	0.86	0.93	1.04	1.11
Lu	1.79	2.12	2.24	2.20	1.89	0.84	0.95	1.02	1.16
Y	606.0	689.0	625.0	582.3	513.7	0.88	1.10	1.07	1.13
∑REEs	1604.1	1730.5	1818.8	1764.0	1383.1	0.93	0.95	1.03	1.28
注：各样品中P₂O₅含量单位为%，REEs含量单位为10^-6。

下载: 导出CSV

参考文献(30)

[1]
[2]	http://www.cnki.com.cn/Article/CJFDTOTAL-XTXB201205018.htm
[3]	http://www.cnki.com.cn/Article/CJFDTOTAL-XTZZ200701021.htm
[4]	http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB201001017.htm
[5]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201401020.htm
[6]	doi: 10.1016/j.hydromet.2010.01.001
[7]	doi: 10.1007/s11814-010-0383-4
[8]	doi: 10.1016/j.mineng.2012.10.017
[9]	http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201409002.htm
[10]	doi: 10.1016/j.oregeorev.2012.06.003
[11]	http://www.cnki.com.cn/Article/CJFDTOTAL-DQKX201006007.htm
[12]	http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201207058.htm
[13]	http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201303050.htm
[14]	http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201501006.htm
[15]	http://www.cnki.com.cn/Article/CJFDTOTAL-DZLP201102003.htm
[16]	doi: 10.7605/gdlxb.2014.04.040
[17]	doi: 10.1130/G23543A.1
[18]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201401006.htm
[19]	http://www.cnki.com.cn/Article/CJFDTOTAL-DZKT201102022.htm
[20]	http://www.cnki.com.cn/Article/CJFDTOTAL-DZLP201402004.htm
[21]	http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB201406022.htm
[22]	http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201308011.htm
[23]	doi: 10.1016/j.marchem.2009.09.003
[24]	doi: 10.1016/j.precamres.2011.07.004
[25]	doi: 10.1016/j.earscirev.2009.03.001
[26]	http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB201308027.htm
[27]
[28]	doi: 10.1016/j.coal.2009.01.002
[29]	http://www.cnki.com.cn/Article/CJFDTOTAL-CJXB201404013.htm
[30]	doi: 10.1016/j.gca.2009.02.013

施引文献

资源附件(0)

访问统计

图(2)

表(3)

计量

文章访问数: 1420
PDF下载数: 787
施引文献: 0

应用电感耦合等离子体质谱/光谱法研究上扬子区新华磷块岩稀土元素特征及沉积学意义

1. 中化地质矿山总局化工地质调查总院, 北京 100013 2. 中国地质科学院矿产资源研究所, 北京 100037 3. 中化地质矿山总局地质研究院分析测试中心, 河北 涿州 072750

作者简介: 段凯波, 博士, 高级工程师, 主要从事沉积矿床地质学研究. E-mail:duankaibo@sina.com

Study on Geochemical Characteristics of Rare Earth Elements of Xinhua Phosphate Rocks in the Upper Yangtze, South China by ICP-MS/AES and Its Sedimentology Implications

计量

出版历程

目录

1.
中化地质矿山总局化工地质调查总院, 北京 100013

2.
中国地质科学院矿产资源研究所, 北京 100037

3.
中化地质矿山总局地质研究院分析测试中心, 河北涿州 072750