遵义下寒武统富硒黑色岩系地球化学: 成因和硒富集机理

冯彩霞; 刘燊; 胡瑞忠; 刘家军; 罗泰义; 池国祥; 齐有强

doi:10.3799/dqkx.2010.109

遵义下寒武统富硒黑色岩系地球化学: 成因和硒富集机理

doi: 10.3799/dqkx.2010.109

1.
中国科学院地球化学研究所矿床地球化学国家重点实验室, 贵州贵阳 550002
2.
中国地质大学地质过程与矿产资源国家重点实验室, 北京 100083
3.
Department of Geology, University of Regina, Saskatchewan S4S0A2, Canada

基金项目:

国家自然科学基金项目 40972071

国家自然科学基金项目 40773036

国家自然科学基金项目 40634020

贵州省科学技术基金项目黔科合J字[2008]2015号

详细信息

作者简介:
冯彩霞(1976-), 女, 副研究员, 主要从事分散元素地球化学研究.E-mail: fengcaixia@vip.gyig.ac.cn

中图分类号: P618.76
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- 被引次数: 0
出版历程
- 收稿日期: 2009-12-22
- 刊出日期: 2010-11-01

Geochemistry of Lower Cambrian Se-Rich Black Rock Series in Zunyi, Guizhou Province, Southwest China: The Petrogenesis and Enrichment Mechanism of Selenium

1.
State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China
2.
State Key Laboratory of Geological Process and Mineral Resources, China University of Geosciences, Beijing100083, China
3.
Department of Geology, University of Regina, Saskatchewan S4S0A2, Canada

摘要

摘要: 利用XRF、ICP-MS和氢化物原子荧光光谱测试方法系统分析了贵州遵义下寒武统富硒黑色岩系中钾质斑脱岩、磷块岩、黑色页岩、硅质岩和Ni-Mo金属层样品中的主元素、微量元素、稀土元素及分散元素Se的组成.地球化学研究表明: 该套黑色岩系在成因上主要表现为热水沉积特征, 同时存在火山活动的影响.另外, 各层位样品都具有分散元素硒的富集异常特征.综合研究表明, 研究区分散元素硒的富集可能与大量硫化物的存在、热水沉积作用和火山作用有关.
- 地球化学 /
- 黑色岩系 /
- 下寒武统 /
- 遵义
Abstract: Herein, XRF, ICP-MS and hydride generation atomic fluorescence spectrometry (HGAFS) techniques were used to analyze the major, trace elements and Se contents of the Se-rich black rock series in Zunyi, Guizhou Province, respectively. Based on the elemental geochemistry, we suggest that the Se-rich black rock series, including K-bentonite, phosphrite, black shales, cherts and Ni-Mo ore samples, mainly formed by hydrothermal deposition. Meanwhile, the petrogenesis of the black rock series was related with volcanism. Furthermore, K-bentonite, phosphrite, black shales, chert and Ni-Mo ore samples are characterized by high Se contents, and high enrichment coefficients correspond to those of the crust (801, 531.2, 449, 123 and 11 133). Combining with previous studies, we propose that the enrichment of Se in study area is related to many factors, such as existence of abundant sulfide, hydrothermal deposition and volcanism.
- geochemistry /
- black rock series /
- Lower Cambrian /
- Zunyi

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图 1 研究区地质略图以及采样位置(据张光弟等，2002修改)

1.南沱组；2.陡山沱组；3.灯影组；4.牛蹄塘组；5.明心寺组；6.明心寺组与金顶山组并层；7.清虚洞组；8.断层；9.地质界线；10.采样地点

Fig. 1. Sample location and geological sketch map of the study area

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图 2 遵义下寒武统富硒黑色岩系微量元素蛛网

Fig. 2. Trace elements spider diagram of the Lower Cambrian Se-rich black rock series in Zunyi

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图 3 遵义下寒武统富硒黑色岩系陨石和北美页岩稀土元素标准化模式

Fig. 3. Chondrite-normalized and North American shale-normalized REE patterns of the Lower Cambrian Se-rich black rock series in Zunyi, Guizhou Province

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图 4 黑色岩系Zn-Co-Ni图解(Jai and Yu, 1992)

Ⅰ.海底热水沉积；Ⅱ.水成沉积型深海锰结核

Fig. 4. Zn-Co-Ni diagram of the black rock series

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表 1 遵义下寒武统富硒黑色岩系常量元素含量(%)

Table 1. Major element contents (%) of the Lower Cambrian Se-rich black rock series in Zunyi, Guizhou Province

样品号	岩性	SiO₂	Al₂O₃	Fe₂O₃	MgO	CaO	Na₂O	K₂O	MnO	P₂O₅	TiO₂	LOI	Total
znrp3-2	钾质斑脱岩	54.26	22.54	2.10	2.16	0.06	0.07	5.59	0.11	1.17	0.22	11.54	99.82
znrp3-3	钾质斑脱岩	54.17	25.45	1.68	2.23	0.00	0.01	6.80	0.12	0.20	0.21	9.51	100.38
znrp3-4	钾质斑脱岩	52.11	22.85	9.15	2.61	0.39	0.04	5.89	0.02	0.47	0.18	6.71	100.43
znrp3-6	钾质斑脱岩	57.72	25.38	3.09	2.61	0.07	0.05	6.72	0.01	0.19	0.18	4.37	100.39
znrp3-8	钾质斑脱岩	55.80	15.94	1.30	2.02	0.10	0.08	4.30	0.06	0.58	0.62	12.06	92.86
znc-8	钾质斑脱岩	50.23	15.83	13.85	3.99	0.80	0.04	4.39	0.01	1.11	0.61	9.52	100.39
znrp3-12	磷块岩	18.43	9.47	14.23	2.26	10.92	0.05	1.91	0.02	14.06	0.37	28.67	100.39
znrp3-13	磷块岩	18.51	9.87	22.62	1.51	0.49	0.05	1.05	0.01	16.07	0.20	30.03	100.40
znrp3-14	钙质磷块岩	0.06	1.17	2.02	0.05	37.20	0.04	0.22	0.02	28.27	0.02	31.12	100.20
znc-6	钙质磷块岩	0.80	2.00	5.49	0.25	31.16	0.04	0.34	0.01	27.34	0.04	32.45	99.92
znc-9	钙质磷块岩	6.61	6.19	8.64	1.43	24.38	0.06	1.33	0.00	20.23	0.18	31.30	100.35
znrp3-15	黑色页岩	36.88	12.80	6.49	1.29	8.41	0.07	2.93	0.12	8.07	0.53	22.75	100.33
znrp3-16	黑色页岩	65.69	11.78	5.39	1.11	1.62	0.64	2.50	0.08	0.73	0.58	8.73	98.86
xz-1	黑色页岩	61.09	11.05	4.83	1.58	2.20	1.23	1.97	0.08	0.67	0.49	14.30	99.50
xz-2	黑色页岩	54.57	18.37	1.23	2.97	0.13	0.09	4.73	0.08	0.31	0.18	16.04	98.70
xz-7	黑色页岩	59.67	12.99	4.88	1.85	3.53	1.47	2.38	0.19	0.18	0.49	12.01	99.65
znc-7-1	黑色页岩	62.23	20.31	6.35	2.46	0.06	0.00	5.13	0.02	1.17	0.29	8.80	106.81
znc-10-1	碳硅质页岩	72.87	16.97	3.73	1.35	0.32	0.33	4.02	0.01	0.11	0.57	0.12	100.40
znrp3-5	碳硅质页岩	65.86	16.21	4.94	1.97	0.37	0.02	3.95	0.14	1.01	0.17	5.78	100.41
xz-8	碳硅质页岩	63.55	13.68	5.11	1.39	0.75	0.96	2.71	0.04	0.44	0.55	10.63	99.81
znc-1	碳硅质页岩	72.44	10.28	0.76	0.78	0.11	0.47	2.63	0.02	0.33	0.66	10.90	99.38
znc-2	碳硅质页岩	71.59	8.81	2.09	0.81	0.13	0.05	2.34	0.01	1.80	0.42	12.32	100.37
znc-3	碳硅质页岩	65.29	6.65	0.65	0.56	0.41	0.11	1.64	0.02	0.64	0.26	23.32	99.55
znc-4	碳硅质页岩	66.38	7.05	0.69	0.63	2.23	0.08	1.76	0.01	2.72	0.29	18.97	100.81
znc-5	碳硅质页岩	70.98	6.93	1.16	0.61	2.76	0.05	1.73	0.02	3.48	0.29	13.33	101.34
xz-6	钙质页岩	34.80	4.72	1.84	10.72	19.45	0.09	0.83	0.71	0.08	0.20	26.48	99.92
znrp3-7	硅质岩	91.13	1.77	1.68	0.16	0.01	0.01	0.42	0.12	0.36	0.07	4.73	100.46

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表 2 遵义下寒武统富硒黑色岩系微量元素含量(μg/g)

Table 2. Trace element and REE content (μg/g) of the Lower Cambrian Se-rich black rock series in Zunyi, Guizhou Province

样品号	V	Cr	Co	Ni	Cu	Zn	As	Rb	Sr	Mo	Sb	Ba	Pb	Bi	Th	U	Ba/Sr	U/Th
znrp3-2	2 100	149	5.76	37.0	51.4	70.7	49.4	188	36.8	68.9	1.88	3 790	13.4	0.76	31.1	26.7	103	0.86
znrp3-3	1 810	151	2.89	14.7	40.5	16.1	21.2	161	13.0	32.1	1.98	4 270	10.3	0.70	28.0	29.8	328	1.06
znrp3-4	1 390	113	3.52	13.4	92.2	24.3	25.0	148	15.5	36.6	1.63	3 970	13.1	0.68	25.1	27.7	256	1.10
znrp3-6	276	9.11	3.70	10.1	45.6	24.4	33.7	136	65.2	23.9	2.23	8 680	66.6	1.11	31.8	13.0	133	0.41
znrp3-8	727	696	58.8	40.4	59.6	35.7	26.3	165	59.7	20.5	1.99	6 960	20.8	0.58	12.6	46.4	117	3.68
znc-8	132	99	47.8	37.5	87.3	119	39.2	156	37.2	31.0	3.29	3 470	48.4	0.29	5.06	26.5	93.3	5.24
Ⅰ	7.50	1.60	0.83	0.31	1.12	0.63	16.00	1.47	0.10	24.83	4.28	11.21	2.05	0.36	2.93	13.70
znrp3-12	783	351	13.6	16.7	55.9	26.8	25.5	103	200	29.6	2.71	2 920	150	0.25	6.73	151	14.6	22.4
znrp3-13	1 410	1 030	24.3	16.8	39.2	52.9	45.8	53.1	87.4	36.7	3.23	5 160	120	0.29	7.04	94.4	59.04	13.4
znrp3-14	535	413	16.4	47.2	18.7	65.1	14.6	12.3	517	4.71	1.00	985	70.0	0.19	2.69	149	1.91	55.3
znc-6	621	408	24.8	48.7	21.9	24.8	20.4	19.7	307	17.1	1.51	1 670	101	0.14	1.71	276	5.44	161
znc-9	772	343	19.0	33.7	40.8	43.7	30.0	73.2	555	27.7	1.97	5 330	69.1	0.15	3.42	107	9.60	31.3
Ⅱ	5.76	4.01	0.79	0.40	0.63	0.56	13.43	0.48	0.87	16.20	4.12	6.94	7.29	0.11	0.57	75.08
znrp3-15	1 810	2 620	46.6	413	92.9	808	64.7	120	187	14.6	6.35	2 530	30.5	0.36	18.5	31.6	13.5	1.71
znrp3-16	251	103	45.4	865	59.6	686	98.2	94.5	87.2	428	9.96	1 470	71.7	0.54	11.1	73.0	16.9	6.58
xz-1	322	82.5	57.4	516	85.1	632	64.4	92.9	128	545	7.63	1 020	76.7	0.57	10.1	120	8.0	11.9
xz-2	1 530	165	16.8	75.50	29.5	77.7	29.8	142	45.9	298	2.28	11 900	22.2	0.75	30.0	19.6	259	0.65
xz-7	348	78.6	26.6	228	51.2	244	33.2	116	144	94.3	4.56	1 490	39.5	0.31	9.35	26.5	10.3	2.83
znc-7-1	920	131	38.8	42.9	39.9	61.5	56.2	189	37.1	42.2	2.09	3 570	38.8	0.67	23.3	46.6	96.2	2.00
znc-10-1	52.6	21.0	22.9	16.3	3.14	61.4	8.62	143	48.6	0.74	0.44	431	6.03	0.11	12.1	2.18	8.87	0.18
znrp3-5	694	211	39.8	59.8	50.7	143	58.6	128	76.0	67.2	2.60	8 230	52.2	0.69	22.4	28.0	108	1.25
xz-8	461	100	45.9	1110	79.7	485	162	131	68.3	360	8.64	1 500	76.4	0.55	11.2	98.8	22.0	8.82
znc-1	3 720	735	31.2	50.9	7.56	23.9	58.4	119	23.7	53.4	7.51	2 210	32.6	0.32	8.85	19.7	93.2	2.23
znc-2	1 090	1 290	27.0	56.0	42.6	22.3	28.1	97.1	14.9	32.0	1.86	2 030	18.0	0.35	7.07	25.5	136	3.61
znc-3	1 000	953	83.2	69.7	11.9	42.6	19.1	69.1	22.3	41.6	1.82	1 420	14.8	0.24	5.30	19.0	63.7	3.58
znc-4	1 050	1 080	102	68.4	18.9	38.9	19.0	73.2	46.6	23.1	1.99	1 460	16.0	0.26	5.23	22.4	31.3	4.28
znc-5	744	542	68.4	44.9	31.6	19.6	18.0	74.4	63.6	31.0	1.92	2 650	18.4	0.22	5.63	25.8	41.7	4.58
xz-6	138	25	23.2	449	11.6	122	25.5	36.8	242	18.9	2.22	919	17.1	0.08	3.92	6.75	3.80	1.72
Ⅲ	6.59	4.27	1.82	3.33	0.73	3.03	24.42	1.00	0.22	95.57	8.14	6.17	2.53	0.21	1.61	18.21
znrp3-7	706	664	56.9	37.9	56.4	34.2	26.1	165	59.8	20.0	1.94	7 030	21.2	0.62	12.8	48.3	118	3.77
Ⅳ	4.94	5.23	2.30	0.47	1.01	0.45	12.87	1.53	0.16	13.99	3.82	15.18	1.51	0.33	1.68	23.33
ZNRP3-18	221	54.3	178	18 700	852	2 140	4 469	8.44	167	38 900	235	862	440	11.9	3.27	48.2	5.16	14.7
ZY-2	584	48.1	207	24 500	755	5 530	5 226	21.0	349	59 600	287	519	882	5.56	3.63	515	1.49	142
Ⅴ	2.81	0.40	7.79	266	14.35	50.26	2 388	0.14	0.68	34 441	514	1.49	47.21	4.59	0.45	136
Ⅵ	143	127	24.7	81.3	56	76.3	2.03	108	382	1.43	0.507	463	14	1.9	7.6	2.07
注：Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ和Ⅵ分别代表钾质斑脱岩、磷块岩、黑色页岩、硅质岩、Ni-Mo和地壳元素丰度值；富集层样品中各微量元素平均值相对地壳元素丰度值的富集系数；地壳元素丰度值据黎彤，1992.

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表 3 遵义下寒武统富硒黑色岩系稀土元素含量(μg/g)及相关参数

Table 3. REE content (μg/g) and relative parameters of the Lower Cambrian Se-rich black rock series in Zunyi, Guizhou Province

样品号	La	Ce	Pr	Nd	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu	∑REE	LREE/HREE	(La/Yb)_n	(La/Sm)_n	(Gd/Yb)_n	δ Eu_s	δCe_s
znrp3-2	63.1	131.0	17.7	69.5	16.3	1.00	13.4	2.56	15.5	3.56	9.91	1.53	10.3	1.44	357	5.13	4.14	2.44	1.05	0.30	0.85
znrp3-3	23.7	49.8	7.05	28.5	6.93	0.37	6.28	1.34	9.32	2.27	6.86	1.09	7.95	1.16	153	3.21	2.01	2.15	0.64	0.24	0.84
znrp3-4	28.4	57.9	8.15	32.7	7.94	0.43	7.22	1.59	10.8	2.67	7.64	1.22	8.48	1.20	176	3.32	2.26	2.25	0.69	0.25	0.83
znrp3-6	79.8	164.0	21.7	83.7	20.3	0.61	16.3	3.02	18.0	4.12	11.6	1.68	11.1	1.55	437	5.50	4.86	2.47	1.19	0.15	0.86
znrp3-8	12.6	20.0	4.94	26.0	8.45	0.59	9.56	1.84	11.7	2.72	7.52	1.18	8.28	1.20	117	1.65	1.03	0.94	0.94	0.29	0.55
znc-8	11.5	18.8	5.3	28.5	8.22	1.36	8.01	1.34	7.61	1.59	3.86	0.49	2.96	0.40	100	2.81	2.63	0.88	2.19	0.73	0.52
znrp3-12	132.0	161.0	39.2	166.0	36.8	7.57	32.9	5.66	31.6	6.64	16.1	1.99	11.7	1.34	651	5.02	7.62	2.26	2.28	0.95	0.49
znrp3-13	49.3	87.5	18.0	70.2	14.7	3.12	9.73	1.95	9.83	2.06	5.96	0.94	8.21	1.24	283	6.08	4.06	2.11	0.96	1.15	0.64
znrp3-14	156.0	146.0	37.0	163	33.5	7.78	34.0	6.77	40.2	9.71	25.8	3.06	16.7	2.17	682	3.93	6.31	2.93	1.65	1.01	0.42
znc-6	127.0	124.0	29.5	127	26.3	5.82	26.3	4.55	27.1	6.51	17.1	2.16	12.3	1.59	537	4.50	6.98	3.04	1.73	0.97	0.44
znc-9	184.0	215.0	50.5	210	45.3	9.49	40.3	7.07	40.0	8.84	21.6	2.62	14.3	1.64	851	5.24	8.69	2.56	2.28	0.98	0.49
znrp3-15	52.3	63.5	11.8	52.1	12.30	2.70	11.55	2.37	14.00	3.26	9.09	1.30	8.78	1.33	246	3.77	4.03	2.68	1.07	1.00	0.56
znrp3-16	49.6	89.4	9.13	35.7	6.69	1.56	5.85	1.17	6.58	1.55	4.33	0.55	3.37	0.49	216	8.04	9.95	4.67	1.41	1.09	0.92
xz-1	48.3	78.4	9.15	35.8	6.83	1.38	6.07	1.05	6.13	1.45	3.85	0.51	3.03	0.41	202	7.99	10.77	4.45	1.62	0.94	0.81
xz-2	57.6	120.0	16.0	64.1	17.0	0.51	16.4	3.22	20.3	4.58	12.5	1.86	12.3	1.67	348	3.78	3.16	2.13	1.08	0.14	0.86
xz-7	21.9	42.2	5.30	20.6	4.52	0.80	3.67	0.66	4.02	0.94	2.66	0.37	2.42	0.36	110	6.32	6.12	3.05	1.23	0.86	0.85
znc-7-1	48.5	98.8	14.2	59.6	14.6	1.14	11.8	2.16	12.5	2.79	7.46	1.09	7.21	0.96	283	5.15	4.55	2.09	1.32	0.38	0.82
znc-10-1	37.9	78.4	9.18	34.9	6.71	1.18	4.79	0.92	5.42	1.23	3.42	0.50	3.59	0.49	189	8.26	7.13	3.56	1.08	0.91	0.92
znrp3-5	53.4	103.0	14.8	60.5	16.0	1.28	15.7	3.11	19.5	4.40	11.7	1.68	10.4	1.41	317	3.67	3.47	2.10	1.22	0.35	0.80
xz-8	29.9	56.3	6.86	27.1	5.30	1.01	4.34	0.77	4.31	1.00	2.66	0.37	2.43	0.34	143	7.80	8.31	3.55	1.45	0.92	0.86
znc-1	27.7	40.8	5.30	18.5	2.74	0.45	1.97	0.36	2.16	0.57	1.82	0.29	2.00	0.29	105	10.1	9.36	6.36	0.80	0.86	0.73
znc-2	20.6	21.8	3.96	16.7	3.37	0.57	4.00	0.75	5.74	1.72	5.37	0.81	5.37	0.77	92	2.73	2.59	3.85	0.60	0.69	0.53
znc-3	27.7	31.1	6.12	25.4	5.42	0.94	5.36	0.97	6.43	1.64	4.65	0.64	3.94	0.53	121	4.00	4.75	3.22	1.10	0.77	0.52
znc-4	18.0	24.5	5.32	23.1	5.36	1.01	5.04	0.89	5.75	1.49	4.15	0.59	3.63	0.51	99	3.51	3.35	2.11	1.12	0.85	0.55
znc-5	16.7	27.5	6.24	27.3	6.75	1.31	5.46	0.97	5.68	1.27	3.48	0.47	2.98	0.41	107	4.14	3.79	1.56	1.48	0.94	0.59
xz-6	12.2	22.1	2.82	11.0	2.60	0.42	2.31	0.41	2.59	0.59	1.68	0.24	1.59	0.22	61	5.31	5.18	2.95	1.18	0.75	0.82
znrp3-7	12.4	20.1	4.95	26.3	8.60	0.63	9.26	1.80	11.8	2.78	7.62	1.19	8.09	1.23	117	1.67	1.04	0.91	0.93	0.31	0.56
ZNRP3-18	37.9	66.1	7.55	32.5	6.50	1.69	5.81	1.08	6.00	1.35	3.29	0.39	2.03	0.28	172	7.53	12.6	3.67	2.32	1.21	0.85
ZY-2	98.1	126.0	20.2	88.4	16.9	4.25	17.08	2.77	16.1	3.76	9.27	1.08	5.67	0.68	410	6.27	11.7	3.65	2.44	1.10	0.62
注：北美页岩标准化REE数据据Sun and McDonough, 1989；δCe_s和δEu_s指北美页岩标准化后计算的值；δCe=Ce_s/Ce^；Ce^=(La_s·Pr_s)^1/2；δEu_s=Eu_s/Eu^；Eu^=(Sm_s·Gd_s)^1/2.

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表 4 遵义下寒武统富硒黑色岩系分散元素Se含量(μg/g)

Table 4. The Se content (μg/g) of the Lower Cambrian Se-rich black rock series in Zunyi, Guizhou Province

样品	Se	样品	Se	样品	Se	样品	Se	样品	Se	富集系数
znrp3-2	30.3	znrp3-12	118	znrp3-15	2.34	znc-10-1	20.1	znc-4	20.1	Ⅰ	801
znrp3-3	16.9	znrp3-13	46.1	znrp3-16	34.6	znrp3-5	82.2	znc-5	15.6	Ⅱ	531.2
znrp3-4	78.6	znrp3-14	1.20	xz-1	39.2	xz-8	44.9	xz-6	21.8	Ⅲ	449
znrp3-6	219	znc-6	5.24	xz-2	36.9	znc-1	20.9	ZNRP3-18	1 006	Ⅳ	123
znrp3-8	11.4	znc-9	68.5	xz-7	44.9	znc-2	89.4	ZY-2	998	Ⅴ	11 133
znc-8	76.3	znrp3-7	11.1	znc-7-1	104	znc-3	28.7	地壳丰度	0.09
注：Ⅰ、Ⅱ、Ⅲ、Ⅳ和Ⅴ分别代表钾质斑脱岩、磷块岩、黑色页岩、硅质岩和Ni-Mo富集层样品中分散元素Se平均含量相对地壳元素丰度值的富集系数；地壳元素丰度值据黎彤，1992.

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