贵州紫云方解石矿床地球化学特征及成因研究

摘要/Abstract

摘要：

贵州紫云方解石矿床是在贵州西南部新发现的非金属矿床,方解石矿体呈脉状、透镜状和似层状产出。对紫云火山关、达则等方解石矿床开展同位素地球化学及微量元素、稀土元素研究,结果表明碳、氧同位素显示成矿物质来源于海相碳酸盐岩,成矿流体以富含$\mathrm{HCO}_{3}{ }^{-}$为主,大气水参与成矿,与岩浆作用关系不大。其中达则矿段相对于围岩,成矿物质具有较高的Sr、Zn和Ni含量,稀土元素配分曲线明显区别于围岩,δEu显示正异常等特征,暗示可能有深部流体参与成矿。火山关、打劳等其他矿段,矿体和围岩具有相似的稀土配分模式和∑REE变化规律,表明成矿物质来源于碳酸盐岩围岩。通过区域成矿作用比较,认为成矿时代可能属于印支—燕山期。

关键词: 地球化学特征, 碳、氧同位素, 方解石矿床, 紫云, 贵州

Abstract:

The Ziyun calcite deposit is a newly discovered non-metallic deposit in southwest of Guizhou Pro-vince. Orebodies are veined, lenticulared or stratoid in form and are hosted in the carbonate rocks and are found to have been developed in the faults. Calcite is the dominant mineral.The ores revealed a variety of hydrothermal structural characteristics. Ore samples were collected from Huoshanguan, Daze, etc. at Ziyun County and were tested for the isotope geochemistry, trace and rare earth element contents. The carbon and oxygen isotope geochemistry indicate that metallogenetic material came from marine carbonate rocks. Ore-forming fluids are dominated by $\mathrm{HCO}_{3}{ }^{-}$, and thus a great amount of precipitation is added in the following mineralization, which has not a close relationship with magma. In contrast to the surrounding rocks, the Daze ore block has obvious characteristics by analysis of different REE distribution patterns, Eu positive anomalies and high content of Sr, Zn and Ni. This indicates that the ore-forming fluid was probably from deep source evolved in the process of mineralization of the Daze ore block. Both the orebodies and the surrounding rocks have similar REE distribution pattern and regularity variation of ∑REE in the Huoshanguan, Dalao and other ore blocks, which shows that the metallogenetic material may come from carbonate rocks. Compared with the regional mineralization, metallogenetic epoch of the calcite deposit could be Indo-Yanshanian.

Key words: geochemical characteristic, carbon and oxygen isotope, calcite deposit, Ziyun County, Guizhou Province

中图分类号:

P619.2

曹正端, 杨瑞东, 高军波, 陈军, 张伟, 沈明联, 张旭, 李纪. 贵州紫云方解石矿床地球化学特征及成因研究[J]. 现代地质, 2017, 31(04): 757-767.

CAO Zhengduan, YANG Ruidong, GAO Junbo, CHEN Jun, ZHANG Wei, SHEN Minglian, ZHANG Xu, LI Ji. Study on Geochemical Characteristics and Genesis of Calcite Deposit from Ziyun County, Guizhou Province, China[J]. Geoscience, 2017, 31(04): 757-767.

图/表 9

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样品号	样品产地	测试对象	δ¹³C_PDB/ ‰	δ¹⁸O_PDB/ ‰	δ¹⁸O_SMOW/ ‰
Dz1	达则	顶板(灰岩)	2.878	-4.763	26.000
Dz2	达则	顶板(灰岩)	3.110	-4.474	26.298
Dz5	达则	夹石(灰岩)	2.723	-3.729	27.066
Dz11	达则	底板(灰岩)	3.233	-4.115	26.668
Dz12	达则	底板(灰岩)	3.299	-3.265	27.544
Dz3	达则	矿体(方解石)	-3.064	-14.019	16.458
Dz4	达则	矿体(方解石)	-1.455	-13.663	16.824
Dz7	达则	矿体(方解石)	-0.696	-12.492	18.032
Dz8	达则	矿体(方解石)	-0.779	-13.509	16.984
Dz10	达则	矿体(方解石)	-2.961	-15.732	14.692
HSG1	火山关	围岩(灰岩)	-0.209	-4.947	25.810
HSG2	火山关	围岩(灰岩)	-0.796	-4.725	26.039
HSG10	火山关	围岩(灰岩)	1.202	-3.689	27.107
HSG11	火山关	围岩(灰岩)	1.398	-4.750	26.013
HSG4	火山关	矿体(方解石)	0.603	-12.795	17.719
HSG5	火山关	矿体(方解石)	4.534	-14.671	15.785
HSG6	火山关	矿体(方解石)	0.081	-12.957	17.552
HSG7	火山关	矿体(方解石)	0.422	-13.225	17.276
HSG8	火山关	矿体(方解石)	2.838	-14.983	15.464
HSG9	火山关	矿体(方解石)	4.488	-15.069	15.375
gz01	狗漳	矿体(方解石)	0.304	-14.146	16.327
dl01	打劳	矿体(方解石)	4.608	-15.080	15.364
dl03	打郎	矿体(方解石)	3.630	-14.014	16.463
db02	大坝	矿体(方解石)	2.865	-16.301	14.105
cb01	仓旁	矿体(方解石)	1.580	-13.451	17.043
nb02	泥巴地	矿体(方解石)	2.784	-14.332	16.135

样品号	样品产地	测试对象	δ¹³C_PDB/ ‰	δ¹⁸O_PDB/ ‰	δ¹⁸O_SMOW/ ‰
Dz1	达则	顶板(灰岩)	2.878	-4.763	26.000
Dz2	达则	顶板(灰岩)	3.110	-4.474	26.298
Dz5	达则	夹石(灰岩)	2.723	-3.729	27.066
Dz11	达则	底板(灰岩)	3.233	-4.115	26.668
Dz12	达则	底板(灰岩)	3.299	-3.265	27.544
Dz3	达则	矿体(方解石)	-3.064	-14.019	16.458
Dz4	达则	矿体(方解石)	-1.455	-13.663	16.824
Dz7	达则	矿体(方解石)	-0.696	-12.492	18.032
Dz8	达则	矿体(方解石)	-0.779	-13.509	16.984
Dz10	达则	矿体(方解石)	-2.961	-15.732	14.692
HSG1	火山关	围岩(灰岩)	-0.209	-4.947	25.810
HSG2	火山关	围岩(灰岩)	-0.796	-4.725	26.039
HSG10	火山关	围岩(灰岩)	1.202	-3.689	27.107
HSG11	火山关	围岩(灰岩)	1.398	-4.750	26.013
HSG4	火山关	矿体(方解石)	0.603	-12.795	17.719
HSG5	火山关	矿体(方解石)	4.534	-14.671	15.785
HSG6	火山关	矿体(方解石)	0.081	-12.957	17.552
HSG7	火山关	矿体(方解石)	0.422	-13.225	17.276
HSG8	火山关	矿体(方解石)	2.838	-14.983	15.464
HSG9	火山关	矿体(方解石)	4.488	-15.069	15.375
gz01	狗漳	矿体(方解石)	0.304	-14.146	16.327
dl01	打劳	矿体(方解石)	4.608	-15.080	15.364
dl03	打郎	矿体(方解石)	3.630	-14.014	16.463
db02	大坝	矿体(方解石)	2.865	-16.301	14.105
cb01	仓旁	矿体(方解石)	1.580	-13.451	17.043
nb02	泥巴地	矿体(方解石)	2.784	-14.332	16.135

采样地点	样号	岩性	Co	Ni	Cu	Zn	Rb	Sr	Zr	Nb	Ba	Hf	Ta	Pb	Th	U	Th/U
达则矿段	Dz3	矿体(方解石)	1.080	23.50	2.316	172.331	-	206.0	0.209	0.008	-	0.020	0.005	3.34	0.014	0.364	0.038
	Dz4	矿体(方解石)	0.971	18.40	1.158	169.652	-	508.0	0.235	0.028	-	0.041	0.005	5.17	0.009	0.421	0.021
	Dz5	夹石(灰岩)	0.824	8.21	0.428	101.791	-	97.3	0.309	0.010	-	0.005	0.002	4.36	0.035	0.193	0.181
	Dz7	矿体(方解石)	1.030	17.70	1.488	200.011	-	378.0	0.229	0.013	-	-	0.003	4.55	0.006	0.564	0.010
	Dz8	矿体(方解石)	0.973	19.00	0.763	132.150	-	361.0	0.270	0.009	-	0.027	0.006	3.57	0.011	0.659	0.016
	Dz10	矿体(方解石)	0.785	24.80	1.719	127.686	-	221.0	0.282	0.008	-	0.008	0.002	3.71	0.013	0.068	0.191
	Dz12	底板(灰岩)	0.948	9.56	0.344	61.075	0.031	112.0	0.423	0.032	-	0.027	0.001	4.12	0.031	0.093	0.333
火山关矿段	HSG2	围岩(灰岩)	0.780	8.93	0.341	107.149	0.009	166.0	0.578	0.019	1.09	-	0.004	7.77	0.033	0.235	0.140
	HSG4	矿体(方解石)	0.901	9.77	0.272	208.940	0.009	87.0	1.390	0.009	-	0.025	-	2.38	0.024	0.414	0.058
	HSG6	矿体(方解石)	0.872	9.39	0.282	170.545	-	116.0	1.190	0.009	-	0.010	0.009	1.87	0.014	0.105	0.133
	HSG7	矿体(方解石)	0.961	8.80	0.578	116.971	-	70.5	0.511	0.011	-	-	0.004	2.72	0.008	0.143	0.056
	HSG10	围岩(灰岩)	0.847	9.93	0.398	118.757	0.066	125.0	0.464	0.033	2.86	0.018	0.006	19.50	0.049	0.167	0.293
其他矿段	dl01	矿体(方解石)	3.53	43.130	0.953	28.817	0.082	218.0	1.140	0.036	2.100	0.016	0.002	1.36	0.037	0.797	0.046
	dl02	矿体(方解石)	3.24	42.472	0.907	51.146	0.056	188.0	0.917	0.028	0.813	0.014	0.001	5.46	0.017	1.350	0.012
	dl03	矿体(方解石)	3.33	42.554	0.983	65.807	0.035	149.0	1.020	0.016	0.268	0.015	-	2.84	0.012	1.200	0.010
	db02	矿体(方解石)	3.49	43.130	1.044	52.241	0.008	184.0	0.177	0.010	9.520	0.016	0.012	2.20	0.055	0.108	0.512
	dw01	矿体(方解石)	3.45	50.209	2.172	131.446	0.006	168.0	0.264	0.014	2.980	0.002	-	1.60	0.010	0.251	0.040
	dp04	矿体(方解石)	3.20	40.661	5.046	40.192	0.015	253.0	0.341	0.013	3.520	0.005	-	2.23	0.023	0.047	0.486
	dp03	矿体(方解石)	3.53	41.813	0.831	33.030	0.060	71.1	0.963	0.019	0.990	0.024	0.001	1.53	0.100	0.074	1.345
	db01	矿体(方解石)	3.29	47.081	1.151	69.262	0.026	227.0	0.364	0.022	2.800	0.007	0.005	0.714	0.058	0.038	1.501
	nb01	矿体(方解石)	2.63	41.813	1.128	116.279	-	120.0	0.169	0.006	1.720	0.004	0.002	1.21	0.010	0.068	0.153
	gz01	矿体(方解石)	2.33	27.985	1.166	63.279	0.046	365.0	0.426	0.015	4.600	0.007	0.052	3.50	0.010	0.045	0.233
	gz02	矿体(方解石)	2.86	34.241	0.770	49.461	0.001	212.0	0.207	0.007	-	0.008	0.001	1.69	0.004	0.021	0.209
	hs01	矿体(方解石)	4.05	52.431	1.029	85.945	0.036	678.0	0.705	0.013	2.970	0.009	0.001	0.669	0.011	0.093	0.118
	hz01	矿体(方解石)	3.51	52.760	1.067	56.201	-	169.0	0.606	0.008	3.090	0.002	0.001	0.64	0.006	0.153	0.042
	cb01	矿体(方解石)	3.83	67.165	1.082	49.124	0.018	329.0	0.335	0.012	3.360	0.014	0.001	0.943	0.012	0.182	0.065

采样地点	样号	岩性	Co	Ni	Cu	Zn	Rb	Sr	Zr	Nb	Ba	Hf	Ta	Pb	Th	U	Th/U
达则矿段	Dz3	矿体(方解石)	1.080	23.50	2.316	172.331	-	206.0	0.209	0.008	-	0.020	0.005	3.34	0.014	0.364	0.038
	Dz4	矿体(方解石)	0.971	18.40	1.158	169.652	-	508.0	0.235	0.028	-	0.041	0.005	5.17	0.009	0.421	0.021
	Dz5	夹石(灰岩)	0.824	8.21	0.428	101.791	-	97.3	0.309	0.010	-	0.005	0.002	4.36	0.035	0.193	0.181
	Dz7	矿体(方解石)	1.030	17.70	1.488	200.011	-	378.0	0.229	0.013	-	-	0.003	4.55	0.006	0.564	0.010
	Dz8	矿体(方解石)	0.973	19.00	0.763	132.150	-	361.0	0.270	0.009	-	0.027	0.006	3.57	0.011	0.659	0.016
	Dz10	矿体(方解石)	0.785	24.80	1.719	127.686	-	221.0	0.282	0.008	-	0.008	0.002	3.71	0.013	0.068	0.191
	Dz12	底板(灰岩)	0.948	9.56	0.344	61.075	0.031	112.0	0.423	0.032	-	0.027	0.001	4.12	0.031	0.093	0.333
火山关矿段	HSG2	围岩(灰岩)	0.780	8.93	0.341	107.149	0.009	166.0	0.578	0.019	1.09	-	0.004	7.77	0.033	0.235	0.140
	HSG4	矿体(方解石)	0.901	9.77	0.272	208.940	0.009	87.0	1.390	0.009	-	0.025	-	2.38	0.024	0.414	0.058
	HSG6	矿体(方解石)	0.872	9.39	0.282	170.545	-	116.0	1.190	0.009	-	0.010	0.009	1.87	0.014	0.105	0.133
	HSG7	矿体(方解石)	0.961	8.80	0.578	116.971	-	70.5	0.511	0.011	-	-	0.004	2.72	0.008	0.143	0.056
	HSG10	围岩(灰岩)	0.847	9.93	0.398	118.757	0.066	125.0	0.464	0.033	2.86	0.018	0.006	19.50	0.049	0.167	0.293
其他矿段	dl01	矿体(方解石)	3.53	43.130	0.953	28.817	0.082	218.0	1.140	0.036	2.100	0.016	0.002	1.36	0.037	0.797	0.046
	dl02	矿体(方解石)	3.24	42.472	0.907	51.146	0.056	188.0	0.917	0.028	0.813	0.014	0.001	5.46	0.017	1.350	0.012
	dl03	矿体(方解石)	3.33	42.554	0.983	65.807	0.035	149.0	1.020	0.016	0.268	0.015	-	2.84	0.012	1.200	0.010
	db02	矿体(方解石)	3.49	43.130	1.044	52.241	0.008	184.0	0.177	0.010	9.520	0.016	0.012	2.20	0.055	0.108	0.512
	dw01	矿体(方解石)	3.45	50.209	2.172	131.446	0.006	168.0	0.264	0.014	2.980	0.002	-	1.60	0.010	0.251	0.040
	dp04	矿体(方解石)	3.20	40.661	5.046	40.192	0.015	253.0	0.341	0.013	3.520	0.005	-	2.23	0.023	0.047	0.486
	dp03	矿体(方解石)	3.53	41.813	0.831	33.030	0.060	71.1	0.963	0.019	0.990	0.024	0.001	1.53	0.100	0.074	1.345
	db01	矿体(方解石)	3.29	47.081	1.151	69.262	0.026	227.0	0.364	0.022	2.800	0.007	0.005	0.714	0.058	0.038	1.501
	nb01	矿体(方解石)	2.63	41.813	1.128	116.279	-	120.0	0.169	0.006	1.720	0.004	0.002	1.21	0.010	0.068	0.153
	gz01	矿体(方解石)	2.33	27.985	1.166	63.279	0.046	365.0	0.426	0.015	4.600	0.007	0.052	3.50	0.010	0.045	0.233
	gz02	矿体(方解石)	2.86	34.241	0.770	49.461	0.001	212.0	0.207	0.007	-	0.008	0.001	1.69	0.004	0.021	0.209
	hs01	矿体(方解石)	4.05	52.431	1.029	85.945	0.036	678.0	0.705	0.013	2.970	0.009	0.001	0.669	0.011	0.093	0.118
	hz01	矿体(方解石)	3.51	52.760	1.067	56.201	-	169.0	0.606	0.008	3.090	0.002	0.001	0.64	0.006	0.153	0.042
	cb01	矿体(方解石)	3.83	67.165	1.082	49.124	0.018	329.0	0.335	0.012	3.360	0.014	0.001	0.943	0.012	0.182	0.065

采样地点	样号		岩性		La		Ce		Pr		Nd		Sm		Eu		Gd		Tb		Dy		Ho		Er
达则矿段	Dz3		矿体(方解石)		0.018		0.006		0.001		0.017		-		0.002		0.009		-		0.009		-		0.016
	Dz4		矿体(方解石)		0.020		0.009		0.004		0.010		-		-		-		-		0.003		-		-
	Dz5		夹石(灰岩)		0.552		0.305		0.096		0.406		0.134		0.019		0.108		0.016		0.134		0.043		0.105
	Dz7		矿体(方解石)		0.076		0.042		0.012		0.026		0.003		0.006		-		0.004		0.022		-		0.010
	Dz8		矿体(方解石)		0.024		0.059		0.003		0.013		-		-		0.002		0.002		0.007		-		0.006
	Dz10		矿体(方解石)		0.010		0.019		0.002		0.003		-		-		-		0.001		0.004		-		-
	Dz12		底板(灰岩)		0.328		0.273		0.066		0.276		0.032		0.011		0.058		0.018		0.07		0.019		0.081
火山关矿段	HSG2		围岩(灰岩)		1.290		0.593		0.164		0.678		0.174		0.045		0.198		0.033		0.246		0.057		0.171
	HSG4		矿体(方解石)		0.629		0.756		0.148		0.604		0.129		0.041		0.095		0.039		0.200		0.041		0.112
	HSG6		矿体(方解石)		4.590		4.940		0.806		3.700		0.734		0.236		0.801		0.139		1.040		0.188		0.607
	HSG7		矿体(方解石)		0.271		0.270		0.037		0.141		0.066		0.010		0.076		0.014		0.121		0.021		0.088
	HSG10		围岩(灰岩)		2.720		1.100		0.414		1.760		0.390		0.086		0.512		0.091		0.552		0.136		0.345
采样地点	样号		岩性		Tm		Yb		Lu		Y		∑REE		LREE		HREE		LREE/ HREE		(La/Yb)_N		δEu		δCe
达则矿段	Dz3		矿体(方解石)		-		-		-		0.032		0.080		0.040		0.040		1.180				1.530		0.370
	Dz4		矿体(方解石)		-		0.009		-		0.019		0.060		0.040		0.020		2.580		1.520		3.060		0.260
	Dz5		夹石(灰岩)		0.015		0.137		0.014		2.100		2.080		1.510		0.570		2.640		2.890		0.480		0.330
	Dz7		矿体(方解石)		0.003		0.006		0.002		0.248		0.210		0.160		0.050		3.410		8.890		10.56		0.340
	Dz8		矿体(方解石)		-		-		-		0.023		0.120		0.100		0.020		5.120				2.460		1.770
	Dz10		矿体(方解石)		-		0.001		0.003		0.008		0.050		0.030		0.010		2.590		5.980		1.000		1.020
	Dz12		底板(灰岩)		0.006		0.046		0.007		1.380		1.290		0.990		0.300		3.250		5.110		0.770		0.460
火山关矿段	HSG2		围岩(灰岩)		0.015		0.102		0.013		3.530		3.779		2.944		0.834		3.528		9.072		0.744		0.316
	HSG4		矿体(方解石)		0.015		0.074		0.015		2.280		2.898		2.307		0.591		3.904		6.114		1.133		0.608
	HSG6		矿体(方解石)		0.081		0.609		0.052		8.140		18.523		15.006		3.517		4.266		5.406		0.940		0.630
	HSG7		矿体(方解石)		0.001		0.020		0.003		0.976		1.139		0.795		0.344		2.313		9.623		0.445		0.662
	HSG10		围岩(灰岩)		0.054		0.262		0.034		5.660		8.457		6.470		1.986		3.257		7.447		0.590		0.254
采样地点	样号		岩性		La		Ce		Pr		Nd		Sm		Eu		Gd		Tb		Dy		Ho		Er
其他矿段	dl01		矿体(方解石)		0.572		0.638		0.123		0.469		0.110		0.019		0.088		0.018		0.085		0.016		0.055
	dl02		矿体(方解石)		1.950		1.850		0.337		1.470		0.227		0.057		0.263		0.044		0.282		0.056		0.169
	dl03		矿体(方解石)		4.100		3.320		0.559		2.380		0.412		0.086		0.383		0.050		0.261		0.064		0.161
	db02		矿体(方解石)		2.980		1.440		0.457		1.940		0.365		0.095		0.489		0.071		0.532		0.123		0.406
	dw01		矿体(方解石)		0.112		0.027		0.019		0.099		0.016		0.001		0.011		0.003		0.017		0.006		0.017
	dp04		矿体(方解石)		0.141		0.092		0.021		0.127		0.022		0.002		0.015		0.005		0.037		0.004		0.015
	dp03		矿体(方解石)		0.612		0.449		0.123		0.491		0.141		0.017		0.138		0.026		0.203		0.041		0.136
	db01		矿体(方解石)		0.128		0.075		0.026		0.167		0.024		0.003		0.041		0.008		0.052		0.016		0.056
	nb01		矿体(方解石)		0.248		0.040		0.049		0.244		0.040		0.012		0.077		0.007		0.092		0.017		0.04
	gz01		矿体(方解石)		0.579		0.532		0.077		0.337		0.097		0.025		0.139		0.017		0.114		0.029		0.094
	gz02		矿体(方解石)		0.848		0.932		0.129		0.628		0.097		0.038		0.155		0.024		0.170		0.043		0.116
	hs01		矿体(方解石)		0.061		0.041		0.010		0.043		0.012		0.001		0.013		0.001		0.022		0.005		0.010
	hz01		矿体(方解石)		0.610		0.065		0.096		0.366		0.116		0.024		0.123		0.023		0.181		0.033		0.120
	cb01		矿体(方解石)		0.178		0.072		0.029		0.118		0.022		0.010		0.025		0.004		0.051		0.012		0.034
采样地点	样号	岩性		Tm		Yb		Lu		Y		∑REE		LREE		HREE		LREE/ HREE		(La/Yb)_N		δEu		δCe
其他矿段	dl01	矿体(方解石)		0.008		0.047		0.006		0.935		2.250		1.930		0.320		5.990		8.710		0.600		0.590
	dl02	矿体(方解石)		0.019		0.124		0.017		2.900		6.870		5.890		0.980		6.040		11.280		0.710		0.560
	dl03	矿体(方解石)		0.017		0.107		0.018		2.980		11.920		10.860		1.0600		10.240		27.490		0.660		0.540
	db02	矿体(方解石)		0.054		0.281		0.054		7.500		9.290		7.280		2.010		3.620		7.610		0.690		0.300
	dw01	矿体(方解石)		0.001		0.009		0.002		0.312		0.340		0.270		0.070		4.090		8.560		0.300		0.140
	dp04	矿体(方解石)		0.002		0.014		0.005		0.446		0.500		0.400		0.100		4.110		7.070		0.280		0.420
	dp03	矿体(方解石)		0.025		0.116		0.020		2.210		2.540		1.830		0.700		2.600		3.780		0.380		0.400
	db01	矿体(方解石)		0.009		0.052		0.005		0.721		0.660		0.420		0.240		1.760		1.780		0.270		0.320
	nb01	矿体(方解石)		0.005		0.033		0.005		0.836		0.910		0.630		0.270		2.300		5.440		0.670		0.090
	gz01	矿体(方解石)		0.009		0.048		0.008		2.360		2.100		1.650		0.460		3.600		8.710		0.650		0.620
	gz02	矿体(方解石)		0.016		0.063		0.008		2.730		3.270		2.670		0.600		4.490		9.690		0.960		0.690
	hs01	矿体(方解石)		0.002		0.006		0.001		0.373		0.230		0.170		0.060		2.810		7.580		0.360		0.410
	hz01	矿体(方解石)		0.017		0.083		0.010		2.580		1.870		1.280		0.590		2.170		5.300		0.620		0.070
	cb01	矿体(方解石)		0.004		0.021		0.004		0.878		0.580		0.430		0.150		2.780		6.200		1.300		0.240