拉拉IOCG矿床萤石的微量元素地球化学特征及其指示意义

doi:10.11867/j.issn.1001-8166.2015.09.1063

康滇地区元古宙拉拉IOCG矿床中有与铜、钼矿化密切相关的萤石产出,其中,变质期有萤石（I）和萤石（II）2个世代萤石产出,前者与鳞片状辉钼矿共生,后者与条带状辉钼矿共生;热液期萤石（III）呈脉状穿插含变质期萤石的矿石;萤石的微量元素记录了成矿流体来源方面的重要信息。通过ICP-MS方法分析矿床中2期萤石样品的微量元素组成,运用微量元素含量、比值及蛛网图探讨微量元素特征、成矿流体来源及性质。结果表明：变质期萤石中各微量元素含量有一定的变化范围,热液期中各微量元素含量比较稳定,元素在萤石中的含量主要由元素在原始流体中的含量及元素本身性质所决定。结论认为：①变质期萤石(I)和萤石(II)为同源流体不同阶段演化产物,成矿流体来自于围岩,为具有高F-,Cu,Mo和Y含量的低pH值海水相流体,活动范围有限,没有发生大规模流动或迁移;②热液期萤石(III)与变质期萤石不同源,成矿流体由大气降水或地下水渗透淋滤围岩形成,为具有低F-含量的高pH值大陆淡水相流体,可能发生较远距离的渗入性流体流动或迁移。

关键词: 萤石, 微量元素, IOCG, 拉拉

The Lala Fe-Cu-REE deposit, reported as a typical IOCG deposit in the Kangdian region, is located at the western margin of Yangtze Block. Fluorite is one of the most important gangue minerals in the Lala IOCG deposit, which is intergrown with chalcopyrite and molybdnite, and recorded important information about the source and evolution of the ore-forming fluid. Trace elements geochemistry of fluorite and its implications for source of ore-forming fluid are discussed through content, ratio and spider diagram of trace elements. Two stages of fluorite with three generations are identified in the Lala IOCG deposit. Fluorite (I) and fluorite (II) belongs to metamorphic metallization stage. Fluorite (I) is intergrown with flaky molybdenite (I), and are isolated cube shaped. Fluorite (II) is intergrown with banded molybdenite (II) in the vein or massive-disseminated ores, light purple. Fluorite (III) belongs to hydrothermal mineralization stage, intergrown with chalcopyrite and calcite veins, which cut the ores with fluorite (I) and fluorite (II), with a cubic habit. It turned out that: the content of trace elements is variable in fluorite (I) and fluorite (II) while it is stable in fluorite (III), which is dominated by its content in the original fluid and the nature themselves. The results suggested that: ①Fluorite (I) and fluorite (II) are homogenous products at different generations, seawater phase ore-forming fluids derived from the host rock, characterized by high content of F , Cu, Mo, Y and low pH, and exhumation might migrated at small scale.②Fluorite (III) has a different source from fluorite (I) and fluorite (II). Infiltration and leaching host rock by meteoric water or groundwater formed its freshwater phase ore-forming fluids, which is characterized by high pH and low content of F^-, and exhumation might infiltration flew or migrated at a long distance.

Key words: Fluorite, Trace elements geochemistry, IOCG, Lala.

中图分类号:

P595
P597

图1. 拉拉IOCG矿床矿区地质简图 (据文献文献[ 17 ]修改)

Fig 1. Simplified geological map of the Lala IOCG deposit (modified after reference[ 17 ]）

图2 拉拉IOCG矿床中萤石的代表性手标本及显微照片 (a)孤立状紫色萤石(I)分布于黑云母片岩型矿石中 (LO-6);(b)萤石(II)与辉钼矿(II)和黄铜矿组成的脉体平行石榴石黑云母片岩的片理产出（L-26）;(c)方解石+萤石(III)脉(LD-7-2)切割浸染状—块状的含萤石（II）和辉钼矿（II）的黑云母片岩型矿石(LD-7-1);(d)黄铜矿围绕萤石(I)和鳞片状辉钼矿(I)生长(LO-6,反射光）;(e)和(f)为同一视域（前者为反射光,后者为透射单偏光）,条带状辉钼矿(II)与萤石(II)共生(L-26),萤石交代黑云母形成交代残余结构; Fl：萤石;Ccp：黄铜矿;Mo：辉钼矿;Cal：方解石;Bi：黑云母;Grt:石榴石;Foliation:片理。

Fig.2 Representative ore samples and photomicrographs of fluorite from the Lala IOCG deposit (a)Individual fluorite(I) in biotite-schist ore(LO-6); (b)The vein comprised of fluorite(II), molybdenite(II) and chalcopyrite parallel to the foliation of the garnet-biotite schist(L-26); (c) dismissive-massive biotite-schist ore (LD-7-1)cross cut by the vein of fluorite(III) and calcite(LD-7-2); (d)fluorite(I) and flaky molybdenite(I) surrounded by chalcopyrite (LO-6, Reflected light); (e) and (f) are the same place of the thin section, showing the banded molybdenite(II) intergown with fluorite(II) and the biotite(II) was altered by fluorite(II) (L-26, e is Reflected light, and f is plane-polarized light); Fl: fluorite; Ccp: chalcopyrite; Mo: molybdnite; Cal: calcite; Bi: biotite; Grt: garnet

表1 拉拉IOCG 矿床矿物生成顺序表

Table 1 Paragenetic sequence of mineralization and alteration in the Lala IOCG deposit

表2 拉拉IOCG矿床中萤石的微量元素组成/10 ^-6及特征参数

Table 2 Trace elements composition and parameters of the fluorite and host rocks from the Lala IOCG deposit

期次	变质成矿期							热液期		围岩
世代	萤石Ⅰ			萤石Ⅱ				萤石Ⅲ		黑云母片岩		钠长石变粒岩
样号	LO-88-2	LO-6	LO-85	LO-74	LO-20	LD-7-2	L-25	OP-77	LD-7-1	LO-38-2	Op-79	LO-36	Op-12
Li	0.570	0.453	0.259	0.311	0.532	0.251	1.021	0.937	0.839
Be	0.000	0.086	0.274	0.180	0.078	0.092	0.039	0.180	0.000
Sc	1.411	1.793	1.333	1.292	1.258	0.904	1.163	0.709	0.764
Ti	13.146	14.325	13.864	11.236	12.428	12.734	11.603	1.642	1.568	3718.00	5988.00	2894.00	4839.00
V	0.608	1.427	1.493	0.786	0.978	0.233	4.943	0.542	0.311
Cr	23.626	4.318	31.650	21.784	6.278	5.256	11.817	21.619	19.562
Co	11.947	6.976	13.603	21.682	3.348	5.541	26.336	2.703	2.674
Ni	18.712	20.266	18.091	19.379	18.708	20.406	24.454	30.870	30.658
Zn	17.035	6.629	15.525	8.616	6.286	13.439	12.382	8.281	9.028
Ga	13.328	11.290	7.035	7.073	5.819	7.347	3.809	0.293	0.315
Rb	0.423	1.020	1.340	0.655	1.409	0.359	0.787	0.667	0.735	64.00	95.00	8.00	5.00
Sr	149.724	129.471	122.022	108.025	103.400	83.395	160.962	18.735	18.638	64.00	100.00	79.00	52.00
Y	217.075	457.011	526.499	758.773	981.544	710.753	450.785	112.695	112.869	216.00	138.00	200.00	204.00
Zr	1.170	1.573	1.768	1.012	1.356	0.972	2.238	0.921	0.975	297.00	432.00	116.00	389.00
Nb	2.801	6.626	2.999	8.476	2.224	1.381	3.027	0.624	0.736	113.00	62.00	45.00	51.00
Cs	0.014	0.021	0.016	0.015	0.027	0.035	0.020	0.081	0.101
Ba	6.289	13.739	3.920	6.490	7.342	10.242	4.783	29.785	31.896	347.00	199.00	45.00	41.00
Hf	0.307	0.549	0.400	0.407	0.616	0.455	0.394	0.031	0.056	7.90	10.30	3.20	9.70
Ta	0.113	0.390	0.179	0.198	0.224	0.184	0.201	0.092	0.331	3.00	2.60	1.30	2.20
Pb	22.910	9.198	8.555	13.013	6.335	1.499	28.149	1.151	1.492
Th	0.159	0.597	0.205	0.149	0.189	0.156	4.408	0.089	0.118	14.90	12.80	11.90	12.00
U	45.001	18.559	17.793	20.079	13.448	2.492	51.449	0.614	0.686	174.90	68.10	79.50	37.20
Ge	1.727	1.835	0.942	1.100	0.913	1.312	0.832	0.063	0.185
Mo	136.344	137.332	102.314	232.353	182.114	246.194	620.200	30.475	24.919
Cu	1248.865	865.438	1292.746	1241.710	655.340	779.246	470.916	431.354	425.105
La	782.339	655.530	304.988	358.567	364.879	336.211	115.402	11.486	11.771	1331.00	795.00	598.00	969.00
Ce	1190.376	1059.492	486.578	595.122	572.480	585.340	237.485	19.934	20.905	2085.00	1307.00	1031.00	1615.00
Nd	386.532	361.354	223.589	259.568	218.618	274.844	129.700	7.421	7.555	636.00	439.00	366.00	553.00
Sm	58.567	67.562	48.222	48.758	39.328	55.922	33.380	1.352	1.471	101.70	69.3	64.80	95.30
Yb	10.931	20.508	28.043	24.580	19.518	21.716	10.927	0.712	0.718	14.10	9.00	13.60	16.10
Lu	1.064	2.009	2.776	2.420	2.007	1.964	1.040	0.068	0.092	1.73	1.14	1.62	2.07
Rb/Sr	2.823	7.879	10.986	6.061	13.631	4.301	4.891	35.617	39.462	1000	950	101	96.0
Sr/Ba	23.807	9.424	31.131	16.645	14.084	8.143	33.65	0.629	0.584	0.18	0.50	1.76	1.27
Nb/Ta	24.714	16.983	16.727	42.781	9.947	7.508	15.049	6.792	2.221	37.67	23.85	34.62	23.18
Zr/Hf	3.818	2.866	4.42	2.483	2.2	2.135	5.673	29.348	17.492	37.59	41.94	36.25	40.10

表2 拉拉IOCG矿床中萤石的微量元素组成/10 ^-6及特征参数

Table 2 Trace elements composition and parameters of the fluorite and host rocks from the Lala IOCG deposit

期次	变质成矿期							热液期		围岩
世代	萤石Ⅰ			萤石Ⅱ				萤石Ⅲ		黑云母片岩		钠长石变粒岩
样号	LO-88-2	LO-6	LO-85	LO-74	LO-20	LD-7-2	L-25	OP-77	LD-7-1	LO-38-2	Op-79	LO-36	Op-12
Li	0.570	0.453	0.259	0.311	0.532	0.251	1.021	0.937	0.839
Be	0.000	0.086	0.274	0.180	0.078	0.092	0.039	0.180	0.000
Sc	1.411	1.793	1.333	1.292	1.258	0.904	1.163	0.709	0.764
Ti	13.146	14.325	13.864	11.236	12.428	12.734	11.603	1.642	1.568	3718.00	5988.00	2894.00	4839.00
V	0.608	1.427	1.493	0.786	0.978	0.233	4.943	0.542	0.311
Cr	23.626	4.318	31.650	21.784	6.278	5.256	11.817	21.619	19.562
Co	11.947	6.976	13.603	21.682	3.348	5.541	26.336	2.703	2.674
Ni	18.712	20.266	18.091	19.379	18.708	20.406	24.454	30.870	30.658
Zn	17.035	6.629	15.525	8.616	6.286	13.439	12.382	8.281	9.028
Ga	13.328	11.290	7.035	7.073	5.819	7.347	3.809	0.293	0.315
Rb	0.423	1.020	1.340	0.655	1.409	0.359	0.787	0.667	0.735	64.00	95.00	8.00	5.00
Sr	149.724	129.471	122.022	108.025	103.400	83.395	160.962	18.735	18.638	64.00	100.00	79.00	52.00
Y	217.075	457.011	526.499	758.773	981.544	710.753	450.785	112.695	112.869	216.00	138.00	200.00	204.00
Zr	1.170	1.573	1.768	1.012	1.356	0.972	2.238	0.921	0.975	297.00	432.00	116.00	389.00
Nb	2.801	6.626	2.999	8.476	2.224	1.381	3.027	0.624	0.736	113.00	62.00	45.00	51.00
Cs	0.014	0.021	0.016	0.015	0.027	0.035	0.020	0.081	0.101
Ba	6.289	13.739	3.920	6.490	7.342	10.242	4.783	29.785	31.896	347.00	199.00	45.00	41.00
Hf	0.307	0.549	0.400	0.407	0.616	0.455	0.394	0.031	0.056	7.90	10.30	3.20	9.70
Ta	0.113	0.390	0.179	0.198	0.224	0.184	0.201	0.092	0.331	3.00	2.60	1.30	2.20
Pb	22.910	9.198	8.555	13.013	6.335	1.499	28.149	1.151	1.492
Th	0.159	0.597	0.205	0.149	0.189	0.156	4.408	0.089	0.118	14.90	12.80	11.90	12.00
U	45.001	18.559	17.793	20.079	13.448	2.492	51.449	0.614	0.686	174.90	68.10	79.50	37.20
Ge	1.727	1.835	0.942	1.100	0.913	1.312	0.832	0.063	0.185
Mo	136.344	137.332	102.314	232.353	182.114	246.194	620.200	30.475	24.919
Cu	1248.865	865.438	1292.746	1241.710	655.340	779.246	470.916	431.354	425.105
La	782.339	655.530	304.988	358.567	364.879	336.211	115.402	11.486	11.771	1331.00	795.00	598.00	969.00
Ce	1190.376	1059.492	486.578	595.122	572.480	585.340	237.485	19.934	20.905	2085.00	1307.00	1031.00	1615.00
Nd	386.532	361.354	223.589	259.568	218.618	274.844	129.700	7.421	7.555	636.00	439.00	366.00	553.00
Sm	58.567	67.562	48.222	48.758	39.328	55.922	33.380	1.352	1.471	101.70	69.3	64.80	95.30
Yb	10.931	20.508	28.043	24.580	19.518	21.716	10.927	0.712	0.718	14.10	9.00	13.60	16.10
Lu	1.064	2.009	2.776	2.420	2.007	1.964	1.040	0.068	0.092	1.73	1.14	1.62	2.07
Rb/Sr	2.823	7.879	10.986	6.061	13.631	4.301	4.891	35.617	39.462	1000	950	101	96.0
Sr/Ba	23.807	9.424	31.131	16.645	14.084	8.143	33.65	0.629	0.584	0.18	0.50	1.76	1.27
Nb/Ta	24.714	16.983	16.727	42.781	9.947	7.508	15.049	6.792	2.221	37.67	23.85	34.62	23.18
Zr/Hf	3.818	2.866	4.42	2.483	2.2	2.135	5.673	29.348	17.492	37.59	41.94	36.25	40.10

图3 拉拉IOCG矿床中萤石微量元素含量变化趋势图

Fig 3 Change trend chart of trace elements content of fluorite in the Lala IOCG deposit

图4 拉拉IOCG矿床萤石及全岩微量元素原始地幔标准化蛛网图（原始地幔值据参考文献[ 28 ]） (a)萤石(I);(b)萤石(II) ;(c)萤石(III);(d)围岩

Fig.4 Spider diagram of trace elements in fluorite and host rock from the Lala IOCG deposit after primitive mantle-normalized(primitive mantle values after reference[ 28 ] ) (a)fluorite(I);(b)fluorite(II);(c)fluorite(III);(d)host rock

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摘要

Trace Elements Geochemistry of Fluorite and Its Implications in the Lala IOCG Deposit