贵州织金新华戈仲伍组含磷岩系沉积环境对成磷作用的制约

汪宇航; 谢宏; 张兰; 王昌建; 卢正浩; 白洋; 王孟斋

doi:10.19509/j.cnki.dzkq.tb20220204

贵州织金新华戈仲伍组含磷岩系沉积环境对成磷作用的制约

doi: 10.19509/j.cnki.dzkq.tb20220204

汪宇航^1a,,
谢宏^{1a, 1b, ,},
张兰²,
王昌建^1a,
卢正浩^1a,
白洋^1a,
王孟斋^1a

1a.
贵州大学资源与环境工程学院, 贵阳 550025
1b.
贵州大学喀斯特地质资源与环境教育部重点实验室, 贵阳 550025
2.
兰州大学地质科学与矿产资源学院, 兰州 730000

基金项目:

国家自然科学基金项目 42062009

贵州省科技计划项目黔科合基础[2020]1Y158

贵州大学引进人才科研项目贵大人基合字[2015]第37号

详细信息

作者简介:
汪宇航(1998—), 男, 现正攻读地质学专业硕士学位, 主要从事沉积矿床的研究。E-mail: 15286517949@qq.com

通讯作者:
谢宏(1969—), 女, 教授, 主要从事沉积矿床的研究与教学工作。E-mail: xh5033@163.com

中图分类号: P619.2
计量
- 文章访问数: 431
- PDF下载量: 50
- 被引次数: 0
出版历程
- 收稿日期: 2022-05-09
- 录用日期: 2022-09-20
- 修回日期: 2022-09-17

Constraints of sedimentary environment on phosphorization of phosphorus-bearing rock series in the Xinhua Gezhongwu Formation, Zhijin County, Guizhou Province

Wang Yuhang^{1a
,},
Xie Hong^{1a, 1b
, ,},
Zhang Lan²,
Wang Changjian^1a,
Lu Zhenghao^1a,
Bai Yang^1a,
Wang Mengzhai^1a

1a.
College of Resource and Environmental Enginerring, Guizhou University, Guiyang 550025, China
1b.
Key Laboratory of Karst Georesources and Environment of Ministry of Education, Guizhou University, Guiyang 550025, China
2.
School of Earth Sciences, Lanzhou University, Lanzhou 730000, China

摘要

摘要:
贵州织金新华早寒武世超大型富稀土磷矿床属于典型的海相沉积型矿床, 长期以来, 对其成矿环境及成矿机制的认识尚存在分歧。在重点研究含磷岩系岩(矿)石显微特征的基础上, 结合元素地球化学证据, 求证了戈仲伍组含磷岩系沉积环境及其形成机制, 丰富了扬子陆块同类型矿产的研究资料。该含磷岩系从下到上, 矿石结构构造发生了规律性的变化: 颗粒稍变细; 粒间填隙物由以亮晶白云石胶结物为主变为硅质、胶磷矿等泥晶基质, 再变为以亮晶白云石胶结物为主, 最后变为泥晶胶磷矿、硅质等; 胶结方式由以孔隙式胶结为主转换为孔隙式-基底式胶结, 支撑类型由颗粒支撑变化为颗粒-杂基支撑; 岩层单层厚度变薄, 颜色变深, 交错层理变得不发育; 反映含磷岩系沉积于强水动力的潮下带, 上部沉积水体较下部有所加深、水动力条件稍变弱。含磷岩系显著的Ce负异常(δCe介于0.32~0.39)、较低的Ni/Co比值(0.98~6.07)和V/Cr比值(0.57~12.50), 表现出沉积水体具有与现代海洋环境相似的氧化特征; 较低的10³·Sr/Ca比值(2.00~3.38)及1/Σ(Al₂O₃+TiO₂)比值(0.57~3.45)说明古水深总体较浅, 但变化频繁; Fe, Cu, Ba含量分布特点指示下部碳酸盐古生产力比上部高。在各种条件耦合的古环境中, 磷块岩经历沉淀-冲搅-颠选-胶结-固结作用最终富集形成。
- 含磷岩系 /
- 沉积结构构造 /
- 地球化学 /
- 贵州织金
Abstract: Objective
The Early Cambrian superlarge rare earth-rich phosphate deposit in Xinhua, Zhijin County, Guizhou Province, is a typical marine sedimentary deposit. There have long been controversial on the mineralisation environment and mineralisation mechanism.
Methods
In this paper, the sedimentary environment and formation mechanism of the phosphorus-bearing rock series in the Gezhongwu Formation are verified, through the study of the microscopic characteristics of phosphorus-bearing rock series rocks or ores and the evidence of elemental geochemistry.
Results
This study reveal the regular changes in the structure of phosphorite from the bottom up of the phosphorous-bearing rock series: the grain sizes decreasing; the interstitial materials between grains vary from bright dolomite cement to micritic matrix, such as siliceous and collophanite, followed by bright dolomite cement and finally micrite collophanite and siliceous. The cementation mode has mainly converted from pore cementation to pore-based cementation, and the supports change from grain to grain-matrix supports. Moreover, the single layers of the rocks become thinner and darker, and the development of staggered bedding was decreased.
Conclusion
These characteristics reflect that the sedimentary environment of the phosphorus-bearing rock series is a subtidal zone with strong hydrodynamic forces, and of the upper section has sedimentary depths higher and hydrodynamic conditions slightly weaker than those of the lower section. The significant negative Ce anomalies (δCe between 0.32-0.39) and low Ni/Co (0.98-6.07) and V/Cr ratios (0.57-12.50) of the phosphorus-bearing rock series show that the sedimentary water had oxidation characteristics similar to those of a modern marine environment. The lower 10³·Sr/Ca(2.00-3.38) and 1/Σ(Al₂O₃+TiO₂) ratios (0.57-3.45) indicate that the ancient water depth was generally shallow, but the relative depth changed frequently. The distribution characteristics of Fe, Cu and Ba contents indicate that the palaeoproductivity of carbonate in the lower section is higher than that in the upper section. In the palaeoenvironment where various conditions are coupled, the phosphorite was finally enriched and formed by precipitation-stirring-subdivision-cementation-solidification.
- phosphorus-bearing rock series /
- sedimentary structure /
- geochemistry /
- Zhijin County, Guizhou Province
注释:

(所有作者声明不存在利益冲突)

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图 1 贵州织金新华磷矿地质简图(据文献[7]修编)

Figure 1. Geological sketch of the Xinhua phosphate deposit in Zhijin County, Guizhou Province

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图 2 贵州织金戈仲伍组含磷岩系采样位置图(a)及野外剖面照片(b)

Figure 2. Sampling location map (a) and field profile photos (b) of the phosphorus-bearing rock series in the Gezhongwu Formation, Zhijin County, Guizhou Province

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图 3 贵州贵织金戈仲伍组磷块岩岩(矿)结构特征

a.长条形小壳化石(ZJH-1)；b.尖锥形小壳化石(ZJH-2)；c.钉子形软舌螺(ZJH-3)；d.软舌螺内部特征(ZJH-5)；e~g.胶磷矿砂屑(ZJH-6、ZJH-8、ZJH-9)；h.砾屑(ZJH-1)；i.复鲕(ZJH-1)；j.真鲕(ZJH-2)；k.薄皮鲕(ZJH-2)；l.椭圆形团块(ZJH-1)；m.藻团块(ZJH-4)；n.长条形团块(ZJH-6)；o.不规则形团块(ZJH-3)；p.黄铁矿团粒及有机质(ZJH-10)

Figure 3. Structural features of phosphorite rocks(ores) in the Gezhongwu Formation, Zhijin County, Guizhou Province

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图 4 贵州织金戈仲伍组磷块岩构造特征

a.戈仲伍组下部条带状构造(第1层)；b.戈仲伍组上部条带状构造(第4层)；c.层纹状构造(第3层)；d, e.槽状交错层理(第2层)；f.人字形交错层理(第3层)；g.透镜状(第3层)；h.同生角砾(第3层)；i.受应力挤压变形的楔状交错层理(第5层)

Figure 4. Structural characteristics of phosphorite in the Gezhongwu Formation, Zhijin County, Guizhou Province

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图 5 贵州织金戈仲伍组磷块岩显微特征

Dol.白云石；Clh.胶磷矿；CM.黏土矿物；Q.石英；Ap.磷灰石。a.白云质磷块岩(ZJH-1)，粒屑主要为生物屑和砾屑，生物屑呈定向排列，白云质胶结，颗粒支撑，(+)；b.白云质磷块岩(ZJH-6)，粒屑主要为生物屑和砂屑，生物屑呈半定向排列，白云质胶结，颗粒支撑，(-)；c.磷块岩(ZJH-8)，砂屑、生物屑定向排列，填隙物以胶磷矿、硅质为主，颗粒-杂基支撑，(+)；d.硅质磷块岩(ZJH-5)，硅化明显，砾屑、生物屑定向排列，填隙物以硅质、胶磷矿为主，颗粒-杂基支撑，(-)

Figure 5. Microscopic features of phosphorite in the Gezhongwu Formation, Zhijin County, Guizhou Province

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图 6 戈仲伍组磷块岩中w(CaO)、w(MgO)与w(P₂O₅)的相关性

Figure 6. Co-variations of CaO, MgO and P₂O₅ contents from phosphorites in the Gezhongwu Formation, Zhijin County, Guizhou Province

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图 7 戈仲伍组含磷岩系沉积特征与沉积环境

Figure 7. Sedimentary characteristics and environments of phosphorus-bearing rock series in the Gezhongwu Formation

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图 8 戈仲伍组含磷岩系特征元素变化图

Figure 8. Variation diagram of characteristic elements of phosphorus-bearing rock series in the Gezhongwu Formation

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图 9 戈仲武组磷块岩δCe与ΣREE相关性

Figure 9. Diagram of δCe and ΣREE of phosphorite in the Gezhongwu Formation

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图 10 戈仲伍组磷块岩稀土元素PAAS标准化配分模式曲线图

Figure 10. PAAS normalized REE+Y distribution patterns of phosphorite in the Gezhongwu Formation

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图 11 贵州织金戈仲伍磷矿成矿模式示意图

Figure 11. Ore-forming model of phosphorite in the Gezhongwu profile, Zhijin County, Guizhou Province

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表 1 贵州织金戈仲伍组含磷岩系矿层及围岩主量元素质量分数及比值

Table 1. Content of major elements in the ore horizon and wall-rock of the phosphorus-bearing rock series in the Gezhongwu Formation, Zhijin County, Guizhou Province

样品	ZJH-1	ZJH-2	ZJH-3	ZJH-4	ZJH-5	ZJH-6	ZJH-7	ZJH-8	ZJH-9	ZJH-10	ZJH-11	ZJH-12	ZJH-13	磷块岩平均值
CaO	44.8	42.5	46.2	40.4	26.7	42.9	36.0	51.1	54.5	52.4	0.50	0.59	2.77	43.7
P₂O₅	26.6	21.9	33.3	27.9	11.9	22.1	16.2	35.6	39.3	38.7	0.21	0.32	0.68	27.4
SiO₂	4.92	3.16	12.4	23.8	37.0	4.5	14.8	3.20	0.55	2.76	55.9	56.9	55.4	10.7
MgO	5.85	9.14	0.50	1.22	6.67	8.83	9.00	2.13	0.20	0.17	1.65	1.41	1.56	4.37
Fe₂O₃	2.34	1.91	2.90	0.47	0.56	0.64	0.68	0.82	0.80	0.81	5.24	3.72	2.95	1.19
Al₂O₃	0.71	0.36	0.73	0.85	1.53	0.37	1.65	0.68	0.21	0.90	16.5	17.4	16.1	0.80
Na₂O	0.13	0.09	0.17	0.14	0.09	0.09	0.11	0.15	0.15	0.19	0.12	0.13	0.15	0.13
K₂O	0.11	0.05	0.22	0.23	0.38	0.07	0.41	0.13	0.02	0.18	4.80	4.96	4.71	0.18
TiO₂ w_B/%	0.05	0.02	0.04	0.04	0.01	0.01	0.10	0.02	0.08	0.04	0.69	0.94	0.65	0.05
MnO	0.19	0.11	0.09	0.04	0.06	0.09	0.09	0.03	0.04	0.02	0.01	0.01	0.01	0.08
SrO	0.08	0.07	0.10	0.08	0.04	0.07	0.05	0.10	0.12	0.10	0.01	0.01	0.02	0.08
BaO	0.05	0.08	0.24	0.13	0.01	0.02	0.02	0.03	0.04	0.04	0.06	0.06	0.45	0.07
Cr₂O₃	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	0.01	0.04	0.01	0.01
烧失量	14.1	20.4	3.03	4.01	14.8	19.9	20.2	5.46	2.19	2.41	13.5	12.9	14.5	10.6
总计	99.9	99.7	99.9	99.2	99.8	99.6	99.2	99.5	98.2	98.7	99.2	99.4	100	99.4
Ca	28.7	26.5	29.6	26.7	17.6	28.1	23.8	32.6	34.6	34.0	0.38	0.42	1.87	28.2
Fe	1.47	1.18	1.84	0.35	0.41	0.44	0.47	0.54	0.54	0.55	3.75	2.65	2.10	0.78
Al w_B/%	0.41	0.20	0.40	0.48	0.83	0.22	0.91	0.39	0.15	0.50	7.61	7.98	7.73	0.45
Mn	0.13	0.07	0.06	0.03	0.04	0.06	0.06	0.02	0.02	0.01	0.01	0.01	0.01	0.05
Fe/Mn	11.5	16.1	31.8	12.7	10.6	7.28	7.97	30.7	26.2	43.3	721	564	438	19.8
Al/Ti	12.1	12.5	14.3	20.9	27.7	14.7	45.5	21.7	3.41	20.0	21.0	15.7	21.1	19.3
Ca/(Ca+Fe)	0.95	0.96	0.94	0.99	0.98	0.98	0.98	0.98	0.98	0.98	0.09	0.14	0.47	0.97
1/∑(Al₂O₃+TiO₂)	1.32	2.63	1.30	1.12	0.65	2.63	0.57	1.43	3.45	1.06	0.06	0.05	0.06	1.62
岩性	白云质磷块岩	白云质磷块岩	磷块岩	硅质磷块岩	硅质磷块岩	白云质磷块岩	硅质白云质磷块岩	磷块岩	磷块岩	磷块岩	黑色页岩	黑色页岩	镍钼富集层	—

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表 2 织金戈仲伍组含矿岩系及围岩微量、稀土元素质量分数及比值

Table 2. Contents of trace elelments and REEs of phosphorus-bearing rock series and wall-rock and specific ratios in the Gezhongwu Formation, Zhijin County, Guizhou Province

样品	ZJH-1	ZJH-2	ZJH-3	ZJH-4	ZJH-5	ZJH-6	ZJH-7	ZJH-8	ZJH-9	ZJH-10	ZJH-11	ZJH-12	ZJH-13	磷块岩平均值	地壳丰度
As	5.00	71.0	142	7.00	8.00	< 5.00	5.00	24.0	12.0	14.0	88.0	419	519	29.3	1.80
Ba	550	870	2460	1400	210	290	240	300	430	520	410	500	190	727	425
Co	0.60	3.80	3.00	1.20	8.70	0.90	1.10	2.70	5.50	2.50	11.4	9.20	8.90	3.00	25.0
Cr	13.0	8.00	12.0	11.0	7.00	7.00	17.0	10.0	14.0	14.0	87.0	168	94.0	11.3	100
Cu	8.60	156	371	102	12.7	6.60	15.6	7.30	8.40	152	35.7	35.6	72.1	84.0	55.0
Ga	2.88	2.79	3.46	3.43	2.51	1.81	3.74	3.09	2.9	3.59	21.0	24.2	23.4	3.02	15.0
Ni	3.10	13.7	18.2	3.10	10.4	1.00	1.40	5.20	5.40	12.3	57.7	394	742	7.38	75.0
Sb	5.59	41.4	86.1	15.3	2.42	1.40	8.45	3.63	4.07	72.0	12.2	14.6	40.0	24.0	0.20
Sc w_B/10^-6	4.30	3.30	5.30	3.10	3.10	2.30	3.40	3.00	2.40	2.20	13.6	11.9	13.2	3.24	22.0
Sr	789	658	1 000	787	351	741	536	967	1135	967	53.7	53.0	125	793	375
Th	5.10	2.60	5.00	4.60	3.10	2.60	4.50	4.60	7.30	4.20	12.3	11.8	9.70	4.36	9.60
Ti	0.03	0.02	0.03	0.02	0.03	0.02	0.02	0.02	0.04	0.03	0.36	0.51	0.37	0.03	—
U	8.60	11.5	12.9	10.1	4.70	4.90	7.70	9.90	12.8	12.8	22.6	28.1	39.5	9.59	2.70
V	21.0	100	73.0	22.0	13.0	13.0	23.0	12.0	8.00	57.0	307	2440	395	34.2	135
W	0.40	0.60	0.50	0.40	0.30	0.30	0.50	0.40	0.80	0.60	1.60	3.10	1.90	0.48	1.50
Zr	4.30	9.70	19.0	1.80	2.80	2.10	2.30	3.00	3.50	9.30	124	126	122	5.82	165
Zn	8.00	200	369	43.0	26.0	8.00	34.0	370	368	354	46.0	178	672	178	70.0
Sr/Ba	1.43	0.76	0.41	0.56	1.67	2.56	2.23	3.22	2.64	1.86	0.13	0.11	0.66	1.73	0.88
10³·Sr/Ca	2.75	2.48	3.38	2.95	2.00	2.64	2.25	2.97	3.28	2.84	14.1	12.6	6.68	2.75	—
Ni/Co	5.17	3.61	6.07	2.58	1.20	1.11	1.27	1.93	0.98	4.92	5.06	42.8	83.4	2.88	3.00
Cu/Zn	1.08	0.78	1.01	2.36	0.49	0.83	0.46	0.02	0.02	0.43	0.78	0.20	0.11	0.75	0.79
V/Cr	1.62	12.50	6.08	2.00	1.86	1.86	1.35	1.20	0.57	4.07	3.53	14.5	4.20	3.31	1.35
La	296	213	310	280	100	195	170	316	429	332	32.9	30.2	30.1	264	30.0
Ce	176	159	209	193	70.8	110	119	183	245	190	72.1	43.7	69.4	165	60.0
Pr	47.3	40.3	55.0	51.7	19.0	32.0	31.6	53.3	70.8	55.3	7.36	3.89	7.44	45.6	8.20
Nd	210	184	246	232	80.3	131	129	221	286	225	25.7	12.1	24.5	194	28.0
Sm	37.0	35.6	45.0	42.4	15.4	23.3	23.7	40.2	51.9	41.0	4.17	1.61	4.27	35.6	6.00
Eu	9.08	11.3	13.9	12.5	4.65	6.38	6.72	10.6	13.5	11.2	0.94	0.38	0.99	9.97	1.20
Gd	47.0	44.9	57.6	52.6	19.9	31.3	32.2	53.8	69.1	56.9	4.84	2.15	4.49	46.5	5.40
Tb w_B/10^-6	6.71	6.23	8.08	7.27	2.75	4.51	4.70	7.62	9.96	8.03	0.70	0.27	0.65	6.59	0.90
Dy	37.8	34.0	44.6	39.7	14.7	26.0	26.6	43.5	55.4	46.1	4.20	1.68	3.75	36.8	3.00
Ho	7.91	6.91	9.23	8.10	3.10	5.44	5.59	9.15	11.4	9.66	0.89	0.37	0.83	7.65	1.20
Er	21.9	18.4	25.2	22.3	8.39	15.6	15.4	25.5	32.2	26.6	2.76	1.34	2.67	21.1	2.80
Tm	2.42	1.96	2.69	2.36	0.93	1.69	1.71	2.78	3.48	2.83	0.42	0.23	0.37	2.29	0.48
Yb	12.05	9.65	13.35	11.60	4.84	8.83	8.69	14.05	17.25	14.10	2.91	1.92	2.61	11.44	3.00
Lu	1.48	1.17	1.69	1.41	0.63	1.13	1.11	1.75	2.15	1.81	0.45	0.31	0.40	1.43	0.50
Y	429	346	491	428	159	305	283	502	636	520	25.0	12.8	24.8	410	33.0
∑REE	1341	1112	1532	1385	504	896	858	1484	1933	1540	185	113	177	1259	184
∑LREE	775	643	879	812	290	497	479	824	1096	854	143	91.9	137	715	133
∑HREE	566	469	653	573	214	399	379	660	837	686	42.2	21.1	40.6	544	50.3
(La/Yb)_N	2.46	2.21	2.32	2.41	2.07	2.21	1.96	2.25	2.49	2.35	1.13	1.57	1.15	2.31	1.00
∑LREE/∑HREE	1.37	1.37	1.34	1.42	1.35	1.24	1.26	1.25	1.31	1.24	3.40	4.36	3.37	1.32	2.65
δCe	0.34	0.39	0.37	0.37	0.37	0.32	0.37	0.32	0.32	0.32	1.07	0.89	1.07	0.35	0.42
注：δCe=2Ce_N/La_N+Pr_N，N代表澳大利亚后太古宙页岩标准化后的值^[30]，地壳元素丰度数据引自文献[31]

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表 3 颗粒与泥晶比值及水动力能量

Table 3. Ratio of grains to micrity and hydrodynamic energy

颗粒/泥晶	颗粒φ_B/%	沉积环境水动力能量
9∶1	90	强动荡水体沉积
9∶1	75	强-中等动荡水体沉积
1∶1	50	中等动荡水体沉积
1∶9	25	弱-间歇动荡水体沉积
1∶9	10	静水沉积

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