稀土元素对褐帘石晶体结构的精细影响研究

doi:10.19657/j.geoscience.1000-8527.2024.042

摘要/Abstract

摘要：

褐帘石作为花岗岩、矽卡岩以及花岗伟晶岩中常见的副矿物,是岩浆中轻稀土元素(LREE)、Th、U和Sr等微量元素的重要载体,在俯冲带的临界温度范围内褐帘石能够很好的控制LREE含量,其成分对结构变化所产生的影响对地球科学研究具有非常重要的指示作用。本文通过单晶X射线衍射、粉晶X射线衍射、LA-ICP-MS等一系列系统的结构和化学成分对比分析了不同地质环境中褐帘石族矿物单晶的晶胞参数特征,并在此基础之上深入讨论了帘石族矿物中稀土元素对晶体结构微调的过程。根据实验数据的比较随着REE³⁺替代Ca²⁺占据A2占位使得帘石族矿物晶体的a、b、c、V各个晶胞参数得到了相应程度增大,其中晶胞体积的变化较为明显由457.92 Å³增大至479.93 Å³,体积增大接近4.8%;褐帘石的(110)、( $31 1 ¯$ )、(222+123+114)、(322+ $42 4 ¯$ )和(307)等面网可以间接指示褐帘石中稀土元素的含量和占位情况。本研究通过分析褐帘石的晶体结构和化学成分,揭示了稀土元素替代Ca²⁺对其晶体结构的调控机制及其地球化学意义。

关键词: 褐帘石, 稀土元素, 晶体结构, 晶胞参数, 多面体体积

Abstract:

Allanite is a common accessory phase in granite, skarn and granite pegmatite. As the major carrier of light rare earth elements (LREE) and trace elements such as Th, U and Sr, allanite can control LREE content well within the critical temperature range of the subduction zone. The effect of changes that its composition to structure have directive influence to the research of earth science. This paper summarise the characteristics of the cell parameters of the three epidote group minerals contain allanite, epidote and zoisite through a series systematic structural and chemical compositional analyses. Such as single-crystal X-ray diffraction (XRD), powder X-ray diffraction, and LA-ICP-MS. We discuss the effects of composition on the structure in the epidote group minerals on the basis of the series of analyses. According to experimental data comparisons, as REE³⁺ substitutes for Ca²⁺ and occupies the A2 site, the unit cell parameters a, b, c and V of the epidote-group minerals exhibit corresponding increases. The change in unit cell volume is particularly significant, expanding from 457.92 Å³ to 479.93 Å³, representing a volume increase of approximately 4.8%. Additionally, the (110), ($31\overline{1}$311¯), (222+123+114), (322+$42\overline{4}$424¯), and (307) lattice planes of allanite can indirectly reflect the content and occupancy of REEs within the mineral structure.This study investigates the crystal structure and chemical composition of allanite, revealing the regulatory mechanism of rare earth elements (REEs) substituting for Ca²⁺ and its geochemical significance.

Background collection

Key words: allanite, REE, crystal structure, cell parameters, polyhedral volume

中图分类号:

徐晶晶, 李林, 杨小男. 稀土元素对褐帘石晶体结构的精细影响研究[J]. 现代地质, 2025, 39(03): 704-714.

XU Jingjing, LI Lin, YANG Xiaonan. Research on the Atomic Level Structure Effects by Rare Earth Elements Substitutions in Allanite of Different Occurrence[J]. Geoscience, 2025, 39(03): 704-714.

图/表 11

参考文献 40

[1]	HERMANN J. Allanite: Thorium and light rare earth element carrier in subducted crust[J]. Chemical Geology, 2002, 192(3/4): 289-306.
[2]	张华锋, 叶青培, 翟明国. 岩浆绿帘石特征及其地质意义研究进展[J]. 地球科学进展, 2005, 20(4): 442-448 DOI
[3]	KOSTERIN A V. Ratios of rare earth elements in allanites from some igneous rocks of northern Kirgiziya[J]. Geochemistry, 1961, 5: 481-484.
[4]	DORR A S W A. Refinement of the crystal structures of epidote, allanite and hancockite[J]. American Mineralogist: Journal of Earth and Planetary Materials, 1971, 56(3-4_Part_1): 447-464.
[5]	DEER W A, HOWIE R A, ZUSSMAN J. Rock-Forming Minerals. Vol IB: Disilicates and Ring Silicates[J]. Mineralogical Magazine, 1986, 51(361): 471.
[6]	JANOTS E, ENGI M, BERGER A, et al. Prograde metamorphic sequence of REE minerals in pelitic rocks of the Central Alps: Implications for allanite-monazite-xenotime phase relations from 250 to 610 ℃[J]. Journal of Metamorphic Geology, 2008, 26(5): 509-526.
[7]	GREGORY C J, RUBATTO D, HERMANN J, et al. Allanite behaviour during incipient melting in the southern Central Alps[J]. Geochimica et Cosmochimica Acta, 2012, 84: 433-458.
[8]	TANG J W, JOHANNESSON K H. Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters[J]. Geochimica et Cosmochimica Acta, 2010, 74(23): 6690-6705.
[9]	LU L, WANG D H, WANG C H, et al. Mineralization regularity of ion-adsorption type REE deposits on Lincang granite in Yunnan Province[J]. Acta Geologica Sinica, 2019, 93(6): 1466-1478.
[10]	GUASTONI A, NESTOLA F, SCHIAZZA M. Post-magmatic solid solutions of CaCeAl₂(Fe³⁺2/3 1/3) [Si₂O₇][SiO₄]O(OH), allanite-(Ce) and REE-bearing epidote in miarolitic pegmatites of Permian Baveno granite (Verbania, central-southern Alps, Italy)[J]. Mineralogy and Petrology, 2017, 111(3): 315-323.
[11]	ZHAO X, LI N B, NIU H C, et al. Hydrothermal alteration of allanite promotes the generation of ion-adsorption LREE deposits in South China[J]. Ore Geology Reviews, 2023, 155: 105377.
[12]	FREI D, LIEBSCHER A, FRANZ G, et al. Trace element geochemistry of epidote minerals[J]. Reviews in Mineralogy and Geochemistry, 2004, 56(1): 553-605.
[13]	SCHMIDT M W, POLI S. Experimentally based water budgets for dehydrating slabs and consequences for arc magma generation[J]. Earth and Planetary Science Letters, 1998, 163(1/2/3/4): 361-379.
[14]	KLEMD R. Fluid inclusions in epidote minerals and fluid development in epidote-bearing rocks[J]. Reviews in Mineralogy and Geochemistry, 2004, 56(1): 197-234.
[15]	CORTI L, ZANONI D, GATTA G D, et al. Strain partitioning in host rock controls light rare earth element release from allanite-(Ce) in subduction zones[J]. Mineralogical Magazine, 2020, 84(1): 93-108.
[16]	FRANZ G, LIEBSCHER A. Physical and chemical properties of the epidote minerals-an introduction-[J]. Reviews in Mineralogy and Geochemistry, 2004, 56(1): 1-81.
[17]	GIERE R, SORENSEN S S. Allanite and other REE-rich epidote-group minerals[J]. Reviews in Mineralogy and Geochemistry, 2004, 56(1): 431-493.
[18]	GATTA G D, MILANI S, CORTI L, et al. Allanite at high pressure: Effect of REE on the elastic behaviour of epidote-group minerals[J]. Physics and Chemistry of Minerals, 2019, 46(8): 783-793.
[19]	GATTA G D, PAGLIARO F, LOTTI P, et al. Allanite at high temperature: Effect of REE on the thermal behaviour of epidote-group minerals[J]. Physics and Chemistry of Minerals, 2021, 48(9): 32.
[20]	REISSNER C E, BISMAYER U, KERN D, et al. Mechanical and structural properties of radiation-damaged allanite-(Ce) and the effects of thermal annealing[J]. Physics and Chemistry of Minerals, 2019, 46(10): 921-933.
[21]	BONAZZI P, MENCHETTI S. Monoclinic members of the epidote group: Effects of the AI ⇌ Fe³⁺ ⇌ Fe²⁺ substitution and of the entry of REE³⁺[J]. Mineralogy and Petrology, 1995, 53(1): 133-153.
[22]	SHEN C, SHU Z X, GU X P, et al. Site splitting at M3 in allanite-(Ce)[J]. Mineralogical Magazine, 2022, 86(1): 134-140.
[23]	KEYES C R. Epidote as a primary component op eruptive rocks[J]. Geological Society of America Bulletin, 1892, 4(1): 305-312.
[24]	UEDA T. The Crystal Structure of Allanite, OH(Ca, Ce)₂ (Fe^III, Fe^II) Al₂O Si₂O₇SiO₄[J]. Memoirs of the College of Science, University of Kyoto. Series B, 1955, 22(2): 145-163.
[25]	李厚民, 李立兴, 李以科, 等. 内蒙古白云鄂博铁-铌-稀土矿床矿化蚀变矿物组合及流体组成[J]. 现代地质, 2024, 38(1): 13-24.
[26]	宋彦博, 王建平, 沈存利, 等. 内蒙古扎拉格阿木铜矿床成矿岩体地质地球化学及其成矿学意义[J]. 现代地质, 2023, 37(6): 1482-1494.
[27]	胡明月, 何红蓼, 詹秀春, 等. 基体归一定量技术在激光烧蚀-等离子体质谱法锆石原位多元素分析中的应用[J]. 分析化学, 2008, 36(7): 947-953.
[28]	DOLOMANOV O V, BOURHIS L J, GILDEA R J, et al. OLEX2: A complete structure solution, refinement and analysis program[J]. Journal of Applied Crystallography, 2009, 42(2): 339-341.
[29]	SHELDRICK G M, DAUTER Z, WILSON K S, et al. The application of direct methods and Patterson interpretation to high-resolution native protein data[J]. Acta Crystallographica Section D, 1993, 49(1): 18-23.
[30]	BOURHIS L J, DOLOMANOV O V, GILDEA R J, et al. The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment- Olex2 dissected[J]. Acta Crystallographica. Section A, Foundations and Advances, 2015, 71(Pt 1): 59-75.
[31]	SHELDRICK G M. SHELXT-Integrated space-group and crystal-structure determination[J]. Acta Crystallographica Section A, 2015, 71(1): 3-8.
[32]	PERDIKATSIS V., PAPASTAVROU S. 6th Congress of the Geology. Soc. of Greece[C]// Athens, Greece: Geological Society of Greece, 1992.
[33]	CECH F, VRANA S, POVONDRA P. A non-metamict allanite from Zambia[J]. Neues Jahrbuch für Mineralogie/Abhandlungen, 1972, 116(2): 208-223.
[34]	REISSNER C E, REISSNER M, KERN D, et al. Iron sites in radiation-damaged allanite-(Ce): The effects of thermally induced oxidation and structural reorganization[J]. Hyperfine Interactions, 2020, 241(1): 18.
[35]	BONAZZI P, HOLTSTAM D, BINDI L, et al. Multi-analytical approach to solve the puzzle of an allanite-subgroup mineral from Kesebol, Vastra Gotaland, Sweden[J]. American Mineralogist, 2009, 94(1): 121-134.
[36]	ORLANDI P, PASERO M. Allanite-(La) from buca della vena mine, apuan Alps, Italy, an epidote-group mineral[J]. The Canadian Mineralogist, 2006, 44(1): 63-68.
[37]	BONAZZI P, MENCHETTI S. Manganese in monoclinic members of the epidote group: Piemontite and related minerals[J]. Reviews in Mineralogy and Geochemistry, 2004, 56(1): 495-552.
[38]	DAVIS D W, SCHANDL E S, WASTENEYS H A. U-Pb dating of minerals in alteration halos of Superior Province massive sulfide deposits: Syngenesis versus metamorphism[J]. Contributions to Mineralogy and Petrology, 1994, 115(4): 427-437.
[39]	郭海浩, 肖益林, 谷湘平, 等. 广东新丰稀土花岗岩中褐帘石LA-ICP-MS的U-Th-Pb定年研究[J]. 地质学报, 2014, 88(6): 1025-1037.
[40]	SHAW D M. Geochemistry of pelitic rocks. part iii: Major elements and general geochemistry[J]. Geological Society of America Bulletin, 1956, 67(7): 919.

ICP-MS
Thermo Finnigan ElementII 扇形磁场高分辨质谱
RF功率	Forward power	1200 W
冷却气(Ar)	Cooling gas	16.25 Lmin^-1
辅助气(Ar)	Auxiliary gas	0.9 Lmin^-1
样品气(Ar)	Sample gas	0.85 Lmin^-1
载气(He)	Carrier gas	0.82 Lmin^-1
Laser
New Wave ResearchESI 193nm ArF激光器
波长	Wavelength	193 nm
激光斑束	Spot size	40 μm
频率	Repetition	8 Hz
激光能量密度	Laserenergy	~3J/cm²
分析方法	Data acquisition parameters
分辨率	Resolution	低
扫描模式	Scan mode	E-Scan
磁定位时间	Settling time	0.001-0.300 s
点分析时间	Sample time	4 ms
分析点数/质量峰	Samples per peak	100
总扫描次数	Number of Scans	80
背景采集时间	Background collection	20 s
激光剥蚀时间	Ablation	40 s
吹扫时间	Washout	20 s
标准样品	External standard	NIST 610/NIST 612/KL2G
数据处理	Data reduction	多外标结合内标基体归一定量

ICP-MS
Thermo Finnigan ElementII 扇形磁场高分辨质谱
RF功率	Forward power	1200 W
冷却气(Ar)	Cooling gas	16.25 Lmin^-1
辅助气(Ar)	Auxiliary gas	0.9 Lmin^-1
样品气(Ar)	Sample gas	0.85 Lmin^-1
载气(He)	Carrier gas	0.82 Lmin^-1
Laser
New Wave ResearchESI 193nm ArF激光器
波长	Wavelength	193 nm
激光斑束	Spot size	40 μm
频率	Repetition	8 Hz
激光能量密度	Laserenergy	~3J/cm²
分析方法	Data acquisition parameters
分辨率	Resolution	低
扫描模式	Scan mode	E-Scan
磁定位时间	Settling time	0.001-0.300 s
点分析时间	Sample time	4 ms
分析点数/质量峰	Samples per peak	100
总扫描次数	Number of Scans	80
背景采集时间	Background collection	20 s
激光剥蚀时间	Ablation	40 s
吹扫时间	Washout	20 s
标准样品	External standard	NIST 610/NIST 612/KL2G
数据处理	Data reduction	多外标结合内标基体归一定量

元素	M14556	M14558	000468 -001	M14817	000481 -004	000481 -007	21DBX 84015	000894 -039(2)	M01229	M07315	绿帘石
Ca	124626	121816	101786	91914	70393	84135	116921	98325	105225	87164	237827
Si	339584	341125	328819	304224	307623	302276	317387	324656	313571	291979	351786
Fe	137176	147008	155652	129665	262869	267067	165859	171336	176466	256783	105928
Al	175447	166683	157366	189493	39850	59919	163741	138685	138833	82166	263848
Mg	7675	5470	11216	11932	2825	3341	4194	11237	8200	8852	577
Mn	4731	2607	3441	6791	6432	6300	3741	4376	4310	1963	441
Ti	14748	9083	6611	12203	40111	24807	4928	4531	6013	1003	474
La	44436	51202	51557	58732	68082	66384	53382	58821	62184	65645	5
Ce	83329	87594	94578	101579	111824	110948	89176	104333	103289	110155	15
Pr	7700	8101	8791	8074	10993	10428	9351	9670	8989	10393	3
Nd	26088	19849	27612	23511	40305	40599	32107	29402	27111	29376	14
Sm	3174	1523	2525	2613	6874	6851	2514	2376	1871	2831	4
Th	14618	5848	6059	12259	8504	7591	1462	124	140	101	0
U	141	177	14	191	821	257	14	4	5	1	0
Sr	398	352	550	2	259	192	655	336	497	8	8553

元素	M14556	M14558	000468 -001	M14817	000481 -004	000481 -007	21DBX 84015	000894 -039(2)	M01229	M07315	绿帘石
Ca	124626	121816	101786	91914	70393	84135	116921	98325	105225	87164	237827
Si	339584	341125	328819	304224	307623	302276	317387	324656	313571	291979	351786
Fe	137176	147008	155652	129665	262869	267067	165859	171336	176466	256783	105928
Al	175447	166683	157366	189493	39850	59919	163741	138685	138833	82166	263848
Mg	7675	5470	11216	11932	2825	3341	4194	11237	8200	8852	577
Mn	4731	2607	3441	6791	6432	6300	3741	4376	4310	1963	441
Ti	14748	9083	6611	12203	40111	24807	4928	4531	6013	1003	474
La	44436	51202	51557	58732	68082	66384	53382	58821	62184	65645	5
Ce	83329	87594	94578	101579	111824	110948	89176	104333	103289	110155	15
Pr	7700	8101	8791	8074	10993	10428	9351	9670	8989	10393	3
Nd	26088	19849	27612	23511	40305	40599	32107	29402	27111	29376	14
Sm	3174	1523	2525	2613	6874	6851	2514	2376	1871	2831	4
Th	14618	5848	6059	12259	8504	7591	1462	124	140	101	0
U	141	177	14	191	821	257	14	4	5	1	0
Sr	398	352	550	2	259	192	655	336	497	8	8553

样品编号	a(Å)	b(Å)	c(Å)	β(°)	V(Å³)
M14556	8.918(1)	5.724(1)	10.181(1)	115.06(1)	470.74(7)
M14558	8.947(1)	5.747(1)	10.195(1)	115.02(4)	474.89(1)
000468-001	8.960(2)	5.761(1)	10.223(2)	115.16(2)	477.64(2)
M14817	8.926(1)	5.770(1)	10.146(3)	114.82(1)	474.30(5)
000481-004	8.972(1)	5.823(1)	10.297(3)	115.37(2)	486.07(1)
000481-007	8.985(1)	5.808(1)	10.294(1)	115.24(1)	485.87(1)
21DBX84015	8.935(1)	5.761(1)	10.182(1)	114.97(1)	475.12(1)
000894-039(2)	8.920(1)	5.762(3)	10.132(2)	114.71 (1)	473.13(7)
M01229	8.941(3)	5.739(3)	10.225(3)	115.18(4)	474.83(1)
M07315	8.941(1)	5.813(1)	10.170(1)	114.75(2)	479.94(1)