方解石晶体定向性对水的拉曼光谱影响的实验评估

doi:10.13232/j.cnki.jnju.2020.03.001

南京大学学报(自然科学版) ›› 2020, Vol. 56 ›› Issue (3): 297–307.doi: 10.13232/j.cnki.jnju.2020.03.001

• • 下一篇

方解石晶体定向性对水的拉曼光谱影响的实验评估

刘显¹,陈强路²,王小林¹(),丘靥²,杨源显¹

^1.南京大学地球科学与工程学院，南京，210023
^2.中国石化石油勘探开发研究院无锡石油地质研究所，无锡，214126

收稿日期:2020-03-03 出版日期:2020-05-30 发布日期:2020-06-03
通讯作者: 王小林 E-mail:xlinwang@nju.edu.cn
基金资助:
国家自然科学基金(41922023)

Experimental evaluation of the effect of calcite crystal orientation on the Raman spectrum of water: Application to the determination of salinity of natural fluid inclusions

Xian Liu¹,Qianglu Chen²,Xiaolin Wang¹(),Ye Qiu²,Yuanxian Yang¹

^1.School of Earth Sciences and Engineering，Nanjing University，Nanjing，210023，China
^2.Petroleum Exploration and Production Research Institute of SINOPEC，Wuxi，214126，China

Received:2020-03-03 Online:2020-05-30 Published:2020-06-03
Contact: Xiaolin Wang E-mail:xlinwang@nju.edu.cn

摘要/Abstract

摘要：

拉曼光谱是一种原位、快速、无损的分析技术，被广泛用于流体包裹体组分的定性描述和半定量?定量分析.盐水溶液的OH伸缩振动谱峰(ν_s?H₂O)随流体盐度升高向高波数偏移，同时其对称性也逐渐增强，是反映流体盐度的良好指标.需要注意的是，具有双折射性的寄主矿物本身的晶体定向性也会影响ν_s?H₂O谱峰的峰形，是限制该方法应用于自然包裹体盐度测定的重要因素.方解石是最常见的包裹体寄主矿物之一，其晶体定向性对ν_s?H₂O谱峰的影响规律缺少系统的实验研究.应用熔融毛细硅管合成包裹体技术制备了一系列含不同浓度NaCl溶液的透明腔体，在室温条件下收集其拉曼光谱，经过拟合处理后，建立了NaCl浓度和拉曼光谱参数之间的定量关系.而后，系统分析了沿 $1011$ $1121$ 和 $0001$ 方向制备的方解石薄片的方向性对溶液的ν_s?H₂O谱峰的影响规律.方解石晶体定向性对ν_s?H₂O光谱形态的影响表现为使低波数部分得以增强或者减弱.在系统实验观测的基础上，提出了较为可行的方解石中包裹体盐度的原位拉曼光谱测定流程，即将包裹体片旋转0°~180°获取多条拉曼光谱，经拟合处理后获得其光谱参数的平均值，而后计算流体盐度.最后，将该方法应用于地质实例分析，测定了瑶岗仙钨矿晚期热液方解石脉中的包裹体盐度，并与显微测温法进行了对比，其偏差在±5%以内.

关键词: 拉曼光谱, 方解石, 晶体定向性, 流体包裹体, 盐度

Abstract:

Raman spectroscopy is an in situ，fast，and nondestructive analytical technique，which is widely used for qualitative description，semi?quantitative and quantitative analysis of fluid inclusion components. The Raman OH stretching band of water (ν_s?H₂O ) shifts to higher wavenumber and becomes sharper and more symmetric with increasing NaCl concentration，which can be used to investigate the salinity of the aqueous phase inside the fluid inclusion. It should be noted that crystal orientation of the host mineral with birefringence also influences the ν_s?H₂O band shape，which limits the application of this method to the determination of fluid salinity in natural fluid inclusions. Calcite is one of the most common host minerals of fluid inclusions. However，experimental investigations on the effects of calcite crystal orientation on ν_s?H₂O band are lacking. In this paper，a series of fused silica capilary capsules (FSCCs) containing different concentrations of NaCl solutions were prepared. Raman spectra of these solutions were collected at room temprature and the quantitative relationship between NaCl concentration and Raman spectral parameter was established. Three calcite thin sections were prepared along the $1011$ ， $1121$ and $0001$ orientations. The calcite thin section was placed on the FSCC containing water or NaCl solution. Then，the calcite thin section was rotated clockwise for 180°; Raman spectra were collected at intervals of 15°. The effect of calcite crystal orientation on the ν_s?H₂O band was investigated by comparing these spectra collected at different rotation degrees. This effect can be described as eihter the low wavenumber component or the high wavenumber component of ν_s?H₂O band was enhanced.Based on these experimental investigations，a feasible method was proposed for themeasurements of the salnity of fluid inclusions hosted in calcite. It is recommended that multiple Raman spectra should be collected at intervals of 15° when fluid inclusion wafer was rotated by 180°. Then，the average value of the spectral parameter was obtained and used to calculate salinity. At last，we measured the salinity of fluid inclusions in the late hydrothermal stage calcite in vein?type tungsten deposit at Yaogangxian by applying the microthermometric and in situ Raman spectroscopyic methods. The results show that the salinity of natural calcite?hosted fluid inclusion can be measured using in situ Raman spectroscopic method. The salinity deviation obtained by these two methods was reported to be within ±5%.

Key words: Raman spectroscopy, calcite, crystal orientation, fluid inclusion, salinity

中图分类号:

P61，P59

刘显, 陈强路, 王小林, 丘靥, 杨源显. 方解石晶体定向性对水的拉曼光谱影响的实验评估[J]. 南京大学学报(自然科学版), 2020, 56(3): 297–307.

Xian Liu, Qianglu Chen, Xiaolin Wang, Ye Qiu, Yuanxian Yang. Experimental evaluation of the effect of calcite crystal orientation on the Raman spectrum of water: Application to the determination of salinity of natural fluid inclusions[J]. Journal of Nanjing University(Natural Sciences), 2020, 56(3): 297–307.

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参考文献 17

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NaCl浓度 (wt%)	质量摩尔浓度(mol·kg^-1)	ν(HBS)	ν(HBW)	I_HBS	I_HBW	FWHM_HBS	FWHM_HBW	K′	ΔK′
0	0	3209.49	3435.60	21385.10	36374.30	223.83	288.57	1.31931	0.00000
1	0.17284	3211.95	3437.91	10221.20	16980.20	228.51	283.85	1.33737	0.01737
3.5	0.62063	3215.52	3442.45	7141.01	12782.50	228.49	276.17	1.48099	0.16099
5	0.90061	3214.77	3445.02	4942.96	9144.93	237.36	282.07	1.55685	0.23685
8	1.48796	3218.38	3444.58	8704.45	18437.50	218.48	265.90	1.74044	0.42044
9	1.69235	3219.06	3444.97	8988.12	19289.80	217.63	264.26	1.76746	0.44746
10	1.90129	3220.08	3445.71	9043.56	19825.00	215.18	262.73	1.79543	0.47543
15.5	3.13881	3225.09	3448.52	16035.90	42081.80	206.19	249.84	2.16571	0.84571
18.65	3.92293	3226.43	3449.36	7922.71	23322.00	197.71	246.28	2.36314	1.04314
25	5.70386	3229.54	3449.82	6998.69	25727.40	181.12	236.98	2.80956	1.48956

编号	T_m.ice (℃) ^a	盐度 (wt% NaCl equiv.) ^b	ΔK′	拉曼测定盐度 (wt% NaCl equiv.) ^c	误差 (%) ^d
1	-6.1	9.34	0.45	8.89	-4.83
2	-5.3	8.28	0.42	8.52	2.92
3	-5.1	8.00	0.40	8.02	0.24
4	-5.6	8.68	0.43	8.64	-0.44
5	-8.2	11.93	0.62	11.93	0.19
6	-9.8	13.72	0.69	13.16	-4.12

方解石晶体定向性对水的拉曼光谱影响的实验评估

Experimental evaluation of the effect of calcite crystal orientation on the Raman spectrum of water: Application to the determination of salinity of natural fluid inclusions

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