应用元素分析-电子顺磁共振能谱研究不同颜色青海软玉致色元素

于海燕; 阮青锋; 沙鑫; 杨育富

doi:10.15898/j.cnki.11-2131/td.201805140130

应用元素分析-电子顺磁共振能谱研究不同颜色青海软玉致色元素

1.
桂林理工大学地球科学学院, 广西桂林 541004

2.
广西隐伏金属矿产勘查重点实验室, 广西桂林 541004

基金项目:
广西自然科学基金项目(2015GXNSFBA1391);桂林理工大学博士科研启动经费(002401003554);广西隐伏金属矿产勘查重点实验室项目

详细信息

作者简介: 于海燕, 博士, 讲师, 宝石矿物学。E-mail:575976579@qq.com

中图分类号: O614.811;O657.2

收稿日期: 2018-05-14

修回日期: 2018-07-23

录用日期: 2019-04-09

Study on Color-causing Elements in Qinghai Nephrite by Elemental Analysis and Electron Paramagnetic Resonance Spectroscopy

1.
College of Earth Sciences, Guilin University of Technology, Guilin 541004, China

2.
Guangxi Key Laboratory of Hidden Metallic Deposits Exploration, Guilin 541004, China

Received Date: 14 May 2018

Revised Date: 23 July 2018

Accepted Date: 09 April 2019

摘要

摘要: 颜色是软玉价值的重要体现，青海软玉颜色丰富，而致色方面的研究较为滞后。近年来青海软玉致色研究多为翠青玉和烟青玉，认为Cr³⁺和Mn²⁺分别为翠青玉和烟青玉致色元素。青海软玉的颜色非单一色彩，如青白色、翠绿色、灰紫色等，因此青海软玉致色应包含多种致色元素。本文在前人研究的基础上，利用X射线荧光光谱法（XRF）、化学滴定法、电感耦合等离子体质谱法（ICP-MS）和电子顺磁共振能谱（EPR）测试数据，根据分析数据与色调变化之间的关系揭示了8种颜色青海软玉的致色元素。结果表明：白玉致色元素为Fe³⁺；青白玉和碧玉致色元素为Fe²⁺和Fe³⁺；青玉致色元素为Fe²⁺、Fe³⁺和高价态的Mn；翠青玉致色元素为Fe²⁺、Fe³⁺、Cr³⁺；黄玉和糖玉致色元素为Fe³⁺和高价态的Mn；烟青玉致色元素为Fe³⁺和Ti⁴⁺。研究认为青海软玉中绿色调与Fe²⁺有关，黄色调与Fe³⁺和高价态的Mn有关，而蓝紫色调与Fe³⁺和Ti⁴⁺有关。本研究基本确定了不同颜色青海软玉的致色元素，为青海软玉致色机制的研究提供了理论依据。
- 青海软玉 /
- 电子顺磁 /
- 致色元素 /
- 铁
Abstract: BACKGROUNDColor is the important manifestation of nephrite value. Qinghai nephrite has different colors, but there is a lack of research on coloration. In recent years, the study on the coloration of nephrite in Qinghai mainly focused on azure-green and blue-violet, and it was considered that Cr³⁺ and Mn²⁺ were respective coloration elements of azure-green and blue-violet. The color of Qinghai nephrite is not a simple color, such as white-green, azure-green, and blue-violet. Therefore, Qinghai nephrite should contain a variety of color-causing elements. OBJECTIVESTo reveal the color-causing elements of eight colors of nephrite from Qinghai based on the relationship between analysis data and hue changes. METHODSX-ray Fluorescence Spectrometry (XRF), Chemical Titration, Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Electron Paramagnetic Resonance Spectroscopy (EPR) were used to study the color-causing elements of nephrite. RESULTSThe color-causing element of white Qinghai nephrite was Fe³⁺. The color-causing elements of white-green and azure-green Qinghai nephrite were Fe²⁺ and Fe³⁺, respectively. The chromogenic elements of green Qinghai nephrite were Fe²⁺, Fe³⁺ and Mn in high valence. The color-causing elements of azure-green Qinghai nephrite were Fe²⁺, Fe³⁺ and Cr³⁺. The chromogenic elements of yellow and brown Qinghai nephrite were Fe³⁺ and high-valence Mn. Fe³⁺ and Ti⁴⁺ were the color-causing elements of blue-purple Qinghai nephrite. CONCLUSIONSThis study determined the color-causing elements of different colors of Qinghai nephrite, which provided a theoretical basis for the study of the coloration mechanism of Qinghai nephrite.
- Qinghai nephrite /
- Electron Paramagnetic Resonance /
- color-causing elements /
- Fe

HTML全文

图 1 不同颜色青海软玉中Ti、Mn、Cr含量柱状图

Figure 1.

下载: 全尺寸图片幻灯片

图 2 常温下不同颜色青海软玉在两个测试范围(a)3010~4010G、(b)260~6760G电子顺磁能谱对比图

Figure 2.

下载: 全尺寸图片幻灯片

图 3 常温下不同色调青海软玉Fe³⁺在400~2500G范围内EPR吸收谱线对比图

Figure 3.

下载: 全尺寸图片幻灯片

图 4 低温下不同种颜色青海软玉Ti³⁺在3010~4010G范围内EPR吸收谱线

Figure 4.

下载: 全尺寸图片幻灯片

图 5 常温下不同色调青海软玉Mn²⁺在3010~4010G范围内EPR吸收谱线对比图

Figure 5.

下载: 全尺寸图片幻灯片

表 1 不同颜色青海软玉中Fe²⁺和Fe³⁺含量

Table 1. Content of Fe²⁺ and Fe³⁺ in Qinghai nephrites with different colors

软玉类型	样品编号	色调	Fe₂O₃含量(%)	Fe²⁺含量(%)	Fe³⁺含量(%)	Fe_总1(%)=(Fe²+Fe³⁺)	Fe_总2(%)=Fe₂O₃×112/160	误差(%)=$ \frac{{{\rm Fe_{总1}-Fe_{总2}}}}{{{\rm Fe_{总1}}}} \times 100$
白玉	B-4	灰白	0.75	0.23	0.32	0.55	0.53	3.64
白玉	B-2	黄白	1.11	0.12	0.67	0.79	0.78	1.27
烟青玉	Y-2	浅	0.41	0.17	0.13	0.30	0.29	3.33
烟青玉	Y-1	深	0.59	0.13	0.29	0.42	0.41	2.38
糖玉	T-2	浅	0.89	0.27	0.36	0.63	0.62	1.59
糖玉	T-1	深	1.09	0.18	0.62	0.80	0.76	5.00
黄口料	H-1	浅	1.24	0.39	0.51	0.90	0.87	3.33
黄口料	H-2	深	1.55	0.32	0.79	1.11	1.09	1.80
青白玉	QB-1	浅	0.55	0.13	0.27	0.40	0.39	2.50
青白玉	QB-2	深	1.12	0.33	0.48	0.81	0.78	3.70
翠青玉	C-1	浅	0.86	0.32	0.29	0.61	0.60	1.64
翠青玉	C-3	深	1.41	0.49	0.54	1.03	0.99	3.88
青玉	Q-2	浅	4.01	2.33	0.61	2.94	2.81	4.42
青玉	Q-1	深	6.53	3.66	1.07	4.73	4.57	3.38
碧玉	BY-1	浅	5.88	2.35	1.95	4.30	4.12	4.19
碧玉	BY-2	深	8.87	3.76	2.72	6.48	6.21	4.17

下载: 导出CSV

表 2 不同颜色青海软玉中过渡金属元素含量

Table 2. Content of transition metallic elements in Qinghai nephrites with different colors

软玉类型	样品编号	色调	Ti (μg/g)	Mn (μg/g)	Cr (μg/g)	V (μg/g)	Co (μg/g)	Ni (μg/g)	Cu (μg/g)
白玉	B-4浅	灰白	21.93	502.51	22.94	1.7	2.98	14.84	5.83
白玉	B-2深	黄白	27.08	460.97	16.52	7.26	2.8	7.67	4.72
烟青玉	Y-3浅	浅	143.3	57.03	16.49	8.24	2.29	12.37	6.22
烟青玉	Y-1深	深	169.05	101.99	16.92	13.35	2.11	12.41	15.4
糖玉	T-2浅	浅	32.25	483.11	9.99	3.2	2.32	5.53	3.09
糖玉	T-1深	深	37.52	680.17	20.38	1.79	2.56	7.53	4.73
黄玉	H-1浅	浅	314.27	161.2	34.89	7.11	0.4	37.44	10.98
黄玉	H-2深	深	273.12	282.23	26.60	13.1	5.8	12.7	10.3
青白玉	QB-1浅	浅	23.42	322.85	18.9	1.64	1.69	6.22	5.36
青白玉	QB-2深	深	23.63	306.62	11.53	4.64	1.87	7.37	4.77
翠青玉	C-1浅	浅	2564.13	128.11	128.80	68.38	1.97	38.08	14.39
翠青玉	C-3深	深	1140.5	108.4	260.26	36.7	2.9	38.2	20.9
青玉	Q-2浅	浅	265.75	1844.4	21.54	9.87	25.43	24.72	3.82
青玉	Q-1深	深	167.12	1357.94	18.76	7.28	9.61	24.39	6.5
碧玉	BY-1浅	浅	61.59	914.55	1943.25	645.78	59.68	1406.16	4.62
碧玉	BY-2深	深	65.96	1413.15	1957.30	648	54.5	1369.7	9.2

下载: 导出CSV

参考文献(23)

[1]	李雯雯, 吴瑞华.和田玉的颜色及其色度学研究[J].矿物岩石地球化学通报, 1999, 18(4):418-422. http://d.old.wanfangdata.com.cn/Conference/325053 Li W W, Wu R H.The colorimetry and chromaticity study of Xinjiang Hetian jade[J].Bulletin of Mineralogy, Petrology and Geochemistry, 1999, 18(4):418-422. http://d.old.wanfangdata.com.cn/Conference/325053
[2]	那宝成, 冷莹莹, 李祥虎.软玉致色元素的研究[J].超硬材料工程, 2008, 20(3):55-58. doi: 10.3969/j.issn.1673-1433.2008.03.014 Na B C, Leng Y Y, Li X H.Research on coloring element of nephrite[J].Uperhard Material Engineering, 2008, 20(3):55-58. doi: 10.3969/j.issn.1673-1433.2008.03.014
[3]	Wang Y Y, Gan F X.Coloration mechanism and chromaticity of Xiuyan jade of China[J].Spectroscopy and Spectral Analysis, 2012, 32(9):2305-2310. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=gpxygpfx201209001
[4]	冯晓燕, 陆太进, 张辉, 等.拉曼光谱分析在软玉颜色评价中的应用[J].矿物岩石, 2015, 35(1):1-6. doi: 10.3969/j.issn.1007-2802.2015.01.001 Feng X Y, Lu T J, Zhang H, et al.Application of Raman spectroscopic technique to investigation on nephrite color[J].Journal of Mineralogy and Petrology, 2015, 35(1):1-6. doi: 10.3969/j.issn.1007-2802.2015.01.001
[5]	韩文, 洪汉烈, 吴钰, 等.和田玉糖玉的致色机理研究[J].光谱学与光谱分析, 2013, 33(6):1446-1450. doi: 10.3964/j.issn.1000-0593(2013)06-1446-05 Han W, Hong H L, Wu Y, et al.Color genesis of brown jade from Hetian nephrite[J].Spectroscopy and Spectral Analysis, 2013, 33(6):1446-1450. doi: 10.3964/j.issn.1000-0593(2013)06-1446-05
[6]	周征宇, 陈盈, 廖宗廷, 等.溧阳软玉的岩石矿物学研究[J].岩石矿物学杂志, 2009, 28(5):490-494. doi: 10.3969/j.issn.1000-6524.2009.05.010 Zhou Z Y, Chen Y, Liao Z T, et al.A petrological and mineralogical study of Liyang nephrite[J].Acta Petrologica et Mineralogica, 2009, 28(5):490-494. doi: 10.3969/j.issn.1000-6524.2009.05.010
[7]	卢保奇.四川石棉软玉猫眼和蛇纹石猫眼的宝石矿物学及其谱学研究[D].上海: 上海大学, 2005.http://cdmd.cnki.com.cn/Article/CDMD-11903-2006176062.htm Lu B Q.The Gemological Mineralogy and Spectroscopy of Nephrite Cat's Eye and Serpentine Cat's Eye from Shimian, Sichuan Province, Southwest of China[D]: Shanghai: Shanghai University, 2005.
[8]	杨林.贵州罗甸玉矿物岩石学特征及成因机理研究[D].成都: 成都理工大学, 2013.http://cdmd.cnki.com.cn/Article/CDMD-10616-1013288435.htm Yang L.Study on Petro-mineral Features and Genetic Mechanism of Luodian Jade, Guizhou Province[D].Chengdu: Chengdu University of Technology, 2013.
[9]	刘虹靓, 杨明星, 杨天翔, 等.青海翠青玉的宝石学特征及颜色研究[J].宝石和宝石学杂志, 2013, 15(1):7-14. doi: 10.3969/j.issn.1008-214X.2013.01.002 Liu H L, Yang M X, Yang T X, et al.Study on colour and gemological characteristics of viridis nephrite from Qinghai Province[J].Journal of Gems & Gemmology, 2013, 15(1):7-14. doi: 10.3969/j.issn.1008-214X.2013.01.002
[10]	罗泽敏, 沈锡田, 杨明星.青海三岔河灰紫色软玉颜色定量表达与紫色成因研究[J].光谱学与光谱分析, 2017, 37(3):822-828. http://d.old.wanfangdata.com.cn/Periodical/gpxygpfx201703028 Luo Z M, Shen X T, Yang M X.Study on color quantitative expression, replication and color origin of gray-purple nephrite from Qinghai, China based on spectroscopy methods[J].Pectroscopy and Spectral Analysis, 2017, 37(3):822-828. http://d.old.wanfangdata.com.cn/Periodical/gpxygpfx201703028
[11]	Manoogian A.The electron spin resonance of Mn²⁺ in tremolite[J].Canadian Journal of Physics, 2011, 46(2):129-133. https://www.nrcresearchpress.com/doi/abs/10.1139/p68-019
[12]	Manoogian A.Intensity of allowed and forbidden electron spin resonance lines of Mn²⁺ in tremolite[J].Canadian Journal of Physics, 2011, 46(9):1029-1033. https://www.researchgate.net/publication/237153777_Intensity_of_allowed_and_forbidden_electron_spin_resonance_lines_of_Mn2_in_tremolite
[13]	Mcgavin D G, Palmer R A, Tennant W C, et al.Use of ultrasonically modulated electron resonance to study S-state ions in mineral crystals:Mn²⁺, Fe³⁺in tremolite[J].Physics & Chemistry of Minerals, 1982, 8(5):200-205. https://link.springer.com/article/10.1007%2FBF00309478
[14]	Vinokurov V M, Zaripov M M, Stepanov V G.Paramagnetic resonance of Mn²⁺ions in diopside[J].Solid State Communications, 1964, 2(5):Ⅲ-Ⅳ. https://www.sciencedirect.com/science/article/pii/0038109864904132
[15]	Pan Y, Nilges M J.Electron paramagnetic resonance spectroscopy:Basic principles, experimental techniques and applications to earth and planetary sciences[J].Reviews in Mineralogy & Geochemistry, 2014, 78(1):655-690. http://cn.bing.com/academic/profile?id=576f131d0d7a61b8fccf8d8305c4c237&encoded=0&v=paper_preview&mkt=zh-cn
[16]	Vasyukov V N, Shapovalov V V, Schwarz S A, et al.Temperature-induced changes in the EPR spectrum of the magnetic center in kaolin[J].Journal of Magnetic Resonance, 2002, 154(1):15-21. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=2888abdc553afe04eb71302533f193e9
[17]	Pan Y, Mao M, Lin J.Single-crystal EPR study of Fe³⁺ and VO²⁺ in prehnite from the Jeffrey mine, Asbestos, Quebec[J].Canadian Mineralogist, 2009, 47(4):933-945. doi: 10.3749/canmin.47.4.933
[18]	Balan E.Structural Fe³⁺ in natural kaolinites:New insights from electron paramagnetic resonance spectra fitting at X and Q-band frequencies[J].Clays & Clay Minerals, 1999, 47(5):605-616. https://link.springer.com/article/10.1346%2FCCMN.1999.0470507
[19]	Gaite J M, Izotov V V, Nikitin S I, et al.EPR and optical spectroscopy of impurities in two synthetic beryls[J].Applied Magnetic Resonance, 2001, 20(3):307-315. doi: 10.1007/BF03162283
[20]	Ollier N, Fuchs Y, Cavani O, et al.Influence of impurities on Cr³⁺ luminescence properties in Brazilian emerald and alexandrite[J].European Journal of Mineralogy, 2015, 27(6):783-792. doi: 10.1127/ejm/2015/0027-2484
[21]	Zheng W C, Zhou Q, Wu X X, et al.Theoretical investigations of the EPR parameters of Ti³⁺ in beryl crystal[J].Zeitschrift Für Naturforschung A, 2006, 61(5-6):286-288. http://adsabs.harvard.edu/abs/2006ZNatA..61..286Z
[22]	Yuan Z, Wu X X, Lü H, et al.EPR parameters and defect structures of the off-center Ti³⁺ ion on the Sr²⁺ site in neutron-irradiated SrTiO₃ crystal[J].Journal of Physics & Chemistry of Solids, 2007, 68(9):1652-1655. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=5caa74e930f5066ad6447f2bea1db16d
[23]	赵敏光.晶体场和电子顺磁共振理论[M].北京:科学出版社, 1991:204-216. Zhao M G.Theory on Crystal Field and Electron Paramagnetic Resonance[M].Beijing:Science Press, 1991:204-216

施引文献

资源附件(0)

访问统计

图(5)

表(2)

计量

文章访问数: 2088
PDF下载数: 89
施引文献: 0

应用元素分析-电子顺磁共振能谱研究不同颜色青海软玉致色元素

1. 桂林理工大学地球科学学院, 广西 桂林 541004 2. 广西隐伏金属矿产勘查重点实验室, 广西 桂林 541004

作者简介: 于海燕, 博士, 讲师, 宝石矿物学。E-mail:575976579@qq.com

Study on Color-causing Elements in Qinghai Nephrite by Elemental Analysis and Electron Paramagnetic Resonance Spectroscopy

1. College of Earth Sciences, Guilin University of Technology, Guilin 541004, China 2. Guangxi Key Laboratory of Hidden Metallic Deposits Exploration, Guilin 541004, China

计量

出版历程

目录

1.
桂林理工大学地球科学学院, 广西桂林 541004

2.
广西隐伏金属矿产勘查重点实验室, 广西桂林 541004

1.
College of Earth Sciences, Guilin University of Technology, Guilin 541004, China

2.
Guangxi Key Laboratory of Hidden Metallic Deposits Exploration, Guilin 541004, China