德国Johanngeorgenstadt的绿柱石、黄硫石和KNi3(AsO4)(As2O7)的天然类似物的化学组成和拉曼光谱

IF 1.1 4区 地球科学 Q3 GEOCHEMISTRY & GEOPHYSICS
Iwona KORYBSKA-SADŁO, Adam Szuszkiewicz, Marta Prell, Piotr Gunia
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引用次数: 0

摘要

在德国萨克森州Johanngeorgenstadt的一份历史样品中,发现了两种罕见的无水砷酸盐绿柱石Ni8.5(AsO4)2As5+O8和黄硫石Ni3(AsO4)2。首次通过扫描电子显微镜、电子探针分析和拉曼光谱对这些矿物进行了表征。它们大多为深绿色(绿柱石)至浅绿色(黄硫石)细粒或微晶结壳,位于石英基质上,与重晶石、辉玄岩、白云石和绿柱石有关。绿柱石形成高达200μm的大型伪六方片状晶体,而黄硫石形成短棱柱,形状几乎相等,通常具有模糊、发育不良和圆形的表面。这两种矿物的化学组成可以用经验公式表示:(Ni 7.92 Co 0.52 Cu 0.06)∑8.50。这两种矿物的拉曼光谱都缺乏与OH伸缩振动相关的谱带,并且在砷铁矿的情况下,以817、846和886 cm–1为中心的AsO4多面体中,以反对称的Γ3和对称的Γ1 As–O振动为主,在黄硫矿的情况下为786、808、826和843 cm–1。AsO4多面体中拉伸振动As-O的谱带在绿柱石中分别位于728和735 cm–1处,在黄硫石中分别略微位移到726和747 cm–1。由于NiO6八面体的拉伸模式,绿柱石的拉曼光谱还包含明确的692、675和658 cm–1波段,这是576 cm–2的一个广泛特征,可能来自与AsO6八面的许多模式。另一方面,在700 cm–1以下的AsO4中,黄硫石光谱显示出许多低强度、定义明确的谱带,这些谱带与反对称的Γ4和Γ2对称弯曲振动有关,也与250 cm–1下方的晶格振动模式和Ni-O相互作用有关。局部而言,黄硫矿颗粒之间的间隙充满了隐晶质,其平均化学组成为(K0.90 Ba 0.01)∑0.91(Ni 2.86 Co 0.11 Cu 0.05)∑3.02(As 1.00 O4)(As 2.1 O7),并含有微量Na(基于11种氧的7次分析的平均值)。记录的拉曼光谱具有强烈重叠的黄硫酸盐相关信号,缺乏水分子或OH基团的谱带,并且包含与焦砷酸盐As 2 O 7基团的As–O–As振动模式相关的谱带。虽然无法获得更详细的晶体结构数据,但我们认为这是首次报道KNi3(AsO4)(As2O7)相的自然出现。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Chemical composition and Raman spectroscopy of aerugite, xanthiosite, and a natural analog of KNi3(AsO4)(As2O7) from Johanngeorgenstadt, Germany
Aerugite Ni 8.5 (AsO 4 ) 2 As 5+ O 8 and xanthiosite Ni 3 (AsO 4 ) 2 , two rare anhydrous arsenates, have been identified in a historic sample from Johanngeorgenstadt, Saxony, Germany. The minerals have been characterized through scanning electron microscopy, electron microprobe analysis and Raman spectroscopy for the first time. They are mostly dark-green (aerugite) to light-green (xanthiosite) fine-grained or microcrystalline crusts on a quartz matrix in association with barite, bunsenite, dolomite, and rooseveltite. Aerugite forms up to 200 μm large pseudo-hexagonal platy crystals, whereas xanthiosite forms short prisms to nearly equant forms, often with indistinct, poorly-developed and rounded faces. The chemical composition of the two minerals can be expressed by the empirical formulas: (Ni 7.92 Co 0.52 Cu 0.06 ) Σ8.50 (As 1.00 O 4 ) 2 As 1.00 O 8 with traces of Bi (aerugite, mean of 4 analyses, based on 32 oxygens) and (Ni 2.85 Co 0.12 Cu 0.03 ) Σ3.00 (As 1.00 O 4 ) 2 (xanthiosite, mean of 5 analyses, based on 32 oxygens). The Raman spectra of both minerals lack bands related to OH stretching vibrations and are dominated by antisymmetric ν 3 and symmetric ν 1 As–O vibrations in AsO 4 polyhedra centered at 817, 846 and 886 cm –1 in the case of aerugite and at 786, 808, 826 and 843 cm –1 in xanthiosite. Bands from stretching vibrations As-O in AsO 4 polyhedra are located at 728 and 735 cm –1 in aerugite and are slightly displaced to 726 and 747 cm –1 in xanthiosite. The Raman spectrum of aerugite also contains well-defined 692, 675 and 658 cm –1 bands due to the stretching mode of NiO 6 octahedra, a broad feature at 576 cm –1 probably from a number of modes connected with AsO 6 octahedra. On the other hand, the xanthiosite spectrum displays a number of low-intensity, well-defined bands related to antisymmetric ν 4 and ν 2 symmetric bending vibrations in AsO 4 below 700 cm –1 as well as to lattice vibrational modes and Ni-O interactions below 250 cm –1 . Locally, the interstices between xanthiosite grains are filled with cryptocrystalline mass with the mean chemical composition of (K 0.90 Ba 0.01 ) Σ0.91 (Ni 2.86 Co 0.11 Cu 0.05 ) Σ3.02 (As 1.00 O 4 )(As 2.1 O 7 ) with traces of Na (mean of 7 analyses, based on 11 oxygens). The recorded Raman spectrum, with a strongly overlapping xanthiosite-related signal, lacks bands of water molecules or OH groups and contains bands related to the As–O–As vibration modes attributed to pyroarsenate As 2 O 7 groups. Although it was impossible to obtain more detailed data on crystal structure, we suggest this is the first reported natural occurrence of KNi 3 (AsO 4 )(As 2 O 7 ) phase.
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来源期刊
Journal of Geosciences
Journal of Geosciences GEOSCIENCES, MULTIDISCIPLINARY-MINERALOGY
CiteScore
2.30
自引率
7.10%
发文量
15
审稿时长
>12 weeks
期刊介绍: The Journal of Geosciences is an international peer-reviewed journal published by the Czech Geological Society with support from the Czech Geological Survey. It accepts high-quality original research or review papers dealing with all aspects of the nature and origin of igneous and metamorphic rocks. The Journal focuses, mainly but not exclusively, on: -Process-oriented regional studies of igneous and metamorphic complexes- Research in structural geology and tectonics- Igneous and metamorphic petrology- Mineral chemistry and mineralogy- Major- and trace-element geochemistry, isotope geochemistry- Dating igneous activity and metamorphic events- Experimental petrology and mineralogy- Theoretical models of igneous and metamorphic processes- Mineralizing processes and mineral deposits. All the papers are written in English, even though they may be accompanied by an additional Czech abstract. Each contribution is a subject to peer review by at least two independent reviewers, typically at least one from abroad. The Journal appears 2 to 4 times a year. Formally it is divided in annual volumes, each of them including 4 issues.
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