新疆、青海、俄罗斯糖白玉的宝石学特征对比分析

为了查明新疆、青海、俄罗斯三地所产糖白玉的结构、成分和成因差异,在观察原料外观特征的基础上,采用常规宝石学方法、偏光显微镜、X射线粉末衍射仪和电子探针研究新疆、青海、俄罗斯糖白玉样品,从结构类型、矿物组成、化学成分和成因特征等方面进行对比分析。结果表明,以上三地糖白玉的主要矿物组成均为透闪石,次要矿物组成则各有不同。新疆、俄罗斯糖白玉以毛毡状变晶结构为主,青海糖白玉以纤维状变晶结构和纤维-隐晶质变晶结构为主;初步认定以上三地糖白玉的糖色为次生色,主要由褐铁矿导致。结合相关地质背景和风化作用特征,推测以上三地糖白玉不同的外观特征主要受玉体成矿后期和成矿期结束后周围环境变化的影响。     

应用激光诱导离解光谱自由定标法测定黄金首饰成分初探

利用激光诱导离解光谱自由定标法对一系列高纯度黄金样品进行定量分析与研究,初步证明了将此方法应用于黄金首饰成分测定的可行性。采用波长1 064nm的Nd∶YAG脉冲激光器激发黄金样品,波长范围为200～760nm的4CCD光纤光谱仪采集发射光谱,对Au元素质量分数范围为85.0%～99.6%的6件黄金标准样品进行激光诱导离解光谱测试。对所得黄金样品光谱中的Au,Cu,Ag三种元素分别选择合适的原子（离子）谱线代入自由定标法模型,通过所得参数拟合得到了所有元素原子（离子）的二维波尔兹曼平面曲线,并以此为基础进行元素的质量分数计算。激光诱导离解光谱自由定标法定量分析黄金样品中Au元素的质量分数与标准值的相对误差〈3%。     

和田软玉的化学成分和显微结构研究

采用场发射扫描电子显微镜（FE-SEM）系统对产自新疆和田的软玉样品的主要矿物组成、化学成分、显微结构等进行了较详细的研究,并与产自中国青海、辽宁、河南及韩国的软玉样品进行了比较。结果表明,各产地软玉样品的矿物组成、化学成分和显微结构有一定的差异。和田软玉样品中含有镁质绿泥石,而辽宁软玉样品中含有较多的闪锌矿,青海软玉样品中有含Zr元素矿物的颗粒,河南软玉样品中有含La与Ce元素较高矿物的颗粒;对纯度较高的软玉样品,仅依靠主成分很难区分其产地,但依靠其微量元素成分却能起到较好的鉴别作用;和田软玉样品中透闪石的显微结构较致密,纤维尺寸要小于其它产地软玉样品的。以上信息对确定软玉的产地具有较好的参考意义。     

吉林蛇纹石玉特征初步研究

对产自吉林省白山市抚松县沿江乡的蛇纹石玉样品分别从地质背景、激光诱导离解光谱、X射线粉末衍射和红外吸收光谱等方面进行了研究,并与辽宁岫玉样品进行了对比。结果表明,吉林蛇纹石玉样品的主要颜色为深浅不一的绿色,主要含Si,Al,Cr,Fe,Mn,Mg,Ca,Sr和Na等元素,其中Ca与Mg的谱线较强,Al,Mn与Sr的质量分数少;X射线粉末衍射结果显示,样品的主要矿物组成为纤蛇纹石,红外光谱结果也显示了其具有纤蛇纹石峰值的特征。     

俄罗斯奥斯泊(7号)矿碧玉的宝石学及致色离子研究

俄罗斯碧玉进入中国市场以来,以其艳丽的颜色和细腻的质地而深受广大爱玉者的喜爱。前人对俄罗斯碧玉的研究中,样品大部分采自市场,具体产地不清,且未对水线、猫眼进行研究。本文在前人研究的基础上,运用电子探针和微量元素测试等现代测试方法对俄罗斯奥斯泊矿碧玉进行分析,并对其致色离子进行研究。结果表明,奥斯泊矿碧玉主要矿物成分为透闪石,黑色点状杂质为铬铁矿,周围含有绿泥石;水线成分为透闪石;碧玉鲜艳的绿色调主要与Cr元素含量有关,Cr元素含量在400~1 500μg/g时,可使碧玉呈现比较鲜艳的翠绿色。     

拉曼光谱分析在软玉颜色评价中的应用

应用拉曼光谱分析方法对新疆、青海、台湾等地的软玉进行研究,分析针对白玉、青白玉、青玉、黄玉、碧玉等不同颜色品种软玉晶体结构中M1,M3位置阳离子的占位情况。指纹区拉曼光谱显示软玉主要组成矿物为透闪石,杂质离子的取代导致不同颜色品种软玉化学成分上的细微差异;M—OH伸缩振动区内主要吸收峰对表征软玉化学组成及颜色分级别具有重要意义,即利用3 675cm-1,3 661cm-1,3 645cm-1的峰强比值法计算Mg2+/(Mg2++Fe2+)的比值及Fe的相对含量。利用能量色散荧光光谱仪测试样品中Fe元素的相对含量,并选择有针对性的样品用电子探针测试Fe,Mg元素的含量,以此进一步验证拉曼光谱仪的测试结果的可靠性,最终得出3 675cm-1,3 661cm-1,3 645cm-1的峰强比值法可作为评价软玉颜色的色调及饱和度的重要参考。     

红外光谱-拉曼光谱无损检测技术对透闪石和阳起石鉴定特征的研究

透闪石属于角闪石族矿物,与阳起石构成完全类质同象,有关透闪石和阳起石的红外光谱和拉曼光谱的特征差异还未见有报道。本文以外观特征相似的5件广西大化黑青色阳起石样品和2件新疆塔县青玉样品为研究对象,在前期矿物成分测试的基础下,采用红外光谱和拉曼光谱进行测试和对比分析。结果表明,阳起石的红外光谱和拉曼光谱都表现为闪石类矿物的特征峰,与透闪石的特征峰存在细微差异,漫反射红外光谱的差异特征是鉴别两者最准确、快速、无损的依据,并且适用于任意形状的样品,符合珠宝玉石饰品实验室检测领域的要求,可为和田玉的分类分级和产地鉴别等提供科学依据。按照GB/T 16552-2017与GB/T 16553-2017规定,广西大化黑青色阳起石可定名为和田玉。     

基于太赫兹时域光谱技术的白色软玉产地鉴定研究

不同产地的白色软玉组成矿物成分和结构构造十分相近,但价值差异很大。太赫兹(terahertz,THz)时域光谱技术可以提供物质的化学组成、结构及构像等信息,光谱指纹特征信息可用于物质鉴别。利用透射式太赫兹时域光谱技术分别对新疆、韩国、青海和俄罗斯这4个产地的白色软玉进行了测试,将得到的时域光谱进行快速傅里叶变换(fast Fourier transform,FFT)和计算后使用Savitzky-Golay(S-G)平滑处理进行降噪,得到4个产地白色软玉的0. 2～2. 5 THz频域内折射率和吸收系数。研究表明,4个产地白色软玉THz光谱折射率存在数值差异;不同产地太赫兹特征吸收峰的存在形式不同,新疆、青海的白色软玉在2. 0 THz波段有1个突出的小型特征吸收峰,而韩国和俄罗斯的白色软玉在1. 5～2. 0 THz波段有1个宽大的吸收包络。这些结果为进一步开发基于太赫兹时域光谱技术的白色软玉产地识别方法提供了基础数据。     

不同颜色青海软玉微观形貌和矿物组成特征

青海软玉颜色丰富,近年来对青海软玉矿物学的研究不少,但针对不同颜色青海软玉矿物学特征的研究还存在欠缺。本文利用偏光显微镜、扫描电子显微镜、电子探针及粉晶X射线衍射仪器,从透闪石微形貌特征、微观结构、矿物组成及结晶度四个方面,研究了青海软玉颜色与矿物学特征的对应关系。结果表明:白玉、烟青玉、糖玉中透闪石主要为纤维状,显微纤维变晶结构,结晶度为96. 12%～96. 88%;青白玉和翠青玉中透闪石主要为叶片状,显微叶片变晶结构,结晶度为97. 35%,97. 32%;青玉和碧玉中透闪石主要为叶片状,显微叶片-隐晶质变晶结构,结晶度为95. 48%,95. 29%;黄玉中透闪石主要为柱状,显微柱状变晶结构,结晶度为97. 84%。青海软玉主要组成矿物均为透闪石,含量在95%以上,部分次要矿物如翠青玉中的榍石、黄玉中的钙长石、青玉中的菱镁矿、碧玉中的铬铁矿、糖玉中的斜黝帘石只出现在特定颜色的青海软玉样品中。研究认为不同颜色青海软玉矿物学特征确实存在差异,这些特征为研究不同颜色青海软玉成矿环境及成矿条件提供了科学依据。     

和田玉的物质组分和物理性质研究

和田玉属软玉类玉石,是透闪石矿物的集合体,也可称透闪石玉.白玉、青白玉和青玉是和田玉的主要品种.经电子探针分析,和田白玉、青白玉和青玉基本上由透闪石组成;透闪石主要由SiO2、MgO和CaO组成,含少量Al2O3、FeO、TiO2和MnO.玉石颜色主要与Fe2+、Ti4+、Mn2+的含量有关;具致密块状构造,扫描电子显微镜下显示毡毯状和显微交织结构,部分可见到显微粒状结构.和田玉中还含有少数杂质矿物.     

青海不同矿区软玉地球化学特征及Ar-Ar定年研究

为了探讨青海软玉的成矿物质来源、成矿环境及成矿年代,对三岔口矿点、拖拉海沟矿点及大灶火矿点的样品进行了主量元素、微量元素、稀土元素及Ar-Ar法定年的测试。结果显示,软玉样品的主量元素变化不大,与透闪石的理论值相符;微量元素差异较大,说明不同矿点成矿环境不同;稀土元素总量较低(0.29×10-6~40.72×10-6),Eu中度负异常(0.49~0.84),除大灶火青玉样品具左倾的重稀土元素富集模式[(La/Yb)N=0.16~0.61]外,其他样品都具有右倾的轻稀土元素富集模式,(La/Yb)N=2.87~6.34。三岔口矿点、拖拉海沟矿点软玉样品的稀土元素分配曲线与纳赤台基性辉长岩相似,大灶火矿点黄玉的稀土元素分配模式与二长花岗岩相似,而青玉的分配模式与斜长花岗岩相似。样品的~TAl~(3+)、~CAl~(3+)和Ti含量变化表明,翠青玉的成矿温度最高、压力最大,黄玉成矿温度较高、压力较大;烟青玉和青玉成矿温度较高、压力较低;白玉、青白玉和糖玉成矿温度较低、压力较低。翠青玉和黄玉中明显较低的Zr/Hf、Nb/Ta和Sr/Ba值提示其成矿环境酸性明显加强。3个矿点样品的成矿年代301.38~237.28 Ma介于晚石炭世—中三叠世之间,属于印支-海西运动阶段。成矿年代均晚于侵入岩形成年代,说明矿体经历了多次热液交代过程。     

A single-crystal neutron and X-ray diffraction study of pezzottaite, Cs(Be2Li)Al2Si6O18

The chemical composition and the crystal structure of pezzottaite [ideal composition Cs(Be₂Li)Al₂Si₆O₁₈; space group: ${\it{R}} \overline{\text{3}} $ c, a?=?15.9615(6) ?, c?=?27.8568(9) ?] from the type locality in Ambatovita (central Madagascar) were investigated by electron microprobe analysis in wavelength dispersive mode, thermo-gravimetric analysis, Fourier-transform infrared spectroscopy, single-crystal X-ray (at 298?K) and neutron (at 2.3?K) diffraction. The average chemical formula of the sample of pezzottaite resulted ^Cs1,Cs2(Cs_0.565Rb_0.027K_0.017)_Σ0.600 ^Na1,Na2(Na_0.101Ca_0.024)_Σ0.125Be_2.078Li_0.922 ^Al1,Al2(Mg_0.002Mn_0.002Fe_0.003Al_1.978)_Σ1.985 ^Si1,Si2,Si3(Al_0.056Si_5.944)_Σ6O₁₈·0.27H₂O. The (unpolarized) IR spectrum over the region 3,800–600?cm^?1 was collected and a comparison with the absorption bands found in beryl carried out. In particular, two-weak absorption bands ascribable to the fundamental H₂O stretching vibrations (i.e. 3,591 and 3,545?cm^?1) were observed, despite the mineral being nominally anhydrous. The X-ray and neutron structure refinements showed: (a) a non-significant presence of aluminium, beryllium or lithium at the Si1, Si2 and Si3 sites, (b) the absence (at a significant level) of lithium at the octahedral Al1, Al2 and Al3 sites and (c) a partial lithium/beryllium disordering between tetrahedral Be and Li sites.     

Friedrichbeckeite, K (□0.5Na0.5)2 (Mg0.8Mn0.1Fe0.1)2 (Be0.6 Mg0.4)3 [Si12O30], a new milarite-type mineral from the Bellerberg volcano, Eifel area, Germany

Friedrichbeckeite is a new milarite-type mineral. It was found in a single silicate-rich xenolith from a quarry at the Bellerberg volcano near Ettringen, eastern Eifel volcanic area, Germany. It forms thin tabular crystals flattened on {0001}, with a maximum diameter of 0.6 mm and a maximum thickness of 0.1 mm. It is associated with quartz, tridymite, augite, sanidine, magnesiohornblende, enstatite, pyrope, fluorapatite, hematite, braunite and roedderite. Friedrichbeckeite is light yellow, with white to light cream streak and vitreous lustre. It is brittle with irregular fracture and no cleavage, Mohs hardness of 6, calculated density is 2.686 gcm^?3. Optically, it is uniaxial positive with n_ω = 1.552(2) and n_ε = 1.561(2) at 589.3 nm and a distinct pleochroism from yellow (//ω) to light blue (//ε). Electron microprobe analyses yielded (wt.%): Na₂O 2.73, K₂O 4.16, BeO 4.67, MgO 11.24, MnO 2.05, FeO 1.76, Al₂O₃ 0.15, SiO₂ 73.51, (Σ CaO, TiO₂ = 0.06) sum 100.33 (BeO determined by LA-ICP-MS). The empirical formula based on Si = 12 is K_0.87 Na_0.86 (Mg_1.57Mn_0.28Fe_0.24)_Σ2.09 (Be_1.83?Mg_1.17)_Σ3.00 [Si₁₂O₃₀], and the simplified formula can be given as K (□_0.5Na_0.5)₂ (Mg_0.8Mn_0.1Fe_0.1)₂ (Be_0.6?Mg_0.4)₃ [Si₁₂O₃₀]. Friedrichbeckeite is hexagonal, space-group P6/mcc, with a = 9.970(1), c = 14.130(3) Å, V = 1216.4(3) ų, and Z = 2. The strongest lines in the X-ray powder diffraction pattern are (d in Å / I _obs / hkl): 3.180 / 100 / 121, 2.885 / 70 / 114, 4.993 / 30 / 110, 4.081 / 30 / 112, 3.690 / 30 / 022. A single-crystal structure refinement (R1 = 3.62 %) confirmed that the structure is isotypic with milarite and related ^[12] C ^[9] B ₂ ^[6] A ₂ ^[4] T2₃ [^[4] T1₁₂O₃₀] compounds. The C-site is dominated by potassium, the B-site is almost half occupied by sodium, and the A-site is dominated by Mg. The site-scattering at the T2-site can be refined to a Be/(Be?+?Mg) value close to 0.61; the T1-site is occupied by Si. Micro-Raman spectroscopy reveals an increasing splitting of scattering bands around 550 cm^?1 for friedrichbeckeite. The mineral can be classified as an unbranched ring silicate or as a beryllo-magnesiosilicate. With respect to the end-member formula K (□0.5Na0.5)₂ Mg₂ Be₃ [Si₁₂O₃₀] friedrichbeckeite represents the Mg-dominant analogue of almarudite, milarite or oftedalite. The mineral and its paragenesis were formed during pyrometamorphic modifications of the silicate-rich xenoliths enclosed in Quaternary leucite-tephritic lava of the Bellerberg volcano. Holotype material of friedrichbeckeite has been deposited at the mineral collection of the Naturhistorisches Museum Wien, Austria. The mineral is named friedrichbeckeite in honour of the Austrian mineralogist and petrographer Friedrich Johann Karl Becke (1855–1931).     

Dissolution of illite in saline-acidic solutions at 25 °C

The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K_1.38Na_0.05)(Al_2.87Mg_0.46Fe³⁺_0.39Fe²⁺_0.28Ti_0.07)[Si_7.02Al_0.98]O₂₀(OH)₄ was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H₂SO₄) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K⁺ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na⁺ from the solution and K⁺ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower R_Al (dissolution rate calculated from steady state Al release) than R_Si (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.     

The effects of sulfur intercalation on the optical properties of artificial ‘hackmanite’, Na8[Al6Si6O24]Cl1.8S0.1; ‘sulfosodalite’, Na8[Al6Si6O24]S; and natural tugtupite, Na8[Be2Al2Si8O24](Cl,S)2?δ

The minerals ??hackmanite?? and tugtupite exhibit tenebrescence (reversible photochromism) and photoluminescence. These features are generally attributed to the presence of sulfide species within their structures. But how these optical properties might be affected by intercalating additional amounts of sulfur into their structures was until now unknown. Artificial ??hackmanite??, Na₈[Al₆Si₆O₂₄]Cl_1.8S_0.1, and ??sulfosodalite??, Na₈[Al₆Si₆O₂₄]S, were heated with sulfur in evacuated quartz-glass ampoules over the temperature range 450?C1,050°C. This work has shown that sulfur intercalation into Na₈[Al₆Si₆O₂₄]Cl_1.8S_0.1 destroys the tenebrescence and induces a permanently pale blue and, at higher temperature, a pale green coloration. The effect on Na₈[Al₆Si₆O₂₄]S induced similar colorations but of a deeper hue. Annealing tugtupite, Na₈[Be₂Al₂Si₈O₂₄](Cl,S)_2??? under a sulfur atmosphere over the range 600?C700°C, destroyed the tenebrescence and resulted in a colorless tugtupite; but did not effect the photoluminescence. This suggests that the chemical species responsible for the tenebrescence in tugtupite is unlikely to be the same as that for the luminescence.     

Distance least squares modelling of the cubic sodalite structure and of the thermal expansion of Na8(Al6Si6O24)I2

The Distance Least Squares (DLS) structure modelling technique is used to determine the room-temperature structures of the sodalites Li₈(Al₆Si₆O₂₄)Cl₂, Na₈(Al₆Si₆O₂₄)Cl₂, K₈(Al₆Si₆O₂₄)Cl₂, Na₈(Al₆Si₆O₂₄)Br₂, and Na₈(Al₆Si₆O₂₄)I₂. The technique is also used to calculate the thermal expansion behaviour of Na₈(Al₆Si₆O₂₄)I₂ assuming that the discontinuity in its thermal expansion curve occurred either when the ideal fully-expanded state was achieved (case 1) or when the x-coordinate of the sodium atom became 0.25 (case 2). The results are given as plots of bond lengths and bond angles as a function of temperature. Case 2 was preferred and analysis of the results implied that the driving force for the untwisting of the partially-collapsed sodalite framework was in the framework bonds with the cavity ion bonds resisting the untwisting. Best estimates indicate that the expansion of the Na-O and Na-I bonds are 9% and 27.4% respectively, between room temperature and 810° C, and there is an apparent shortening of the framework bond distances of about 1.5%.     

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

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Cr~(3+)和Mn~(2+)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Fe~(3+);青白玉和碧玉致色元素为Fe~(2+)和Fe~(3+);青玉致色元素为Fe~(2+)、Fe~(3+)和高价态的Mn;翠青玉致色元素为Fe~(2+)、Fe~(3+)、Cr~(3+);黄玉和糖玉致色元素为Fe~(3+)和高价态的Mn;烟青玉致色元素为Fe~(3+)和Ti~(4+)。研究认为青海软玉中绿色调与Fe~(2+)有关,黄色调与Fe~(3+)和高价态的Mn有关,而蓝紫色调与Fe~(3+)和Ti~(4+)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。     

青海软玉的岩石矿物学特征

对采自青海东昆仑三岔口软玉矿区的样品进行了显微硬度、扫描电镜、X射线粉晶衍射物相定性和结晶度等分析,并将分析结果与新疆和田软玉进行了对比研究,发现青海软玉普遍显示出硬度较高、透闪石含量稍低、结晶度偏高的特点;透闪石主要呈毛毡状交织结构、显微纤维结构和显微片状结构,定向性普遍较好。对比两地软玉矿区的矿床地质特征,发现青海软玉成矿母岩相对贫Mg、Si而富Ca,动力改造相对较弱,成矿温度较高,这是造成两地所产软玉在上述岩石矿物学特征上巨大差异的根本原因;也是造成青海软玉透明度偏高、油润度不足的根本原因。