样品重量在矿物热分析中的作用

目前,热分析的发展趋向于微量化,但样品重量过少时有些矿物差热曲线的形态特征就要发生改变。本文从实践的结果论述样品重量与差热曲线、热量曲线特征之间的关系,以寻求合理的样品重量。     

定量分析宝石材料化学成分的激光诱导离解光谱方法研究

主要针对宝石材料进行了激光诱导离解光谱技术定量分析方法的总结以及对比研究。选择外标法、自由定标法和归一化的外标法三种较为适用于宝石材料分析的方法进行了介绍。选取陨石玻璃、绿辉石、紫色翡翠以及硅酸盐玻璃等成分较为均匀的样品作为分析对象,使用中国地质大学（武汉）珠宝学院自制的激光诱导离解光谱设备,分别运用三种方法对其进行了定量分析的计算。定量分析结果显示,外标法易受成分变化及结构差异而造成的基体效应的影响,分析的准确度不高;自由定标法在分析成分复杂的样品时,其影响因素十分复杂,会产生较大的误差;归一化的外标法可有效校正基体效应的影响,其定量分析结果要优于前两者,虽然在微量元素分析准确度上尚需改进,但不失为一种较好的快速定量分析宝石材料的定量分析方法。     

高岭石-多水高岭石演化系列的热谱特征

高岭石-多水高岭石演化系列共包括四种矿物:结晶良好的高岭石、结晶差的或b轴无序的高岭石、7Å多水高岭石和10Å多水高岭石。我们将结晶良好的高岭石和10Å多水高岭石分别视为这一演化系列的两个端元矿物,其余两种矿物则是演化系列的中间矿物。该系列中的矿物同属于1:1型含水的层状铝硅酸盐矿物,因而它们的化学成分基本相同,主要差别是在晶体结构上由于单位结构层沿c轴彼此堆叠的方式而引起从有序向无序变化,同时层间键力的减弱引起水分子进入,促使层间水的含量逐渐增大。基于以上特征,这一系列中的四种类型矿物受热以后的热效应很灵敏,详细研究它们在加热脱水过程中的变化规律,可以加深对矿物特性的认识和鉴别。     

Non-destructive infrared analyses: a method for provenance analyses of sandstones

Infrared spectroscopy (IR spectroscopy) is commonly applied in the laboratory for mineral analyses in addition to XRD. Because such technical efforts are time and cost consuming, we present an infrared-based mobile method for non-destructive mineral and provenance analyses of sandstones. IR spectroscopy is based on activating chemical bonds. By irradiating a mineral mixture, special bonds are activated to vibrate depending on the bond energy (resonance vibration). Accordingly, the energy of the IR spectrum will be reduced thereby generating an absorption spectrum. The positions of the absorption maxima within the spectral region indicate the type of the bonds and in many cases identify minerals containing these bonds. The non-destructive reflection spectroscopy operates in the near infrared region (NIR) and can detect all common clay minerals as well as sulfates, hydroxides and carbonates. The spectra produced have been interpreted by computer using digital mineral libraries that have been especially collected for sandstones. The comparison of all results with XRD, RFA and interpretations of thin sections demonstrates impressively the accuracy and reliability of this method. Not only are different minerals detectable, but also differently ordered kaolinites and varieties of illites can be identified by the shape and size of the absorption bands. Especially clay minerals and their varieties in combination with their relative contents form the characteristic spectra of sandstones. Other components such as limonite, hematite and amorphous silica also influence the spectra. Sandstones, similar in colour and texture, often can be identified by their characteristic reflectance spectra. Reference libraries with more than 60 spectra of important German sandstones have been created to enable entirely computerized interpretations and identifications of these dimension stones. The analysis of infrared spectroscopy results is demonstrated with examples of different sandstones used as dimension stones. All analyses have been done with the “portable infrared mineral analyser” (PIMA) of Integrated Spectronics Pty Ltd. at the Bundesanstalt für Geowissenschaften und Rohstoffe in Berlin. This spectrometer has been designed to be light, portable and easy to handle. Investigations can be performed without any sample preparation for complete buildings as well as at small samples with diameters up to about one centimeter. Analyses of pulverized samples and granules are also possible. Consequently, infrared reflectance spectroscopy provides a reliable working, non-destructive technique to identify and characterize sandstones used for buildings and monuments.     

Vergleich einiger Methoden zur Untersuchung von geochemischen Vorgängen bei der Verwitterung

Summary Chemical analyses are used by many authors to describe processes of soil development or laterite formation. In this paper some methods of balance calculations are compared by using samples of a laterite profile on granite from India as testing material. It should be proved which of these calculations of transported matter between the different layers are fitting to the mineral analyses of the laterite profile.Only the results of the method proposed byMashall by using an index-mineral as a base for comparison is confirmed by the mineral analyses.The method ofStreng differs from the above described calculation by using a chemical element as an index. FollowingStreng it is supposed that this element remains unchanged during the weathering processes. But certain chemical elements can be constituents of several minerals of a parent rock. During laterite formation all or almost all minerals of the original rock will be altered and the elements will be transported by weathering solutions. Therefore chemical elements do not serve as an index for balance calculations within a laterite complex.UsingGrossers method one cannot decide wether the abundance of a certain element is caused by accumulation of this element or by lost of other constituents and vice-versa.The use of the method developed byMillot u.Bonifas is not advisable except the structure of the original rock is preserved unaltered during laterite formation. This is not indicated in our case.     

金云母—蛭石间层矿物分晶层晶体化学式的计算及意义

金云母－蛭石间层矿物由金云母晶层与蛭石晶层交叠排列而成，采用一般计算方法得出的晶体化学式不能充分揭示结构中金云母晶层与蛭石晶层各自的晶体化学特征。本文以化学成分分析与阳离子容量为基础，假定可交换性阳离子均为蛭石晶层层间阳离子，非交换性阳离子为金云母晶层层间阳离子，金云母晶层与蛭石晶层具有相同的八面体层等，计算出了结构中两种晶层的分晶层晶体化学式，确定了结构中两种晶层的比例和蛭石晶层的电荷数。并在此基础上讨论了新疆尉犁蛭石矿金云母－蛭石间层矿物的晶体化学特征。结果表明该方法设计合理，符合晶体化学原理，所计算的数据可靠。利用该方法计算出的两种晶层的比例为金云母－蛭石1：1规则间层矿物的确定提供了必要的依据。也为其它类似间层矿物的研究提供了一种计算分晶层晶体化学式的可行方法。     

二八面体水云母矿物及其热分析

用XRD、DTA、TG、IR等手段,对产于十来个省区的、不同产状的二八面体水云母矿物进行了测试研究。样品分为2M、1Md、1M₁+1M等几种多型。文中列出了它们的XRD数据及图谱、加热前后的IR谱及部分化学成分和化学试,详述了其热学特征。建议以矿物的脱羟温度高低参,照XRD谱的无序程度,在日常鉴定工作中区分出绢云母（脱羟温度>700℃）、水（白）云母（脱羟温度600-700℃）及伊利石（脱羟温度<699℃）。     

桂林某些岩溶洞穴矿物

洞穴矿物是在洞穴环境下由冷的地下水活动所产生的表生化学沉积作用产物。桂林地区(包括兴安—桂林—阳朔一带)岩溶洞穴中的次生矿物已发现有方解石、文石、石膏、氢氧磷灰石、磷铝石、磷铝钾石、磷钙铝石和半蛋白石等。文章中列举了这些矿物的偏光显微镜、化学分析、x光粉晶衍射、差热分析和扫描电镜等鉴定结果,并概要地探讨了其成因。      

A study on the interaction between ferric ion and silicic acid in hydrosphere: Si-containing ferruginous deposits formed in neutral hot spring waters

Five ferruginous deposit samples formed from neutral hot springs were analyzed to determine whether they consisted of a mixture of silica, hydrous iron oxide or iron silicate by differential thermal analysis (DTA), infrared (IR) spectroscopy, powder X-ray diffraction (XRD), and 57Fe Mssbauer spectroscopy. The Si/Fe atomic ratios of the deposits ranged from 0.25 to 0.45, and were smaller than those of hisingerite (12), but apparently close to those of siliceous ferrihydrite (0.250.5). Si was confirmed to be present as monomeric or oligomeric silicate from the Si-O stretching vibration frequencies on the IR spectra. Judging from the results of DTA, which minerals starting to produce after heating, and a relationship between Si-O stretching vibration frequency and Si/Fe atomic ratio proposed by Henmi et al. (1981), all the deposits in this study were concluded to be mixtures of various siliceous ferri-hydrites with low and high Si/Fe atomic ratios. Moreover, by comparing the chemical properties of hot spring waters, the formation conditions of siliceous ferrihydrite were also discussed.     

STDGL3, a Reference Material for Analysis of Sulfide Minerals by Laser Ablation ICP-MS: An Assessment of Matrix Effects and the Impact of Laser Wavelengths and Pulse Widths

A new reference material, STDGL3, for the calibration of in situ analyses of sulfide minerals by LA-ICP-MS has been developed and characterised. It represents a lithium-borate-based glass containing a mixture of Zn- and Fe-sulfide concentrates doped with several chalcophile elements as well as Zr, Gd, Hf and Ta required for assessing common interferences on Ag, Au and Pt. STDGL3 has a wider range of elements and a better homogeneity compared with existing reference materials for LA-ICP-MS analysis of sulfides. Compositional variations for most elements are below 3% RSD, below 5% RSD for Ag, Au and Pt, and below 7% RSD for Se, when performing spot analyses with a 50 μm beam size. Its preparation recipe is reproducible allowing for multiple batches to be made. Use of STDGL3 significantly improves accuracy of sulfide mineral analysis by LA-ICP-MS when compared with use of other available reference materials. Performance of STDGL3 was evaluated using several different laser systems. No significant change was observed between 193 nm ArF excimer lasers with 5 and 20 ns pulse widths, but use of 213 and 248 nm lasers displays more systematic differences, especially when analysing galena. Correction coefficients are needed for some elements (Zn and Cd in particular) when analysing sulfide minerals using STDGL3 as a calibration reference material.     

X射线荧光分析中理论α系数经验修正方法研究

在地质样品粉末任片法X射线荧光分析中,使用理论α系数校正基体效应尚有一定的局限性。为了获得最佳校正效果,本文提出了一种简易的理论α系数经验修正方法。     

应用X射线衍射-扫描电镜-光学显微镜鉴定黑龙江石墨尾矿中的绢云母

石墨尾矿作为一类二次资源,当云母类矿物的含量在10%以上时,具有回收利用价值。黑龙江某地石墨尾矿中含有10%以上的云母类矿物,但其细度(500~800目)低于常规的云母矿,本文采用X射线衍射(XRD)分析矿物组成,再结合化学分析、扫描电镜-能谱、光学显微镜与纯矿物进行对比,由此鉴定云母类矿物种属。XRD研究初步表明石墨尾矿含有的云母族矿物属于白云母亚类或黑云母亚类。扫描电镜分析表明尾矿中的云母矿物与纯绢云母矿物均以片状和鳞片状为主要存在形态,而纯黑云母主要以片状形式存在。尾矿的Si O2含量为5%~13%,Al2O3含量为4%~8%,与纯绢云母接近。光学显微镜鉴定显示在正交偏光下石墨尾矿中的云母颜色和纯绢云母类似,而与纯黑云母截然不同。综合以上结果最终可确定该地石墨尾矿中的云母族矿物为白云母亚类中的绢云母。本研究为后续石墨尾矿的选矿工艺奠定了基础,也可应用于类似细度绢云母的鉴定。     

Ferric/ferrous iron ratios in sodic amphiboles: Mössbauer analysis, stoichiometry-based model calculations and the high-resolution microanalytical flank method

Although the electron microprobe has become the standard microanalytical tool in modern geosciences, conventional electron microprobe analysis does not allow determination of the valence states of elements such as Fe. The correct classification of minerals and interpretation of reaction microfabrics and grain zonation require high-quality information on ferric/ferrous ratios on a scale of micrometers. The flank method developed by Höfer et?al. (1994, Eur J Mineral 6:407–418) has revived new interest in electron-induced X-ray-spectroscopy to resolve oxidation states in minerals with high spatial resolution. We have recharacterized well-documented sodic amphiboles of the glaucophane–ferroglaucophane–riebeckite–magnesioriebeckite series by electron probe microanalysis and combined the microanalytical data with ferric/ferrous ratios from Mössbauer spectroscopy, Li data from bulk ICP-AES analysis and H₂O data from bulk Karl–Fischer titration. The combination of microanalysis and high-quality analysis on the bulk materials results in a data set that allows comparison of model-based stoichiometric calculations and the calibration of the high-resolution flank method. The calibration obtained allows ferric/ferrous ratios to be determined within an error of ±5%. We have found it necessary to apply an empirical correction for absorption phenomena. The advantages of the method must be weighed against the complex calibration procedures necessary and thus the flank method will probably not find use as a routine method. However, in cases where high-resolution data in terms of valence state are needed, the flank method will provide useful data on ferric/ferrous ratios down to minimum FeO_total content of 6–8 wt%.     

X射线衍射全谱拟合法分析蓝晶石的矿物含量

蓝晶石矿物定量分析通常采用的化学物相法分析流程繁琐,易受同质异象矿物和难熔矿物的干扰;采用X射线衍射内标法需要提纯矿物绘制标准曲线,但矿物包体的存在使得获取纯净单矿物成为难题;由于不同矿区蓝晶石矿物成分之间存在着差异性,以上两种方法都仅仅适用于同一矿区样品的矿物定量分析。为简化分析流程,提高测试效率,本文采用X射线衍射(XRD)全谱拟合法对蓝晶石国家二级标准物质和野外样品进行分析,并与RIR法、绝热法和K值法等衍射定量方法及化学分析结果进行了比较验证方法的可靠性。结果表明:全谱拟合法无需采用标准物质,也不用引入内标物,一次扫谱分析能获得样品中所有成分的信息,操作简单,能有效降低择优取向对衍射定量结果的影响;对于含量大于5%的矿物,组分分析结果的绝对误差小于1%,显著低于绝对误差允许限;采用Highscore和Jade两种衍射数据处理软件获得的定量结果吻合度高,目标矿物蓝晶石分析结果的双差均小于0.8%,相对偏差小于2.5%;蓝晶石的加标回收率在95.3%～101.0%之间,能实现不同矿区蓝晶石矿的快速定量分析。     

乙酰丙酮分光光度法测定水性涂料中甲醛及测量不确定度评估

对用于测定内墙涂料中有害物质甲醛的乙酰丙酮分光光度法进行了详细研究。实验结果表明，乙酰丙酮分光光度法工作曲线有良好的稳定性。工作曲线斜率的相对标准偏差为0．74％。为达到定量分析目的，样品蒸馏时，加入水的体积应不低于200mL，涂料样品残留量应小于5mL。样品蒸馏液中甲醛应在当天测定。涂料样品中高含量甲醛的回收率平均值为98．5％，低含量甲醛的回收率平均值为87．9％。对乙酰丙酮分光光度法测定水性涂料中甲醛含量的不确定度进行了评估。     

CHIME dating of monazite, xenotime, zircon and polycrase: Protocol, pitfalls and chemical criterion of possibly discordant age data

This paper outlines the CHIME (chemical Th–U-total Pb isochron method) dating method, which is based on precise electron microprobe analyses of Th, U and Pb in Th- and U-bearing accessory minerals such as monazite, xenotime, zircon and polycrase. The age-mapping technique that is applicable to young monazite and zircon is also described. CHIME dating consists of analyzing multiple spots within homogeneous age domains that show sufficient compositional variation, and then these data are used to construct a “pseudo-isochron” from which an age can be obtained via regression. This method, when coupled with discrimination of possibly concordant age data by chemical criteria such as the (Ca + Si)/(Th + U + Pb + S) ratio for monazite and Ca and S contents for zircon, has the potential advantage of significant precision, and the ability to work with minerals that have a significant initial common Pb component. This technique can identify two or more homogeneous domains that are separated by age gaps smaller than the error on individual spot age analysis. Many features that are insignificant in major element analysis can have major impact in the acquisition of trace element data. Critical factors include the roles of collimator slit, detector gas, background estimation, accelerating voltage, probe current, X-ray interferences and count rate in affecting the accuracy, and a way to apply the Th and U interference correction without pure Th- and U-oxides or synthesized pure ThSiO₄. The age-mapping procedure for young monazite and zircon includes acquiring PbMα (or PbMβ) intensity of individual pixels with multiple spectrometers, correcting background with background maps computed from a measured background intensity by the intensity relationships determined in advance of the measurement, calibrating of intensity with standards and calculating of ages from the Th, U and Pb concentrations. This technique provides age maps that show differences in age domains on the order of 20 Ma with in monazite as young as 100 Ma. The effect of sample damage by irradiation of intense and prolonged probe measurement is also described.     

东疆红山高硫型浅成低温Cu-Au矿床氧化带钾铁矾、板铁矾、副基铁矾的首次发现及其意义

新疆哈密红山高硫化物型浅成低温Cu-Au矿床的氧化带呈漏斗状产于原生硫化物矿体的上部,延深50～60m,以硫酸盐矿物为主。X射线粉晶衍射、湿法化学和差热分析研究表明,钾铁矾、板铁矾和副基铁矾3种硫酸盐矿物均系在中国首次发现。钾铁矾湿法化学分析为:H2O6.35%,SO349.72%,Na2O0.15%,Fe2O326.00%,K2O12.47%,FeO0.25%,SiO23.25%,不溶物0.85%,CaO0.11%,总计99.15%;XRD特征谱线为:4.40(100),4.26(70),6.58(47)。板铁矾湿法化学分析为H2O26.51%,SO349.91%,Na2O0.03%,Fe2O322.52%,MgO0.01%,CaO0.03%,总计99.01%;XRD特征谱线为:9.16(100),3.29(9),4.06(8)。副基铁矾湿法化学分析为H2O24.82%,SO338.53%,Al2O30.18%,Fe2O336.10%,MgO0.02%,CaO0.04%,总计99.69%;XRD特征谱线为:5.00(100),3.11(41),5.85(39)。热分析实验进一步验证了化学分析的可靠性,并对这些硫酸盐热反应机制作了解释。该类硫酸盐矿物已作为新型资源直接制酸用于湿法炼铜,具有选矿和环保上的巨大优势。对该类硫酸盐矿物的共生组合、形成次序、形成条件的深入研究还可用来反演古环境和古气候。     

碳酸盐岩中碳酸盐矿物稀土元素分析方法进展

碳酸盐岩中测定碳酸盐矿物的稀土元素主要有酸溶-ICP-MS和LA-ICP-MS方法.酸溶-ICP-MS方法用盐酸、硝酸溶解碳酸盐矿物,但也能溶解部分非碳酸盐矿物,而影响分析结果;用醋酸溶样可避免非碳酸盐矿物的干扰,但可能没有溶样完全,同样影响分析结果.LA-ICP-MS是应用激光对碳酸盐矿物进行原位剥蚀,将蒸发物导入ICP-MS进行分析,对不合粘土等的碳酸盐矿物最有效,由于激光束光斑较大,且碳酸盐岩中普遍含有微小的粘土矿物,可能也存在不确定性.总体而言,酸溶-ICP-MS和LA-ICP-MS获得的稀土元素页岩标准化配分模式及主要参数相似,均可用于沉积环境的示踪.     

Principal physicochemical parameters of natural mineral-forming fluids

The authors’ database (which includes data from more than 17500 publications on fluid and melt inclusions in minerals) was used to generalize information on the principal physicochemical parameters of natural mineral-forming fluids (temperature, pressure, density, salinity of aqueous solutions, and the gas composition of the fluids). For 21 minerals, data are reported on the frequency of occurrence of the homogenization temperatures of fluid inclusions in various temperature ranges, which make it possible to reveal temperature ranges most favorable for the crystallization of these minerals. Data on 5260 determinations were used to evaluate the frequency of occurrence of certain temperature and pressure ranges of natural fluids within the temperature intervals of 20–1200°C and 1–12000 bar. Within these intervals, frequencies of occurrence were evaluated for water-dominated and water-poor or water-free fluid inclusions in minerals. The former are predominant at temperatures below 600°C and pressures below 4000 bar, whereas the latter dominate at temperatures of 600–1200°C and pressures of 4000-12000 bar. Illustrative examples are presented for visually discernible magmatic water that exists as an individual high-density phase in melt inclusions in minerals from various rocks sampled worldwide (in the Caucasus, Italy, Slovakia, United States, Uzbekistan, New Zealand, Chile, and others). Attention is drawn to the fact that extensive data testify to fairly high (>1000–1500 bar) pressures during hydrothermal mineral-forming processes. These pressures are much higher not only than the hydrostatic but also the lithostatic pressures of the overlying rocks. Data on more than 18000 determinations are used to evaluate the frequency of occurrence of certain temperature and salinity ranges of mineral-forming fluids within the intervals of 20–1000°C and 0–80 wt % equiv. NaCl and certain temperature and density ranges of these fluids at 20–1000°C and 0.01–1.90 g/cm³. Information is presented on the gas analysis methods most commonly applied to natural fluids in studying fluid inclusions in minerals in 1965–2007. The average composition of the gaseous phase of natural inclusions is calculated based on more than 3000 Raman spectroscopic analyses (the most frequently used method for analyzing individual inclusions).     

Towards a Higher Comparability of Geothermometric Data obtained by Raman Spectroscopy of Carbonaceous Material. Part I: Evaluation of Biasing Factors

Raman spectroscopy of carbonaceous material (RSCM) is frequently used to determine metamorphic peak temperatures from the structural order of carbonaceous material enclosed in metasediments. This method provides a quick, robust and relatively cheap geothermometer. However, the comparability of the RSCM parameter is low as there are at least three major sources of biasing factors. These sources are the spectral curve‐fitting procedure, the sample characteristics itself and the experimental design including the used Raman system. To assess the impacts of the biasing factors on RSCM, a series of experiments was performed. The experiments showed that curve‐fitting is strongly influenced by individual operator‐bias and the degrees of freedom in the model, implying the need for a standardised curve‐fitting procedure. Due to the diversity of components (optics, light detection device, gratings, etc.) and their combinations within the Raman systems, different Raman instruments generally give differing results. Consequently, to estimate comparable metamorphic temperatures from RSCM data, every Raman instrument needs its own calibration. This demands a reference material series that covers the entire temperature calibration range. Although sample heterogeneity will still induce some variation, a reference material series combined with standardised curve‐fitting procedures will significantly increase the overall comparability of RSCM data from different laboratories.