Quantification of electron microprobe compositional maps of rock thin sections: an optimized method and examples

Quantification of discrete pressure–temperature domains in deformed chlorite + white mica‐bearing metapelites was undertaken on mineral compositions derived by two‐dimensional microprobe compositional mapping of selected areas of rock thin sections. In order to achieve compositional information at sufficient analytical precision, spatial resolution and sample coverage within a typical analysis time of 1 day, an optimization of measurement methods was necessary. The method presented here allows collection of raw counts for eight different element concentrations at an analytical precision of ～1–2 wt%. X‐ray intensity multiplane maps (one map per measured chemical element) are translated into concentration multiplane maps, utilizing selected conventionally measured spot analyses combined with the Castaing approximation for each mineral. As this step requires identification of the different minerals present in the mapped area, a statistical clustering technique to identify different groups of composition was developed, guided by simple petrographic inspection of the thin section, to delineate the important minerals in the mapped area. Finally, the compositions of each pixel are translated into a mineral structural formula thus yielding a new kind of image with a high content of petrological information. The reliability of the mineral composition images was emphasized by carrying out precision tests on the analytical data. The possible use of chemical maps to infer the P–T–deformation history of metamorphic rocks is illustrated with two samples from the Spitzbergen and the Sambagawa blueschist facies belts. In both samples, a strong correlation between structures and chemistry is observed. Qualitative estimates of P–T conditions from the Si‐content of mica and chlorite are in good agreement with their location in microstructures that formed at different times. Therefore, the combination of chemical maps with microstructural observations is a very powerful approach to understand both the evolution of complex metamorphic rocks and the control by deformation of mineral reactivity.     

A method for calculating effective bulk composition modification due to crystal fractionation in garnet-bearing schist: implications for isopleth thermobarometry

Quantitative P–T path determination in metamorphic rocks is commonly based on the variation in composition of growth‐zoned garnet. However, some component of growth zoning in garnet is necessarily the result of an effective bulk composition change within the rock that has been generated by crystal fractionation of components into the core of garnet. Therefore, any quantitative calculation of the P–T regime of garnet growth should be completed using an accurate assessment of the composition of the chemical system from which garnet is growing. Consequently, a method for calculating the extent of crystal fractionation that provides a means of estimating the composition of the unfractionated rock at any stage during garnet growth is developed. The method presented here applies a Rayleigh fractionation model based on measured Mn content of garnet to generate composition v. modal proportion curves for garnet, and uses those curves to estimate the vectors of crystal fractionation. The technique is tested by calculating the precision of the equilibrium between three garnet compositional variables within the chemical system determined to be appropriate for each of a series of microprobe analyses from garnet. Application of the fractionation calculations in conjunction with the P–T estimates based on intersecting compositional isopleths provides a means of calculating P–T conditions of garnet growth that is based on individual point‐analyses on a garnet grain. Such spatially precise and easily obtainable P–T data allow for detailed parallel studies of the microstructural, the P–T, and the chemical evolution of metamorphosed pelites. This method provides a means of studying the dynamics of orogenic systems at a resolution that was previously unattainable.     

CAMAM: A Miniature Laser Ablation Ionisation Mass Spectrometer and Microscope‐Camera System for In Situ Investigation of the Composition and Morphology of Extraterrestrial Materials

Performance studies of a microscope‐camera system (MCS) and a laser ablation/ionisation mass spectrometer (LIMS) instrument (referred to here as a laser mass spectrometer or LMS) are presented. These two instruments were designed independently for in situ analysis of solids on planetary surfaces and will be combined to a single miniature instrument suite for in situ chemical and morphological analysis of surface materials on planetary bodies. LMS can perform sensitive chemical (elemental, isotope and molecular) analyses with spatial resolution close to micrometre‐sized grains. It allows for studies with mass resolution (M/ΔM) up to 800 in ablation mode (elemental composition) and up to 1500 in desorption mode (molecular analysis). With an effective dynamic range of at least eight orders of magnitude, sensitive and quantitative measurements can be conducted of almost all elements and isotopes with a concentration larger than a few ppb atoms. Hence, in addition to the major element composition, which is important for the determination of mineralogical constituents of surface materials, trace elements can also be measured to provide information on mineral formation processes. Highly accurate isotope ratio measurements can be used to determine in situ geochronology of sample material and for investigations of various isotope fractionation processes. MCS can conduct optical imagery of mm‐sized objects at several wavelengths with micrometre spatial resolution for the characterisation of morphological surface details and to provide insight into surface mineralogy. Furthermore, MCS can help in the selection of sample surface areas for further mass spectrometric analysis of the chemical composition. Surface auto‐fluorescence measurements and images in polarised light are additional capabilities of the MCS, to identify either fluorescing minerals or organic materials, if present on the analysed surface, for further investigation by LMS. The results obtained by investigations of NIST reference materials, amino acid films and a natural graphite sample embedded in silicate rock are presented to illustrate the performance of the instruments and their potential to deliver chemical information for mineral and organic phases in their geological context.     

Evaluation of a Quality Control Monitor Material for the Routine Electron Probe Microanalysis of Kimberlite Exploration Garnets

Election probe microanalysis of indicator minerals is extensively used in the exploration for kimberlite deposits, the evaluation of specific kimberlite occurrences for their diamond bearing potential and to classify grains into different chemical and lithological mantle associations. Kimberlite exploration programmes can involve several tens of thousands of indicator mineral analyses. Procedures for monitoring data quality and consistency of analyses across large data sets are commonly absent. Suitable monitor minerals should be used to verify the data quality of kimberlite exploration and evaluation data sets. This material should have a suitable composition, be homogenous, be available in sufficient quantities and have a similar appearance to the unknown samples. Garnet P1, a megacryst garnet from the Premier kimberlite, was found to have a suitable composition as a monitor for kimberlite garnet analyses. Data were collected on the monitor material at regular intervals during routine analyses, over an extended period, both as a fixed grain mounted on the sample holder and as separate grains set within batches of routine samples. The data were evaluated to assess the quality and consistency in the analyses of large data sets over time. The monitor material was also analysed at independent laboratories using their routine analytical set-up and calibration procedures for comparative purposes. Values are given for the mean ± 2s range, which can serve as guide values for acceptable analyses for all elements.     

Mineral weathering rates calculated from spring water data: a case study in an area with intensive agriculture,the Morais Massif,northeast Portugal

This study identifies and quantifies the water–rock interactions responsible for the composition of 25 spring waters, and derives the weathering rates of rock-forming minerals in a complex of petrologic units containing ultramafics, amphibolites, augengneisses and micaschists. Bulk chemical analyses were used to calculate the mineralogical composition of these rocks; the composition of the rock-forming minerals were determined by microprobe analyses. The soils developed on augengneisses and micaschists contain predominantly halloysite; on the other units mixtures of halloysite and smectites. The mineralogical and chemical data on rocks and soils are essential for writing the proper weathering reactions and for solving mole balances between the amounts of weathered primary minerals and secondary products formed (soils and solutes in groundwater). Ground waters emanating in springs were collected in 3 consecutive seasons, namely late Summer, Winter and Spring, and analyzed for major components. Using an algorithm based on mole and charge balance equations, the average concentrations of the solutes were linked with a combination of possible weathering reactions. To sort out the best match of weathering reactions and the concomitantly generated water composition, the results were checked against the limiting condition of similarity between the predicted and actual clay mineral abundance in the soils. Having selected the best-fit weathering reactions, the mineral weathering rates could also be calculated by combining the median discharge rates and recharge areas of the springs and normalizing the rates by the mineral abundance. For the one case—plagioclase—for which comparison with published results was possible, the results compare favorably with rates calculated by other groups. For the most abundant primary minerals the following order of decreasing weathering rates was found (in moles/(ha·a·%mineral)): forsterite (485) > clinozoisite (114) > chlorite (49) > plagioclase (45) > amphibole (28). In as far as this order differs from commonly used orders of weatherability, this has to be due to differences in the hydrologic regime within this area and between this and other case studies. As additional objective, the authors wanted to explain the effects of contributions by sources other than water-rock interactions. The latter processes are coupled with acquisition of carbonate alkalinity and dissolved silica. Contributions by sources other than water–rock interactions are manifest by the Cl⁻, SO²⁻₄ and NO⁻₃ concentrations. It was possible to approximate the contribution of atmospheric deposition. More importantly, knowledge of the application and composition of fertilizers enabled assessment of the effects of farming on the composition of ground waters emanating in the springs. It was also possible to estimate how selective uptake of nutrients and cations by vegetation as well as ion-exchange processes in the soil modified the spring water composition. Using this rather holistic approach, it is possible to satisfactorily explain how spring waters, in this petrologically and agriculturally diverse area, acquired their composition.     

On micas from magmatic and metamorphic rocks

Micas from magmatic and metamorphic rocks differ from one another in chemical composition and in trace element content. The chemical composition of micas is discussed in relation to their occurrence, paragenesis and sequence of crystallization. On the basis of previous studies of the relationship between the physical properties and the chemical composition of 34 chemically analysed micas, reliable physical methods have been established which permit identification of different mica varieties in the same rock. Structural formulae and trace element content of micas from basic and granitic rocks, as well as from skarns, schists, ortho- and paragneisses are discussed. The relationship between the components of the tetrahedral and octahedral layers and of the interlayer are illustrated as ratios. Poorly differentiated, hybrid and metasomatic rocks often contain more than one variety of mica. Some prophyritic basalts and lamprophyres contain an early phlogopite which is paragenetically related to pyroxene phenocrysts and late biotite which occurs in the groundmass and in the fractures as a result of the crystallization of residual magma. The biotitemuscovite assemblage was observed in granodiorites, quartz-monzonites, schists and gneisses. In the albite-K-feldspar granites, muscovite predominates and the biotite is usually altered. The chemical composition of micas from metamorphic rocks depends on the grade of metamorphism and on the nature of associated minerals. The biotite from paragneisses contains considerable quantities of octahedral alumina. Pre-metamorphic micas show variable deficiencies of the (OH, F) group. The micas are useful minerals in determining the degree of differentiation and subsequent alteration of igneous rocks. The present study was carried out on the basis of 34 recent complete chemical analyses andca 100 X-ray fluorescence analyses. Dedicated to Professor Dr.Carl W. Correns on the occasion of his 70th birthday.     

LA-ICPMS analyses of silicate melt inclusions in co-precipitated minerals: Quantification, data analysis and mineral/melt partitioning

We present a new approach to determine the composition of silicate melt inclusions (SMI) using LA-ICPMS. In this study, we take advantage of the occurrence of SMI in co-precipitated mineral phases to quantify their composition without depending on additional sources of information. Quantitative SMI analyses are obtained by assuming that the ratio of selected elements in SMI trapped in different phases are identical. In addition Fe/Mg exchange equilibrium between olivine and melt was successfully used to quantify LA-ICPMS analyses of SMI in olivine. Results show that compositions of SMI from the different host minerals are identical within their uncertainty. Thus (1) the quantification approach is valid; (2) analyses are not affected by the composition of the host phase; (3) the derived melt compositions are representative of the original melt, excluding significant syn- or postentrapment modification such as boundary layer effects or diffusive reequilibration with the host mineral. With this data we established a large dataset of mineral/melt partition coefficients for the investigated mineral phases in hydrous calc-alkaline basaltic-andesitic melts. The clinopyroxene/melt and plagioclase/melt partition coefficients are consistent with the lattice strain model of Blundy and Wood [Blundy, J., Wood B., 1994. Prediction of crystal-melt partition-coefficients from elastic-moduli. Nature372, 452-454].     

Plate loading tests on sloping rock

The plate loading test is performed in order to determine the deformation modulus of a rock mass in situ. In the standard execution of this test the loading is applied perpendicular to the rock surface. The displacements are measured on the axis of symmetry, since for an isotropic material with linear deformation characteristics exact formulae are known which are valid at this location. For horizontal strata this presents no problem as it is easy to provide loading in a vertical direction. When the rock strata are dipping it is imprectical to use nonvertical load and it is then necessary to calculate the modulus from the displacements in a non-axisymmetrical arrangement. Using the well-known method of the Taylor series approximate formulae are derved which are sufficiently accurate for all practical cases of sloping rock.     

Contact metamorphism of impure dolomitic limestone in the Boulder Aureole,Montana

Progressive metamorphism of impure dolomitic limestone in the 1.5 to 2.5 km wide contact aureole surrounding the northernmost portion of the boulder batholith has resulted in a consistent sequence of uniformly distributed zones of low-variance mineral parageneses separated by abrupt and distinctive isograds. In silica-undersaturated, aluminous marbles, the following mineral assemblages occur, in order of increasing grade: calcite-dolomite-calcic amphibole-chlorite, calcite-dolomite-calcic amphibole-chlorite-spinel, calcite-dolomite-calcic amphibole-chlorite-olivine-spinel, calcite-dolomite-chlorite-olivine-spinel, calcite-dolomite-olivine-spinel. The spatial distribution of parageneses and the occurrence of low-variance parageneses indicate buffering of the pore fluid composition by the local mineral assemblages. The observed sequence of mineral reactions and the spacing of isograds is in good agreement with experimental and calculated equilibria in terms of P-T-X _{CO 2}and temperatures of equilibration inferred from calcite-dolomite geothermometry, which range from 435 to 607 °C across the aureole.Microprobe analyses of coexisting minerals indicate attainment of exchange equilibrium. Calcic amphibole and chlorite coexisting with calcite and dolomite become progressively more aluminous with increasing grade; calcic amphibole changes rapidly from Al-poor tremolite to pargasite, while Al^IV in Cte increases from 2.0 to 2.3 atoms per 8 tetrahedral sites. Observed low-variance assemblages fix the activities of calcic amphibole and chlorite end-member components as a function of P and T, and hence the systematic compositional variation in these phases is not an independent variable, but is controlled by the local mineral assemblage.     

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.     

Trace element partitioning in the granulite facies

Analyses of trace elements in the mineral phases of granulites provide important information about the trace element distribution in the lower crust. Since granulites are often considered residues of partial melting processes, trace element characteristics of their mineral phases may record mineral/melt equilibria thus giving an opportunity to understand the nature and composition of melts in the lower continental crust. This study provides an extensive set of mineral trace element data obtained by LA-ICP-MS analyses of mafic and intermediate granulites from Central Finland. Mass balance calculations using the analytical data indicate a pronounced contribution of the accessory minerals apatite for the REE and ilmenite for the HFSE. Coherent mineral/mineral ratios between samples point to a close approach to equilibrium except for minerals intergrown with garnet porphyroblasts. Mineral trace element data were used for the formulation of a set of D ^mineral/melt partition coefficients that is applicable for trace element modelling under lower crustal conditions. D ^mineral/melt were derived by the application of predictive models and using observed constant mineral/mineral ratios. The comparison of the calculated D ^mineral/melt with experimental data as well as the relationship between mineral trace element contents and a leucosome with a composition close to an equilibrium melt provides additional constraints on mineral/melt partitioning. The D values derived in this study are broadly similar to magmatic partition coefficients for intermediate melt compositions. They provide a first coherent set of D values for Sc, V, Cr and Ni between clinopyroxene, amphibole, garnet, orthopyroxene, ilmenite and melt. In addition, they emphasize the strong impact that ilmenite exerts on the distribution of Nb and Ta.     

Garnet lherzolite xenoliths in the kimberlites of northern Lesotho: revised P-T equilibration conditions and upper mantle Palaeogeotherm

Evidence is presented that the inflected palaeogeotherm for northern Lesotho, previously highlighted by Boyd (1973), Boyd and Nixon (1973, 1975), Finnerty and Boyd (1984, 1987), is essentially an artifact of the unsatisfactory, over-simplified barometer formulation (based on MacGregor 1974) employed. The absence of an inflection in the palaeogeotherm for Udachnaya, Siberia based on P-T estimates for garnet lherzolite xenoliths calculated with the same barometer, does not prove the reality of an inflected palaeogeotherm for northern Lesotho. Rather, it reflects, at least in part, chemical differences between the equivalent deformed, high-T xenoliths in these two areas — most importantly expressed in the respective contents of Jadeite relative to ureyite in the constituent orthopyroxenes. Accurate estimation of P-T equilibration conditions for garnet lherzolite xenoliths requires both complete and precise mineral analyses and adequate consideration of the influence of minor elements, such as Cr and Na, on the element exchange reaction thermometers and barometers employed. The barometer formulation of Nickel and Green (1985) is judged to be the best currently available. As no single thermometer is entirely satisfactory and dependable throughout the P-T range of interest, equilibration temperatures are currently best assessed as a mean value obtained from application of the most accurate formulations for both the two-pyroxene solvus thermometer (Bertrand and Mercier 1985) and Fe²⁺-Mg²⁺ exchange reactions between garnet-clinopyroxene (Powell 1985), garnet-orthopyroxene (Harley 1984a) and garnet-olivine (O'Neill and Wood 1979) mineral pairs. Such best P-T estimates for xenoliths in the kimberlites of northern Lesotho indicate a somewhat elevated, non-inflected, upper mantle palaeogeotherm, compatible with a 120–145 km thick thermally conductive lithosphere above a convecting asthenosphere. The common coarse textured, chemically depleted, garnet lherzolite xenoliths appear mostly to have originated from close to the base of the lithosphere whilst the contrasting deformed, higher T, more chemically fertile xenoliths have come from the underlying asthenosphere. There is evidence for slight variations in the heat flux within the mantle beneath northern Lesotho at the time of emplacement of the Thaba Putsoa and Mothae kimberlites, only some 16 km apart, and also possibly for a regional variation in the thickness of the lithosphere.     

Orthopyroxene–sillimanite–quartz assemblages: distribution, petrology, quantitative P–T–X constraints and P–T paths

Granulite facies magnesian metapelites commonly preserve a wide array of mineral assemblages and reaction textures that are useful for deciphering the metamorphic evolution of a terrane. Quantitative pressure, temperature and bulk composition constraints on the development and preservation of characteristic peak granulite facies mineral assemblages such as orthopyroxene + sillimanite + quartz are assessed with reference to calculated phase diagrams. In NCKFMASH and its chemical subsystems, peak assemblages form mainly in high‐variance fields, and most mineral assemblage changes reflect multivariant equilibria. The rarity of orthopyroxene–sillimanite–quartz‐bearing assemblages in granulite facies rocks reflects the need for bulk rock X_Mg of greater than approximately 0.60–0.65, with pressures and temperatures exceeding c. 8 kbar and 850 °C, respectively. Cordierite coronas mantling peak minerals such as orthopyroxene, sillimanite and quartz have historically been used to infer isothermal decompression P–T paths in ultrahigh‐temperature granulite facies terranes. However, a potentially wide range of P–T paths from a given peak metamorphic condition facilitate retrograde cordierite growth after orthopyroxene + sillimanite + quartz, indicating that an individual mineral reaction texture is unable to uniquely define a P–T vector. Therefore, the interpretation of P–T paths in high‐grade rocks as isothermal decompression or isobaric cooling may be overly simplistic. Integration of quantitative data from different mineral reaction textures in rocks with varying bulk composition will provide the strongest constraints on a P–T path, and in turn on tectonic models derived from these paths.     

Origin of ultramafic inclusions and megacrysts in a monchiquite dyke at Streap,inverness-shire,Scotland

Spinel lherzolite nodules, composed of olivine (Fo_88.7?89.2), clinepyroxene (6.5% Al₂O₃) and Al-rich spinel, and websterite nodules as well as megacrysts of clinopyroxene, orthopyroxene and magnetite occur in a monchiquite at Streap, Scotland. Petrographic data are given and microprobe analyses of coexisting phases in six spinel lherzolite nodules and one websterite nodule are reported, along with analyses of both types of pyroxene megacrysts. The spinel lherzolites show internal chemical homogeneity, and their mineral chemistries suggest equilibrium conditions of 1100–1200°C and 14–23 kb. The websterite nodules are, on the basis of mineral chemistry and petrography, considered to be crustal material. The megacrysts constitute a separate group, differing in composition from analogous phases in associated lherzolites and websterites as well as from monchiquite phenocryst phases, and show systematic chemical variations corresponding to low pressure crystal fractionation processes.     

The correction of X-ray fluorescence analyses for scattered background peaks of target elements

A method for correcting X-ray spectrochemical analyses for scattered tube lines in the background is described. In cases where the bulk composition of a sample is known, a computational correction can be made on the basis of X-ray scattering theory. In the absence of detailed chemical knowledge of the sample, an approximate technique involving little calculation may be employed. The method should improve the accuracy of trace analyses for elements which are present as contaminants in the target of the X-ray tube.     

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。     

Vector analysis of chemical variation in the lavas of Parícutin volcano,Mexico

Compositional variations in the lavas of Parícutin volcano, Mexico, have been examined by an extended method of Q-mode factor analysis. Each sample composition is treated as a vector projected from an original eight-dimensional space into a vector system of three dimensions. The compositions represented by the vectors after projection are closely similar to the original compositions except for Na₂Oand Fe₂O₃.The vectors in the three-dimensional system cluster about three different planes that represent three stages of compositional change in the Parícutin lavas. Because chemical data on the compositions of the minerals in the lavas are presently lacking, interpretations of the mineral phases that may have been involved in fractional crystallization are based on CIPW norm calculations. Changes during the first stage are attributed largely to the fractional crystallization of plagioclase and olivine. Changes during the second stage can be explained by the separation of plagioclase and pyroxene. Changes during the final stage may have resulted mostly from the assimilation of a granitic material, as previously proposed by R. E. Wilcox.     

Rietveld全图拟合法定量分析伊利石矿的精确度及误差来源

伊利石是一种重要的矿产资源,准确获得矿石中矿物组成和含量具有重要的理论和实际意义.Rietveld全图拟合法采用整个衍射图进行分析,具有较高的准确度.然而由于缺少纯的伊利石样品,目前对于该方法在分析伊利石矿样的精确度和误差来源尚不清楚.本文采用Rietveld全图拟合法对人工配制和天然的伊利石典型矿样进行了分析和计算,...