Geological Applications of Laser‐Induced Breakdown Spectroscopy

Laser‐induced breakdown spectroscopy (LIBS) records light emitted from the decay of electrons to lower‐energy orbitals during cooling of laser‐induced ablation plasmas; the resultant spectra can be used in a variety of geoanalytical applications. Four aspects of LIBS analysis distinguish LIBS from traditional laboratory‐based analytical techniques: (i) the lack of necessary sample preparation, allowing rapid analysis of many samples, (ii) the ability to analyse both 20 to 100 μm‐diameter spots and whole rocks, (iii) the detailed chemical signature contained in a LIBS spectrum and (iv) the ability to take LIBS into the field in backpack portable instrumentation. Three case studies illustrate potential applications of LIBS in the geosciences. First, analysis of the Carrizozo basalt flow in New Mexico, USA, illustrated that LIBS spectra could discriminate between samples of similar composition within uncertainties typical of whole‐rock analysis by X‐ray fluorescence spectrometry. Second, spectra from four sets of rubies from Madagascar and Tanzania illustrate the use of LIBS and multivariate analysis to determine provenance with success rates of > 95%. This technique can also be applied to correlation of units. Finally, a chemical map of a copper ore from Butte, MT, USA, illustrates the use of spatially defined LIBS spectra to understand chemical variations within textural context.     

Geochemical Fingerprinting by Handheld Laser‐Induced Breakdown Spectroscopy

A broad suite of geological materials was studied a using a handheld laser‐induced breakdown spectroscopy (LIBS) instrument. Because LIBS is simultaneously sensitive to all elements, the full broadband emission spectrum recorded from a single laser shot provides a ‘chemical fingerprint’ of any material – solid, liquid or gas. The distinguishing chemical characteristics of the samples analysed were identified through principal component analysis (PCA), which demonstrates how this technique for statistical analysis can be used to identify spectral differences between similar sample types based on minor and trace constituents. Partial least squares discriminant analysis (PLSDA) was used to distinguish and classify the materials, with excellent discrimination achieved for all sample types. This study illustrates through four examples (carbonate minerals and rocks, the oxide mineral pair columbite–tantalite, the silicate mineral garnet and native gold) how portable, handheld LIBS analysers can be used for real‐time chemical analysis under simulated field conditions for element or mineral identification, plus such applications as stratigraphic correlation, provenance determination and natural resource exploration.     

Apatite Chlorine Concentration Measurements by LA‐ICP‐MS

Apatite incorporates variable and significant amounts of halogens (mainly F and Cl) in its crystal structure, which can be used to determine the initial F and Cl concentrations of magmas. The amount of chlorine in the apatite lattice also exerts an important compositional control on the degree of fission‐track annealing. Chlorine measurements in apatite have conventionally required electron probe microanalysis (EPMA). Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) is increasingly used in apatite fission‐track dating to determine U concentrations and also in simultaneous U‐Pb dating and trace element measurements of apatite. Apatite Cl measurements by ICP‐MS would remove the need for EPMA but the high (12.97 eV) first ionisation potential makes analysis challenging. Apatite Cl data were acquired using two analytical set‐ups: a Resonetics M‐50 193 nm ArF Excimer laser coupled to an Agilent 7700× quadrupole ICP‐MS (using a 26 μm spot with an 8 Hz repetition rate) and a Photon Machines Analyte Excite 193 nm ArF Excimer laser coupled to a Thermo Scientific iCAP Qc (using a 30 μm spot with a 4 Hz repetition rate). Chlorine concentrations were determined by LA‐ICP‐MS (1140 analyses in total) for nineteen apatite occurrences, and there is a comprehensive EPMA Cl and F data set for 13 of the apatite samples. The apatite sample suite includes different compositions representative of the range likely to be encountered in natural apatites, along with extreme variants including two end‐member chlorapatites. Between twenty‐six and thirty‐nine isotopes were determined in each apatite sample corresponding to a typical analytical protocol for integrated apatite fission track (U and Cl contents) and U‐Pb dating, along with REE and trace element measurements. ³⁵Cl backgrounds (present mainly in the argon gas) were ~ 45–65 kcps in the first set‐up and ~ 4 kcps in the second set‐up. ³⁵Cl background‐corrected signals ranged from ~ 0 cps in end‐member fluorapatite to up to ~ 90 kcps in end‐member chlorapatite. Use of a collision cell in both analytical set‐ups decreased the low mass sensitivity by approximately an order of magnitude without improving the ³⁵Cl signal‐to‐background ratio. A minor Ca isotope was used as the internal standard to correct for drift in instrument sensitivity and variations in ablation volume during sessions. The ³⁵Cl/⁴³Ca values for each apatite (10–20 analyses each) when plotted against the EPMA Cl concentrations yield excellently constrained calibration relationships, demonstrating the suitability of the analytical protocol and that routine apatite Cl measurements by ICP‐MS are achievable.     

3D geological modeling for prediction of subsurface Mo targets in the Luanchuan district,China

Three-dimensional (3D) district-scale geoscience information for the Luanchuan Mo district was integrated for understanding the development of its regional geology and ore-forming processes and for decision-making about potential targets for mineral exploration. The methodology and datasets used were: (1) construction of an initial geological model (25 km × 20 km × 2.5 km) using 1:10,000 scale geological map, nine geological cross-sections and gravity and magnetic data; (2) construction of three large-scale Mo deposits model (5 km × 4 km × 2.5 km) using 1:2000 scale geological and topographic maps, 288 boreholes (total core length of 158,700 m), and 32 1:2000 scale cross-sections; (3) 3D inversion of 1:25,000 scale gravity and magnetic data for identification metallogenic anomaly zones which are associated with Jurassic intrusions; (4) extraction of ore-controlling formation and sequence of the Luanchuan Group using the large-scale 3D models of Mo deposits and results of analysis of lithogeochemical samples from outcrops and borehole cores; (5) identification of ore-forming and ore-controlling faults using the large-scale 3D model of Mo deposits and mineralized Jurassic granite porphyry stocks; (6) boost weights-of-evidence and concentration–volume (C–V) fractal analyses to integrate metallogenic information and to identify and classify potential Mo targets. Four classes of exploration targets were identified using C–V modeling and 3D known orebodies model: the first and second class targets are mainly located in three large magma-skarn type deposit camps, occupying ~ 1.4 km³ with total estimated reserve of ~ 2.3 Mt; the third class targets, which are mainly located in Huangbeiling and Yuku deposit camps comprising concealed magma-skarn type deposits, occupy ~ 2.8 km³ and represent a new target exploration zone in the Luanchuan district; the fourth class targets, which are located in the Huoshenmiao, Majuan, and Daping zones, occupy ~ 15 km³ and represent potential mineral resources with likely similar orebody features as the Yuku deposit.     

Titanite dates crystallization: Slow Pb diffusion during super‐solidus re‐equilibration

Titanite can be found in rocks of wide compositional range, is reactive, growing or regrowing during metamorphic and hydrothermal events, and is generally amenable to U–Pb geochronology. Experimental evidence suggest that titanite has a closure temperature for Pb ranging from 550 to 650°C, and thus titanite dates are commonly interpreted as cooling ages. However, this view has been challenged in recent years by evidence from natural titanite which suggests the closure temperature may be significantly higher (up to 800°C). Here, we investigate titanite in an enclave of migmatitic gneiss included within a granite intrusion. The titanite crystals exhibit textural features characteristic of fluid‐mediated mass transfer processes on length scales of <100 µm. These textural features are associated with variation in both Pb concentrations and distinct U–Pb isotopic compositions. Zr‐in‐titanite thermometry indicates that modification of the titanite occurred at temperatures in excess of 840°C, in the presence of a high‐T silicate melt. The Pb concentration gradients preserved in these titanite crystals are used to determine the diffusivity of Pb in titanite under high‐T conditions. We estimate diffusivities ranging from 2 × 10^?22 to 5 × 10^?25 m²/s. These results are significantly lower than experimental data predict yet are consistent with other empirical data on natural titanites, suggesting that Pb diffusivity is similar to that of Sr. Thus our data challenge the wide‐held assumption that U–Pb titanite dates only reflect cooling ages.     

Duluth Complex apatites: Age reference material for LA–ICP–MS‐based fission‐track dating

Anorthositic series apatites of the Duluth Complex, Minnesota, USA, have high spontaneous fission‐track densities of up to ~10⁷ cm^–2 and a homogeneous age of ~900 Ma, allowing high‐precision fission‐track dating based on LA–ICP–MS U analysis. Absolute fission‐track dating, track‐length measurement and chemical composition analysis were performed to evaluate a cooling history, which is essential for age reference materials. Preliminary inverse modelling for a sample with a shortened track‐length distribution yielded a monotonic cooling history from ~100°C at 925 Ma. The apatites incur an over‐etching problem when employing the commonly used etching protocol involving 5.5 M HNO₃.     

Barium Isotopic Compositions in Thirty‐Four Geological Reference Materials Analysed by MC‐ICP‐MS

Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g^?1, SiO₂ from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ^138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ^138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ^138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.     

Numerical modeling of the development of a preferentially leached layer on feldspar surfaces

Compositional depth profiles in the leached layer of feldspar surfaces are usually interpreted by using analytical solutions which introduce oversimplifying assumptions. Here we present a general multicomponent interdiffusion numerical model for simulating cation release from a preferentially leached layer on feldspar surfaces in acid solutions. The numerical model takes into account interdiffusion, dissolution of the solid phase (represented by a moving boundary problem), and adsorption in the leached layer. Effective diffusion coefficients of ions vary with concentration along the leached layer. Governing equations of ions diffusion in the leached layer are solved numerically with a finite element method implemented in a multicomponent reactive transport code, CORE^3D, previously verified against analytical solutions of compositional depth profiles. The numerical model is tested with published X-ray photoelectron spectroscopy (XPS) data on early development of compositional profiles of labradorite leached in pH 2 HCl solutions. Model parameters are estimated by fitting depth profiles of Ca and Al measured at 12, 26, 48, 72, and 143 h. The best fit is achieved with tracer diffusion coefficients of 4 × 10⁻¹⁸, 8 × 10⁻¹⁷, 3.4 × 10⁻¹⁷, and 7 × 10⁻¹⁸ cm²/s for H, Na, Ca, and Al, respectively, which fall within the range of values reported in the literature. Our estimate of the retreat velocity corresponding to the dissolution rate is 3 × 10⁻¹³ cm/s. Results of sensitivity runs show that computed compositional profiles are sensitive to most model parameters.     

Laser-induced breakdown spectroscopy – An emerging chemical sensor technology for real-time field-portable,geochemical, mineralogical,and environmental applications

Laser induced breakdown spectroscopy (LIBS) is a simple spark spectrochemical sensor technology in which a laser beam is directed at a sample surface to create a high-temperature microplasma and a detector used to collect the spectrum of light emission and record its intensity at specific wavelengths. LIBS is an emerging chemical sensor technology undergoing rapid advancement in instrumentation capability and in areas of application. Attributes of a LIBS sensor system include: (i) small size and weight; (ii) technologically mature, inherently rugged, and affordable components; (iii) real-time response; (iv) in situ analysis with no sample preparation required; (v) a high sensitivity to low atomic weight elements which are difficult to determine by other field-portable sensor techniques, and (vi) point sensing or standoff detection. Recent developments in broadband LIBS provide the capability for detection at very high resolution (0.1 nm) of all elements in any unknown target material because all chemical elements emit in the 200–980 nm spectral region. This progress portends a unique potential for the development of a rugged and reliable field-portable chemical sensor that has the potential to be utilized in variety of geochemical, mineralogical, and environmental applications.     

The Potassium‐Argon Laser Experiment (KArLE): In Situ Geochronology for Planetary Robotic Missions

Geochronology is a fundamental measurement for planetary samples, providing global and solar system context for the conditions prevailing on the planet at the time of major geological events. The potassium (K)‐Argon (Ar) laser experiment (KArLE) will make in situ noble gas geochronology measurements aboard planetary robotic missions such as rovers and landers. Laser‐induced breakdown spectroscopy (LIBS) is used to measure the K abundance in a sample and to release its noble gases; the evolved Ar is measured by mass spectrometry, and relative K content is related to absolute Ar abundance by sample mass, determined by optical measurement of the ablated volume. This approach allows K and Ar to be measured on identical volumes multiple times to create an isochron, which improves the age determination and reveals irregularities in the rock if they exist. The KArLE technique measures a whole‐rock K‐Ar age with 10% uncertainty or better for rocks 2 Ga or older, sufficient to resolve the absolute age of many planetary samples. The LIBS–mass spectrometry approach is attractive because the analytical components have been flight‐proven, do not require further technical development and provide essential measurements (complete elemental abundance, evolved volatile analysis, micro‐imaging) as well as in situ geochronology.     

LIBS analysis of geomaterials: Geochemical fingerprinting for the rapid analysis and discrimination of minerals

Laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopy technique capable of real-time, essentially non-destructive determination of the elemental composition of any substance (solid, liquid, or gas). LIBS, which is presently undergoing rapid research and development as a technology for geochemical analysis, has attractive potential as a field tool for rapid man-portable and/or stand-off chemical analysis. In LIBS, a pulsed laser beam is focused such that energy absorption produces a high-temperature microplasma at the sample surface resulting in the dissociation and ionization of small amounts of material, with both continuum and atomic/ionic emission generated by the plasma during cooling. A broadband spectrometer-detector is used to spectrally and temporally resolve the light from the plasma and record the intensity of elemental emission lines. Because the technique is simultaneously sensitive to all elements, a single laser shot can be used to track the spectral intensity of specific elements or record the broadband LIBS emission spectra, which are unique chemical ‘fingerprints’ of a material. In this study, a broad spectrum of geological materials was analyzed using a commercial bench-top LIBS system with broadband detection from ∼200 to 965 nm, with multiple single-shot spectra acquired. The subsequent use of statistical signal processing approaches to rapidly identify and classify samples highlights the potential of LIBS for ‘geochemical fingerprinting’ in a variety of geochemical, mineralogical, and environmental applications that would benefit from either real-time or in-field chemical analysis.     

An Innovative Approach to Meteorite Analysis by Laser‐Induced Breakdown Spectroscopy

An innovative approach of double pulse laser‐induced breakdown spectroscopy (DP‐LIBS) coupled with optical microscopy was applied to the characterisation and quantitative analysis of the Agoudal iron meteorite in bulk sample and in petrographic thin section. Qualitative analysis identified the elements Ca, Co, Fe, Ga, Li and Ni in the thin section and the whole meteorite. Two different methods, calibration‐free LIBS and one‐point calibration LIBS, were used as complementary methodologies for quantitative LIBS analysis. The elemental composition data obtained by LIBS were in good agreement with the compositional analyses obtained by traditional methods generally applied for the analysis of meteorites, such as ICP‐MS and EDS‐SEM. Besides the recognised advantages of LIBS over traditional techniques, including versatility, minimal destructivity, lack of waste production, low operating costs, rapidity of analysis, availability of transportable or portable systems, etc., additional advantages of this technique in the analysis of meteorites are precision and accuracy, sensitivity to low atomic number elements such as Li and the capacity to detect and quantify Co contents that cannot be obtained by EDS‐SEM.     

KArMars: A Breadboard Model for In Situ Absolute Geochronology Based on the K–Ar Method Using UV‐Laser‐Induced Breakdown Spectroscopy and Quadrupole Mass Spectrometry

We present a breadboard prototype to perform in situ dating applicable to planetary exploration. Based on the K–Ar dating method and using instruments inspired by flight‐proven analytical components, ‘KArMars’ ablated a geological sample under high vacuum with a quadrupled ultraviolet (UV at 266 nm) Nd:YAG laser. During ablation, the K content of the target material was given by laser‐induced breakdown spectroscopy and the released ⁴⁰Ar was measured with a quadrupole mass spectrometer. Because K was measured as a concentration and ⁴⁰Ar as a count of atoms, these values were converted using the ablated mass given by the product of the density and the ablated volume. The uncertainties of the age measurement were < 15%. The quality of the K–Ar measurements was enhanced by the advantages of UV laser ablation such as the minimisation of thermal effects on argon diffusion. This work demonstrates that a specialised instrument inspired by this set‐up could provide in situ absolute geochronology with sufficient precision for scientific investigations, particularly where the crater density counting provides higher uncertainties on Mars.     

Compositional analysis of Yayoi‐Heian period ceramics from Okinawa: Examining the potential for provenance study

In Okinawa, locally produced pottery dates back to the Initial Jomon period (˜6500 ¹⁴C yr B.P.). Later in time, especially during the Early Yayoi‐Heian period (˜300 B.C.–A.D. 300), ceramic assemblages appear to contain mainland (Japan) Yayoi pottery. A greater number of these sherds present in Okinawa over time coincide with an increasing amount of interaction with mainland Japan, as evidenced by other exchange items. In this preliminary study, the authors analyzed sherds from several Early Yayoi‐Heian period deposits from sites in Okinawa using thin‐section petrography and laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS). The objective was to examine the applicability of these techniques for Okinawan ceramic provenance studies, assess intra‐ and intersite variation in mineralogical and chemical composition, and determine whether some sites exhibited a higher frequency of pottery from one locale versus another that might suggest the importation of pottery from mainland Japan. Results are equivocal, suggesting that the region's geological complexity may inhibit successful provenance study of ceramics using these and possibly other compositional techniques. © 2006 Wiley Periodicals, Inc.     

Iron Distribution in Size‐Resolved Aerosols Generated by UV‐Femtosecond Laser Ablation: Influence of Cell Geometry and Implications for In Situ Isotopic Determination by LA‐MC‐ICP‐MS

The influence of ablation cell geometry (Frames single‐ and HelEx two‐volume cells) and laser wavelength (198 and 266 nm) on aerosols produced by femtosecond laser ablation (fs‐LA) were evaluated. Morphologies, iron mass distribution (IMD) and ⁵⁶Fe/⁵⁴Fe ratios of particles generated from magnetite, pyrite, haematite and siderite were studied. The following two morphologies were identified: spherules (10–200 nm) and agglomerates (5–10 nm). Similarity in IMD and ablation rate at 198 and 266 nm indicates similar ablation mechanisms. ⁵⁶Fe/⁵⁴Fe ratios increased with aerodynamic particle size as a result of kinetic fractionation during laser plasma plume expansion, cooling and aerosol condensation. The HelEx cell produces smaller particles with a larger range of ⁵⁶Fe/⁵⁴Fe ratios (1.85‰) than particles from the Frames cell (1.16‰), but the bulk aerosol matches the bulk substrate for both cells, demonstrating stoichiometric fs‐LA sampling. IMD differences are the result of faster wash out of the HelEx cell allowing less time for agglomeration of small, low‐δ ⁵⁶Fe particles with larger, high‐δ ⁵⁶Fe particles in the cell. Even with a shorter ablation time, half the total Fe ion intensity, and half the ablation volume, the HelEx cell produced Fe isotope determinations for magnetite that were as precise as the Frames cell, even when the latter included an aerosol‐homogenising mixing chamber. The HelEx cell delivered a more constant stream of small particles to the ICP, producing a more stable Fe ion signal (0.7% vs. 1.5% RSE for ⁵⁶Fe in a forty‐cycle single analysis), constant instrumental mass bias and thus a more precise measurement.     

Rapid Determination of Trace and Ultra Trace Level Elements in Diverse Silicate Rocks in Pressed Powder Pellet Targets by LA‐ICP‐MS using a Matrix‐Independent Protocol

A simple, single sample preparation involving pressed rock powder pellets was utilised to determine the trace and ultra trace abundances of petrogenetically important elements including high field‐strength elements and REEs by laser ablation‐ICP‐MS. One of the elements predetermined by XRF spectrometry served as an internal standard. The influence of sample preparation parameters (grain size, pellet compactness and amount of binding media) on analytical performance was also investigated, including sample homogeneity issues at the laser sampling scale. Line scanning with a high repetition frequency (20 Hz) and large beam diameter (200 μm) ensured ablation from a larger sample surface area, eliminating issues related to sample heterogeneity. A median grain size of about 10 μm for silicate rock powders was found to be sufficiently representative at this scale of laser sampling. Granitic rocks or samples containing resistant minerals such as zircon needed extra grinding to achieve grain sizes down to < 5 μm for better precision for elements that are concentrated in these phases. Using ¹³⁷Ba as an internal standard, reasonable accuracies within 15–20% for most of the high mass trace elements were achieved; in the case of low mass elements, it may deviate up to 40%. Precision of measurements rarely exceeded 15% RSD.     

Abundances of Sulfur,Selenium, Tellurium,Rhenium and Platinum‐Group Elements in Eighteen Reference Materials by Isotope Dilution Sector‐Field ICP‐MS and Negative TIMS

Geological reference materials (RMs) with variable compositions and NIST SRM 612 were analysed by isotope dilution mass spectrometry for bulk rock concentrations of chalcogen elements (sulfur, selenium and tellurium), rhenium and platinum‐group elements (PGEs: Ru, Pd, Os, Ir and Pt), including the isotope amount ratios of ¹⁸⁷Os/¹⁸⁸Os. All concentrations were obtained from the same aliquot after HCl‐HNO₃ digestion in a high pressure asher at 320 °C. Concentrations were determined after chemical separation by negative TIMS, ICP‐MS and hydride generation ICP‐MS (Se, Te). As in previous studies, concentrations of the PGEs in most RMs were found to be highly variable, which may be ascribed to sample heterogeneity at the < 1 g level. In contrast, S, Se and Te displayed good precision (RSD < 5%) in most RMs, suggesting that part of the PGE budget is controlled by different phases, compared with the chalcogen budget. The method may minimise losses of volatile chalcogens during the closed‐system digestion and indicates the different extent of heterogeneity of chalcogens, Re and PGEs in the same sample aliquot. OKUM, SCo‐1, MRG‐1, DR‐N and MAG‐1 are useful RMs for the chalcogens. NIST SRM 612 displays homogenous distribution of S, Se, Te, Pt and Pd in 30 mg aliquots, in contrast with micro‐scale heterogeneity of Se, Pd and Pt.     

Determination of Abundances of Fifty‐Two Elements in Natural Waters by ICP‐MS with Freeze‐Drying Pre‐concentration

To precisely determine the abundances of fifty‐two elements found within natural water samples, with mass fractions down to fg g^?1 level, we have developed a method which combines freeze‐drying pre‐concentration (FDC) and isotope dilution internal standardisation (ID‐IS). By sublimation of H₂O, the sample solution was reduced to < 1/50 of the original volume. To determine element abundance with accuracy better than 10%, we found that for solutions being analysed by mass spectrometry the HNO₃ concentration should be > 0.3 mol l^?1 to avoid hydrolysis. Matrix‐affected signal suppression was not significant for the solutions with NaCl concentrations lower than 0.2 and 0.1 cg g^?1 for quadrupole ICP‐MS and sector field ICP‐MS, respectively. The recovery yields of elements after FDC were 97–105%. The detection limits for the sample solutions prepared by FDC were ≤ 10 pg g^?1, except for Na, K and Ca. Blanks prepared using FDC were at pg‐levels, except for eleven elements (Na, Mg, Al, P, Ca, Mn, Fe, Co, Ni, Cu and Zn). The abundances of fifty‐two elements in bottled drinking water were determined from five different geological sources with mass fractions ranging from the fg g^?1 to μg g^?1 level with high accuracy.     

Uphill diffusion,zero-flux planes and transient chemical solitary waves in garnet

Diffusion profiles in minerals are increasingly used to determine the duration of geological events. For this purpose, the distinction between growth and diffusion zoning is critical; it requires the understanding of complex features associated with multicomponent diffusion. Seed-overgrowth interdiffusion experiments carried out in the range 1,050–1,250°C at 1.3 GPa have been designed to quantify and better understand Fe–Mg–Ca interdiffusion in garnet. Some of the diffusion profiles measured by analytical transmission electron microscope show characteristic features of multicomponent diffusion such as uphill diffusion, chemical solitary waves, zero-flux planes and complex diffusion paths. We implemented three different methods to calculate the interdiffusion coefficients of the D matrix from the experimental penetration curves and determined that with Ca as the dependent component, the crossed coefficients of the D matrix are negative. Experiments and numerical simulations indicate that: (1) uphill diffusion in garnet can be observed indifferently on the three components Fe, Mg and Ca, (2) it takes the form of complementary depletion/repletion waves and (3) chemical waves occur preferentially on initially flat concentration profiles. Derived D matrices are used to simulate the fate of chemical waves in time, in finite crystals. These examples show that the flow of atoms in multicomponent systems is not necessarily unidirectional for all components; it can change both in space along the diffusion profile and in time. Moving zero-flux planes in finite crystals are transitory features that allow flux reversals of atoms in the diffusion zone. Interdiffusion coefficients of the D matrices are also analyzed in terms of eigenvalues and eigenvectors. This analysis and the experimental results show that depending on the composition of the diffusion couple, (1) the shape of chemical waves and diffusion paths changes; (2) the width of the diffusion zone for each component may or may not be identical; and (3) the width of diffusion calculated at a given D and duration may greatly vary. D matrices were retrieved from thirteen sets of diffusion profiles. Data were cast in Arrhenius relations. Linear regressions of the data yield activation energies equal to 368, 148, 394, 152 kJ mol⁻¹ at 1 bar and frequency factors D_o equal to 2.37 × 10⁻⁶, −4.46 × 10⁻¹⁶, −1.31 × 10⁻⁵, 9.85 × 10⁻¹⁵ m² s⁻¹ for [(D)\tilde]_FeFe^Ca \tilde{D}_{FeFe}^{Ca} , [(D)\tilde]_FeMg^Ca \tilde{D}_{FeMg}^{Ca} , [(D)\tilde]_MgFe^Ca \tilde{D}_{MgFe}^{Ca} , [(D)\tilde]_MgMg^Ca \tilde{D}_{MgMg}^{Ca} , respectively. These values can be used to calculate interdiffusion coefficients in Fe–Mg–Ca garnets and determine the duration of geological events in high temperature metamorphic or magmatic garnets.     

三维地质建模及可视化系统的设计与开发

三维地学模拟是三维地质信息GIS可视化的核心内容。基于基础GIS软件平台MAPGIS,利用功能强大的三维可视化开发平台MAPGIS-TDE,设计、开发具有自主版权的三维地质建模及可视化系统。MAPGIS-TDE包括MAPGIS内核模块、MAPGIS-TDE基础平台、MAPGIS-TDE构建平台和基于MAPGIS-TDE的应用系统等4个层次。基于MAPGIS-TDE的三维地质建模及可视化系统分为地质数据管理、二维地质分析、地质断面处理、地质结构建模和地质属性建模等5大功能模块。系统实现时,将空间数据库划分为基础地理图形库、区域地质数据库、工程地质数据库、水文地质数据库、地球物理数据库、地球化学数据库等6类。该系统不仅提供了强大的地质数据管理、三维地质建模以及模型的可视化功能,还为专业技术人员提供了一个可视化的分析、设计平台。