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The Witwatersrand Basin in South Africa is one of the best-preserved records of fluvial sedimentation on an Archaean continent. The basin hosts the worlds biggest gold resource in thin pebble beds, but the process for gold enrichment is debated. Mechanical accumulation of gold particles from flowing river water is the prevailing hypothesis, yet there is evidence for hydrothermal mobilization of gold by fluids invading the metasedimentary rocks after their burial. Earth’s atmosphere three billion years ago was oxygen free, but already sustained some of the oldest microbial life on land. Here I use thermodynamic modelling and mass-balance calculations to show that these conditions could have led to the chemical transport and precipitation of gold in anoxic surface waters, reconciling the evidence for fluvial deposition with evidence for hydrothermal-like chemical reactions. I suggest that the release of sulphurous gases from large volcanic eruptions created acid rain that enabled the dissolution and transport of gold in surface waters as sulphur complexes. Precipitation of the richest gold deposits could have been triggered by chemical reduction of the dissolved gold onto organic material in shallow lakes and pools. I conclude that the Witwatersrand gold could have formed only during the Archaean, after the emergence of continental life but before the rise of oxygen in the Earth’s atmosphere.

We report data that allow us to evaluate the method of trapping immiscible, saline aqueous fluids (i.e., vapor and brine in the NaCl-KCl-HCl-FeCl2-AuHCl2-H2O system) as synthetic fluid inclusions in pre-fractured quartz cores in order to quantify the concentrations of Au, Fe, K, and Na, among coexisting three-phase, immiscible fluids (i.e., haplogranite melt, brine, and vapor) at magmatic conditions. Coexisting vapor and brine were trapped experimentally at 800 °C and 100-110 MPa as synthetic fluid inclusions in both quartz microfractures and quenched silicate melt (i.e., glass), and also sampled indirectly using the recovered quenched aqueous fluid. Quartz-hosted and glass-hosted brine inclusions were analyzed by laser-ablation inductively-coupled-plasma mass spectrometry (LAICPMS) and instrumental neutron activation analysis (INAA), respectively. Quenched aqueous fluid from each experiment containing a quartz core was recovered and analyzed by atomic absorption spectrophotometry (AAS). The composition of aqueous fluids trapped as quartz-hosted inclusions, glass-hosted inclusions, and those recovered after quench yield consistent and precise data, at the 2σ uncertainty level, for the elements of interest. The overlapping Au, Fe, K, and Na concentrations in aqueous fluids trapped and analyzed via three entirely different instrumental techniques (i.e., LAICPMS, INAA, and AAS) suggest strongly that quartz microfractures heal on a slow enough time scale to permit entrapment of fully equilibrated aqueous fluids at our experimental PTX conditions. The data evince clearly that the chemical composition of fluids in quartz microfractures at the time of self-healing represents equilibrium conditions; hence, synthetic fluid inclusions in experiments with low thermal gradients across the charge provide a reasonable estimate of fluid composition at least at the experimental conditions examined in this study.

We present a new finite element – finite volume (FEFV) method combined with a realistic equation of state for NaCl–H2O to model fluid convection driven by temperature and salinity gradients. This method can deal with the nonlinear variations in fluid properties, separation of a saline fluid into a high-density, high-salinity brine phase and low-density, low-salinity vapor phase well above the critical point of pure H2O, and geometrically complex geological structures. Similar to the well-known implicit pressure explicit saturation formulation, this approach decouples the governing equations. We formulate a fluid pressure equation that is solved using an implicit finite element method. We derive the fluid velocities from the updated pressure field and employ them in a higher-order, mass conserving finite volume formulation to solve hyperbolic parts of the conservation laws. The parabolic parts are solved by finite element methods. This FEFV method provides for geometric flexibility and numerical efficiency. The equation of state for NaCl–H2O is valid from 0 to 750°C, 0 to 4000 bar, and 0–100 wt.% NaCl. This allows the simulation of thermohaline convection in high-temperature and high-pressure environments, such as continental or oceanic hydrothermal systems where phase separation is common.We present a new finite element – finite volume (FEFV) method combined with a realistic equation of state for NaCl–H2O to model fluid convection driven by temperature and salinity gradients. This method can deal with the nonlinear variations in fluid properties, separation of a saline fluid into a high-density, high-salinity brine phase and low-density, low-salinity vapor phase well above the critical point of pure H2O, and geometrically complex geological structures. Similar to the well-known implicit pressure explicit saturation formulation, this approach decouples the governing equations. We formulate a fluid pressure equation that is solved using an implicit finite element method. We derive the fluid velocities from the updated pressure field and employ them in a higher-order, mass conserving finite volume formulation to solve hyperbolic parts of the conservation laws. The parabolic parts are solved by finite element methods. This FEFV method provides for geometric flexibility and numerical efficiency. The equation of state for NaCl–H2O is valid from 0 to 750°C, 0 to 4000 bar, and 0–100 wt.% NaCl. This allows the simulation of thermohaline convection in high-temperature and high-pressure environments, such as continental or oceanic hydrothermal systems where phase separation is common.

We present the benchmarking of a new finite element – finite volume (FEFV) solution technique capable of modeling transient multiphase thermohaline convection for geological realistic p-T-Xconditions. The algorithm embeds a new and accurate equation of state for the NaCl–H2O system. Benchmarks are carried out to compare the numerical results for the various component-processes of multiphase thermohaline convection. They include simulations of (i) convection driven by temperature and/or concentration gradients in a single-phase fluid (i.e., the Elder problem, thermal convection at different Rayleigh numbers, and a free thermohaline convection example), (ii) multiphase flow (i.e., the Buckley–Leverett problem), and (iii) energy transport in a pure H2O fluid at liquid, vapor, supercritical, and two-phase conditions (i.e., comparison to the U.S. Geological Survey Code HYDROTHERM). The results produced with the new FEFV technique are in good agreement with the reference solutions. We further present the application of the FEFV technique to the simulation of thermohaline convection of a 400°C hot and 10 wt.% saline fluid rising from 4 km depth. During the buoyant rise, the fluid boils and separates into a high-density, high-salinity liquid phase and a low-density, low-salinity vapor phase.We present the benchmarking of a new finite element – finite volume (FEFV) solution technique capable of modeling transient multiphase thermohaline convection for geological realistic p-T-Xconditions. The algorithm embeds a new and accurate equation of state for the NaCl–H2O system. Benchmarks are carried out to compare the numerical results for the various component-processes of multiphase thermohaline convection. They include simulations of (i) convection driven by temperature and/or concentration gradients in a single-phase fluid (i.e., the Elder problem, thermal convection at different Rayleigh numbers, and a free thermohaline convection example), (ii) multiphase flow (i.e., the Buckley–Leverett problem), and (iii) energy transport in a pure H2O fluid at liquid, vapor, supercritical, and two-phase conditions (i.e., comparison to the U.S. Geological Survey Code HYDROTHERM). The results produced with the new FEFV technique are in good agreement with the reference solutions. We further present the application of the FEFV technique to the simulation of thermohaline convection of a 400°C hot and 10 wt.% saline fluid rising from 4 km depth. During the buoyant rise, the fluid boils and separates into a high-density, high-salinity liquid phase and a low-density, low-salinity vapor phase.

Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H2O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H2O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.

Fluid-phase relationships and thermodynamic reaction modelling based on published mineral solubility data are used to re-assess the Cu–Au-mineralising fluid processes related to calc-alkaline magmatism. Fluid inclusion microanalyses of porphyry ore samples have shown that vapour-like fluids of low to intermediate salinity and density (~2–10 wt% NaCl eq.; ~0.1–0.3 g cm−3) can carry percentage-level concentrations of copper and several ppm gold at high temperature and pressure. In epithermal deposits, aqueous fluids of similar low to intermediate salinity but liquid-like density are ubiquitous and commonly show a magmatic isotope signature. This paper explores the physical evolution of low-salinity to medium-salinity magmatic fluids of variable density, en route from their magmatic source through the porphyry regime to the near-surface epithermal environment, and investigates the chemical conditions required for effective transport of gold and other components from the magmatic to the epithermal domain. Multicomponent reaction modelling guided by observations of alteration zonation and vein overprinting relationships predicts that epithermal gold deposits are formed most efficiently by a specific succession of processes during the evolution of a gradually cooling magmatic–hydrothermal system. (1) The low-salinity to medium-salinity fluid, after separating from the magma and possibly condensing out some hypersaline liquid in the high-temperature porphyry environment, must physically separate from the denser and more viscous liquid, and then cool within the single-phase fluid stability field. By cooling under adequate confining pressure, such a vapour will evolve above the critical curve and contract, without any heterogeneous phase change, to an aqueous liquid of the same salinity. (2) High concentrations of gold, transported as stable Au bisulphide complexes supporting >1 ppm Au even at 200°C, can be maintained throughout cooling, provided that the fluid initially carries an excess of H2S over Cu+Fe on a molal scale. This condition is favoured by an initially high sulphide content in a particularly low-salinity magmatic fluid, or by preferential partitioning of sulphur into a low-salinity vapour and partial removal of Fe into a hypersaline liquid at high temperature. (3) Acid neutralisation further optimises gold transport by maximising the concentration of the HS−ligand. This may occur by feldspar destructive alteration along pyrite±chalcopyrite±sulphate veins, in the transition zone between the porphyry and epithermal environments. An alternative acid/base control is the dissolution of calcite in sediments, which may enable long-distance gold transport to Carlin-type deposits, because of the positive feedback between acid neutralisation and permeability generation. The three physical and chemical transport requirements for high-grade epithermal gold mineralisation are suggested to be the common link of epithermal gold deposits to underlying magmatic–hydrothermal systems, including porphyry-Cu–Au deposits. Both mineralisation types are the result of gradual retraction of isotherms around cooling hydrous plutons in similar tectonic and hydrologic environments. As magmatic fluid is generated at increasing depths below the surface the importance of vapour contraction increases, leading to the typical overprinting of potassic, phyllic and advanced argillic alteration and their related ore styles.Fluid-phase relationships and thermodynamic reaction modelling based on published mineral solubility data are used to re-assess the Cu–Au-mineralising fluid processes related to calc-alkaline magmatism. Fluid inclusion microanalyses of porphyry ore samples have shown that vapour-like fluids of low to intermediate salinity and density (~2–10 wt% NaCl eq.; ~0.1–0.3 g cm−3) can carry percentage-level concentrations of copper and several ppm gold at high temperature and pressure. In epithermal deposits, aqueous fluids of similar low to intermediate salinity but liquid-like density are ubiquitous and commonly show a magmatic isotope signature. This paper explores the physical evolution of low-salinity to medium-salinity magmatic fluids of variable density, en route from their magmatic source through the porphyry regime to the near-surface epithermal environment, and investigates the chemical conditions required for effective transport of gold and other components from the magmatic to the epithermal domain. Multicomponent reaction modelling guided by observations of alteration zonation and vein overprinting relationships predicts that epithermal gold deposits are formed most efficiently by a specific succession of processes during the evolution of a gradually cooling magmatic–hydrothermal system. (1) The low-salinity to medium-salinity fluid, after separating from the magma and possibly condensing out some hypersaline liquid in the high-temperature porphyry environment, must physically separate from the denser and more viscous liquid, and then cool within the single-phase fluid stability field. By cooling under adequate confining pressure, such a vapour will evolve above the critical curve and contract, without any heterogeneous phase change, to an aqueous liquid of the same salinity. (2) High concentrations of gold, transported as stable Au bisulphide complexes supporting >1 ppm Au even at 200°C, can be maintained throughout cooling, provided that the fluid initially carries an excess of H2S over Cu+Fe on a molal scale. This condition is favoured by an initially high sulphide content in a particularly low-salinity magmatic fluid, or by preferential partitioning of sulphur into a low-salinity vapour and partial removal of Fe into a hypersaline liquid at high temperature. (3) Acid neutralisation further optimises gold transport by maximising the concentration of the HS−ligand. This may occur by feldspar destructive alteration along pyrite±chalcopyrite±sulphate veins, in the transition zone between the porphyry and epithermal environments. An alternative acid/base control is the dissolution of calcite in sediments, which may enable long-distance gold transport to Carlin-type deposits, because of the positive feedback between acid neutralisation and permeability generation. The three physical and chemical transport requirements for high-grade epithermal gold mineralisation are suggested to be the common link of epithermal gold deposits to underlying magmatic–hydrothermal systems, including porphyry-Cu–Au deposits. Both mineralisation types are the result of gradual retraction of isotherms around cooling hydrous plutons in similar tectonic and hydrologic environments. As magmatic fluid is generated at increasing depths below the surface the importance of vapour contraction increases, leading to the typical overprinting of potassic, phyllic and advanced argillic alteration and their related ore styles.

The solubility of Au metal in rhyolite melt and coexisting magnetite has been determined at 800 °C, 140 MPa, and ƒO2≈ NNO in a Au-metal saturated, sulfur-free, vapor-brine-silicate melt system. Whole crystals of magnetite suspended within quenched rhyolite glass were analyzed by LA-ICPMS. These data yield a solubility of Au in magnetite on the order of 2 mg/g. The solubility of Au metal in rhyolite melt hosting the magnetite crystals is on the order of 500 μg/g. These data indicate a partition coefficient for Au between magnetite and melt, DAuMt/melt≈ 4. Using reasonable estimates of the mass fraction of magnetite that crystallizes in crustal magmatic systems, we modeled the proportion of Au sequestered by magnetite during fractional crystallization. We considered fractionation in two steps: the idealized derivation of a rhyolite by fractionation of basalt at depth, and the closedsystem crystallization of the rhyolite in a magma chamber below the site of ore deposition. Magnetite sequesters 14-54% Au from basaltic parent melt that produces a rhyolite melt via crystal fractionation, at modal abundances of 1-5%. Less then 4% Au is sequestered from a crystallizing rhyolite melt because of low modal abundances of magnetite (<~2%). Our experimental and model results suggest that early crystallization of magnetite can play a mitigating role in the ability of a calc-alkaline magmatic system to yield a Au-rich ore fluid.

Fluid inclusions have been studied in selected quartz-cassiterite veins of the Huanuni tin deposit, Bolivia. Fluid inclusion assemblages were found in quartz that bracket at least one stage of cassiterite deposition, and some were found in quartz crystallised during a later sulphide mineralisation stage. All fluid inclusions consisted of two phases only (liquid+vapour), which homogenised to a liquid upon heating and were classified to be of pseudosecondary or secondary in origin. Salinities in fluid inclusions related to the cassiterite deposition were up to 22 wt% NaCl equiv., and homogenisation temperatures of low and high salinity inclusions overlap in the range of 370 to 390 °C. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to determine element concentrations in selected fluid inclusions. The high salinity fluid inclusions show elevated contents of Li, B, Na, K, Mn, Fe, Zn, Ge, As, Rb, Sn, Sb, Cs, La and Pb compared with the lower salinity samples (wt% NaCl equiv. lower than 6%). High concentrations of incompatible lithophile elements including Li, B and Cs are characteristic for fluids derived from highly fractionated granitic systems. Fe, Zn, Pb, and Ge are the most important heavy metals transported with tin in the aqueous fluid. Sn, Fe, Zn, Pb are probably transported as chloride complexes, and the initial fluid-chemical data for successive fluid-inclusion generations indicates that SnO2precipitation occurred by injection of a hot saline magmatic fluid into heated low-salinity waters of possible meteoric origin.

Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has become a powerful tool in geochemistry, but for some important elements it is prone to interferences. The detection capabilities of optical emission spectroscopy (OES) might be superior to quadrupole mass spectrometry (QMS) in certain cases. Experiments for Na, Mg, Si, K, Ca and Fe showed limits of detection (LOD) with QMS of 0.9, 0.3, 700, 7.1, 180, 22 µg g⁻¹, respectively, obtained for continuous ablation of the Glass standard SRM 612 from NIST at a rate of ≈5.5 ng s⁻¹ in a 40 µm ablation pit. A modern OES system linked to the same LA setup showed poorer LOD of one to two orders of magnitude for these elements except for Ca. This is mainly due to the better sensitivities of QMS resulting from higher signal-to-background ratios. Yet, from the recording of short transient signals by QMS generated by the ablation of ~500 pg of material using a single laser shot, 20–40 times higher LOD have to be accepted relative to continuous ablation. For menus exceeding ≈10 isotopes with dwell times above 10 ms, the scan speed of the sequential QMS filter relative to the signal duration may be insufficient for representative sampling of short (&lt;≈3 s) transient signals, leading to less reproducible results. Simultaneous signal recording by OES has the potential to eliminate this problem, if the LOD of OES are low enough to detect such signals. Unfortunately, the duty cycle of the OES system degraded significantly with increasing number of spectral lines, due to the slow data readout, from 35% (10 elements) to 12% measurement efficiency (18 elements). The example of natural fluid inclusions shows that, for multi-element menus and short transient signals, LA-ICP-QMS is currently the best method, until the sensitivity, dynamic range of the CCD and data readout speed of OES instruments are improved.

Laser ablation-ICP-MS is a sensitive and accurate technique for major to trace multi-element analysis at high spatial resolution on the scale of 10 μm. A wide variety of samples can be studied quantitatively, including minerals and their solid, liquid or melt inclusions as required for geochemical studies. As the desired spatial resolution increases, however, detection limits become severely constrained by the total amount of sample material reaching the ICP. Detection limits are therefore determined by the ablation rate and by the efficiency of removal of ablated aerosol particles from the ablation spot and their transport into the plasma. Properties of the carrier gas are known to affect the ablation process and the efficiency of particle transportation. This study explores the effects of different ablation-cell configurations and the use of helium, dry argon and argon moistened with water for the transport of aerosols into an ICP-MS, using a prototype 193 nm ArF excimer laser. Deposition of visible particles deposited around the ablation pit is significantly reduced when helium is used instead of argon. A moderate flux of helium through the chamber, mixed with moistened argon immediately downstream from the ablation chamber, leads to at least a 2-3-fold increase in the signal intensities across the entire mass range when compared with argon gas only. Background intensities above mass 85 are significantly reduced, but polyatomic interferences in the low mass region increase by an order of magnitude, owing to oxide formation caused by the water load. A high flux of helium, mixed just behind the ablation cell with dry argon, yields a 2-3-fold sensitivity enhancement, in addition to greatly reduced background intensity across the entire mass range. This results in one order of magnitude improvement in detection limits for most elements. These modifications permit the routine determination of minor concentrations of chlorine in microscopic fluid inclusions or the analysis of minerals, such as trace element concentrations in quartz (e.g., Na and Li down to 500 ng g⁻¹, using a 40 μ ablation pit). Furthermore, this improved sensitivity has recently yielded the first quantitative determination of gold concentrations (~0.1 μg g⁻¹) and full rare-earth element patterns in single 25 μm fluid inclusions.

The ablation characteristics of a 266 nm Nd:YAG laser and a 193 nm excimer laser were compared by successive experiments by inductively coupled plasma mass spectrometry (ICP-MS), using the same ablation cell without changing the carrier-gas flows within comparative experiments. Both laser-optical systems have a fairly flat-topped lateral energy distribution yielding pan-shaped ablation pits on the sample. Comparative experiments with the two optical systems were carried out with argon and with helium+argon as carrier gases. For both lasers and both gas set-ups, signals of 40 s duration were recorded with a pulse rate of 10 Hz, with similar fluence adjusted to give comparable rates of material ablation. ICP-MS signal intensities were normalised to the total ablated volume, to compare the effects of lasers and gases on transport efficiency, ionisation efficiency and response and time-dependent element fractionation. The accuracy of trace element results was tested using two materials that allow stable ablation with both lasers but have significantly different matrix compositions (SRM 612 silicate glass from NIST and AGV-1 geological reference material in lithium tetraborate fusion). The time-averaged rate of material ablation is similar for both lasers and independent of the carrier gas in the sample chamber, but decays more rapidly with the 266 nm system. In argon, the signal unit response per volume of ablated material is similar with both lasers. In helium, the signal intensity with the 266 nm laser is enhanced slightly (maximum two-fold) compared with argon, but with the 193 nm system a consistent 2-3-fold signal enhancement is achieved. The use of helium reduces the amount of visible (>1 μm size) particle deposition in the ablation cell, irrespective of laser wavelength, and tests with successive ablations of chemically contrasting samples indicate memory effects with the 266 nm system that are absent in the same experiment with the 193 nm system. The limits of detection for both lasers were further improved by the use of He owing to the decrease in background intensities. Time-dependent element fractionation during a 40 s single-spot ablation is almost eliminated with the 193 nm system (&lt;10%), but with the 266 nm laser inter-element intensity ratios comparing the first and the second halves of the ablation period varied by up to 60% for some elements. Results for the cross-calibration between silicate (SRM 612) and borate glasses (AGV-1) obtained with both lasers indicate that the fractionation with the 266 nm system is similar for these two matrices, but this is not generally true for silicate minerals. The 193 nm system gives slightly better reproducibility between multiple analyses of one sample compared with the 266 nm system, yielding 2-5% RSDs for major and minor elements and 7-15% for concentrations below 10 ppm.

Recent developments in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have demonstrated its potential forin situ microanalysis for major, minor and trace elements in solids, such as minerals. With the low backgrounds and high sensitivity of new ICP-MS instruments, limits of detection of 1–10 ng g-1 in a 40 m ablation pit for many elements can be reached. Fractionation effects due to different ablation rates of various elements have prevented quantification without matrix-matched standards with 1064 nm Nd:YAG lasers. These effects have been reduced but not eliminated using shorter UV wavelengths (e.g. a quadrupled Nd:YAG 266 nm). Excimer lasers with wavelengths below 200 nm are expected to reduce fractionation effects further, but they present a serious challenge to the design of optical systems, especially if high-resolution UV ablation needs to be combined with high quality visual observation, which is essential for the study of complex materials, such as geological samples. An LA system was developed using an homogenized UV laser beam (193 nm, Argon Fluoride excimer) with a common UV–visual objective on a modified petrographic microscope with reflected and transmitted light illumination, in combination with a Perkin-Elmer Elan 6000 ICP-MS instrument. The optical system allows imaging of both visible and UV laser light onto the sample surface at the same time. Laser operating parameters and their influence on the ablation process were investigated using NIST SRM 612/610. Fractionation effects due to differential ablation of various elements as a function of time can be reduced to interelement correlation coefficients of r=0.9 or better and have become insignificant within the precision of quadrupole ICP-MS using this new optical design. Energy densities and repetition rates need to be kept within limited ranges for accurate and reproducible determinations of trace elements such as Zn, U and Pb, which have previously presented strong fractionation problems. LA-ICP-MS determinations on natural hornblende, augite, and garnet, calibrated against NIST SRM 612 using any major element as an internal standard, agree well with independent literature data. These experiments with the Argon Fluoride 193 nm excimer system demonstrate a greatly reduced matrix dependence of the ablation process, which facilitates in situ analysis of unknown samples.

In the southern Adula nappe (Central Alps), two stages of regional metamorphism have affected mafic and pelitic rocks. Earlier eclogite facies with a regional zonation from glaucophane eclogites to kyanite-hornblende eclogites was followed by a Tertiary overprint which varied from greenschist to high-grade amphibolite facies. Despite a common metamorphic history, contrasting equilibration conditions are often recorded by high-pressure mafic eclogite and adjacent predominantly lower-pressure pelite assemblages. This pressure contrast may be explained by different overprinting rates of the two bulk compositions during unloading. The rates are controlled by a mechanism in which dehydrating metapelites provide the H2O required for simultaneous overprinting of enclosed mafic eclogites by hydration.

Microscopic fluid inclusions in minerals are the main source of information about the chemical composition of fluids associated with large-scale material transport in the Earth's interior. Hydrothermal transport processes are responsible for the natural enrichment of metal resources in many ore deposits. For the multi-element analysis of the microscopic fluid inclusions (typically 5–50 μm in diameter), LA-ICP-MS has become one of the most promising techniques owing to the recent progress in laser optics design and the development of high-sensitivity ICP mass spectrometers. The quantitative analyses of 19 major, minor and trace elements covering a concentration range of five orders of magnitude were carried out on 39 single natural fluid inclusions, together with a number of experiments to optimise controlled ablation and to test the calibration procedure. A modified commercial ICP-MS instrument was used together with a prototype ablation system based on a 193 nm excimer laser. In a stepwise opening procedure for complex polyphase inclusions, a small hole (4 μm pit) was first drilled for the partial release of liquid and vapor, followed by complete drilling out using a pit covering the entire inclusion. Controlled ablation improves the reproducibility of element ratios to less than 20% for most major, minor and trace elements measured in an assemblage of cogenetic inclusions (including elements that are initially present as solid precipitates within the inclusion), provided that the entire transient ICP-MS signal is integrated. Element ratios were calculated from integrated intensity ratios using an external standard, either a NIST SRM glass or an aqueous standard solution ablated directly through a plastic film. Absolute concentrations were calculated from the element ratiosviaan internal standard element, whose concentration was determined prior to ablation. Microthermometric measurements of phase transitions were used to determine total salinity from known phase diagrams, by measuring either the depression of ice-melting temperature, or the temperature of dissolution of NaCl crystals. Salinity can be related to the concentration of Na (or in some cases Cl), which serves as the internal standard element for the quantification of trace element concentrations. Calculated limits of detection are in the ng g⁻¹to μg g⁻¹region, depending on the volume of the inclusions. The accuracy of the overall analysis, including internal and external calibration, is typically between 5 and 20%, as demonstrated on alkali elements in synthetic fluid inclusions of known composition.

We comment on a Letter by Toytman et al. [Opt. Lett.32, 1941 (2007)] in which a novel setup for wide-field imaging in coherent anti-Stokes Raman scattering (CARS) microscopy is demonstrated. There the authors state that our phase-matching implementation of a wide-field CARS system [Appl. Phys. Lett.84, 816 (2004); New J. Phys.8, 36 (2006)] suffers from a strong background from the bulk medium. However, our results show quite the contrary, i.e., that our setup provides a very good signal contrast, due to an almost vanishing background level from the bulk solvent.

Die weltweit reichsten Quellen von Kupfer, Molybdän, Wolfram, Zinn, und ein wesentlicher Anteil an Gold stammen aus porphyrischen Erzlagerstätten wie die riesige Kupfer-Gold-Mine von Bajo de la Alumbrera in Argentinien. Hier werden Erzreserven von 800 Millionen Tonnen mit Gehalten von rund 0, 6 Gewichtsprozent Kupfer und 0, 6 g/t Gold im Tagebau gewonnen. Vorstellungen zur Bildung dieser Metallvorkommen gehen davon aus, dass in 5—10 Kilometern Tiefe in vulkanisch aktiven Gebieten Magmakammern existieren.