Elements In Olivine Research Articles

The mantle source of thermal plumes: Trace and minor elements in olivine and major oxides of primitive liquids (and why the olivine compositions don't matter)

The mantle source of thermal plumes: Trace and minor elements in olivine and major oxides of primitive liquids (and why the olivine compositions don't matter)

On the equilibration timescales of isolated trace phases in mantle peridotites: Implications for the interpretation of grain-scale isotope heterogeneity in peridotitic sulfides

Geochemical studies of mid-ocean-ridge basalts (MORB) and mantle peridotites (e.g., abyssal peridotites) provide independent constraints on the composition and evolution of the convecting mantle. Recent studies have revealed systematic differences in the radiogenic isotope compositions of MORB and abyssal peridotites that call into question the complementary nature of these two windows to the upper mantle. The origin of these differences is fundamental to our understanding of MORB petrogenesis and the composition and depletion history of the upper mantle. The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting. However, several studies have reported Os- and Pb-isotope disequilibrium in distinct populations of peridotite-derived sulfides, with sulfides included within silicate grains typically possessing more “depleted” isotopic compositions than interstitial sulfides. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable parent/daughter ratios, or partial re-equilibration of low-Re/Os and U/Pb sulfides with more radiogenic silicate phases along grain boundaries during mantle melting. This would require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long (∼ Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed in several studies to the armoring effect of low-[Os] silicates, which limits diffusive exchange between isolated Os-rich sulfides. This raises the prospect that peridotite-derived melts may not inherit the Os- (or Pb-) isotope composition of their source, which could account for the recently documented systematic differences in the Os- and Pb-isotope compositions of MORB and mantle peridotites.Although the preservation of isotopic heterogeneity in mantle sulfides is commonly ascribed to the above “armoring effect”, the diffusive equilibration timescale of spatially separated sulfides in mantle peridotites has not previously been rigorously estimated. This study examines the parameters that control this equilibration timescale (average sulfide size and spacing, Os and Pb diffusivity in armoring silicate minerals, and element partitioning between silicate and sulfide phases). Equilibration timescale estimates using available constraints on these parameters reveal that most mantle sulfides are expected to isotopically re-equilibrate with neighboring sulfides in less than a few 10 s of Myr at convecting mantle temperatures. Maintenance of isotopic disequilibrium over the ∼ Ga timescales suggested by observed intra-sample Os- and Pb-isotope heterogeneity requires very large sulfides (>100 μm) separated by several mm or diffusion rates (D <10−18 m2/s), slower than for most elements in olivine. Combined with the observation of intra-sample major element heterogeneity in sulfide Ni and Fe abundances (which should equilibrate quickly in the convecting mantle), these results suggest that the observed isotopic disequilibrium is unlikely to be an ancient feature in mantle peridotites. Instead, recent sulfide metasomatism linked to interaction with melts derived from isotopically enriched eclogite or pyroxenite (or fertile and/or metasomatized peridotite) components is a more likely explanation for observed intra-sample isotopic heterogeneity in peridotites. This interpretation is also consistent with systematic differences between the Nd- and Hf-isotope compositions of MORB and abyssal peridotites. These results further strengthen the proposal that MORB do not accurately reflect the average isotopic composition of the convecting upper mantle, and that upper mantle peridotite is, on average, significantly more depleted and refractory than suggested by MORB-based estimates. The effects of melt generation in a heterogeneous marble-cake mantle need to be explicitly considered when using basalt compositions to constrain mantle composition and evolution.

Insights into the petrogenesis of the West Kimberley lamproites from trace elements in olivine

The Miocene lamproites of the West Kimberley region, Western Australia include olivine-leucite lamproites (≤10 wt% MgO) containing olivine and leucite microphenocrysts, and diamondiferous olivine lamproites (20–30 wt% MgO) containing olivine phenocrysts and larger (1–10 mm) olivine as mantle xenocrysts and dunite micro-xenoliths. Olivine phenocrysts and thin (<100 μm) magmatic rims define trends of decreasing Cr and Ni, and increasing Ca and Mn, with decreasing olivine Mg#, consistent with fractional crystallisation of olivine (and minor chromite). Many phenocrysts are zoned, and those with cores of similar Mg# and trace element abundances to the mantle xenocrysts may be xenocrysts overgrown by later olivine crystallised from the lamproite magma. Magmatic olivines Mg#91–92 are estimated to have been in equilibrium with olivine lamproite magma(s) containing ~22–24 wt% MgO. The xenocrystic mantle olivines Mg90–92.5 in the olivine lamproites are inferred from trace element abundances to be mostly derived from garnet peridotite with equilibration temperatures estimated from the Al-in-olivine thermometer (Bussweiler et al. 2017) to be ~1000–1270 °C at depths of 115–190 km. Olivines from the deeper lithosphere are less depleted (lower Mg#, higher Na, Al, P, Ti, Zr etc) than those at shallower depths, a feature suggested to reflect the combined effects of metasomatic re-enrichment of the craton roots (Ti, Fe, Zr etc) and increasing temperature with depth of origin (Na, Al, Ca). The West Kimberley lamproite olivines are not enriched in Li, as might be expected if their source regions contained continental sedimentary material as has been previously inferred from lamproite large-ion-lithophile trace elements, and Sr and Pb isotopes.

Disequilibrium growth of olivine in mafic magmas revealed by phosphorus zoning patterns of olivine from mafic–ultramafic intrusions

Olivine from mafic–ultramafic intrusions rarely displays growth zoning in major and some minor elements, such as Fe, Mg and Ni, due to fast diffusion of these elements at high temperatures. These elements in olivine are thus not useful in deciphering magma chamber processes, such as magma convection, multiple injection and mixing. High-resolution X-ray elemental intensity mapping reveals distinct P zoning patterns of olivine from two mafic–ultramafic intrusions in SW China. Polyhedral olivine grains from lherzolite and dunite of the Abulangdang intrusion show P-rich dendrites similar to those observed in volcanic rocks. Rounded olivine grains from net-textured Fe–Ti oxide ores of the Baima layered intrusion have irregular P-rich patches/bands crosscut and interlocked by P-poor olivine domains. P-rich patches/bands contain 250 to 612 ppm P, much higher than P-poor olivine domains with 123 to 230 ppm P. In electron backscattered diffraction (EBSD) maps, P-rich patches/bands within a single olivine grain have the same crystallographic orientation, indicating that they were remnants of the same crystal. Thus, both P-rich patches/bands and P-poor olivine domains in the same grain show a disequilibrium texture and clearly record two-stage growth. The P-rich patches/bands are likely the remnants of a polyhedral olivine crystal that formed in the first stage, whereas the P-poor olivine domains containing rounded Ti-rich magnetite and Fe-rich melt inclusions may have formed from an Fe-rich ambient melt in the second stage. The complex P zoning of olivine can be attributed to the dissolution of early polyhedral olivine and re-precipitation from the Fe-rich ambient melt. The early polyhedral olivine was in chemical disequilibrium with the ambient melt that may have been developed by silicate liquid immiscibility in a crystal mush. Our study implies that olivine crystals in igneous cumulates with an equilibrium appearance may have experienced disequilibrium growth processes during slow cooling. Therefore, the crystallization sequence of mafic magmas based on textural relationships should be treated with caution.

Chondrule heritage and thermal histories from trace element and oxygen isotope analyses of chondrules and amoeboid olivine aggregates

AbstractWe report combined oxygen isotope and mineral‐scale trace element analyses of amoeboid olivine aggregates (AOA) and chondrules in ungrouped carbonaceous chondrite, Northwest Africa 5958. The trace element geochemistry of olivine inAOA, for the first time measured byLA‐ICP‐MS, is consistent with a condensation origin, although the shallow slope of its rare earth element (REE) pattern is yet to be physically explained. Ferromagnesian silicates in type I chondrules resemble those in other carbonaceous chondrites both geochemically and isotopically, and we find a correlation between16O enrichment and many incompatible elements in olivine. The variation in incompatible element concentrations may relate to varying amounts of olivine crystallization during a subisothermal stage of chondrule‐forming events, the duration of which may be anticorrelated with the local solid/gas ratio if this was the determinant of oxygen isotopic ratios as proposed recently. While aqueous alteration has depleted many chondrule mesostases inREE, some chondrules show recognizable subdued groupII‐like patterns supporting the idea that the immediate precursors of chondrules were nebular condensates.

Trace elements in olivine of ultramafic lamprophyres controlled by phlogopite-rich mineral assemblages in the mantle source

Carbonate-rich ultramafic lamprophyres (aillikites) and associated rocks characteristically occur during the early stages of thinning and rifting of cratonic mantle lithosphere, prior to the eruption of melilitites, nephelinites and alkali basalts. It is accepted that they require volatile-rich melting conditions, and the presence of phlogopite and carbonate in the source, but the exact source rock assemblages are debated. Melts similar to carbonate-rich ultramafic lamprophyres (aillikites) have been produced by melting of peridotites in the presence of CO2 and H2O, whereas isotopes and trace elements appear to favor distinct phlogopite-bearing rocks.Olivine macrocrysts in aillikites are usually rounded and abraded, so that it is debated whether they are phenocrysts or mantle xenocrysts. We have analyzed minor and trace element composition in olivines from the type aillikites from Aillik Bay in Labrador, Canada. We characterize five groups of olivines: [1] mantle xenocrysts, [2] the main phenocryst population, and [3] reversely zoned crystals interpreted as phenocrysts from earlier, more fractionated, magma batches, [4] rims on the phenocrysts, which delineate aillikite melt fractionation trends, and [5] rims around the reversely zoned olivines. The main phenocryst population is characterized by mantle-like Ni (averaging 3400μgg−1) and Ni/Mg at Mg# of 88–90, overlapping with phenocrysts in ocean island basalts and Mediterranean lamproites. However, they also have low 100Mn/Fe of 0.9–1.3 and no correlation between Ni and other trace elements (Sc, Co, Li) that would indicate recycled oceanic or continental crust in their sources. The low Mn/Fe without high Ni/Mg, and the high V/Sc (2–5) are inherited from phlogopite in the source that originated by solidification of lamproitic melts at the base of the cratonic lithosphere in a previous stage of igneous activity. The olivine phenocryst compositions are interpreted to result from phlogopite and not high modal pyroxene in the source. The presence of kimberlites and ultramafic lamprophyres of Mesozoic age in Greenland indicates the persistence of a steep edge to the cratonic lithosphere at a time when this had been removed from the western flank in Labrador.

Trace elements in olivine and the petrogenesis of the intermediate, olivine‐phyric shergottite NWA 10170

AbstractOlivine‐phyric shergottites represent primitive basaltic to picritic rocks, spanning a large range of Mg# and olivine abundances. As primitive olivine‐bearing magmas are commonly representative of their mantle source on Earth, understanding the petrology and evolution of olivine‐phyric shergottites is critical in our understanding of Martian mantle compositions. We present data for the olivine‐phyric shergottite Northwest Africa (NWA) 10170 to constrain the petrology with specific implications for magma plumbing‐system dynamics. The calculated oxygen fugacity and bulk‐rock REE concentrations (based on modal abundance) are consistent with a geochemically intermediate classification for NWA 10170, and overall similarity with NWA 6234. In addition, we present trace element data using laser ablation ICP‐MS for coarse‐grained olivine cores, and compare these data with terrestrial and Martian data sets. The olivines in NWA 10170 contain cores with compositions of Fo77 that evolve to rims with composition of Fo58, and are characterized by cores with low Ni contents (400–600 ppm). Nickel is compatible in olivine and such low Ni content for olivine cores in NWA 10170 suggests either early‐stage fractionation and loss of olivine from the magma in a staging chamber at depth, or that Martian magmas have lower Ni than terrestrial magmas. We suggest that both are true in this case. Therefore, the magma does not represent a primary mantle melt, but rather has undergone 10–15% fractionation in a staging chamber prior to extrusion/intrusion at the surface of Mars. This further implies that careful evaluation of not only the Mg# but also the trace element concentrations of olivine needs to be conducted to evaluate pristine mantle melts versus those that have fractionated olivine (±pyroxene and oxide minerals) in staging chambers.

Electron probe determination of trace elements in olivine: thermometry of depleted peridotites

A method for calculation of the maximum permissible (for thermometry) error of analyte determination by trace elements is presented based on the example of the De Hoog-Gall Al-in-olivine thermometer. Analytical conditions ensuring an acceptable analytical error have been established, and the possibility to reach them has been estimated. A technique of JEOL JXA-8100 analysis of olivines for trace elements has been elaborated: Accelerating voltage is 20 kV, probe current is 400 nA, and counting time per line and background measurement is 10 s. The number of measurements per analysis is 25. Metrological characteristics of determination of Na2O, Al2O3, CaO, Cr2O3, and MnO have been calculated. Their detection limit (with confidence probability of 0.842) does not exceed 9 ppm. For an error of 10 rel.%, the quantitation limit of these oxides is within 45-100 ppm. Compositional peculiarities of olivines from depleted megacrystalline peridotites of the Udachnaya pipe have been revealed. The content of Mn significantly decreases with Mg# increase. The contents of Na, Al, Ca, and Cr show a strong mutual positive correlation. It is shown that electron probe microanalysis can provide an error sufficient for evaluating temperature by trace elements. The results of temperature determination by the Al-in-olivine thermometer agree with the thermometry data by H. O’Neil and B. Wood and differ considerably from the lower values estimated by D. Canil and C. Ryan with Ni thermometers.

Experimental petrology of the Tissint meteorite: Redox estimates, crystallization curves, and evaluation of petrogenetic models

AbstractTissint is an olivine‐phyric shergottite from an incompatible element depleted Martian mantle source. Oxythermobarometry applied to Tissint mineral phases demonstrates that the Tissint magma underwent an increase in oxygen fugacity, from ~3.5 log units below the quarz‐fayalite‐magnetite (QFM) buffer during the early stages of crystallization, to QFM−1.4 during the latter stages. This is the first time that such an oxidation event has been observed in a depleted shergottite. The reason for the oxidation event is unclear; however, calculations using the MELTS thermodynamic model suggest that auto‐oxidation is insufficient to cause more than ~1 log unit of oxidation, and therefore an external oxidation mechanism—such as oxidation by degassing—is required. If volatiles are responsible for the oxidation, then it indicates that volatiles are not exclusively tied to the enriched Martian mantle reservoir. A series of experiments using the Tissint parental magma were carried out under fixed (isothermal) or variable (cooling rate) temperature control, and at either reducing (QFM−3.2) or oxidizing (QFM−1) redox conditions. The observed liquid line of descent supports a potential genetic relationship between basaltic shergottites and olivine‐phyric shergottites. A peritectic relation where olivine is resorbed to form pyroxene is favored by increased oxygen fugacity; if oxidation during crystallization is more common than presently believed, it may explain why olivine is typically anhedral in olivine‐phyric shergottites. Results from a cooling‐rate experiment in which the oxygen fugacity was changed during the latter stages of crystallization resulted in olivine with a Cr compositional profile consistent with oxidized isothermal experiments, despite forming primarily under reducing conditions. A similar profile is observed in Tissint olivines, consistent with its redox history. Our results provide insights into the potential influence of oxidation events on the compositional zoning of minor or trace elements in olivine in olivine‐phyric basalts.

Low Ni olivine in silica-undersaturated ultrapotassic igneous rocks as evidence for carbonate metasomatism in the mantle

Subduction drags a large amount of CO2 into the Earth's interior, which is partly returned to the atmosphere by arc volcanism. Processes involved in the recycling of subducted carbon within the upper mantle are mainly related to mineralogical transformation. Subducted CO2 may dramatically affect the equilibria among peridotitic minerals (olivine vs. pyroxenes) changing their stability fields and hence their modal abundances. This process is accompanied by a subduction-induced change in the budget of some incompatible trace and major elements (e.g., K, Ca, HFSE), whereas it has a minimal effect on the mass balance of compatible elements (e.g., Ni). We report trace elements in olivine in subduction-related mafic alkaline ultrapotassic rocks from Italy, which are used as a proxy to define mantle wedge mineralogy and metasomatic processes. Minor element concentrations, and in particular the high Li and low Ti of all the olivines, confirm a major role for recycled sediment in the generation of Italian ultrapotassic magmas. The distinct contents of Ni, Mn, and Ca in olivine reflect the bimodal character of silica-rich and silica-poor ultrapotassic Italian rocks and constrain two distinct mineralogical reactions between metasomatic agents and peridotite. Olivine chemistry from silica-saturated rocks reflects the reaction of silicate melts with the ambient mantle, with consequent consumption of olivine in favour of orthopyroxene. In contrast, the low-Ni, high-Mn/Fe of olivine crystallised from silica-undersaturated leucitites require a mantle source enriched in olivine (and clinopyroxene) compared to orthopyroxene, as a result of the interaction between the ambient peridotitic mantle and CaCO3-rich metasomatic agents. The change from silica-oversaturated lamproites to silica-undersaturated leucitites and thus the difference in the olivine composition is due to a change in composition of the subducting sediment from pelitic to carbonate-rich. The results of this study provide new insights into how CO2 is recycled via subduction processes deep into the mantle.

Dehydrogenation as the mechanism of formation of the oriented spinel-pyroxene symplectites and magnetite-hematite inclusions in terrestrial and extraterrestrial olivines

A new approach is developed to explain the nature of oriented pyroxene-spinel symplectites and magnetite-hematite inclusions in olivines. Symplectites are considered the products of dehydrogenation and solid-state substitution of OH-bearing olivine-like precursor phases occured as lamellar inclusions in olivine. According to the dehydrogenation model, the precursor of the oriented symplectic pyroxene-spinel intergrowths in olivine hydrous olivine [3(Mg,Fe)2SiO4] · (MgH2SiO4), while the appearance of hematite-magnetite intergrowths in olivine is related to the dehydrogenation and dehydration of humite-like interlayers [n(Mg,Fe)2SiO4] · [Mg(OH2)]. The dehydrogenation reactions are accompanied by the transformation of divalent transition metals into a trivalent state and interdiffusion of Fe, Cr, Ca, Mg, and Al between precursor phase and host olivine under the long-term decompression at temperatures >800°C. The transformation of a pre-existing phase into symplectite was driven through the topotaxic reaction, fulfilling the following conditions: inheritance of crystallographic orientation of precursor phase by symplectite; preservation of volume during reaction, i.e. tendency to zero volume effect of the reaction1; the mass conservation, which is consistent with a solid state reaction in a closed system without external input of chemical elements in olivine.

Characterization of hydration in the mantle lithosphere: Peridotite xenoliths from the Ontong Java Plateau as an example

We report concentrations of hydrogen (H) in upper mantle minerals of peridotites (olivine and pyroxenes) transported by alnöitic lavas, which erupted on the southwestern border of the Ontong Java Plateau (Malaita, Solomon Islands, West Pacific). Unpolarized FTIR analyses show that olivine, orthopyroxene, and diopside contain 2–32 ppm, 162–362 ppm and 159–459 ppm wt H2O, respectively. In the studied lherzolites, garnets are anhydrous. The concentration of hydrogen within individual olivine and pyroxene grains is almost homogeneous, indicating no evidence of dehydration or hydration by ionic diffusion. In the lherzolite, the concentration of hydrogen in olivine tends to increase weakly with depth (based on geothermobarometry), consistent with the increase of water solubility with increasing water fugacity as a function of pressure, but concentrations remain well below water-saturation values determined experimentally. The highest concentration of H in olivine (32 ppm wt H2O) is, however, found in refractory spinel harzburgites, which equilibrated at depths of 85 km., while deeper specimens as the high-temperature spinel harzburgites, and some of the garnet lherzolites, contain less hydrogen in olivine. Olivines from pyroxene- or pargasite-rich peridotites have also lower hydrogen concentrations. We interpret the high hydrogen concentrations in olivine from the refractory spinel harzburgites as due to (1) simultaneous hydration and metasomatism of the lithospheric mantle by a water-rich silicate melt/fluid, during which hydrogen follows MREE and where spinel harzburgite have experienced ‘stealth’ metasomatism, and/or (2) to a late ‘fleeting’ hydrogen metasomatism, which would hydrate the rock after this first ‘stealth’ metasomatism event. In the second case, the composition of the ‘fleeting’ percolating fluid (small volume fraction of very evolved fluids, with high volatiles concentration and transient properties) is likely to be linked to the decrease of the plume activity and resulting in the downwelling of the lithosphere asthenosphere boundary. The difference in hydrogen concentration between harzburgites and lherzolites could be linked to variation in trace elements in olivine induced by the first ‘stealth’ metasomatism alone or associated to the late ‘fleeting’ hydrogen metasomatism, triggered by the lack of secondary crystallization of clinopyroxenes in the harzburgite. To conclude, H concentrations in upper mantle minerals may thus be correlated to metasomatic events, with the later yielding variation of the mineral assemblage and trace element composition that constitute the peridotites.

Tracking flux melting and melt percolation in supra-subduction peridotites (Josephine ophiolite, USA)

Here, we investigate the scale and nature of melting and melt percolation processes recorded by 17 supra-subduction peridotites collected in a ~70 km2 area in the northern portion of the Josephine ophiolite (Western USA). We present major and trace element variations in whole rocks; major elements in olivine, orthopyroxene, clinopyroxene and spinel; and trace elements [including rare earth element (REE)] in clinopyroxene and orthopyroxene. In the Josephine peridotites, compositional variability occurs at different scales. On the one hand, large systematic changes from depleted to fertile peridotites occur on large kilometer scales. Field, petrological and geochemical data can be consistently explained if the Josephine mantle experienced variable degrees of hydrous flux melting (10 to >20–23 %), and we argue that small fractions of subduction-derived fluids (0.015–0.1 wt%) were pervasive in the ~70 km2 studied area, and continuously supplied during wedge melting. Fluid localization probably led to increased extent of flux melting in the harzburgitic areas. On the other hand, in single outcrops, sharp transitions from dunite to harzburgite to lherzolite and olivine websterite can be found on meter to centimeter scales. Thus, some fertile samples may reflect limited degrees of refertilization at the outcrop scale. In addition, clinopyroxene and orthopyroxene in ultra-depleted harzburgites (Spinel Cr# > 58) show variable degrees of LREE enrichment, which reflect percolation of and partial re-equilibration with, small fractions of boninite melt. Because the enriched samples also show the highest spinel Cr#, we argue that these enrichments are local features connected to the presence of dunite channels nearby. Lastly, trace element concentrations of pyroxenes in Josephine harzburgites show that they are one of the most depleted harzburgites among worldwide ophiolitic peridotites, indicating particularly high degrees of melting, potentially past the exhaustion of clinopyroxene.

Electron probe determination of trace elements in olivine

Evaluation of the error of computations using analysis results requires knowing the error of determining the analyte. The necessity of limiting the error of computations conditions the value of the permissible error of determining the concentration: it should not exceed a certain predetermined limit. In particular, such a requirement is made for determining a component by the content of which the temperature of rock formation is calculated in a mineral. This study demonstrates derivation of a formula for quantitation limit Clim of an analyte. Relations have been obtained connecting Clim, the detection limit Cmin, and the relative standard deviation V of the element quantitation. The equations connecting metrological characteristics allowed identifying the required analysis conditions and their practicability. The characteristics of the methodology for quantitation of Na2O, Al2O3, CaO, Cr2O3 и MnO in the olivines of depleted peridotites have been identified using microanalyzer JXA‐8100, with the accelerating voltage of 20 kV and the probe current of 400 nA. The count rate per measurement was 10 s in the line and background positions. The number of measurements per quantitation was 25. Under these conditions, Cmin of the aforementioned oxides does not exceed 9 ppmw for 1σ‐criterion. For V = 0.1, Clim is within the range of 45–100 ppmw. The example of an ‘aluminum’ geothermometer serves to demonstrate that electron probe micro analysis may ensure the error required for calculating the temperature by the content of trace elements. Copyright © 2014 John Wiley &amp; Sons, Ltd.

The effect of silica activity on the diffusion of Ni and Co in olivine

The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg2SiO4) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO2 and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D M (M = Ni or Co) for the combined data set can be fitted to the equation: $$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$ with Ea(Ni) = − 284.3 kJ mol−1 and Ea(Co) = − 275.9 kJ mol−1, with an uncertainty of ±10.2 kJ mol−1. This equation fits the data (24 experiments) to ±0.1 in log D M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg1.8Fe0.2SiO4 at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe3+ in the Fe-bearing olivines. However, the dependence on fO2 is small, with D \(\propto\) (fO2)0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO2 magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO2 magmas, such as tholeiitic basalts, at equal temperatures and fO2.

Mantle–crust interactions in the oceanic lithosphere: Constraints from minor and trace elements in olivine

Minor and trace element compositions of olivines are used as probes into the melt-rock reaction processes occurring at the mantle–crust transition in the oceanic lithosphere. We studied mantle and lower crustal sections from the Alpine Jurassic ophiolites, where lithospheric remnants of a fossil slow-spreading ocean are exposed. Olivines from plagioclase-harzburgites and replacive dunites (Fo=91–89mol%) and from olivine-rich troctolites and troctolites (Fo=88–84mol%) were considered. Positive correlations among the concentrations of Mn, Ni, Co, Sc and V characterize the olivines from the dunites. These chemical variations are reconciled with formation by melts produced by a mixed source consisting of a depleted peridotite and a pyroxene-rich, garnet-bearing component melted under different pressure conditions. We thereby infer that the melts extracted through these dunites channels were not fully aggregated after their formation into the asthenospheric mantle.Olivines from the olivine-rich troctolites and the troctolites are distinct by those in the dunites by lower Ni and higher concentrations of Mn and incompatible trace elements (Ti, Zr, Y and HREE). Fractional crystallization cannot reproduce the chemical variations of the olivines from the olivine-rich troctolites and the troctolites. In these rock-types, the olivines commonly show heterogeneous Ti, Zr, Y and HREE compositions, which produce variable Ti/Y and Zr/Y values. We correlate these olivine characteristics with events of reactive melt migration occurred during the formation of the primitive lower oceanic crust. We propose that the migrating melts formed at the mantle–crust transition via interaction with mantle peridotites during periods of low melt supply.

DIPRA: A user‐friendly program to model multi‐element diffusion in olivine with applications to timescales of magmatic processes

AbstractModeling the diffusion of elements in olivine from volcanic rocks has recently become one of the most useful techniques to determine the timescales of the processes that occur in magma reservoirs before eruptions. However, many potential users are not versed in the numerical methods needed to solve the diffusion equation for timescale determinations. Here we present DIPRA (Diffusion Process Analysis), a user‐friendly computer tool that models easily and intuitively the olivine chemical zoning by performing an automatic, visual, and quick fit to the natural profiles. The code is developed under a finite difference scheme and allows simultaneous modeling of diffusion of Fe, Mg, Mn, Ni, and Ca. DIPRA accounts for most variables that affect the diffusivity, including temperature, pressure, oxygen fugacity, major element composition, and anisotropy. Initial and boundary conditions can be done as complex as desired, including changing boundary composition with time. Such versatility allows modeling the large variety of scenarios that are characteristic of volcanic systems. We also have implemented a methodology to estimate objectively the uncertainties of the timescales from the uncertainties of the data and temperature. We expect that our application will increase the number and quality of timescale determinations from crystal zoning studies. It may be also useful as a teaching resource for higher education courses.

Minor elements in unusual olivines from high-pressure peridotites of the kokchetav massif (Northern Kazakhstan)

Olivine is one of the most abundant minerals inupper mantle rocks, such as garnet and spinel peridotites of HP/UHP collisional zones and xenoliths inkimberlites and alkali basalts, as well as mineral inclusions in diamonds [1–3]. Having a simple chemicalcomposition, it contains some minor elements ofpetrogenetic importance. In spite of the widespreadabundance of olivine in such rocks, there are only afew studies of its minorelement composition (see thereview in [3]). This is explained by the low concentrations of minor elements in olivine, usually not exceeding 0.1 wt % (except for NiO and MnO), which makesanalytical difficulties for their measurements duringcommon electron microprobe investigations [4].In this paper we discuss the first study of the minorelement composition of olivines from peridotites ofthe wellknown Kokchetav massif in Northern Kazakhstan. These peridotites have an unusual chemicalcomposition characterized by a high concentration ofFeO (13–22 wt %), TiO

Comparative diffusion coefficients of major and trace elements in olivine at ∼950 °C from a xenocryst included in dioritic magma

which is a prerequisite for studying those trace elements for which substitution into a crystal requires some means of charge balance. In addition, the concentrations of the trace elements at the crystal-melt interface yield partition coeffi cients that may be checked against those obtained from equilibrium partitioning experiments, to test whether the concentrations of the diffusing elements are compatible with equilibrium substitution mechanisms. The method’s disadvantage is that relatively long diffusion profi les (>100 µm) are needed, which has prevented it being used in laboratory experiments at low temperatures where only short profi les could be generated in reasonable times. However, xenocrysts included in an exotic magma constitute a natural diffusion experiment of this type, in which concentration profi les of a suitable length can develop on geological as opposed to laboratory time scales (Costa and Chakraborty, 2004; Costa and Dungan, 2005). Here, we use a particularly propitious occurrence of diffusion profi les generated in olivine xenocrysts of upper-mantle composition immersed in a dioritic magma to constrain the rates of diffusion relative to Mg-Fe interdiffusion of several key trace elements (Li, Na, P, Ca, Sc, Ti, V, Mn, Co, Ni, and Y) at natural concentrations and at a temperature well below that practicable in the laboratory.

Trace-element geochemistry of mantle olivine and application to mantle petrogenesis and geothermobarometry

Trace-element compositions of olivine from 75 mantle rocks of diverse origin, including xenoliths from kimberlites, basaltic lavas and orogenic peridotites, were determined by laser ablation ICP-MS to study systematic variations between mantle lithologies, partitioning mechanisms in olivine and their potential for geothermobarometry and unravelling mantle processes. Samples were selected to cover a wide range of forsterite contents (89.1–93.4), equilibration temperatures and pressures (750–1450 °C; 15–80 kbar). Trace elements in olivine can be divided into three groups. Group I elements (Ni, Mn, Co, Cu, Zn and Li) show small concentration ranges and olivine is the major host mineral. These are mostly divalent elements and have ionic radii close to that of Mg. Group II elements (Cr, Al, V, Sc, Ca and Na) show large concentration ranges, which are mainly controlled by the equilibration temperature of the host rock. The elements are strongly concentrated in co-existing mantle minerals (garnet, clinopyroxene and spinel) and show a narrow range of bulk rock concentrations. They fit less comfortably in the olivine lattice than Group I elements because of their charge or size. Differences between garnet and spinel-facies rocks are apparent for Al, Ca and Sc. Group III elements (Ti, Zr, Nb and Y) show large ranges of concentration in olivine as well as in co-existing minerals, and are strongly dependent on bulk rock contents. Concentration differences between olivine from garnet and spinel-facies rocks are apparent for all these elements. They are strongly incompatible in olivine and other rock-forming mantle minerals because of their charge or size. Various mantle lithologies can be discriminated using olivine composition. Spinel, garnet and garnet–spinel peridotites can be distinguished in olivine Sc–Zr and MnO–Al 2O 3 diagrams, whereas volcanic olivine is distinguished by high Ca and Al contents (picritic olivine) or high Nb contents (kimberlitic olivine). Since concentrations of Group III elements in olivine are diagnostic of whole-rock contents they can be used to trace the petrogenetic history of the rock. For instance, Ti contents and Cr# (Cr/(Cr + Al)) of olivine correlate with the amount of melt extracted from a mantle residue, although refertilisation may subsequently have increased Ti contents in high- T peridotites from the base of the lithosphere. The olivine dataset can be used to examine substitution reactions. Uptake of Al and Cr appears to be largely charge-balanced by Na in garnet-facies olivine, and olivine Cr# strongly correlates with that of co-existing minerals, in particular clinopyroxene and spinel. In spinel-facies olivine a large excess of trivalent cations is present in olivine, which can be fully attributed to excess Al. This suggests a Tschermak-style substitution, in which replacement of Mg by Al in the octahedral site is charge-balanced by replacement of Si by Al in the tetrahedral site. Partition coefficients of Group II elements are highly temperature sensitive with most of the element variability being shown by olivine. This allows the definition of simple geothermometers based solely on the concentrations of these elements in olivine. The most widely applicable of these is Al-in-olivine for garnet peridotites, following the expression T Al-ol ( ° C ) = 9423 + 51.4 P + 1860 Cr # ol ( 13.409 − ln [ Al ] ol ) − 273 with P in kbar, Al ol the Al concentration of olivine in ppm, and Cr# ol is Cr/(Cr + Al) in olivine. This thermometer predicts the temperature with a residual of 15 °C based on calibration with two-pyroxene and Al-in-opx geothermobarometers (Brey and Köhler, 1990). Although calibrated using lherzolites only, the thermometer performs well for clinopyroxene-free harzburgites and also spinel peridotites. An alternative thermometer is presented for the case where the presence of Cr 2+ is expected, e.g., for olivine inclusions in diamonds. The geochemical and thermobarometric information recorded by olivine can be a useful tool in studies of the petrogenesis of lithospheric mantle, olivine xenocrysts in mantle-derived magmas, the formation of diamonds and diamond exploration using detrital olivine.