Nitrogen in peridotite xenoliths: Lithophile behavior and magmatic isotope fractionation

In order to document the origin and speciation of nitrogen in mantle-derived rocks and minerals, the N and Ar contents and isotopic compositions were investigated for hydrous and anhydrous peridotite xenoliths from Ataq, Yemen, from Eifel, Germany, and from Massif Central, France. Nitrogen and Ar were extracted by stepwise combustion with a fine temperature resolution, followed by fusion in a platinum crucible. A large isotopic disequilibrium of up to 25.4‰ is observed within single peridotite xenoliths, with δ¹⁵N values as low as −17.3‰ in phlogopite whereas clinopyroxene and olivine show positive δ¹⁵N values. Identical Sr isotopic ratios of phlogopite, clinopyroxene and whole rock in this wehrlite sample are consistent with crystallization from a common reservoir, suggesting that the light N signature of phlogopite might be the result of isotopic fractionation during N uptake from the host magma. The nitrogen concentration is systematically high in phlogopite, (7.6-25.7 ppm), whereas that of bulk peridotite xenoliths is between 0.1 and 0.8 ppm. The high N content of phlogopite is at least partly due to host magma-mineral interaction, and may also suggest the occurrence of N as that substituted for K⁺ during mineral growth in mafic magmas. Such speciation is consistent with the fact that N and Rb contents correlate well for a set of samples from mantle regions that were affected by subduction-related metasomatism and magmatism. The N/Rb ratios of these samples are comparable with values estimated for subduction zone magmas, but are one order of magnitude lower than the N/Rb ratios characterizing subducting slabs. This difference suggests preferential release of N relative to alkalis in the forearc region. N/⁴⁰Ar^∗ ratios of minerals from analyzed mantle xenoliths are much higher than those of vesicles in MORBs and OIBs, requiring either the occurrence of nitrogen speciation in the mantle more compatible than Ar, significant loss of fluid phase during entrainment, or long residence time of volatile elements in the mantle source(s) of fluids to increase drastically the ⁴⁰Ar^∗ budget of the latter.     

Experimentally determined partitioning of Rb between richterites and aqueous (Na, K)-chloride solutions

The distribution of Rb-Na and Rb-K between richterite and a 2-molal aqueous (Na, K, Rb)-chloride solution has been investigated with hydrothermal experiments at 800^∘C and 200 MPa. Experiments were performed as syntheses in which amphiboles grew in the presence of an excess fluid containing the exchangeable cations Na⁺-Rb⁺ or Na⁺-K⁺-Rb⁺. The obtained amphiboles were large enough (up to 20 m in width) for reliable EMP analysis. They were chemically homogeneous and HRTEM investigations showed that they were structurally well ordered. The Rb, Na, K, Ca and Mg concentrations in coexisting fluids were measured by ICP-AES. According to the possible incorporation of Na, K and Rb on the A-site, solid solutions in the ternary Na(NaCa) Mg₅[Si₈O₂₂/(OH)₂] (richterite)-K(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (K-richterite)-Rb(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (Rb-richterite) were expected. However, Rb-rich richterites always had significant amounts of A-site vacancy concentrations (X _□ ^amph=□ ^A /(Rb^A+K^A +Na^A+□^A) of up to 0.42 in the K-free (Na,Rb)-richterites and of up to 0.67 in the (Na, K, Rb)-richterites which corresponds to the same content of tremolite+cummingtonite-component. Amphiboles containing practically only Rb besides vacancies and no Na and/or K on the A-site were also synthesized, however. The Rb-Na and Rb-K exchange coefficients between fluid and richterites are similar. Rubidium always fractionated strongly into the fluid phase. For low Rb-concentrations in richterite (X _Rb ^amph<0.1) a linear correlation between X _Rb ^fluid and X _Rb ^amph exists. In this concentration range, the derived exchange coefficients K _D(Rb−K) ^amph−fluid and K _D(Rb−Na) ^amph−fluid were 0.08 ± 0.04 and 0.04 ± 0.02, respectively. These low exchange coefficients show that significant amounts of Rb in amphiboles require a Rb-rich fluid phase. The results indicate that K-Rb fractionation between alkali amphiboles and fluids is significantly different from K-Rb fractionation between alkali feldspar/ phlogopite and fluid, with K_Ds of about 0.5 and 1.2, respectively. Formation of richterites will drastically alter the K/Rb-ratios of fluids or melts. These results may have important implications for the genetical interpretation of various geological settings, e.g., MARID-type rocks. Received: 6 October 1997 / Accepted: 7 July 1998     

Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers

Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X _Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10^?11 to 10^?17 bar. Diffusion couples were prepared by ablating an olivine (X _Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D ^Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di₉₃–Di₆₅) or oxygen fugacity could be detected within the resolution of the study. The lack of fO₂-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D ^Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D ^Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D ^Ca–Mg) while it is slower than D ^Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks).     

Part II. Evaluation of Ar-Ar quartz ages: Implications for fluid inclusion retentivity and determination of initial Ar/Ar values in Proterozoic samples

The argon isotope systematics of vein-quartz samples with two different K-reservoirs have been evaluated in detail. Potassium is hosted by ultra-high-salinity fluid inclusions in quartz samples from the Eloise and Osborne iron-oxide-copper-gold (IOCG) deposits of the Mt Isa Inlier, Australia. In contrast, K is hosted by accidentally trapped mica within lower-salinity fluid inclusions of a sample selected from the Railway Fault, 13 km south of the Mt Isa copper mine, Australia. Imprecise apparent ages have been obtained for all of the samples studied and conclusively demonstrate that quartz fluid inclusions are retentive to Ar and have not leaked over billions of years. IOCG samples that host K in fluid inclusions only, have K/Cl values of <1 and the ages obtained represent the maximum ages for mineralization. In contrast, the Railway Fault samples that include accidentally trapped mica have K/Cl values of ?1. Excess ⁴⁰Ar_E plus Cl hosted by fluid inclusions, and radiogenic ⁴⁰Ar_R plus K, are strongly correlated in these samples and define a plane in 3D ⁴⁰Ar-³⁶Ar-K-Cl space. In this case, the plane yields an ‘excess ⁴⁰Ar_E’ corrected age of ∼1030 Ma that is 100’s of Ma younger than nearby Cu-mineralization at Mt Isa. The age is interpreted to reflect ⁴⁰Ar-loss from the accidentally trapped mica into the surrounding fluid inclusions, and is not related to the samples’ age of formation. The initial ⁴⁰Ar/³⁶Ar value of fluid inclusions is widely used to provide information on fluid origin. For the IOCG samples that host K in fluid inclusions only, the initial ⁴⁰Ar/³⁶Ar values are close to the measured values at every temperature of stepped heating experiments. For samples that include accidentally trapped mica, the correction for post-entrapment radiogenic ⁴⁰Ar_R production is significant. Furthermore, because ³⁹Ar_K present in accidentally trapped mica crystals is released at different temperatures to radiogenic ⁴⁰Ar_R lost to the surrounding fluid inclusions, intra-sample ⁴⁰Ar/³⁶Ar variation cannot be reliably documented. The results demonstrate that noble gas analysis is readily applicable to Proterozoic, or older, samples but that if K-mineral impurities are present within quartz the abundance of K must be determined before calculation of mean ⁴⁰Ar/³⁶Ar values that are representative of the samples’ initial composition.     

Ar degassing and the origin of the sialic crust

The degassing of radiogenic Ar⁴⁰ is defined as coherent if only the Ar⁴⁰ associated with parent K is degassed as K is transferred from the mantle to crust. Coherency predicts, for a 4.55 b.y. Earth, a sialic crust with 2.50 per cent K, using only the Ar content of the atmosphere and present crust (from a Hurley and Rand, 1969, age distribution). This is a maximum limit to K content of the sialic crust if the age of the Earth is no younger than 4.55 b.y. A K content of the sialic crust of 1.9 per cent (Holland and Lambert, 1972) implies an efficiency (E) less than 100 per cent for K transfer from oceanic basalt to sialic crust in subduction zones and/or some non-coherent (preferential) degassing of Ar from the mantle.K, Ar coherence for mantle differentiation to crust is supported however, by the agreement of the predicted oceanic He flux and radiogenic He-Ar ratios of volcanic gases with the observed limits if the best estimate of K, U, Th influx rates at oceanic ridges is used.Assuming K, Ar coherence, various sea-floor spreading rates as functions of time, and limiting K contents of the sialic crust, computed models give E and the portion of the sialic crust derived from melting oceanic basalt in subduction zones. Except for models with very high spreading rates in the Precambrian, they also predict that a significant part of the sialic crust was derived from vertical differentiation of the mantle, presumably early in Earth history. The results are in accord with Armstrong's model of an early sialic crust that is recycled to give a Hurley-type age pattern with the proviso that the ‘vertical’ sial K_υis formed early in Earth history for models with a high K_υcomponent.The coherent K, Ar models with preferred estimates of input parameters are also consistent with a limited mixing model (only old and new sial are equilibrated) for Sr isotopic evolution and the probable average $\text{Sr}{}^{87}\text{Sr}{}^{86}$ ratio now of the sialic crust.     

Conditions of diamond growth: a proton microprobe study of inclusions in West Australian diamonds

Crystalline primary inclusions in diamonds from the Argyle and Ellendale lamproites have been analyzed for Mn, Ni, Cu, Zn, Ga, Pb, Rb, Sr, Y, Zr, Nb, Ta, Ba and Mo by proton microprobe. Eclogite-suite inclusions dominate at Argyle and occur in equal proportions with peridotite-suite inclusions at Ellendale. Eclogitic phases present include garnet, omphacitic clinopyroxene, coesite, rutile, kyanite and sulfide. Eclogitic clinopyroxenes are commonly rich in K and contain 300–1060 ppm Sr and 3–70 ppm Zr: K/Rb increases with K content up to 1400 at 0.7–1.1% K. Rutiles have high Zr and Nb contents with Zr/Nb=1.5–4 and Nb/Ta 16. Of the peridotite-suite inclusions, olivine commonly contains > 10 ppm Sr and Mo; Cr-pyropes are depleted in Sr, Y and Zr, and enriched in Ni, relative to eclogitic garnets.Eclogite-suite diamonds grew in host rocks that were depleted in Mn, Ni and Cr, and enriched in Sr, Zn, Cu, Ga and Ti, relative to Type I eclogite xenoliths from the Roberts Victor Mine. Crystallization temperatures of the eclogite-suite diamonds, as determined by coexisting garnet and clinopyroxene from single diamonds, range from 1085 to 1575° C. Log K _D (C _i ^cpx /C _i ^gnt ) varies linearly with 1/T for Zr, Sr and Ga in most of the same samples. This supports the validity of the temperature estimates; Argyle eclogite-suite diamonds have grown over a T range 400° C. Comparison with data from eclogite xenoliths in kimberlites suggests that K _D ^Sr and K _D ^Zr are mainly T-dependent, while K _D ^Ga may be both temperature-and pressuredependent. K _D ^Ni , K _D ^Cu and K _D ^Zn show no T dependence in these samples.In several cases, significant major-and/or trace-element disequilibrium is observed between different grains of the same mineral, or between pyroxene and garnet, within single diamonds. This implies that these diamonds grew in an open system; inclusions trapped at different stages of growth record changes in major and trace-element composition occurring in the host rock. Diamond growth may have been controlled by a fluid flux which introduced or liberated carbon and modified the composition of the rock. The wide range of equilibration temperatures and the range of composition recorded in the inclusions of single diamonds suggest that a significant time interval was involved in diamond growth.     

A Reappraisal of the 40Ar/38Ar Dating Technique via Irradiation with γ-Rays

In a reconnaissance study, we investigated the potential of γ-ray induced production of ³⁸Ar_K from ³⁹K for geochronological applications. For this purpose, various age monitors commonly in use for the established ⁴⁰Ar/³⁹Ar-method were co-irradiated for 60 h at 17.6 MeV maximum energy in the ELBE facility, Dresden-Rossendorf, Germany. Because the available energy was low, total production of ³⁸Ar_K was depressed, leading to low J₃₈-values of (2.1–4.1) × 10^-6 and hence resulted in only minor ³⁸Ar excess when compared with atmospheric ³⁸Ar_/³⁶Ar ratios. In spite of these restrictions, ages of younger monitors could be reproduced within error, whereas older age reference materials showed discrepancies due to the low production rate. We observed Ca-derived contributions on ³⁶Ar in analysed CaF₂ reference materials, and calculated a limit for Ca-interference on ³⁸Ar_Ca of (³⁸Ar/³⁶Ar)_Ca = 0.07 ± 0.03 (1s). In addition, we investigated a potential recoil redistribution of ³⁸Ar by stepwise heating experiments, but could not quantify this further because of concurring processes. More work at higher photon energies is necessary to resolve other open issues, in particular the potential of utilising ⁴⁰Ar/³⁷Ar ratios for age determination and the possibility of ⁴²Ar production from ⁴⁴Ca, which would allow correction for Ca-interference reactions on other Ar isotopes. This would be a pre-requisite for dating extra-terrestrial rocks.     

Illite K–Ar dating and crystal growth processes in diagenetic environments: a critical review

K–Ar dating of illitic minerals is commonly used in studies of diagenetic series applied to oil prospecting. In spite of a great number of specialized papers, some problems remain unresolved. These are mostly due to a misunderstanding of the argon accumulation process during illitization. Criteria for identifying detrital–authigenic mineral mixtures, crystal ripening, fast precipitation or continuous nucleation‐growth processes are discussed using K–Ar data available in the literature. Using different parameters, such as Δ_age (age_K–Ar ? age_strati), Δ_cryst (diagenetic age_K–Ar ? age_strati) or Δ_frac (age_{K–Arfraction} ?age_K–Arfinest), it is shown that the K–Ar age significance depends on the illite nucleation–growth processes. A ‘diagenetic age’ is obtained when these processes are rapid (the K₂O accumulation period is shorter than 2σ). If lower than this value, the K–Ar ratio depends on the proportions of new and old particles, respectively, which are controlled by the relative rates of nucleation, crystal growth and ripening.     

Petrogenesis of extension-related alkaline volcanism in Karaburhan (Sivrihisar–Eskisehir), NW Anatolia, Turkey

Alkaline lavas were erupted as phonolites and trachytes around Karaburhan (Sivrihisar–Eskisehir, NW Anatolia) within the Izmir–Ankara–Erzincan suture zone. These volcanic rocks were emplaced as domes, close and parallel to the ophiolite thrust line. According to ⁴⁰Ar/³⁹Ar geochronological analyses of sanidine crystals from the phonolites, the age of the alkaline volcanics is 25 Ma (Late Oligocene–Early Miocene).The flow-textured phonolites are porphyritic and consist mainly of sanidine, clinopyroxene, and feldspathoid crystals. The clinopyroxenes show compositional zoning, with aegirine (Na_0.82–0.96Fe⁺³_0.68–0.83) rims and aegirine–augite cores (containing calcium, magnesium, and Fe⁺²). Some aegirine–augites are replaced with sodium-, calcium-, and magnesium-rich amphibole (hastingsite). Feldspathoid (hauyne) crystals enriched with elemental Na and Ca have been almost completely altered to zeolite and carbonate minerals. The fine-grained trachytes with a trachytic texture consist of feldspar (oligoclase and sanidine) phenocrystals and clinopyroxene microphenocrystals within a groundmass made up largely of alkali feldspar microlites.Although there are some differences in their element patterns, the phonolites and trachytes exhibit enrichment in LILEs (Sr, K, Rb, Ba, Th) and LREEs (La, Ce, Pr, Nd) and negative anomalies in Nb and Ta. These geochemical characteristics indicate a lithospheric mantle enriched by fluids extracted from the subduction component. In addition, the high ⁸⁷Sr/⁸⁶Sr (0.706358–0.708052) and low ¹⁴³Nd/¹⁴⁴Nd (0.512546–0.512646) isotope concentrations of the alkaline lavas reflect a mantle source that has undergone metasomatism by subduction-derived fluids. Petrogenetic modeling indicates that the alkaline lavas generated from the subduction-modified lithospheric mantle have undergone assimilation, fractional crystallization, and crustal contamination, acquiring high Pb, Ba, Rb, and Sr contents and Pb isotopic compositions during their ascent through the thickened crust in an extensional setting.     

High-pressure behaviour of Ca-rich C 2 /c clinopyroxenes along the join diopside-enstatite (CaMgSi2O6-Mg2Si2O6)

 An in situ high-pressure (HP) X-ray diffraction investigation of synthetic diopside and of the Ca_0.8Mg_1.2Si₂O₆ clinopyroxene (Di₈₀En₂₀) was performed up to respectively P=40.8 and 15.1 GPa, using high brilliance synchrotron radiation. The compression of the cell parameters is markedly anisotropic, with β_b ⋙ β_c > β_a > β_asinβ for any pressure range and for both diopside and Di₈₀En₂₀. The compressibility along the crystallographic axes decreases significantly with pressure and is higher in Di₈₀En₂₀ than in diopside. The β cell parameter decreases as well with pressure, at a higher rate in Di₈₀En₂₀. The cell volume decreases at almost the same rate for the two compositions, since in diopside a higher compression along a* occurs. A change in the mechanism of deformation at P higher than about 5–10 GPa is suggested for both compositions from the analysis of the strain induced by compression. In diopside at lower pressures, the deformation mainly occurs, at a similar rate, along the b axis and at a direction 145° from the c axis on the (0 1 0) plane. At higher pressures, instead, the deformation occurs mostly along the b axis. In Di₈₀En₂₀ the orientation of the strain axes is the same as in diopside. The substitution of Ca with Mg in the M2 site induces at a given pressure a higher deformation on (0 1 0) with respect to diopside, but a similar change in the compressional behaviour is found. Changes in the M2 polyhedron with pressure can explain the above compressional behaviour. A third-order Birch-Murnaghan equation of state was fit to the retrieved volumes, with K=105.1(9) GPa, K′=6.8(1) for diopside and K=107.3(1.4) GPa, K′=5.7(3) for Di₈₀En₂₀; the same equation can be applied for any pressure range. The elasticity of diopside is therefore not significantly affected by Mg substitution into the M2 site, in contrast to the significant stiffening occurring for Ca substitution into Mg-rich orthopyroxenes. Received: 3 January 2000 / Accepted: 21 May 2000     

Crystal-melt partitioning of noble gases (helium, neon, argon, krypton, and xenon) for olivine and clinopyroxene

Mineral-melt partition coefficients of all noble gases (^min/meltD_i) have been obtained for olivine (ol) and clinopyroxene (cpx) by UV laser ablation (213 nm) of individual crystals grown from melts at 0.1 GPa mixed noble gas pressure. Experimental techniques were developed to grow crystals virtually free of melt and fluid inclusions since both have been found to cause profound problems in previous work. This is a particularly important issue for the analysis of noble gases in crystals that have very low partition coefficients relative to coexisting melt and fluid phases. The preferred partitioning values obtained for the ol-melt system for He, Ne, Ar, Kr, and Xe are 0.00017(13), 0.00007(7), 0.0011(6), 0.00026(16), and , respectively. The respective cpx-melt partition coefficients are 0.0002(2), 0.00041(35), 0.0011(7), 0.0002(2), and . The data confirm the incompatible behaviour of noble gases for both olivine and clinopyroxene but unlike other trace elements these values show little variation for a wide range of atomic radius. The lack of dependence of partitioning on atomic radius is, however, consistent with the partitioning behaviour of other trace elements which have been found to exhibit progressively lower dependence of ^min/meltD_i on radius as the charge decreases. As all noble gases appear to exhibit similar ^min/meltD_i values we deduce that noble gases are not significantly fractionated from each other by olivine and clinopyroxene during melting and fractional crystallisation. Although incompatible, the partitioning values for noble gases also suggest that significant amounts of primordial noble gases may well have been retained in the mantle despite intensive melting processes. The implication of our data is that high primordial/radiogenic noble gas ratios (³He/⁴He, ²²Ne/²¹Ne, and ³⁶Ar/⁴⁰Ar) characteristic of plume basalt sources can be achieved by recycling a previously melted (depleted) mantle source rather than reflecting an isolated, non-degassed primordial mantle region.     

An absarokite from a phlogopite lherzolite source

An absarokite (SiO₂ 47.72 wt %, K₂O 3.41 wt %) occurs in the Katamata volcano, SW Japan. The rock carries phenocrysts of olivine, phlogopite, clinopyroxene, and hornblende. Chemical compositions of bulk rock (FeO^*/ MgO 0.73) and minerals (Mg-rich olivine and phlogopite, Cr-rich chromite) suggest that the absarokite is not differentiated. Melting experiments at high pressures on the Katamata absarokite have been conducted. The completely anhydrous absarokite melt coexists with olivine, orthopyroxene, and clinopyroxene at 1310° C and 1.0 GPa. The melt with 3.29 wt % of H₂O also coexists with the above three phases at 1230° C and 1.4 GPa; phlogopite appears at temperatures more than 80° C below the liquidus. On the other hand, the melt is not saturated with lherzolite minerals in the presence of 5.13 wt % of H₂O and crystallizes olivine and phlogopite as liquidus phases; the stability limit of phlogopite is little affected at least by the present variation of H₂O content in the absarokite melt. It is suggested that the absarokite magma was segregated from the upper mantle at 1170° C and 1.7 GPa leaving a phlogopite lherzolite as a residual material on the basis of the above experimental results and the petrographical observation that olivine and phlogopite crystallize at an earlier stage of crystallization sequence than clinopyroxene. The contribution of phlogopite at the stage of melting processes is also suggested by the geochemical characteristics that the absarokite is more enriched in Rb, K, and Ba and depleted in Ca and Na than a typical alkali olivine basalt from the same volcanic field.     

Diffusion of Na,K, Rb and Cs in glasses of albite and orthoclase composition

The measurement of diffusion coefficients for Na, K, Rb and Cs has been realized by the technique of active salt deposits on glasses of albite and orthoclase composition, at normal pressure and in the temperature range 300–1000°C. The values of D are between 10^?6 and 10^?12 cm² s^?1 and, for every type of run, they vary with temperature according to Arrhenius laws, with activation energies ranging from 13 to 68 kcal mole^?1. These important variations are related to the size of the diffusing element (at 700°C in albite glass D_Na/D_K/D_RbD_Cs ～- 10⁷/10⁵/10³/1) and to the size of the major alkali element (for rubidium at 800°C D_or·gl/D_ab·gl ～- 20). By comparison with available data on diffusion in feldspars, we emphasize the influence of the defect density on the diffusion process.     

KRb ratios in Precambrian granulite terranes

Concentrations of potassium and rubidium are reported for 62 Precambrian shield whole-rock samples belonging to the pyroxene granulite facies of world-wide distribution. Compared with the Main Trend established by Shaw (1968) for igneous and quasi-igneous rocks of the upper crust, the high-grade metamorphic granulites exhibit a similar correlation but with a measurable depletion in Rb for a given K content. The Metamorphic Trend may be described by the equations: log₁₀ (ppm Rb) = 1.136 log₁₀ (per cent K) + 1.495 or ppm Rb = 31.28 (per cent K)^1.136. The square of the product moment correlation coefficient shows that 80 per cent of the variation in Rb is associated with variation in K.All suites studied have initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios less than 0.707. This low value argues against repeated extraction of Rb and K through time on a regional scale. Rather, the major depletion in these lithophile elements occurred in the early stages of crustal evolution.     

K-Ar法地质年龄标准物质ZBJ角闪石的定值结果

为了满足K-Ar定年中K和⁴⁰Ar^*分析的质量监控及Ar-Ar法样品在反应堆照射时中子通量监测的需要,我国氩同位素年代学工作者研制了一个K-Ar法年龄标准物质ZBJ角闪石,它采自北京房山花岗闪长岩体。它的⁴⁰Ar-³⁹Ar阶段加热分析结果表明:⁴⁰Ar^*在矿物晶格中保存均匀稳定,年龄谱平坦,³⁹Ar析出量高达97%。这些证据充分表明该黑云母结晶以后未受过热扰动,40K-⁴⁰Ar^*同位素计时体系封闭良好。坪年龄为133.3±0.6Ma,总气体年龄为134.4±1.4Ma,³⁶Ar/⁴⁰Ar-³⁹Ar/⁴⁰Ar反等时线年龄为133.2±0.8Ma,⁴⁰Ar/³⁶Ar初始值为297.6±4.8,此值与(⁴⁰Ar/³⁶Ar)a大气氩丰度比(295.5±0.5)处于同一范围,表明样品不含过剩氩。这几个年龄值的一致性,说明该样品具有良好的均匀性和稳定性,它作为K-Ar和Ar-Ar法地质年龄标准物质是适合的。ZBJ角闪石均匀性检验结果表明:在0.05显著性水平下经统计学方法检验,证明K和⁴⁰Ar^*的F分布值小于F临界值,说明该样品是均匀的。国内8个实验室参加了ZBJ角闪石K含量和⁴⁰Ar^*含量的定值分析,经统计学方法检验,结果显示全部定值数据都服从正态分布并具等精度。在置信概率为0.95时,⁴⁰Ar*和K含量的相对标准偏差都小于1%。两个特性量值定值分析结果的一致值(认定值)和不确定度分别为:⁴⁰Ar^*=(2.464±0.018)×10^-10mol/g,K=(1.027±0.008)%,K-Ar年龄(标准值)=133.3±1.5Ma(2σ)。此标准物质纯度为98.1%,粒度为0.15～0.30mm,总重量为740g,缩分成最小样品单元共100瓶,每瓶7.4g,可供我国K-Ar和Ar-Ar法同位素年代学实验室使用37年。     

Trace-element partitioning between garnet,clinopyroxene and Fe-rich picritic melts at 3 to 7 GPa

We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py₆₃Al₂₅Gr₁₂) and clinopyroxene (∼Ca_0.2Mg_0.6Fe_0.2Si₂O₆) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D ^cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca_0.3–0.5Mg_0.3–0.6Fe_0.07–0.2Si₂O₆) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca_0.2Mg_0.7Fe_0.1Si₂O₆). D ^grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py_70–88Al_l7–20Gr_8–14). 97SB68 D _LREE^grt/liq values are higher and D _HREE^grt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py_20–70Al_10–50Gr_10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.     

Phase relations on the diopside-jadeite-hedenbergite join up to 24 GPa and stability of Na-bearing majoritic garnet

Phase relations on the diopside (Di)-hedenbergite (Hd)-jadeite (Jd) system modeling mineral associations of natural eclogites were studied for the compositions (mol %) Di₇₀Jd₃₀, Di₅₀Jd₅₀, Di₃₀Jd₇₀, Di₂₀Hd₈₀, and Di₄₀Hd₁₀Jd₅₀ using a toroidal anvil-with-hole (7 GPa) and a Kawai-type 6-8 multianvil apparatus (12-24 GPa). We established that Di, Hd, and Jd form complete series of solid solutions at 7 GPa, and melting temperatures of pure Di (1980 °C) and Jd (1870 °C) for that pressure were estimated experimentally. The melting temperature for the Di₅₀Jd₅₀ composition at 15.5 GPa is 2270 °C. The appearance of garnet is clearly dependent on initial clinopyroxene composition: at 1600 °C the first garnet crystals are observed at 13.5 GPa in the jadeite-rich part of the system (Di₃₀Jd₇₀), whereas diopside-rich starting material (Di₇₀Jd₃₀) produces garnet only above 17 GPa. The proportion of garnet increases rapidly above 18 GPa as pyroxene dissolves in the garnet structure and pyroxene-free garnetites are produced from diopside-rich starting materials. In all experiments, garnet coexists with stishovite (St). At a pressure above 18 GPa, pyroxene is completely replaced by an assemblage of majorite (Maj) + St + CaSiO₃-perovskite (Ca-Pv) in Ca-rich systems, whereas Maj is associated with almost pure Jd up to a pressure of 21.5 GPa. Above ∼22 GPa, Maj, and St are associated with NaAlSiO₄ with calcium ferrite structure (Cf). We established that an Hd component also spreads the range of pyroxene stability up to 20 GPa. In the Di₇₀Jd₃₀ system at 24 GPa an assemblage of Maj + Ca-Pv + MgSiO₃ with ilmenite structure (Mg-Il) was obtained. The experimentally established correlation between Na, Si, and Al contents in Maj and pressure in Grt(Maj)-pyroxene assemblages, may be the basis for a “majorite” geobarometer. The results of our experiments are applicable to the upper mantle and the transition zone of the Earth (400-670 km), and demonstrate a wide range of transformations from eclogite to perovskite-bearing garnetite. In addition, the mineral associations obtained from the experiments allowed us to simulate parageneses of inclusions in diamonds formed under the conditions of the transition zone and the lower mantle.     

Clinopyroxene dissolution in basaltic melt

The history of magmatic systems may be inferred from reactions between mantle xenoliths and host basalt if the thermodynamics and kinetics of the reactions are quantified. To study diffusive and convective clinopyroxene dissolution in silicate melts, diffusive clinopyroxene dissolution experiments were conducted at 0.47–1.90 GPa and 1509–1790 K in a piston-cylinder apparatus. Clinopyroxene saturation is found to be roughly determined by MgO and CaO content. The effective binary diffusivities, D_MgO and D_CaO, and the interface melt saturation condition, , are extracted from the experiments. D_MgO and D_CaO show Arrhenian dependence on temperature. The pressure dependence is small and not resolved within 0.47–1.90 GPa. in the interface melt increases with increasing temperature, but decreases with increasing pressure. Convective clinopyroxene dissolution, where the convection is driven by the density difference between the crystal and melt, is modeled using the diffusivities and interface melt saturation condition. Previous studies showed that the convective dissolution rate depends on the thermodynamics, kinetics and fluid dynamics of the system. Comparing our results for clinopyroxene dissolution to results from a previous study on convective olivine dissolution shows that the kinetic and fluid dynamic aspects of the two minerals are quite similar. However, the thermodynamics of clinopyroxene dissolution depends more strongly on the degree of superheating and composition of the host melt than that of olivine dissolution. The models for clinopyroxene and olivine dissolution are tested against literature experiments on mineral–melt interaction. They are then applied to previously proposed reactions between Hawaii basalts and mantle minerals, mid-ocean ridge basalts and mantle minerals, and xenoliths digestion in a basalt at Kuandian, Northeast China.     

The influence of crystal field stabilization energy on Fe2+ partitioning in paragenetic minerals

In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d ⁶-configured Fe²⁺ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K _D Fe^{2+ (Ph1/Ph2)} values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSE_Fe2+ values. Other than in the case of Cr³⁺, a clear quantitative relation between K _D ^(Ph1/Ph2) and the ΔCFSE^(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSE_Fe2+ contribution to K _D ^(Ph1/Ph2) amounts to 0.1 to 0.2 log K _D per 100 cm⁻¹ΔCFSE. The conclusion is that ΔCFSE_Fe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe²⁺. The reason for this is seen in the facts that, compared to the 3d ³-configured Cr³⁺ ion, CFSE of the 3d ⁶-configured Fe²⁺ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999     

Clinopyroxene + liquid equilibria to 100 kbar and 2450 K

One of the most active issues in igneous petrology is the investigation of mantle melting, and subsequent differentiation. To evaluate alternative hypotheses for melting and differentiation it is essential to accurately predict clinopyroxene compositions in natural systems. Expressions have thus been derived that describe clinopyroxene-melt equilibria, and allow equilibrium clinopyroxene compositions to be calculated. These equations were constructed from least-squares regression analysis of experimental clinopyroxene-liquid pairs. The calibration database included clinopyroxenes synthesized from both natural and synthetic basalt compositions; experimental conditions ranged from 0 to 100 kbar and 1350 to 2450 K. Regression equations were based on thermodynamic functions. Empirical expressions were also derived, since such models yield more precise estimates of clinopyroxene compositions, and may be easily incorporated into existing liquid line-of-descent models. Such equations may be useful for calculation of high pressure liquid fractionation, or for constraining P-T conditions for basalts produced by partial melting of a pyroxene-bearing source. Models of mantle melting often rely on expressions involving simple element ratios. Partition coefficients (K _d ^cpx/liq ) for the minor elements, Na and Ti, were thus also calibrated as a function of P, T and composition. K _Ti ^cpx/liq , while sensitive to composition was relatively insensitive to P and T. In contrast, K _Na ^cpx/liq increases substantially with increasing P, and exceeded 1 in some experiments. Since oceanic basalts show variations in Na/Ti ratios, the potential exists for partial melting depths to be inferred from K _Na ^cpx/liq . Received: 28 May 1997 / Accepted: 20 November 1998