Ar and K partitioning between clinopyroxene and silicate melt to 8 GPa

The relative incompatibility of Ar and K are fundamental parameters in understanding the degassing history of the mantle. Clinopyroxene is the main host for K in most of the upper mantle, playing an important role in controlling the K/Ar ratio of residual mantle and the subsequent time-integrated evolution of ⁴⁰Ar/³⁶Ar ratios. Clinopyroxene also contributes to the bulk Ar partition coefficient that controls the Ar degassing rate during mantle melting. The partitioning of Ar and K between clinopyroxene and quenched silicate melt has been experimentally determined from 1 to 8 GPa for the bulk compositions Ab₈₀Di₂₀ (80 mol% albite-20 mol% diopside) and Ab₂₀Di₈₀ with an ultraviolet laser ablation microprobe (UVLAMP) technique for Ar analysis and the ion microprobe for K. Data for Kr (UVLAMP) and Rb (ion probe) have also been determined to evaluate the role of crystal lattice sites in controlling partitioning. By excluding crystal analyses that show evidence of glass contamination, we find relatively constant Ar partition coefficients (D_Ar) of 2.6 × 10⁻⁴ to 3.9 × 10⁻⁴ for the Ab₈₀Di₂₀ system at pressures from 2 to 8 GPa. In the Ab₂₀Di₈₀ system, D_Ar shows similar low values of 7.0 × 10⁻⁵ and 3.0 × 10⁻⁴ at 1 to 3 GPa. All these values are several orders of magnitude lower than previous measurements on separated crystal-glass pairs.D_K is 10 to 50 times greater than D_Rb for all experiments, and both elements follow parallel trends with increasing pressure, although these trends are significantly different in each system studied. The D_K values for clinopyroxene are at least an order of magnitude greater than D_Ar under all conditions investigated here, but D_Ar appears to show more consistent behavior between the two systems than K or Rb. The partitioning behavior of K and Rb can be explained in terms of combined pressure, temperature, and crystal chemistry effects that result in changes for the size of the clinopyroxene M2 site. In the Ab₂₀Di₈₀ system, where clinopyroxene is diopside rich at all pressures, D_K and D_Rb increase with pressure (and temperature) in an analogous fashion to the well-documented behavior of Na. For the Ab₈₀Di₂₀ system, the jadeite content of the clinopyroxene increases from 22 to 75 mol% with pressure resulting in a contraction of the M2 site. This has the effect of discriminating against the large K⁺ and Rb⁺ ions, thereby countering the effect of increasing pressure. As a consequence D_K and D_Rb do not increase with pressure in this system.In contrast to the alkalis (Na, K, and Rb), D_Kr values are similar to D_Ar despite a large difference in atomic radius. This lack of discrimination (and the constant D_Ar over a range of crystal compositions) is also consistent with incorporation of these heavier noble gases at crystal lattice sites and a predicted consequence of their neutrality or “zero charge.” Combined with published D_Ar values for olivine, our results confirm that magma generation is an efficient mechanism for the removal of Ar from the uppermost 200 km of the mantle, and that K/Ar ratios in the residuum are controlled by the amount of clinopyroxene. Generally, Ar is more compatible than K during mantle melting because D_Ar for olivine is similar to D_K for clinopyroxene. As a result, residual mantle that has experienced variable amounts of melt extraction may show considerable variability in time-integrated ³⁶Ar/⁴⁰Ar.     

The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

Experimental simulation of melt migration in stromatic metatexite migmatites

Melting experiments on a gneissic protolith using the diamond trap technique produced an accumulation of crystals of biotite in the boundary of the diamond trap. Several hypotheses can be inferred to explain this feature, but textural evidence and calculations of the settling and drag velocities of the crystals suggest a model of extraction of melt due to a pressure gradient inside the capsule as the most likely origin of this biotite layer. This biotite layer and the trapped melt resemble the melanosome and leucosome, respectively, of stromatic metatexite migmatites. The melt extraction model developed is similar to the “filter pressing” model for migmatite formation. The diamond trap technique is a suitable method to develop migmatites experimentally.     

Partitioning behavior of trace elements between dacitic melt and plagioclase, orthopyroxene, and clinopyroxene based on laser ablation ICPMS analysis of silicate melt inclusions

Partitioning behavior of Sc, Ti, V, Mn, Sr, Y, Zr, Nb, Ba, La, Nd, Sm, Eu, Gd, Dy, Ho, Yb, Hf, and Pb between dacitic silicate melt and clinopyroxene, orthopyroxene, and plagioclase has been determined based on laser ablation-inductively coupled plasma mass spectrometric (LA-ICPMS) analysis of melt inclusions and the immediately adjacent host mineral. Samples from the 1988 eruption of White Island, New Zealand were selected because petrographic evidence suggests that all three mineral phases are in equilibrium with each other and with the melt inclusions. All three phenocryst types are found as mineral inclusions within each of the other phases, and mineral inclusions often coexist with melt inclusions in growth-zone assemblages. Compositions of melt inclusions do not vary between the different host minerals, suggesting that boundary layer processes did not affect compositions of melt inclusions and that post-trapping modifications have not occurred.Partition coefficients were calculated from the host and melt inclusion compositions and results were compared to published values. All trace elements examined in this study except Sr are incompatible in plagioclase, and all measured trace elements except for Mn are incompatible in orthopyroxene. In clinopyroxene, Sc, V, and Mn are compatible, and Y, Ti, HREE, and the MREE are only slightly incompatible. Most partition coefficients overlap the wide range of values reported in the literature, but the White Island data are consistently at the lower end of the range in published values. Results from the literature obtained using modern microanalytical techniques such as secondary ion mass spectrometry (SIMS) or proton induced X-ray emission spectroscopy (PIXE) also fall at the lower end of the published values, whereas partition coefficients determined from bulk analysis of glass and crystals separated from volcanic rocks typically extend to higher values. Rapid crystal growth-rates, crystal zonation, or the presence of accessory mineral inclusions in phenocrysts likely accounts for the wide range and generally higher partition coefficients obtained using bulk sampling techniques. The results for 3+ cations from this study are consistent with theoretical predictions based on a lattice strain model for site occupancy. The results also confirm that the melt inclusion-mineral (MIM) technique is a reliable method for determining partition coefficients, as long as the melt inclusions have not experienced post-entrapment reequilibration.     

The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth

We present the variation in trace element partition coefficients measured at the interface between rapidly cooled clinopyroxene crystals and co-existing melts. Results indicate that, as the cooling rate is increased, clinopyroxene crystals are progressively depleted in Si, Ca and Mg counterbalanced by enrichments in Al (mainly tetrahedral Al^iv), Na and Ti. Partition coefficients (Ds) for rare earth elements (REE), high field strength elements (HFSE) and transition elements (TE) increase with increasing cooling rate, in response to clinopyroxene compositional variations. The entry of REE into the M2 site is facilitated by a coupled substitution where either Na substitutes for Ca on the M2 site or Al^iv substitutes for Si in the tetrahedral site. The latter substitution reflects an increased ease of locally balancing the excess charge at M2 as the number of surrounding Al^iv atoms increases. Due to the lower concentration of Ca in rapidly cooled clinopyroxenes, divalent large ion lithophile elements (LILE) on M2 decrease at the expense of monovalent cations. Conversely, higher concentrations of HFSE and TE on the M1 site are facilitated as the average charge on this site increases with the replacement of divalent-charged cations by Al^vi. Although crystallization kinetics modify clinopyroxene composition, deviations from equilibrium partitioning are insufficient to change the tendency of a trace element to be compatible or incompatible. Consequently, there are regular relationships between ionic radius, valence of the trace element and D. At both equilibrium and cooling rate conditions, Ds for isovalent cations define parabola-like curves when plotted against ionic radius, consistent with the lattice strain model, demonstrating that the partitioning of trace elements is driven by charge balance mechanisms; cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations.     

Lamellar exsolution systems in clinopyroxene

Exsolution systems in synthetic pyroxenes were studied by transmission electron microscopy. An iron free sample En₈₀Wo₂₀ was prepared by devitrifying glass at 1300°C. Samples with bulk composition En₅₀Fs₃₀Wo₂₀ and En₃₅Fs₃₈Wo₂₇ were given various but well-defined heat treatments. The exsolution systems observed cannot unambiguously be related to the heat treatment. Periodic lamellar exsolution was observed parallel to (001) and (100) with sharp satellite reflections in the diffraction diagram. In more complex exsolution systems coarse (100) lamellae were found together with fine lamellae parallel to (001) and (100). An unusual phenomenon occurs at a (100) twin boundary where both individuals display exsolution lamellae parallel to (001). Pigeonite lamellae in one twin meet augite lamellae of the other individual at the twin boundary and vice-versa. The precise matching is achieved by a change in width near the boundary. Smoothly curved phase boundaries are developed in the obtuse angle of crosshatched (100) and (001) pigeonite lamellae in augite, whereas the boundaries in the acute angle are straight with sharp edges. This is consistent with elastic energy constraints.     

Relationships between Campi Flegrei and Mt. Somma volcanism: evidence from melt inclusions in clinopyroxene phenocrysts from volcanic breccia xenoliths

Summary We present compositions of reheated melt inclusions in clinopyroxene phenocrysts from three mafic xenoliths in Breccia Museo, Campi Flegrei, Italy. Melt inclusion compositions are remarkably different from the compositions of known contemporary Campi Flegrei lavas, being significantly enriched in K₂O and depleted in Na₂O. Some differences are also evident in FeO^* (total Fe as FeO) and TiO₂ contents. The clinopyroxene phenocrysts could not have crystallised from Campi Flegrei magmas. We suggest that they originated from a volcanic system genetically very similar to, and possibly linked with, the >14 ka volcanic system of Mt. Somma, another Campanian volcano ∼ 30 km east from Campi Flegrei, from which Vesuvius subsequently developed. This result indicates a close relationship (or link) between the two volcanic systems which have until now been considered separate. We speculate that the link was established prior to eruption of the Neapolitan Yellow Tuff (NYT) (∼ 12 ka). The xenoliths were derived from a volcanic system older than the host breccias themselves. We suggest that this older volcanism had close similarities with the volcanism of the older products of Mt. Somma (∼25 ka). Received March 20, 2000; accepted November 2, 2000     

Aluminum-dependent trace element partitioning in clinopyroxene

As technical advances have dramatically increased our ability to analyze trace elements, the need for more reliable data on the compositional dependence of trace element partitioning between minerals and melt has become increasingly important. The late-Cretaceous Carmacks Group of south central Yukon comprises a succession of primitive high-Mg ankaramitic lavas characterized by shoshonitic chemical affinities and containing large complexly zoned clinopyroxene phenocrysts. The compositional zonation of the clinopyroxene phenocrysts is characterized by relatively Fe-rich (Mg^# = Mg/(Mg + Fe) = 0.85), but mottled, cores surrounded by mantles of cyclically-zoned clinopyroxene whose Mg^# varies repeatedly between 0.9 and 0.80. These cyclically zoned clinopyroxene mantles appear to record the repeated influx and mixing of batches of primitive with more evolved magma in a deep sub-crustal (∼1.2 GPa) magma chamber(s). Laser ablation ICP-MS was used to analyze the trace element variation in these zoned clinopyroxenes. The results indicate more than a threefold variation in the absolute concentrations of Th, Zr, rare earth elements (REE), and Y within individual clinopyroxene phenocrysts, with no apparent change in the degree of REE or high field strength element (HFSE) fractionation. The variation in absolute abundances of trace elements correlates closely with the major element composition of the clinopyroxene, with the most enriched clinopyroxene having the lowest Mg^# and highest Al contents. The problem is that the amount of crystal fractionation required to explain the major element variation (∼20%) in these clinopyroxene phenocrysts cannot explain the increase in the abundance of the incompatible trace elements, which would require more than 70% crystal fractionation, if constant partition coefficients are assumed. The anomalous increase in incompatible trace elements appears to reflect an increase in their partition coefficients with increasing Al^IV in the clinopyroxene; with an increase in Al₂O₃ from 1.5 to 4.0 wt.% during ∼20% crystal fractionation over a temperature decrease of ∼100°C being associated with more that a threefold increase in the partition coefficients of Th, Zr, REE, and Y. The magnitude of these increases may indicate that the substitution of these trace elements into clinopyroxene is better modeled in some natural systems by a local charge balance model, rather than the distributed charge model that better replicates the results of annealed experiments. These findings indicate that the effect of Al on the partition coefficients of incompatible trace elements in clinopyroxene may be under appreciated in natural magmatic systems and that the application of experimentally determined clinopyroxene partition coefficients to natural systems must be done with caution.     

Experimental comparison of trace element partitioning between clinopyroxene and melt in carbonate and silicate systems, and implications for mantle metasomatism

Experiments in the systems diopside-albite (Di-Ab) and diopside-albite-dolomite (Di-Ab-Dmt), doped with a wide range of trace elements, have been used to characterise the difference between clinopyroxene-silicate melt and clinopyroxene-carbonate melt partitioning. Experiments in Di-Ab-Dmt yielded clinopyroxene and olivine in equilibrium with CO₂-saturated dolomitic carbonate melt at 3 GPa, 1375 °C. The experiments in Di-Ab were designed to bracket those conditions (3 GPa, 1640 °C and 0.8 GPa, 1375 °C), and so minimise the contribution of differential temperature and pressure to partitioning. Partition coefficients, determined by SIMS analysis of run products, differ markedly for some elements between Di-Ab and Di-Ab-Dmt systems. Notably, in the carbonate system clinopyroxene-melt partition coefficients for Si, Al, Ga, heavy REE, Ti and Zr are higher by factors of 5 to 200 than in the silicate system. Conversely, partition coefficients for Nb, light REE, alkali metals and alkaline earths show much less fractionation (<3). The observed differences compare quantitatively with experimental data on partitioning between immiscible carbonate and silicate melts, indicating that changes in melt chemistry provide the dominant control on variation in partition coefficients in this case. The importance of melt chemistry in controlling several aspects of element partitioning is discussed in light of the energetics of the partitioning process. The compositions of clinopyroxene and carbonate melt in our experiments closely match those of near-solidus melts and crystals in CMAS-CO₂ at 3 GPa, suggesting that our partition coefficients have direct relevance to melting of carbonated mantle lherzolite. Melts so produced will be characterised by elevated incompatible trace element concentrations, due to the low degrees of melting involved, but marked depletions of Ti and Zr, and fractionated REE patterns. These are common features of natural carbonatites. The different behaviour of trace elements in carbonate and silicate systems will lead to contrasted styles of trace element metasomatism in the mantle. Received: 15 July 1999 / Accepted: 18 February 2000     

Consequences of diffuse and channelled porous melt migration on uranium series disequilibria

Magmas erupted at mid-ocean ridges (MORB) result from decompression melting of upwelling mantle. However, the mechanism of melt transport from the source region to the surface is poorly understood. It is debated whether melt is transported through melt-filled conduits or cracks on short time scales (<∼ 10³ yrs), or whether there is a significant component of slow, equilibrium porous flow on much longer time scales (>∼ 10³-10⁴ yrs). Radiogenic excess ²²⁶Ra in MORB indicates that melt is transported from the melting region on time scales less than the half life of ²²⁶Ra (∼1600 yrs), and has been used to argue for fast melt transport from the base of the melting column. However, excess ²²⁶Ra can be generated at the bottom of the melt column, during the onset of melting, and at the top of the melt column by reactive porous flow. Determining the depth at which ²²⁶Ra is generated is critical to interpreting the rate and mechanism of magma migration. A recent compilation of high quality U-series isotope data show that in many young basalts, ²²⁶Ra excess in MORB is negatively correlated with ²³⁰Th excess. The data suggest that ²²⁶Ra excess is generated independently of ²³⁰Th excess, and cannot be explained by “dynamic” or fractional melting, where observed radiogenic excesses are all generated at the base of the melt column. One explanation is that the negative correlation of activity ratios is a result of mixing of slow moving melt that has travelled through reactive, low-porosity pathways and relatively fast moving melt that has been transported in unreactive high-porosity channels. We investigate this possibility by calculating U-series disequilibria in a melting column in which high-porosity, unreactive channels form within a low-porosity matrix that is undergoing melting. The results show that the negative correlation of ²²⁶Ra and ²³⁰Th excesses observed in MORB can be produced if ∼60% of the total melt flux travels through the low-porosity matrix. This melt maintains ²²⁶Ra excesses via chromatographic fractionation of Ra and Th during equilibrium transport. Melt that travels through the unreactive, high-porosity channels is not able to maintain significant ²²⁶Ra excesses because Ra and Th are not fractionated from each other during transport and the transport time for melt in the channels to reach the top of the melt column is longer than the time scale for ²²⁶Ra excesses to decay. Mixing of melt from the high porosity channels with melt from the low-porosity matrix at the top of the melting column can produce a negative correlation of ²²⁶Ra and ²³⁰Th excesses with the slope and magnitude observed in MORB. This transport process can also account for other aspects of the geochemistry of MORB, such as correlations between La/Yb, α_Sm/Nd, and Th/U and ²²⁶Ra and ²³⁰Th excess.     

Experimental determination of partition coefficients for rare earth and high-field-strength elements between clinopyroxene,garnet, and basaltic melt at high pressures

Clinopyroxene/melt and garnet/melt partition coefficients have been determined for Ti, Sr, Y, Zr, Nb, Hf, and rare earth elements from 19 doped experiments on 1921 Kilauea basalt. The experiments were carried out from 2.0 to 3.0 GPa and 1310° to 1470 °C. The purpose was to derive a set of partition coefficients for high-field-strength elements (HFSE) and rare earth elements (REE) in a systematic, linked set of experiments at P and T conditions relevant to basalt petrogenesis. These data are used in melting models to understand the development of negative HFSE anomalies observed in many abyssal peridotite clinopyroxenes. It is shown that melting can account for the observed trace element patterns in some residual peridotites, but that other processes may also be needed to account for most residual mantle compositions in mid-ocean ridge systems. It is also shown that REE are more strongly fractionated by garnet at these P-T conditions than previously thought. Received: 1 July 1997 / Accepted: 11 May 1998     

Elasticity of an upper mantle clinopyroxene

The ambient pressure elastic properties of a natural clinopyroxene (C2/c symmetry) from Kilbourne Hole, NM have been determined. In terms of end-members, diopside (CaMgSi₂O₆), hedenbergite (CaFeSi₂O₆), jadeite (NaAlSi₂O₆), cosmochlor (NaCrSi₂O₆), and Mg-Tschermak (MgAl(AlSi)O₆), its composition is Di₇₂He₉Jd₃Cr₃Ts₁₂. The analytic density, based on chemistry and cell parameters is 3.327 (0.003) g/cm³. The elastic constants [c₁₁, c₁₂, c₁₃, c₁₅, c₂₂, c₂₃, c₂₅, c₃₃, c₃₅, c₄₄, c₄₆, c₅₅, c₆₆] are [273.8 (0.9), 83.5 (1.3), 80.0 (1.1), 9.0 (0.6), 183.6 (0.9), 59.9 (1.6), 9.5 (1.0), 229.5 (0.9), 48.1 (0.6), 76.5 (0.9), 8.4 (0.8), 73.0 (0.4), 81.6 (1.0)] GPa where uncertainties are reported at the 95% confidence level. The aggregate (mean of Hashin-Strikman bounds) adiabatic bulk modulus is 117.2 (0.7) GPa, and the shear modulus is 72.2 (0.2) GPa. Although measured moduli are broadly consistent with trends in elasticity versus atomic volume, deviations from the systematics would produce significant (percent level) changes in calculated velocities for candidate mantle mineral assemblages. The compositional dependence of elasticity for several clinopyroxenes is explored on the basis of just the Di+He and Jd+Ts mole fractions. The bulk modulus lies within experimental uncertainties of the linear mixture of end-member properties while the shear modulus deviates by 3%. Received: 29 September 1997 / Revised, accepted: 4 March 1998     

镁铁质-超镁铁质岩浆岩中单斜辉石的智能分析研究

区分不同构造环境中岩浆作用是认识地幔中岩浆形成过程的基本手段。目前较为成熟的是利用全岩去区分判别,而利用造岩矿物去判别构造环境、演绎岩浆演化的研究还不够深入。本文运用机器学习的方法,以全球新生代大洋中脊、洋岛以及岛弧构造背景中的镁铁质-超镁铁质岩浆岩中单斜辉石的地球化学数据为研究对象,试图区分这3 种不同构造环境的单斜辉石。通过机器学习方法中K-邻近（K-Nearest Neighbor,KNN）和随机森林（Random Forest,RF）的计算和比较,认为RF 是一种有效的地球化学区分方法,它的结果不仅可用来判别构造环境,同时还能够提取特征元素。同时我们发现,在镁铁质-超镁铁质岩浆岩单斜辉石构造环境判别图解中,Rb、La、Ba、Cr、Sr、Yb、V、Ti、Nd、Eu、Gd等微量元素具有较高的贡献率,而主量元素贡献率较低。在此基础上,我们结合前人的对单斜辉石的构造环境判别图的研究成果,提出几个判别效果较好的判别图解。但是整个研究由于缺少进一步可视化的成果,限制了机器学习方法的推广,这也是今后需要进一步研究的课题。     

Distribution of REE between clinopyroxene and basaltic melt along a mantle adiabat: effects of major element composition, water, and temperature

The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D ₀, r ₀ and E) as functions of pressure, temperature, and compositions of cpx and melt. D ₀ is found to positively correlate with Al in tetrahedral site (Al ^T ) and Mg in the M2 site (Mg^M2) of cpx and negatively correlate with temperature and water content in the melt. r ₀ is negatively correlated with Al in M1 site (Al^M1) and Mg^M2 in cpx. And E is positively correlated with r ₀. During adiabatic melting of spinel lherzolite, temperature, Al ^T , and Mg^M2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.     

Crystal-chemistry of clinopyroxene from Sunda volcanic arc

Summary The crystal-chemistry of clinopyroxene from a suite of Sunda arc volcanic rocks was investigated by X-ray structure refinement and microprobe analysis. Relationships with clinopyroxene from volcanic rocks of the intraplate environment were highlighted.Sunda clinopyroxenes were distinguished into two groups. The first consists of clinopyroxene from SiO₂-saturated rock types and crystal rim from SiO₂-undersaturated rock types, the second of crystal core from SiO₂-undersaturated rock types. The crystal chemical behaviour of the two groups differs significantly, mainly in the geometrical relationships between M2 and T sites. While in the first group M2-O3 and T-O3 bond lengths shorten and lengthen respectively due to Ca and Al^IV increase, in the second group in which M2 site is almost fully coordinated by Ca, -O3 bond lengths are forced to lengthen in spite of low Al^IV content, in order to mantain the local charge balance around the O3 oxygens.It is noteworthy that Sunda clinopyroxene shows strong analogies with that from basaltic rocks from the Ethiopian plateau and K-rich lavas from the Roman Province respectively, reflecting similarities between the composition and mineralogical assemblages of the host rocks, although they all came from different tectonic environments. A relationship between intracrystalline Mg-Fe 2+ disorder and the explosive character of the volcanism is demonstrated.

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Kristallchemie von Klinopyroxenen aus Gesteinen des Vulkanbogens der Sunda-Inseln

Zusammenfassung Die Kristallchemie von Klinopyroxenen aus einer Serie von vulkanischen Gesteinen des Sunda-Bogens wurde mit Röntgen-Strukturverfeinerungen und Mikrosonden-analysen untersucht. Beziehungen zu Klinopyroxenen vulkanischer Gesteine aus intra-Plattenpositionen werden beleuchtet. Die Sunda-Klinopyroxene wurden in zwei Gruppen eingeteilt. Die erste umfaßt Klinopyroxene SiO₂-gesättigter Gesteinstypen und Kristallsäume SiO₂-untersättigter Gesteinstypen, die zweite Kristallkerne SiO₂-untersättigter Gesteinstypen. Das kristallchemische Verhalten der beiden Gruppen unterscheidet sich beträchtlich, hauptsächlich in den geometrischen Beziehungen zwischen den M2 und T Positionen. Während in der ersten Gruppe die M2-O3 und T-O3 Bindungsldngen durch Zunahme von Ca und Al^IV kleiner bzw. größer werden, sind in der zweiten Gruppe die T-O3 Bindungslängen trotz niedrigen Al^IV Gehaltes zu einer Vergrößerung gezwungen, damit um die O3 Atome der lokale Ladungsausgleich erhalten bleibt.Es ist bemerkenswert, daß die Sunda-Klinopyroxene große Analogien zu denen aus basaltischen Gesteinen des Abessinischen Plateaus und aus K-reichen Laven sowohl der Römischen Provinz als auch des Westafrikanischen Grabens zeigen. Dies spiegelt Ähnlichkeiten zwischen Zusammensetzung und Mineralbestand der Muttergesteine wider, obwohl sie all aus tektonisch unterschiedlichen Positionen kommen.Eine Beziehung zwischen intrakristalliner Mg-Fe²⁺ Unordnung und dem explosiven Charakter des Vulkanismus wird aufgezeigt.

     

Transcrystalline shear fracturing and pseudotachylite generation in a meta-anorthosite (Harris, Scotland)

The meta-anorthosite is locally deformed by brittle shear fracturing, which progressively increases from isolated fractures with little cataclasite to many generations of closely spaced fractures, the intervening rock being highly deformed, in both a plastic and brittle way. In most cases an E-W compression on gently dipping to steep reverse shear planes occurs, which we relate to a Caledonian thrust zone.In places, the highly deformed rock is cut by pseudotachylite veins, which locally form networks. The pseudotachylite is generally intrusive, but does not appear to be related to movement on major slip surfaces. Very locally it may have formed in situ. Pseudotachylite only occurs in highly deformed rock, is only very occasionally deformed itself and, thus, generally represents at each locality the last stage of a complex deformation history, as if its presence welded the rock and prevented further deformation. These striking differences from the country-rock gneisses (in which pseudotachylite occurs on well developed fractures in very slightly deformed rock) are considered to be due to the low anisotropy of the meta-anorthosite, to its lower shear strength and to the easy propagation and branching of the shear fractures in plagioclase. The source of the heat necessary to generate the pseudotachylite melt is not clear—it may come from crack propagation as well as frictional sliding.     

Exsolution and coarsening in iron-free clinopyroxene during isothermal annealing

Exsolution and coarsening in Fe-free clinopyroxene of composition En_45.1Di_54.9 was studied at temperatures of 1300, 1200, and 1100°C, and annealing times between 10 min and 4320 h. Based on the wavelength of the exsolution lamellae, the exsolution process can be divided into exsolution sensu stricto and coarsening. During exsolution sensu stricto, the average wavelength of the “001” and “100” lamellae remains constant in contrast to the subsequent coarsening process. A progressive development of the microstructure is observed before coarsening which includes formation of island-like regions of dark contrast without phase separation, occurrence of pigeonite and diopside domains predominantly elongated along (100), formation of “100” exsolution lamellae, dissolution of the “100” lamellae, and predominant occurrence of “001” exsolution lamellae. All observations are in accordance with the exsolution mechanism of spinodal decomposition. After termination of the exsolution process, coarsening of the exsolution lamellae is observed. The “001” lamellae coarsen according to the rate law

     

The coarsening kinetics associated with exsolution in an iron-free clinopyroxene

The coarsening kinetics of exsolution lamellae have been determined for an initial composition of 0.541 CaMgSi₂O₆–0.459 Mg₂Si₂O₆ (Di_54.1) at 1300 °, 1200 ° and 1100 ° C. Portions of this material were annealed for varying lengths of time, and the average wavelength () was obtained from measurements made by utilizing transmission electron microscopy (TEM). All experiments were conducted within the (001) coherent spinodal for this system (McCallister and Yund, 1977), and the lamellae are coherent up to and including the largest wavelength observed, 1054 Å.At all three temperatures mentioned previously the data are consistent with the following relationship: The activation energy for the process, as determined from the respective kinetic constants (k), is 99±2 Kcal/mol. This value is similar to that found for Ca self diffusion in pseudo-wollastonite and wollastonite, and suggests the possibility that the diffusion of Ca may be controlling the rate of coarsening.A comparison of exsolution microstructures in the synthetic samples with those observed in clinopyroxenes found in kimberlites and with similar Ca/Ca + Mg indicates that the latter cooled rapidly to the effective quench temperature.