Extremely magnesian olivine in igneous rocks

Published data on extremely magnesian olivine (> 96 mol.% forsterite) in igneous rocks were generalized and compared with data of new high-precision electron probe microanalyses of olivine from oxidized lavas of the Tolbachik Volcano (Kamchatka), chromitites from the Ray-Iz deposit (Russia), alkaline ultrabasic lavas from San Venanzo volcanoes (Italy), and skarns from the Kuh-i-Lal deposit (Tajikistan). All the found olivines resulted from low-temperature processes, such as subsurface oxidation, interaction with carbonates, and subsolidus re-equilibration. Low-temperature formation of olivine is reflected in its structure (hematite lamellae and abundance of inclusions of ore minerals) and abnormal contents of minor components (Mn, Ni, and Ca). The Mg content of olivine increases under the influence of postmagmatic processes and can be manifested in different rocks. This gives grounds to refine the genesis of olivine of exotic composition (93-96 mol.% forsterite) in some kimberlites, komatiites, and peridotites.     

New mineral data from the kamafugitecarbonatite association: The melilitolite from Pian di Celle, Italy

Summary A detailed mineralogical investigation of a Pian di Celle sill rock (San Venanzo, Italy), classified asmelilitolite and associated withvenanzite and carbonatitic pyroclasts, revealed new and rare mineral parageneses, considered as characteristic of thekamafugite-carbonatite association. These are formed by several accessory minerals, including minerals of the cuspidine family, götzenite, khibinskite, minerals of the rhodesite- delhayelite- macdonaldite family, pyrrhotite, bartonite and (Fe, Ni, Co) monoarsenide, mostly optically and chemically identified also in fluid inclusions. The chemical composition of these minerals and their probable crystallisation succession, deduced from textural relationships, demonstrates extensive atomic substitutions, notably for Ca, Ti, Mg and alkali, essentially reflecting high concentrations of REE, Sr, Ba, Nb and Zr, which significantly varied during crystallisation. Molecular alkali excess over Al and high Ca content in (H₂O, F, CO₂)-rich, Siundersaturated liquid(s) are considered the dominant factors in controlling the stability of disilicate-type minerals. Separation of the carbonatite liquid from the silicate magma, constrained by textural and fluid inclusion data, was fundamental in moving the residuum onto a strongly peralkaline trend which stabilised the sulphides under changed redox conditions.

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Die Bedeutung seltener und neuer Mineral-Paragenesen aus der kamafugit-karbonatit-Assoziation: Der melilitolit von San Venanzo, Italien

Zusammenfassung Eine eingehende mineralogische Untersuchung eines Lagerganges von Pian di Celle, der als Melilitolit klassifiziert and mit Venanzit and karbonatitischen Pyroklasten assoziiert ist, ergab neue and seltene Mineral-Paragenesen, die als charakteristisch für die Kamafugit-Karbonatit-Assoziation gelten. Diese bestehen aus verschiedenen akzessorischen Mineralien, darunter Perovskit, Cuspidin, Götzenit, Khibinskit, Delhayelit, Macdonaldit, Bardonit and (Fe, Ni, Co) Monoarsenit; diese werden in Flüssigkeitseinschlüssen mit optischen and chemischen Methoden identifiziert. Die chemische Zusammensetzung dieser Minerale and ihre wahrscheinliche Kristallisationsabfolge, aus texturellen Beziehungen abgeleitet, zeigt extensive Substitutionen, vor allem für Ca, Ti, Mg and Alkelien, die im wesentlichen hohe Gehalte an SEE, Sr, Ba, Mb and Zr andeuten, die während der Kristallisation beträchtlichen Schwankungen unterlagen. Molekularer Alkali überschuß über Al in (H₂O, F, CO₂)-reichen Si-untersättigten Fluiden werden als wichtigste Faktoren für die Stabilität von Mineralen des DisilikatTyps gesehen. Trennung des Karbonatites vom Silikat, die durch texturelle und Flüssigkeitseinschluß-Daten genau fixiert werden konnte, war wichtig für die Verschiebung des Residuums auf einen deutlich peralkalinen Trend, welcher die Sulfide unter veränderten Redox-Bedingungen stabilisieren konnte.

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With 2 Figures     

Late Palaeozoic Ultramafic Lavas in Yunnan, SW China, and their Geodynamic Significance

We report petrological and geochemical data on ultramafic pillowlavas from Late Palaeozoic marine sequences in Yunnan, SW China.These lavas have >26 wt % MgO, euhedral to subhedral olivinephenocrysts and acicular or quench clinopyroxene crystals withor without microlitic plagioclase in a devitrified and alteredglassy matrix. These ultramafic lavas are compositionally komatiitic(>18 wt % MgO), but we term them high-Mg picrites becausethey lack spinifex-textured olivine. Although olivines in thesepicrites are cumulate crystals, causing the high MgO contentsof the bulk rocks, the high forsterite content of these olivines,Fo = 0·902 ± 0·011, suggests that the primitivemagmas parental to the picrites would have had     

The significance of unusual zoning in olivines from FAMOUS area basalt 527-1-1

Major element, Ni, Mn and Ca electron microprobe analyses of olivine phenocrysts in one of the most primitive basalts from the FAMOUS area of the Mid-Atlantic Ridge, 527-1-1, reveal two different olivine populations, distinguished by their zoning characteristics. The often skeletal Group I olivines have zoning profiles with high forsterite, high Ni, low Mn, and low Ca cores. These profiles can be explained by low pressure crystallization from the 527-1-1 magma on cooling. The equant, often megacrystic Group II olivines also have high forsterite, low Mn cores, but the cores have low Ni compared to rims. Thus they are normally zoned with respect to Mg, Fe, and Mn but reversely zoned with respect to Ni. For example, Ni ranges from 1,700 ppm at Fo_90.5 in the core to 2,100 ppm at Fo_89.5 at the rim. In view of the published whole rock and mineral data of le Roex et al. (1981), the most likely explanation for these data is that the Group II olivines are xenocrysts assimilated from solidified plagioclase-pyroxene basalts through which the 527-1-1 basalt ascended. The diffusion rate of Ni and size of the xenocrystic olivines are used to calculate the residence time of the assimilated olivines in the magma. An alternative hypothesis would be a high pressure origin for the Group II olivines. This would be possible if future experiments show that with increasing pressure the partition coefficient for Ni decreases relative to the partition coefficient for Mg for a given bulk composition. Current evidence suggests this is unlikely. The data from 527-1-1 and other samples from the FAMOUS area require magmas with distinct Ni-MgO-FeO characteristics. In general, MORB from different ridge segments fall on distinct trends on plots of MgOvs. Ni as well as MgOvs. FeO. Calculation of the MgO and Ni contents of primary magmas suggests a mechanism by which such distinct trends could come about.     

橄榄石标型特征及其找矿意义

通过国内２０个含铬铁矿、铜镍矿和饥钛磁铁矿的基性、超基性岩体中６８个橄榄石化学成分、产出状态、地球化学特征、有序度和岩浆包裹体橄榄石子矿物、温度、压力等标型特征研究显示，产于不同矿化基性、超基性岩中橄榄石的标型特征明显不同，为找寻铬铁矿、铜镍矿和钒钛磁铁矿矿产提供重要标志。     

西藏罗布莎蛇绿岩豆荚状铬铁矿中镁橄榄石的晶体结构及其意义

在西藏罗布莎蛇绿岩块的豆荚状铬铁矿中，存在包裹体矿物镁橄榄石，这些镁橄榄石为无色透明多晶面形成的自形晶，Fo值可达到97－98，具富镁端员组分，选取一代表性颗粒的单晶进行X单晶和衍射分析，表明其为斜方晶系，空间群Pbnm，镁橄榄石晶胞参数,a,b,c以及M1－0和M2－0键长均小于地幔包裹体和一般地幔岩中橄缆中的对应值，测试出的晶胞参数与人工合成镁橄榄石的一致，镁橄榄石具有橄榄石族中已知最小的晶胞参数，据此推断它是在超高压环境下结晶的。     

High-temperature infrared properties of forsterite

Polarized emittance measurements were acquired for synthetic forsterite, the pure magnesium end member of the olivines group, on the whole infrared spectral range and up to the melting point by using CO₂ laser heating. The experimental data, fitted with a semi-quantum dielectric function model, allowed the retrieval of the temperature dependence of the absorption coefficient of forsterite both in the opaque and semi-transparent regions. The analysis of the phonon parameters indicates that the lattice dynamics evolve drastically with increasing temperature. The normal modes involving motions of the magnesium cations located in site 1 are the more impacted, and some of them vanish around 1,200 K. The results confirm that the enhancement of the lattice anharmonicity and the increasing mobility of the magnesium cations are closely linked and are at the origin of the anomalies observed in the evolution of the thermophysical properties. This complete set of spectroscopic data may be a step toward a more precise evaluation of the impact of thermal radiation heat transfer inside systems involving forsterite and quantification of their heat budget.     

The system CaO-MgO-SiO2-CO2 at 1 GPa, metasomatic wehrlites, and primary carbonatite magmas

New experimental data in CaO-MgO-SiO₂-CO₂ at 1 GPa define the vapor-saturated silicate-carbonate liquidus field boundary involving primary minerals calcite, forsterite and diopside. The eutectic reaction for melting of model calcite (1% MC)-wehrlite at 1 GPa is at 1100 °C, with liquid composition (by weight) 72% CaCO₃ (CC), 9% MgCO₃ (MC), and 18% CaMgSi₂O₆ (Di). These data combined with previous results permit construction of the isotherm-contoured vapor-saturated liquidus surface for the calcite/dolomite field, and part of the adjacent forsterite and diopside fields. Nearly pure calcite crystals in mantle xenoliths cannot represent equilibrium liquids. We recently determined the complete vapor-saturated liquidus surface between carbonates and model peridotites at 2.7 GPa; the peritectic reaction for dolomite (25% MC)-wehrlite at 2.7 GPa occurs at 1300 °C, with liquid composition 60% CC, 29% MC, and 11% Di. The liquidus field boundaries on these two surfaces provide the road-map for interpretation of magmatic processes in various peridotite-CO₂ systems at depths between the Moho and about 100 km. Relationships among kimberlites, melilitites, carbonatites and the liquidus phase boundaries are discussed. Experimental data for carbonatite liquid protected by metasomatic wehrlite have been reported. The liquid trends directly from dolomitic towards CaCO₃ with decreasing pressure. The 1.5 GPa liquid contains 87% CC and 4% Di, much lower in silicate components than our phase boundary. However, the liquids contain approximately the same CaCO₃ (90 ± 1 wt%) in terms of only carbonate components. For CO₂-bearing mantle, all magmas at depth must pass through initial dolomitic compositions. Rising dolomitic carbonatite melt will vesiculate and may erupt as primary magmas through cracks from about ˜70 km. If it percolates through metasomatic wehrlite from 70 km toward the Moho at 35–40 km, primary calcic siliceous carbonatite magma can be generated with silicate content at least 11–18% (70–40 km) on the silicate-carbonate boundary. Received: 22 June 1998 / Accepted: 7 July 1999     

Mg tracer diffusion in synthetic forsterite and San Carlos olivine as a function of P,T and fO2

We present new experimental data on Mg tracer diffusion in oriented single crystals of forsterite (Fo₁₀₀) and San Carlos olivine (Fo₉₂) between 1000–1300° C. The activation energies of diffusion are found to be 400 (±60) kJ/mol (96 kcal/mol) and 275 (±25) kJ/mol (65 kcal/ mol) in forsterite and San Carlos olivine, respectively, along [001] at a fO₂ of 10^–12 bars. There is no change in activation energy of Mg tracer diffusion within this temperature range. Mg tracer diffusion in a nominally pure forsterite is found to be anisotropic (D_c > D_a > D _b) and a function of fO₂. This fO₂ dependence is different from that in olivine containing Fe as a major element, which suggests that the diffusion mechanism of Mg in forsterite is different from that in Fe-bearing olivine at least over some range of fO₂. The diffusion mechanism in nominally pure forsterites may involve impurities present below the limits of detection or alternately, Si or Fe³⁺ interstitial defects, Fe being present as impurity (ppm level) in forsterite. Pressure dependence of Mg tracer diffusivity in forsterite measured to 10 GPa in a multianvil apparatus yields an activation volume of approximately 1–3.5 cm³/ mol. It is found that presence of small amounts of hydrogen bearing species in the atmosphere during diffusion anneal (f_H2 0.2 bars, f_H20 0.24 bars) do not affect Mg tracer diffusion in forsterite within the resolution of our measurement at a total pressure of 1 bar. The observed diffusion process is shown to be extrinsic; hence extrapolation of the diffusion data to lower temperatures should not be plagued by uncertainties related to change of diffusion mechanism from intrinsic to extrinsic.     

Silicate-carbonate-salt liquid immiscibility and origin of the sodalite-haüyne rocks: study of melt inclusions in olivine foidite from Vulture volcano, S. Italy

Melt inclusions in clinopyroxenes of olivine foidite bombs from Serra di Constantinopoli pyroclastic flows of the Vulture volcano (Southern Italy) were studied in detail. The rocks contain abundant zoned phenocrysts and xenocrysts of clinopyroxene, scarce grains of olivine, leucite, haüyne, glass with microlites of plagioclase and K-feldspar. The composition of clinopyroxene in xenocrysts (Cpx I), cores (Cpx II), and in rims (Cpx III) of phenocrysts differs in the content of Mg, Fe, Ti, and Al. All clinopyroxenes contain two types of primary inclusion-pure silicate and of silicate-carbonate-salt composition. This fact suggests that the phenomena of silicate-carbonate immiscibility took place prior to crystallization of clinopyroxene. Homogenization of pure silicate inclusions proceeded at 1 225 – 1 190°C. The composition of conserved melts corresponded to that of olivine foidite in Cpx I, to tephrite-phonolite in Cpx II, and phonolite-nepheline trachyte in Cpx III. The amount of water in them was no more than 0.9 wt.%. Silicate-carbonate inclusions decrepitated on heating. Salt globules contained salts of alkali-sulphate, alkali-carbonate, and Ca-carbonate composition somewhat enriched in Ba and Sr. This composition is typical of carbonatite melts when decomposed into immiscible fractions. The formation of sodalite-haüyne rocks from Vulture is related to the presence of carbonate-salt melts in magma chamber. The melts conserved in clinopyroxenes were enriched in incompatible elements, especially in Cpx III. High ratios of La, Nb, and Ta in melts on crystallization of Cpx I and Cpx II suggest the influence of a carbonatite melt as carbonatites have extremely high La/Nb and Nb/Ta and this is confirmed by the appearance of carbonatite melts in magma chamber. Some anomalies in the concentrations and relatives values of Eu and especially Ga seems typical of Italian carbonatite related melts. The mantle source for initial melts was, most likely, rather uniform, undepleted and was characterized by a low degree of melting and probable presence of garnet in restite.     

Young,olivine xenocryst-bearing alkali-basalt from the oceanward slope of the Japan Trench

Young (6 Ma) alkali-basalts were collected from the toe of the oceanward slope of the northern Japan Trench. Two types of olivine are present in these lavas, xenocrysts with reaction rims and magmatic. The forsterite (Fo) (no. 91–92) values and NiO contents (0.3–0.5 wt%) of the xenocrysts are similar in composition to those of the depleted mantle peridotite. The groundmass olivines have relatively lower Fo values (no. 81–88) and NiO contents (0.1–0.5 wt%). Reaction rims and the vicinity of the silicate inclusion in xenocrysts show the intermediate compositions between the xenocryst and magmatic olivines. Chromian spinel inclusions in the xenocrysts also show the depleted composition in the range of abyssal peridotite. CO₂ fluid inclusions in the xenocryst records pressures before entrainment into the host magma up to 0.4 GPa, which corresponds to a depth of up to 14 km of lithospheric mantle. These data indicate that the xenocrysts originate from MORB-depleted mantle.     

The ~1.85 Ga carbonatite in north China and its implications on the evolution of the Columbia supercontinent

Mantle-derived carbonatites provide a unique window in the understanding of mantle characteristics and dynamics, as well as insight into the assembly and breakup of supercontinents. As a petrological indicator of extensional tectonic regimes, Archean/Proterozoic carbonatites provide important constraints on the timing of the breakup of ancient supercontinents. The majority of the carbonatites reported worldwide are Phanerozoic, in part because of the difficulty in recognizing Archean/Proterozoic carbonatites, which are characterized by strong foliation and recrystallization, and share broad petrologic similarities with metamorphosed sedimentary lithologies. Here, we report the recognition of a ~1.85 Ga carbonatite in Chaihulanzi area of Chifeng in north China based on systematic geological, petrological, geochemical, and baddeleyite U-Pb geochronological results. The carbonatite occurs as dikes or sills emplaced in Archean metasedimentary rocks and underwent intense deformation. Petrological and SEM/EDS results show that calcite and dolomite are the dominant carbonate minerals along with minor and varied amounts of Mg-rich mafic minerals, including forsterite (with Fo > 98), phlogopite, diopside, and an accessory amount of apatite, baddeleyite, spinel, monazite, and ilmenite. The relatively high silica content together with the non-arc and OIB-like trace element signatures of the carbonatite indicates a hot mantle plume as the likely magma source. The depleted Nd isotopic signatures suggest that plume upwelling might be triggered by the accumulation of recycled crust in the deep mantle. As a part of the global-scale Columbia supercontinent, the Proterozoic tectonic evolution of the North China Craton (NCC) provides important insights into the geodynamics governing amalgamation and fragmentation of the supercontinent. The Paleo-Mesoproterozoic boundary is the key point of tectonic transition from compressional to extensional settings in the NCC. The newly identified ~1.85 Ga carbonatite provides a direct link between the long-lasting supercontinental breakup and plume activity, which might be sourced from the “slab graveyard,” continental crustal slabs subducted into asthenosphere, beneath the supercontinent. The carbonatite provides a precise constraint of the initiation of the continental breakup at ~1.85 Ga.     

On the nature and origin of isolated olivine grains in carbonaceous chondrites

Many carbonaceous chondrites contain discrete olivine fragments that have been considered to be primitive material, i.e. direct condensates from the solar nebula or pre-solar system material. Olivine occurring in chondrules and as isolated grains in C3(0) chondrites has been characterized chemically and petrographically. Type I chondrules contain homogeneous forsterite grains that exhibit a negative correlation between FeO and CaO. Type II chondrules contain zoned fayalite olivines in which FeO is positively correlated with CaO and MnO. The isolated olivines in C3(0) chondrites form two compositional populations identical to olivines in the two types of porphyritic olivine chondrules in the same meteorites. Isolated olivines contain trapped melt inclusions similar in composition to glassy mesostasis between olivines in chondrules. Such glasses can be produced by fractional crystallization of olivine and minor spinel in the parent chondrule melts if plagioclase does not nucleate. The isolated olivine grains are apparently clastic fragments of chondrules. Some similarities between olivines in C3(0), C2, and Cl chondrites may suggest that olivine grains in all these meteorites crystallized from chondrule melts.     

Lithium elemental and isotopic variations in rock-melt interaction

Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ⁷Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ⁷Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ⁷Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ⁷Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ⁷Li, the carbonatite and silicate melts produced remarkably contrasting δ⁷Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ⁷Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.     

新疆天山地区榆树沟-铜花山蛇绿岩特征和构造背景

榆树沟-铜花山蛇绿岩出露于南天山北缘,属哈萨克斯坦-伊犁板块和塔里木板块之间的缝合带。蛇绿岩已被构造肢解,主要由超镁铁岩、堆晶岩、熔岩类组成。超镁铁岩以方辉橄榄岩为主,显示典型的亏损地幔岩特征,橄榄石为富镁型,Fo为90;斜方辉石为顽火辉石,En为90,单斜辉石含量少;副矿物铬尖晶石属低铬型,Cr^#值(＝Cr/(Cr+Al)×100)16~28,Mg^#值(=Mg/(Mg+Fe)×100)63~75,反映了深海橄榄岩特征。归一化后榆树沟超镁铁岩MgO含量38.84%~44.53%,Al₂O₃为1.51%~3.63%,CaO为0.42%~5.77%,成分近于大洋二辉橄榄岩;铜花山的超镁铁岩叠加碳酸岩化,LREE强烈富集,可能经历了俯冲洋壳流体改造。熔岩类在榆树沟和铜花山均有较大规模产出,其中榆树沟玄武岩为主,铜花山安山岩和英安岩较多。熔岩多已遭受绿片岩相海底热液蚀变。榆树沟玄武岩的REE含量总体比铜花山的低,稀土配分模式均为轻稀土富集型;玄武岩的微量元素特征表明其源区可能遭受过流体作用影响。铜花山三个高镁火山岩化学成份具有SiO₂(32%~36%)含量很低、MgO(20.12%~28.50%)含量高、K₂O+Na₂O(0.06%~0.46%)含量小于2%的特征,综合分析可归为苦橄岩类。堆晶岩通常以构造小岩块产在超镁铁岩块中或基性熔岩中,以辉长岩为主,有少量橄榄辉石岩等,岩石蚀变、构造变形强烈。堆晶岩的成分接近玄武岩,存在LREE富集和略亏损平坦两种类型。岩石地球化学特征表明榆树沟和铜花山的蛇绿岩形成于MOR构造环境,但具有受俯冲带流体改造特征,并伴生有岛弧火山岩。     

The relationship between websterite and peridotite in the Balmuccia peridotite massif (NW Italy) as revealed by trace element variations in clinopyroxene

 Field, mineralogical and petrological data are presented on a newly found carbonatite occurrence associated with “kamafugite” lava at Cupaello, central Italy. This carbonatite occurrence is part of the Late Pleistocene Umbria-Latium ultra-alkaline district (ULUD) which extends southwards within the Apennines to Mount Vulture, delineating an important magmatic province along the most peripheral belt of the Tyrrhenian extensional tectonic system. This province is distinct, but probably related genetically with the more abundant and common leucite-bearing assemblages of the Roman Comagmatic Region and represents the first reported occurrence of carbonatite assemblages in the Mediterranean Basin. The Cupaello suite indicates that primary or near-primary mantle silicate melts of “kamafugitic” composition are transitional with Ca-carbonatite liquid and provides direct evidence of immiscibility of carbonatite from “kamafugite” magma. It is inferred that a primary mantle origin of Ca-carbonatites is conditional upon a potential silicate magma that may be coupled with the carbonatite, but may not have reached the surface. The data indicate a strong genetic link between ULUD Ca-carbonatites and some African analogues, supporting the view that their genesis depends on similar source and associated tectonic conditions. Received: 17 January 1995 / Accepted: 14 June 1995     

Orthopyroxene rim growth between olivine and quartz at low temperatures (750–950°C) and low water concentration

Orthopyroxene reaction rims were synthesized between polished plates of natural olivine or synthetic forsterite and quartz at 1.9 GPa and temperatures of 750–950°C. The experiments were performed in a piston-cylinder apparatus after drying the samples at 600°C. Each experiment comprised 4 or 7 quartz-olivine contacts that were positioned along a temperature gradient. As a monitor for water content in the samples, the water concentration in the two olivines was determined by FTIR before and after the experiments. The orthopyroxene layers show two different structural variants. Type one (normal layers) has very constant thickness at each contact and formed with equal growth rates at both interfaces. Type two (bulging layers) comprises more irregular areas with 3–5 times thicker rims where porosity provides evidence for the local presence of a fluid. In the bulging layers the growth rate at the olivine-orthopyroxene interface exceeds that at the quartz-orthopyroxene interface. The relative growth rates at the interfaces are in accordance with SiO₂-immobile growth of the normal layers and SiO₂-mobile growth of the bulging layers. The natural olivine contains about 60 wt-ppm intracrystalline water before and after experiment and took up about 20 wt-ppm water molecular adsorbed to micro- and nanocracks and -pores during the runs. The synthetic forsterite contains about 7 wt-ppm internally adsorbed molecular water before and after experiment, and during the runs took up hydrogen equivalent to 3 wt-ppm adsorbed water. The IR spectra indicate that large parts of the point defects (possibly tetrahedral) were frozen-in at the conditions of the experiments. In both olivines a new band appeared at 3,355 or 3,357 cm^?1, respectively, equivalent to about 3 wt-ppm water that at the high pressure of the experiments and opx-buffered aSiO₂ of the experiments might already mean water saturation of the olivines. Despite the effective drying before experiment and the absence of porosity, the bulk diffusivity derived from the rim growth rates is perfectly in line with data from water-bearing piston-cylinder experiments at higher temperatures. The bulk diffusivity during rim growth is 4 to 7 orders of magnitude higher than an extrapolation of really dry experiments to the temperature range of this study.     

Calculated silica activities in carbonatite liquids

Carbonatite magmas precipitate silicates, in addition to the abundant carbonates, oxides, and phosphates. Calculated silica activities for equilibria involving silicates and a silica component in magmatic liquids predict specific assemblages for silicate and oxide phases in carbonatites. These assemblages provide tests of alternative sources (carbonatite magma, coeval silicate magma, or older rock) for silicate minerals in carbonatites. Quartz, feldspars, and orthopyroxene are unlikely to be primary magmatic phases in carbonatites, because the silica activity in carbonatite magmas is too low to stabilize these minerals. Zircon and titanite should be unstable relative to baddeleyite and perovskite, respectively, but they do occur in carbonatites. Liquids dominated by carbonate are strongly nonideal with respect to dissolved silica. Consequently, activity coefficients for a silica component in carbonatite liquids are >>1, so that small mole fractions of SiO₂ translate into silica activities sufficient to stabilize phlogopite, clinopyroxene, amphibole, monticellite, and forsterite, among other silicates. Examination of silicate mineral assemblages in carbonatites in the light of silica activity indicates that many carbonatites are contaminated by solid silicate phases from external sources but these xenocrysts can be discriminated from magmatic minerals.     

Single-crystal absorption and reflection infrared spectroscopy of forsterite and fayalite

Polarized single-crystal absorption and reflection spectra of fundamental modes in both the mid- and far-infrared are presented for microscopic crystals of forsterite and fayalite. All modes predicted by symmetry were observed for forsterite, but two B_3u modes were not observed for fayalite. Consideration of previously determined frequency shifts for isotopically and chemically substituted olivines, along with symmetry analysis, produced a complete set of band assignments satisfying all constraints for forsterite. A plausible assingment was derived for fayalite by analogy. The frequency shifts from forsterite to fayalite are consistently small for bands assigned to SiO₄ stretching and bending, moderate for rotations, and large for translations of M-site ions, suggesting that in olivine, SiO₄ groups vibrate separately from the lattice. Allocating the bending and external modes among multiple continua in Kieffer's (1979c) model considerably improves prediction of quasiharmonic heat capacityC _v and entropy for forsterite (～1% discrepancy from 200–1000 K). The experimental entropy of fayalite is closely accounted for (1.8 to 0.1%) by summing lattice, electronic (from Burns' (1985) optical band assignment), and constant magnetic contributions above 200 K.S _magnetic determined from the difference of the experimental and model lattice entropies shows inflection points at the two magnetic transition temperatures (23 and 66 K) and indicates that complete spin disorder is not achieved below 680 K.     

The isotopic composition of carbonatite and kimberlite carbonates and their bearing on the isotopic composition of deep-seated carbon

New carbon and oxygen isotopic compositions of carbonates from 14 carbonatite and 11 kimberlite occurrences are reported. A review of the available data on the carbon isotopic composition ranges of carbonatite and kimberlite carbonates shows that they are similar and overlap that of diamonds. The mean carbon isotopic composition of carbonates from 22 selected carbonatite complexes (?5.1%., s = ±l.4%.vsPDB) is indistinguishable from that of 13 kimberlite pipes (?4.7%. s = ±1.2%.) as well as that of 60 individual diamond analyses (?5.8%., s = 1.8%.). The oxygen isotopic compositions of kimberlite carbonates, however, are enriched in O¹⁸ by several permil with respect to those of carbonates from the subvolcanic type of carbonatite.The data suggest that not all carbonatite, kimberlite and diamond occurrences have the same average carbon isotopic composition and that significant differences exist between them. Carbon isotopic composition measurements available for the East African Rift system suggest geographic and/or tectonic groupings e.g. carbonate lavas, tuffs and intusive carbonatites associated with the Eastern Rift yield a range of δC¹³ values from ?5.8 to ?7.4%., similar to that of the carbonate rocks associated with the Western Rift volcanism (?5.8 to ?7.9%.). In contrast the interrift area encompassing Lakes Victoria, Malawi (Nyasa) and Chilwa, apparently are characterized by carbonatitic carbonates of higher C¹³ content (?2.4 to ?4.4%.).If carbonatite and kimberlite carbonates as well as diamonds represent deep seated carbon, the mean isotopic composition of this carbon is estimated as ?5.2%. and the range is ?2 to ?8%. The selection of any particular value within this range to be used as a criterion of deep-seated origin is at the moment not warranted. Indeed, the choice of any specific composition for such carbon may be meaningless, as the source of kimberlite, carbonatite and diamond carbon may not be isotopically uniform.