The effect of melt composition on the wetting angle between silicate melts and olivine

The wetting angle between silicate melts containing Ca, Li, Na, or K and olivine single crystals have been measured as part of an investigation of the dependence of the solid-liquid interfacial energy on melt composition and olivine orientation. The wetting angle increases with increasing silica content of the melt on (100) surfaces, but decreases with increasing silica content on (010) and (001) surfaces. For a given silica content, the wetting angle on (100) decreases in going from Ca to Li to Na to K, while the wetting angle on (010) and (001) increases in going from Ca to K-bearing melts. Based on published values for liquid-vapor interfacial energies, the observed changes in wetting angle with changes in melt composition indicate that the solid-liquid interfacial energy increases with increasing silica content of the melt for the (100) surface. However, for (010) and (001) surfaces, the variation of the solid-liquid interfacial energy with silica content depends upon whether Ca or K is present in the melt. In addition, the solid-liquid interfacial energy depends upon the orientation of the olivine in the following manner: _sl ⁽⁰¹⁰⁾ _sl ⁽⁰⁰¹⁾ _sl ⁽¹⁰⁰⁾ .     

The speciation of water in silicate melts

Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H₂O_molecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H₂O (vapor) = H₂O_molecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between f_H2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable.     

Experimental study of the effect of SiO2 on Ni solubility in silicate melts

The solubility of Ni in silicate melts with variable SiO₂ content was studied at a total pressure of 1 atm within a wide range of temperature and oxygen fugacity. The maximum solubility of Ni (minimum activity coefficient of NiO) was observed in melts with ～55–57 wt % SiO₂, regardless of temperature and oxygen fugacity. Melts beyond this range showed significantly lower Ni solubility and, correspondingly, higher NiO activity coefficients. The analysis of our results and literature data led us to the conclusion that the NBO/T (number of nonbridging oxygen atoms per tetrahedrally coordinated atom) is inadequate to describe the effect of melt composition on Ni solubility.     

The onset of non-Newtonian rheology of silicate melts

The viscoelastic behavior of silicate melts has been measured for a range of compositions (NaAlSi₃O₈, NaCaAlSi₂O₇, CaMgSi₂O₆, Li₂Si₄O₉, Na₂Si₄O₉, K₂Si₄O₉, Na₂Si₃O₇, K₂Si₃O₇ and Na₂Si₂O₅) using the fiber elongation method. A1l compositions exhibit Newtonian behavior at low strain-rates, but non-Newtonian behavior at higher strain-rates, with strain-rate increasing faster than the applied stress. The decrease in shear viscosity observed at the high strain-rates ranges from 0.3 to 1.6 log₁₀ units (Pa s). The relaxation strain-rates, _relax, of these melts have been estimated from the low strain-rate, Newtonian, shear viscosity, using the Maxwell relationship; _relax= ^–1=(_s/G)^–1. For all compositions investigated, the onset of non-Newtonian rheology is observed at strain-rates 2.5+0.5 orders of magnitude less than the calculated relaxation strain-rate. This difference between the non-Newtonian onset and the relaxation strain-rate is larger than that predicted by the single relaxation time Maxwell model. Normalization of the experimental strain-rates to the relaxation strain-rate predicted from the Maxwell relation, eliminates the composition. and temperature-dependence of the onset of non-Newtonian behavior. The distribution of relaxation in the viscoelastic region appears to be unrelated to melt chemistry. This conclusion is consistent with the torsional, frequency domain study of Mills (1974) which illustrated a composition-invariance of the distribution of the imaginary component of the shear modulus in melts on the Na₂O-SiO₂ join. The present, time domain study of viscoelasticity contrasts with frequency domain studies in terms of the absolute strains employed. The present study employs relatively large total strains (up to 2). This compares with typical strains of 10^–8 in ultrasonic (frequency domain) studies. The stresses used to achieve the strain-rates required to observe viscoelastic behavior in this study approach the tensile strength of the fibers with the result that some of our experiments were terminated by fiber breakage. Although the breakage is unrelated to the observation of non-Newtonian viscosity, their close proximity in this and earlier studies suggests that brittle failure of igneous melts, may, in general, be preceded by a period of non-Newtonian rheology.     

中酸性硅酸盐熔体-水体系氢同位素分馏的压力效应

对0．2－2000MPa条件下钠长石熔体，钾长石熔体以及0．2－150MPa条件下流纹岩熔体－－水体系的氢同位素分馏实验数据进行了筹压拟合，发现硅酸盐熔体与水之间的氢同位素分馏存在显著的压力效应，在800，1000和1200度条件下对钠长石熔体，水体系和流夺熔体－－水体系氢同位素分馏压力方程进行的等温拟合表明，只有在特定的压力条件下才可以用钠长石熔体－水体系来近似流纹岩熔体－－水体系的氢同位素分馏行为，当压力超过临界值时，硅酸盐熔体－水体系氢同位素分馏会发生变化，本文拟合的硅酸盐熔体－水体系氢同位素分馏等值线在P－T空间的形态变化特征与矿物－水体系存在较大差异，依据流纹岩熔体与水之间氢同位素分馏的压力效应，成功地模拟了美国西部Glass Creek流纹岩δD值和水含量变化规律与岩浆去气之间的关系。     

Trace element compositions of minerals in garnet and spinel peridotite xenoliths from the Vitim volcanic field, Transbaikalia, eastern Siberia

Peridotite xenoliths from the Bereya alkali picrite tuff in the Vitim volcanic province of Transbaikalia consist of garnet lherzolite, garnet–spinel lherzolite and spinel lherzolite varieties. The volcanism is related to the Cenozoic Baikal Rift. All peridotites come from pressures of 20–23 kbar close to the garnet to spinel peridotite transition depth, and the presence of garnet can be attributed to cooling of spinel peridotites, probably during formation of the lithosphere. The peridotites show petrographic and mineral chemical evidence for infiltration by an alkaline silicate melt shortly before their transport to the Earth's surface. The melt infiltration event is indicated petrographically by clinopyroxenes which mimic melt morphologies, and post-dates outer kelyphitic rims on garnets which are attributed to an isochemical heating event within the mantle before transport to the Earth's surface. Single-mineral thermometry gives reasonable temperature estimates of 1050±50°C, whereas two-mineral methods involving clinopyroxene are falsified by secondary components in clinopyroxene introduced during the melt infiltration event. Excimer Laser–ICP-MS analysis has been performed for an extensive palette of both incompatible and compatible trace elements, and manifests the most thorough dataset available for this rock type. Orthopyroxene and garnet show only partial equilibration of trace elements with the infiltrating melt, whereas clinopyroxene and amphibole are close to equilibration with the melt and with each other. The incompatible element composition of the infiltrating melt calculated from the clinopyroxene and amphibole analyses via experimental mineral/melt partition coefficients is similar to the host alkali picrite, and probably represents a low melt fraction from a similar source during rift propagation. The chemistry and chronology of the events recorded in the xenoliths delineates the series of events expected during the influence of an expanding rift region in the upper mantle, namely the progressive erosion of the lithosphere and the episodic upward and outward propagation of melts, resulting in the evolution of the Vitim volcanic field.     

新疆克拉玛依地区百口泉发现尖晶石橄榄岩

新疆克拉玛依地区出露的早古生代蛇绿混杂岩带规模巨大,岩石单元出露齐全。白碱滩地区的地幔橄榄岩相对比较新鲜,单斜辉石、斜方辉石、尖晶石和橄榄石保存完好。研究表明,白碱滩蛇绿岩就位前,地幔岩发生了大于50km的快速隆升,且没有发生部分熔融。百口泉地区发现的地幔岩普遍遭受了改造,辉石多发生了强烈蚀变(透闪石化),但尖晶石和橄榄石保存较好。百口泉地区出露的地幔岩和白碱滩地幔岩的矿物组成基本一致,表明它们属于同一蛇绿混杂岩带。百口泉蛇绿岩剖面的揭露,将该蛇绿混杂岩带的范围向NE方向延伸了35km。     

新疆克拉玛依地区百口泉发现尖晶石橄榄岩

新疆克拉玛依地区出露的早古生代蛇绿混杂岩带规模巨大,岩石单元出露齐全。白碱滩地区的地幔橄榄岩相对比较新鲜,单斜辉石、斜方辉石、尖晶石和橄榄石保存完好。研究表明,白碱滩蛇绿岩就位前,地幔岩发生了大于50km的快速隆升,且没有发生部分熔融。百口泉地区发现的地幔岩普遍遭受了改造,辉石多发生了强烈蚀变(透闪石化),但尖晶石和橄榄石保存较好。百口泉地区出露的地幔岩和白碱滩地幔岩的矿物组成基本一致,表明它们属于同一蛇绿混杂岩带。百口泉蛇绿岩剖面的揭露,将该蛇绿混杂岩带的范围向NE方向延伸了35km。     

Silicic melts produced by reaction between peridotite and infiltrating basaltic melts: ion probe data on glasses and minerals in veined xenoliths from La Palma, Canary Islands

Mantle xenoliths hosted by the historic Volcan de San Antonio, La Palma, Canary Islands include veined spinel harzburgites and spinel dunites. Glasses and associated minerals in the vein system of veined xenoliths show a gradual transition in composition from broad veins to narrow veinlets. Broad veins contain alkali basaltic glass with semi-linear trace element patterns enriched in strongly incompatible elements. As the veins become narrower, the SiO₂-contents in glass increase (46 → 67 wt% SiO₂ in harzburgite, 43 → 58 wt% in dunite) and the trace element patterns change gradually to concave patterns depleted in moderately incompatible elements (e.g. HREE, Zr, Ti) relative to highly incompatible ones. The highest SiO₂-contents (ca. 68% SiO₂, low Ti-Fe-Mg-Ca-contents) and most extreme concave trace element patterns are exhibited by glass in unveined peridotite xenoliths. Clinopyroxenes shift from LREE-enriched augites in basaltic glass, to REE-depleted Cr-diopside in highly silicic glass. Estimates indicate that the most silicic glasses represent melts in, or near, equilibrium with their host peridotites. The observed trace element changes are compatible with formation of the silicic melts by processes involving infiltration of basaltic melts into mantle peridotite followed by reactions and crystallization. The Fe-Mg interdiffusion profiles in olivine porphyroclasts adjacent to the veins indicate a minimum period of diffusion of 600 years, implying that the reaction processes have taken place in situ in the upper mantle. The CaO-TiO₂-La/Nd relationships of mantle rocks may be used to discriminate between metasomatism caused by carbonatitic and silicic melts. Unveined mantle xenoliths from La Palma and Hierro (Canary Islands) show a wide range in La/Nd ratios with relatively constant, low-CaO contents which is compatible with metasomatism of “normal” abyssal peridotite by silicic melts. Peridotite xenoliths from Tenerife show somewhat higher CaO and TiO₂ contents than those from the other islands and may have been affected by basaltic or carbonatitic melts. The observed trace element signatures of ultramafic xenoliths from La Palma and other Canary Islands may be accounted for by addition of small amounts (1–7%) of highly silicic melt to unmetasomatized peridotite. Also ultramafic xenoliths from other localities, e.g. eastern Australia, show CaO-TiO₂-La/Nd relationships compatible with metasomatism by silicic melts. These results suggest that silicic melts may represent important metasomatic agents. Received: 15 November 1998 / Accepted: 17 May 1999     

The mechanisms of water diffusion in polymerized silicate melts

Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz₂₉Or₇₁, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D _water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz₂₈Ab₃₈ Or₃₄, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, D_water is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H₂O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H₂O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H₂O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H₂O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of D_water versus water content implies that increases with water content. The change from linear to exponential dependence of D_water between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996     

不同亚类硅酸盐矿物的中红外光谱学特征

利用热红外发射光谱研究了不同亚类硅酸盐矿物镁橄榄石、透闪石、蛇纹石和钠长石的红外发射光谱特征。在120oC时,通过对400～1650 cm-1的红外波段进行积分计算,发现硅酸盐矿物中镁橄榄石的发射率最高,可达到0.988,钠长石最低为0.947。硅酸盐矿物在850～1300cm-1区间均产生宽的低发射带,该发射带与硅氧四面体层中(Si,Al)-O的伸缩振动相关;在470 cm-1左右则形成相对尖锐的低发射带,与硅氧四面体层中(Si, Al)-O的弯曲振动相关。从岛状、链状、层状到架状硅酸盐矿物由于Si O2聚合程度依次增加,最强发射谷的位置依次向高频方向偏移,说明硅氧四面体中Si-O伸缩振动带的位置受到了n(Si)/n(O)比值的制约。此外,在辐射能量谱里,镁橄榄石、透闪石、蛇纹石和钠长石的最强辐射谷范围趋于变宽,依次为115、162、225和247 cm-1,反映了吸收的辐射能增加。综上可推测,硅酸盐矿物强的发射率可能与硅氧四面体中Si-O的振动模式、Si O2的聚合度、辐射能量谱中最强辐射谷的波长范围有关。     

Infrared spectroscopic study of the silicate anionic structures of some magmatic silicate melts

Summary The relation between the species of silicate anions in a silicate melt and their infrared characteristic frequency is discussed. A simple relation approximated with a quadratic equation is established between the ratio of non-bridging oxygens to silicon atoms of a silicate anion and the characteristic frequency. Based on this relation, the silicate anions in some magmatic silicate melts were estimated. The results obtained in the present study agreed well qualitatively with those estimated by some researchers on the basis of other spectroscopic methods.The constituent silicate segments and the distribution of AlO₄ tetrahedra in fully polymerized melts, albite, jadeite and anorthite, have been investigated. The polymerization degree of the silicate segments in the network seemed to decrease with the increase of AlO₄ tetrahedron. It is also suggested, that AlO₄ in the albite melt distributed more randomly, while those in anorthite melt had a tendency to form an aluminous segment.

---

Infrarot-spektroskopische Untersuchungen der Silikatanionen-Strukturen einiger magmatischer Silikatschmelzen

Zusammenfassung Die Beziehungen zwischen den Spezies der Silikatanionen in den Silikatschmelzen und ihrer charakteristischen Infrarot-Frequenz wurde untersucht. Es gibt eine einfache Beziehung zwischen dem Verhältnis nicht brückenbildender Sauerstoffatome zu Si-Atomen der Silikatanionen und der charakteristischen Frequenz, die mit einer quadratischen Gleichung beschrieben werden kann. Auf Grund dieser Beziehung werden die Silikatanionen in einigen magmatischen Schmelzen abgeschätzt. Das Ergebnis dieser Untersuchung stimmt qualitativ mit den Werten überein, die von einigen Forschern durch andere spektroskopische Methoden erhalten wurden.Die Silikatsegmente und die Verteilung der AlO₄-Tetraeder in vollkommen polymerisierten Schmelzen, in Albit, Jadeit und Anorthit wurden untersucht. Der Polymerisationsgrad der Silikatsegmente in den Netzwerken scheint mit der Zunahme der AlO₄-Tetraeder geringer zu werden. Die Untersuchungläßt erkennen, daß AlO₄-Tetraeder in Albit unregelmäßig verteilt sind, und in Anorthit die Neigung haben, ein Al-Segment zu bilden.

---

---

With 6 Figures     

The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.     

The Partitioning of Tungsten bwtween Aqueous Fluids and Silicate Melts

An experimental study has been carried out to determine the partition coefficients of tungsten between aqueous fluids and granitic melts at 800 °C and 1.5 kb with natural granite as the starting material. The effects of the solutions on the partition coefficients of tungsten show a sequence of P > CO ₃ ²⁻ > B > H₂O. The effects are limited (generallyK _D < 0.3) and the tungsten shows a preferential trend toward the melt over the aqueous fluid. The value ofK _D increases with increasing concentration of phosphorus; theK _D increases first and then reduces with the concentration of CO ₃ ²⁻ when temperature decreases, theK _D between the solution of CO ₃ ²⁻ and the silicate melt increases, and that between the solution of B₄O ₇ ²⁻ and the silicate melt decreases. The partition coefficients of phosphorus and sodium between fluids and silicate melts have been calculated from the concentrations of the elements in the melts. TheK _D value for phosphorus is 0.38 and that for sodium is 0.56. Evidence shows that the elements tend to become richer and richer in the melts.     

The effect of compression on noble gas solubility in silicate melts and consequences for degassing at mid-ocean ridges

The effect of compression on noble gas solubility in silicate melts is still badly understood due to a lack of theoretical guidance. In the experimental literature, noble gases dissolving in liquid silicates are found to concentrate almost linearly with increasing pressure up to several tens of kbar, suggesting that Henry’s law could be valid up to very high pressures, although this law stipulates that the gaseous phase in contact with the liquid must be ideal. Recently, new experiments dealing with the dissolution of argon in synthetic and natural silicate melts have pointed out that the evolution of concentration with pressure exhibits a departure from linearity in the 50-100 kbar range, leading either to a levelling off or to a sudden collapse of the argon concentration above 50 kbar. Here, we investigate by means of liquid state physics how volatile species dissolve into silicate melts under pressure. We use a hard sphere model (the reference fluid in liquid state physics) to describe silicate melts and gas at high pressures. One of our main results is that, when pressure increases, the concurrent compaction of gas and melt explains the almost-linear behaviour of the noble gas concentration up to several tens of kbars, before melt compaction dominates and concentration either levels off or decreases gradually in the 50-100 kbar range. In spite of the existence of a quasi-linear regime over a large pressure range, our work disqualifies the use of the Henry law when dealing with high pressures. The implication of these findings to provide an understanding of degassing at mid-ocean ridges is next investigated. Applying our model to the scenario where CO₂ vesicle generation occurs in the magma at mantle depths during its ascent from melting regions, we evaluate magma vesicularity as well as noble gas concentrations in the basalt melt and in vesicles as a function of pressure at depth. It is stressed that the variable and usually strong noble gas elemental fractionation observed in mid-ocean ridge basalts can be explained by assuming a sequence of several vesiculation stages interrupted by vesicle loss during magma ascent.     

Experiments on preferred orientation of platy minerals

Polycrystalline aggregates of phlogopite, talc, and brucite have been grown hydrothermally from their constituent oxides at 300–600° C, 3–5 kb, and compressed 10–30% in short-term experiments (typically 30 minutes). Under hydrostatic conditions, approximately random orientation of crystals results. When the specimen is strained at high temperature, either during or after growth of the minerals, a preferred orientation of basal planes normal to the axis of compression results. Since a similar result is obtained by straining at room temperature after growth of the minerals, the mechanism of orientation is probably mainly mechanical rotation after formation. Microscope examination showed that the preferred orientation is most marked in coarser grains of the aggregates. A second kind of foliation is defined in some specimens by closely spaced, narrow domains within which coarse grains are slightly rotated. These domains occur in conjugate sets symetrically oriented at about 45° to the axis of compression. They are interpreted as shear domains and are geometrically similar to incipient strain-slip cleavage in foliated rocks. The experiments may represent likely behavior in geological situations where the temperature or time scale precludes recrystallization during deformation, but they are probably not directly revelant to cases of axial-plane cleavage where reorientation through an influence of stress or strain during recrystallization is believed to have occurred. No unequivocal indication of the latter process was obtained in the experiments.     

Experimental modal metasomatism of a spinel lherzolite and the production of amphibole-bearing peridotite

Experiments have been done which simulate the modal metasomatism of spinel lherzolite by partial melts of the subducted slab. The experiments were designed so that the metasomatizing melts were generated during the experiments by partial melting of a slab analog (basaltic composition amphibolite). The melts are thought to be representative of hybridizing melts in that they are derived by high-pressure partial melting under conditions appropriate to a hot slab geotherm. During the experiments, the melts infiltrate into and metasomatize a model depleted peridotite. Chemical modifications to minerals in the peridotite are of the same nature and extent as those found in naturally metasomatized spinel lherzolites. Modal metasomatism produced pargasitic amphiboles in runs at 1.5 GPa and in all but the highest temperature run at 2.0 GPa. The amphiboles are indistinguishable from amphiboles found in amphibole-bearing peridotites from supra-subduction zone environments. Systematic variations in amphibole composition suggest that the melt infiltration process in the experiments involved continuous modification of the composition of the infiltrating melt as observed around inferred quenched melt (i.c., amphibolite or amphibolite/clinopyroxenite) veins in xenoliths and massif peridotites. The compositions of the initial and final mineral phases in the experiments and those of the metasomatizing melts are used to derive amphibole formation reactions at 1.5 and 2.0 GPa that are similar in form to those inferred in studies of natural amphibole-bearing peridotites. The metasomatism reactions show that the extent of amphibole formation in peridotite at 1.5 and 2.0 GPa will, in general, be limited by clinopyroxene and spinel abundance.     

Geochemistry of metasomatised spinel peridotite xenoliths from the Dariganga Plateau, South-eastern Mongolia

Summary One fresh (green), one altered (black) and one composite (green/black) peridotite xenolith from the Neogene-Quaternary basalts of the Dariganga Plateau, SE Mongolia, were studied by electron microprobe, X-ray fluorescence, wet chemical and instrumental neutron activation analysis. The history of the upper mantle underneath the Dariganga Plateau has been complex and is characterised by elemental depletions and enrichments processes. The rocks investigated appear to have been processed in several steps, have been moderately depleted (relative to the primitive upper mantle composition) in incompatible elements and subsequently metasomatically enriched in alkalis, Fe, Ca, LREE, Th and U. As a result, most peridotites are moderately depleted in Si, Cr, Ti, HREE and Hf, are slightly enriched in LREE and have elevated Th and U abundances. The minerals in all rocks are out of chemical equilibrium. In the green peridotites disequilibrium is modest but it is severe in the blackened lherzolites. The latter have experienced strong Fe metasomatism accompanied by strong oxidation. As a result, Mg-rich olivines formed by oxidation and precipitation of Fe oxides in the primary olivines (blackening) and Fe-rich olivines formed in the Fe metasomatic event. The latter could only have taken place after the oxidising event, otherwise the Fe-rich olivines would also have been affected by it. Three of the four rocks show negative anomalies (relative to the Ce abundance) of Hf and Ti, one is enriched in these elements, which is considered an indication of the action of carbonatitic melts/fluids in the upper mantle. Enrichment of U over Th in some of our samples seems also to indicate the presence of water in the fluid phase, however, the lack of (OH)-bearing minerals in the Dariganga xenoliths suggests a low activity of water in these fluids. The latest of the metasomatic events probably took place shortly before entrapment of the rocks by the basaltic lava that carried them to the earth’s surface. The composite sample consisting of a green harzburgite and a black lherzolite suggests that blackening took place at the original location of the rock rather than in the basaltic tuff because the latter should have altered the whole xenolith. It also demonstrates that metasomatic processes in the upper mantle can be confined to rather restricted locations with sharp boundaries towards the wall rocks. Blackening as well as the metasomatic events apparently took place because of a better permeability in one part of the rock as compared to the other, probably the result of tectonisation. Received May 28, 1999; revised version accepted February 24, 2001