Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Low temperature basalt alteration by sea water: an experimental study at 70°C and 150°C

Basaltic glass and diabase were reacted with seawater at 70°C at 1 bar and 150°C at 500 bars to determine fluid composition and alteration mineralogy. All experiments were performed at a water/ rock mass ratio of 10.The changes in seawater chemistry depended on temperature and crystallinity of the basalt. The experiment at 70°C produced a slight but continuous loss of Mg, Na and K and enrichment of Ca and SiO₂ in the seawater while pH decreased slowly. At 150°C, in contrast, Mg and SO₄ were quickly and quantitatively removed while Ca, SiO₂, Na, K, Fe, Mn and Ba were added to the seawater. pH rose to values between 5.5 and 6.5 after an initial drop to lower values. Basalt glass reacted more extensively at 150°C than diabase.Smectite was the major alteration product (iron-rich saponite) at 150°C for both the glass and diabase experiments. Smectite from the diabase experiment was well crystallized while that from the glass experiment was poorly crystallized. The smectites are similar to smectites found in altered oceanic ophiolitic basalts.     

Precipitation of pyroxenes and Mg2SiO4 from majoritic garnet: simulation of peridotite exhumation from great depth

Our experimental simulations of the exhumation path of mantle peridotites show that high‐temperature (1400 °C) decompression of lherzolite from 14 to 13 and 12 GPa results in exsolution of interstitial blebs of diopside and Mg₂SiO₄ (wadsleyite) lamellae from majoritic garnet. At lower pressures (from 8 to 5 GPa, at T = 1400 °C) only enstatite exsolves as blebs at garnet boundaries. Continuous high‐temperature decompression from 14 to 7 GPa produces zoned majoritic garnet containing blebs of exsolved pyroxenes inside garnet rims. No intracrystalline precipitation of pyroxene was observed in garnet, although such lamellae are found in some natural garnet peridotites. The explanation appears to be the three orders of magnitude difference in grain size between experimental and natural specimens. Our data suggest that Mg₂SiO₄ and diopside exsolutions reflect the deepest point of the exhumation path of garnet peridotites, whereas enstatite precipitation may be restricted to garnets with less majoritic component at shallower depths.     

Composition of the Siberian cratonic mantle: evidence from Udachnaya peridotite xenoliths

Bulk compositions and mineral analyses for forty-one, large, garnet- and spinel-facies peridotite xenoliths from the Udachnaya kimberlite in the central Siberian platform have many similarities to those of well-studied peridotites from the Kaapvaal craton in southern Africa. Coarse Mg-rich lherzolites and harzburgites with equilibration temperatures below 1000 °C are abundant and are believed to form the principal rock type in the Siberian lithosphere. The low-temperature Udachnaya peridotites have an average mg number [Mg/(Mg+Fe)] of 92.6 with a wide dispersion in modal enstatite, ranging to over 40 wt%. High-temperature peridotites are relatively richer in Fe and Ti and are commonly deformed, with porphyroclastic or mosaic-porphyroclastic textures, some of the latter having fluidized enstatite. The Udachnaya peridotites have experienced late-stage metasomatism before, during and after eruption. Garnets and pyroxenes in many of the high-temperature rocks are zoned, probably by reaction with melt prior to eruption. Virtually all the peridotites contain secondary diopside, inhomogeneous on a micron scale, that mantles primary orthopyroxene. It is believed to have crystallized along with lesser amounts of intergranular calcite and monticellite during eruption. Bulk analyses for total Fe in many specimens are higher than whole-rock Fe calculated from the electron probe analyses and the modes. The magnitude of the difference between the two measurements of total Fe correlates with loss-on-ignition, suggesting that Fe has been introduced during serpentinization following eruption. These late metasomatic processes have thus affected some major as well minor and trace element compositions. The similarities in bulk composition of peridotites from Udachnaya and the Kaapvaal are evidence of a common origin. Low-temperature cratonic peridotites differ from oceanic peridotites in having higher mg numbers (>92) and in having relatively high but wide-ranging modal enstatite (Mg/Si = 1.06–1.49 weight fraction). The Udachnaya low-temperature peridotites have an inverse correlation between FeO (calculated from the probe analyses and modes) and SiO₂. This correlation is also present in the Kaapvaal data but is complicated by a greater range in fertility that produces a positive variation of Fe with Si. A negative trend for Fe/Si can be seen within a portion of the Kaapvaal data, that for low-Ca harzburgites, in which the variation in fertility is restricted. The negative trends for Fe/Si can be interpreted as a consequence of either segregation of olivine and orthopyroxene by metamorphic differentiation or partial sorting during cumulate formation. Received: 18 June 1996  / Accepted: 11 February 1997     

Hydrothermal alteration of basalt by seawater under seawater-dominated conditions

Fresh mid-ocean ridge basalt glass and diabase have been reacted with seawater at 150–300°C, 500 bar, and water/rock mass ratios of 50, 62, and 125, using experimental apparatus which allowed on-line sampling of solution to monitor reaction progress. These experiments characterize reaction under what we have called “seawater-dominated” conditions of hydrothermal alteration.In an experiment at 300°C, basalt glass undergoing alteration removed nearly all Mg²⁺ from an amount of seawater 50 times its own mass. In the process, the glass was converted entirely to mixed-layer smectite-chlorite, anhydrite, and minor hematite. Removal of Mg from seawater occurred as a Mg(OH)₂ component incorporated into the secondary clay. This produced a precipitous drop in solution pH early in the experiment, accompanied by a dramatic increase in the concentrations of Fe, Mn, and Zn in solution. As Mg removal neared completion and the glass was hydrolyzed, pH rose again and heavy metal concentrations dropped.At water/rock ratios of 62 and 125 and 150–300°C, the mineral assemblage produced was similar to that at a water/rock ratio of 50. Solution chemistry, however, contrasted with the earlier experiment in that Mg concentrations in solution were greater and pH lower. This caused significant leaching of heavy metals. At 300°C nearly all of the Na, Ca, Cu, Zn, and CO₂ and most of the K, Ba, Sr, and Mn were leached from the silicates. H₂S, Al, Si, and possibly Co were also significantly mobilized, whereas V, Cr, and Ni were not. Little or no seawater sulfate was reduced.Although submarine hot spring solutions sampled to date along mid-ocean ridges clearly come from rock-dominated hydrothermal systems, evidence from ocean floor metabasalts and from heat flow studies indicates that seawater-dominated conditions of alteration prevail at least locally both in axial hightemperature systems and in ridge flank systems at lower temperatures.     

The surface chemistry of multi-oxide silicates

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH_IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO₂ in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.     

Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions

Far from equilibrium enstatite dissolution rates both open to atmospheric CO₂ and CO₂ purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO₂ conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO.Steady-state dissolution rates of enstatite increase above pH 10 when CO₂ was purged by performing the experiments in a N₂ atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO₃²⁻ above pH 10.33. It is argued that CO₃²⁻ forms a >Mg₂-CO₃ complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO₂-purged enstatite dissolution in moles per cm² per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.     

Metamorphic history of serpentinite mylonites from the Happo ultramafic complex, central Japan

Serpentinite mylonites from the Happo ultramafic complex show evidence of two stages of mylonitization at different temperature conditions. Peridotite mylonites exhibit two types of olivine – porphyroclasts and neoblasts – produced at the earlier stage. The olivine neoblasts have a stretching lineation with a fabric suggesting plastic deformation along (0 1 0) [0 0 1]. In addition to the olivine fabric, the stable association of olivine, orthopyroxene and tremolite in the peridotites that survived later serpentinization, and the Si and Na contents of tremolite, suggest that the earlier mylonitization took place at temperatures between 700 and 800 °C. Later mylonitization was associated with high‐temperature serpentinization to form serpentinite mylonites. In contrast to a common type of serpentinite in orogenic belts, the serpentinite mylonites are cohesively foliated, rich in olivine and diopside, and poor in antigorite. The diopside has low Al, Cr and Na contents typical of a retrograde origin, and the olivine has a homogeneous composition except in areas subjected to contact metamorphism at a later stage. Modal composition and mineral chemistry suggest that the serpentinite mylonites were formed by a hydration reaction of tremolite and olivine to produce diopside and antigorite under stable conditions of olivine, at temperatures between 400 and 600 °C. Later‐stage mylonitization has preferentially been superimposed on the earlier‐stage mylonite zone with a common direction of foliation. The difference in temperature between the two mylonitization stages suggests that the shear zone was episodically active during the emplacement of the Happo complex. Conditions of relatively high temperature for serpentinization at a convergent plate boundary and high permeability caused by the early mylonitization favoured the formation of the serpentinite mylonites.     

Origin of Neoproterozoic ophiolitic peridotites in south Eastern Desert, Egypt, constrained from primary mantle mineral chemistry

The ophiolitic peridotites in the Wadi Arais area, south Eastern Desert of Egypt, represent a part of Neoproterozoic ophiolites of the Arabian-Nubian Shield (ANS). We found relics of fresh dunites enveloped by serpentinites that show abundances of bastite after orthopyroxene, reflecting harzburgite protoliths. The bulk-rock chemistry confirmed the harzburgites as the main protoliths. The primary mantle minerals such as orthopyroxene, olivine and chromian spinel in Arais serpentinites are still preserved. The orthopyroxene has high Mg# [=Mg/(Mg + Fe²⁺)], ~0.923 on average. It shows intra-grain chemical homogeneity and contains, on average, 2.28 wt.% A1₂O₃, 0.88 wt.% Cr₂O₃ and 0.53 wt.% CaO, similar to primary orthopyroxenes in modern forearc peridotites. The olivine in harzburgites has lower Fo (93?94.5) than that in dunites (Fo_94.3?Fo_95.9). The Arais olivine is similar in NiO (0.47 wt.% on average) and MnO (0.08 wt.% on average) contents to the mantle olivine in primary peridotites. This olivine is high in Fo content, similar to Mg-rich olivines in ANS ophiolitic harzburgites, because of its residual origin. The chromian spinel, found in harzburgites, shows wide ranges of Cr#s [=Cr/(Cr + Al)], 0.46?0.81 and Mg#s, 0.34?0.67. The chromian spinel in dunites shows an intra-grain chemical homogeneity with high Cr#s (0.82?0.86). The chromian spinels in Arais peridotites are low in TiO₂, 0.05 wt.% and Y_Fe [= Fe³⁺/(Cr + Al + Fe³⁺)], ~0.06 on average. They are similar in chemistry to spinels in forearc peridotites. Their compositions associated with olivine’s Fo suggest that the harzburgites are refractory residues after high-degree partial melting (mainly ~25?30 % partial melting) and dunites are more depleted, similar to highly refractory peridotites recovered from forearcs. This is in accordance with the partial melting (>20 % melt) obtained by the whole-rock Al₂O₃ composition. The Arais peridotites have been possibly formed in a sub-arc setting (mantle wedge), where high degrees of partial melting were available during subduction and closing of the Mozambique Ocean, and emplaced in a forearc basin. Their equilibrium temperature based on olivine?spinel thermometry ranges from 650 to 780 °C, and their oxygen fugacity is high (Δlog ?O₂?=?2.3 to 2.8), which is characteristic of mantle-wedge peridotites. The Arais peridotites are affected by secondary processes forming microinclusions inside the dunitic olivine, abundances of carbonates and talc flakes in serpentinites. These microinclusions have been formed by reaction between trapped fluids and host olivine in a closed system. Lizardite and chrysotile, based on Raman analyses, are the main serpentine minerals with lesser antigorite, indicating that serpentines were possibly formed under retrograde metamorphism during exhumation and near the surface at low T (<400 °C).     

Effects of cation substitutions in garnet and pyroxene on equilibrium oxygen isotope fractionations

High-grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet, and to investigate the effects on fractionation factors of the cation substitutions Fe³⁺Al_?1 and Ca(Fe,Mg)_?1. Recrystallized, granulite facies (725 °C) wollastonite ores from the northern Adirondack highlands contain essentially only the minerals clinopyroxene (a Di–Hd solid solution)+garnet (a Grs–Adr solid solution)±wollastonite, and exhibit a systematic dependence of measured fractionations on the Fe³⁺ content of calcic garnet: Δ(Cpx–CaGrt)=(0.14±0.12)+(0.78±0.20)X_Adr and Δ(Wo–CaGrt)=(0.15±0.22)+(0.57±0.33)X_Adr. In eclogites formed at T ≤650 °C, measured compositions of Ca-poor garnet and omphacite combined with experimental data indicate that Ca-poor, Fe-rich garnet is enriched in ¹⁸O compared to both diopside and grossular: extrapolating to 1000 K, Δ(Alm–Di)≈c. 0.2 and Δ(Alm–Grs)≈c. 0.5. Orthopyroxene and clinopyroxene from Gore Mountain, New York, show a constant fractionation that is independent of rock type, as expected if they have the same closure temperature. These data imply Δ(Opx-Cpx)≈c. 0.7 at 1000 K. Measured fractionations among Ca-poor garnet, orthopyroxene, clinopyroxene and hornblende in the Gore Mountain rocks further indicate an ¹⁸O enrichment in Ca-poor garnet over Grs (≈c. 0.5 at 1000 K). The new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite, diopside, grossular, wollastonite and feldspar, but consistently indicate a significant isotope effect for the simple octahedral cation substitutions Fe³⁺Al_?1 (Grs vs. Adr) and Ca(Fe,Mg)_?1 (Ca-poor garnet vs. Grs; Opx vs. Cpx). Neither cation substitution has been directly investigated for its effect on ¹⁸O/¹⁶O fractionation with experiments in silicates. Chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends.     

Electron microprobe measurement of pyroxenes coexisting with H2O-undersaturated liquid in the join CaMgSi2O6-Mg2Si2O6-H2O at 30 kilobars,with applications to geothermometry

Mixtures of synthetic crystalline enstatite and diopside were reacted with small water contents in sealed capsules in piston-cylinder apparatus at 30 kb between 1000° C and 1700° C. The compositions of coexisting enstatite and diopside solid solutions were measured with an ARL-EMX electron microprobe between 1000° C and 1500° C. Between 1100° C and 1500° C the pyroxenes coexisted with H₂O-undersaturated liquid which quenched to inhomogeneous pyroxene crystals. The presence of liquid facilitated growth of pyroxene crystals suitable for microprobe determinations. The solvus of Davis and Boyd (1966) is generally used in geothermometry; our enstatite solvus limb is a few mol-% richer in Mg₂Si₂O₆ in the temperature range 1000–1400° C; our diopside solvus limb is a few mol-% richer in Mg₂Si₂O₆ below 1100°C, in close agreement between 1100° C and 1200° C, but richer in CaMgSi₂O₆ between 1200° C and 1500° C. Estimated equilibration temperatures for a diopside with composition 78.7% Di is 1300° C according to our results compared with 1210° C for the Davis and Boyd solvus.     

Symplectites in upper mantle peridotites: Development and implications for the growth of subsolidus garnet,pyroxene and spinel

Silicate-oxide symplectites in complex mineral intergrowths are relatively common in upper mantle xenoliths and in xenoliths in the Jagersfontein Kimberlite, South Africa.Harzburgites of olivine and high-Al (1.9–3.6 wt%), Ca (0.6–0.9 wt%) and Cr (0.3–0.9 wt%) enstatite contain symplectites of spinel and diopside, or spinel, diopside and lower-Al (0.8–2.2 wt%), Ca (0.1–0.4 wt%) and Cr (0.02–0.8 wt%) enstatite. From textures and mineral chemistries these symplectites are interpreted to have formed by mineral unmixing and migration from Al–Ca–Cr discrete enstatite to adjoining mineral interfaces.Garnet harzburgites are composed of large (0.5–1 cm) olivine, equally large discrete low-Al (0.6–1.1 wt%), Ca (0.1–0.5 wt%), and Cr (0.1–0.3 wt%) enstatite and smaller interstitial garnet, diopside, and high-Cr and low-Al spinel. Symplectites are composed of either spinel+diopside+garnet, or garnet+spinel. Spinel diopside garnet symplectites have cores of spinel+diopside, resembling symplectites inharzburgites, but surrounded by rims of garnet or garnet+undigested globular spinel. From textures and chemistries we suggest that the spinel+diopside cores formed from Ca-Al-Cr-rich orthopyroxene initially as a nonstoichiometric homogeneous single phase clinopyroxene enriched in Fe, Cr and Al. This was followed by decomposition of the clinopyroxene to diopside+spinel, and subsequent garnet formation in a prograde reaction with olivine or enstatite. In bothharzburgites andgarnet harzburgites the metastable cellular structures may also have formed by the simultaneous precipitation of pyroxene and spinel. In all cases there is a strongly preferred embayment of symplectite bodies into olivine. Olivine appears to have activated adjacent     

Chemical exchange during hydrothermal alteration of basalt by seawater—I. Experimental results for major and minor components of seawater

Fresh mid-ocean ridge basalt of varying crystallinity has been powdered and reacted with seawater and an artificial Na-K-Ca-Cl solution at 200–500°C and 500–1000 bar in sealed gold capsules. Water/rock mass ratios of 1–3 were used and durations ranged from 2 to 20 months.These time periods were sufficient for most elements to approach a steady-state concentration in solution which was determined by equilibrium with alteration minerals (Mg, SiO₂, SO₄), by rate of formation of these minerals (Na, Ca), or by depletion from the rock (K, B, Ba). The resulting solutions closely resemble the brines from the basalt-seawater geothermal system at Reykjanes, Iceland. Mg was almost completely removed from seawater into the alteration products smectite, tremolite-actinolite, or talc. Sulfate also was removed to low concentrations, both by precipitation of anyhydrite and by reduction to sulfide. Net transfer of Na from seawater into solids occurred in most experiments by formation of sodic feldspar and possibly analcime. Sr was removed from seawater in some experiments but showed no change or a small gain in others. SiO₂, Ca, K, Ba, B and CO₂ were leached from basalt and enriched in solution. SiO₂ concentrations were controlled by saturation with quartz at 300°C and above. The principal Ca-bearing phases which formed were anhydrite, the hydrated Ca-silicate truscottite, tremolite-actinolite, and possibly wairakite. No K-rich phases formed. For some minerals the crystallinity of the starting basalt affected the amount which formed.Removal of Mg from seawater into solid alteration products occurred rapidly and was balanced largely by leaching of Ca from basalt. Net transfer of Na from seawater into solids occurred more slowly and was balanced mainly by leaching of additional Ca from basalt. Thus, reaction between seawater and basalt at low water/rock ratios can be considered to consist of two exchanges: Mg for Ca, and Na for Ca.     

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle,and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

We performed an experimental study, designed to reproduce the formation of an unusual merwinite?+?olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca?=?1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite?+?olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300–1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca#?=?molar 100?×?Ca/(Ca?+?Mg)?>?0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca?=?1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg₂SiO₄ (olivine)?+?6CaCO₃ (liquid)?=?Ca₃MgSi₂O₈ (merwinite)?+?3CaMg(CO₃)₂ (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.     

Seawater-peridotite interaction at 300°C and 500 bars: implications for the origin of oceanic serpentinites

An experiment has been performed reacting seawater with fresh peridotite (80% olivine, Fo₉₀ and ～- 15% enstatitic orthopyroxene En₉₅ and minor clinopyroxene and spinel) at 300°C, 500 bars and water/rock mass ratio of 20. The duration of the experiment was approximately 1500 hr.Seawater chemistry was appreciably modified during the experiment. Mg, Ca, Sr, SO₄ and H₂O were removed, while H₂S_(aq), Fe, Mn and Zn were added. H₂S_(aq) resulted from the inorganic reduction of seawater SO₄. pH was initially acid (2.8), but then rose slowly to a value of 5.2. The aqueous concentrations of Na, K, Cl and boron (B) changed little from that in seawater prior to reaction. However, as the solution was cooled to room temperature at the end of the experiment, the B concentration decreased. This suggests that the B content of oceanic serpentinites may be the result of retrograde reactions between a previously serpentinized body and ‘cold’ seawater.The primary minerals in the peridotite were replaced to varying degrees by serpentine (lizardite), magnetite. Mg-hydroxysulfate, anhydrite and possibly pyrite and sphalerite. Mg-hydroxysulfate and much anhydrite dissolved on quench.The alteration mineral assemblage generated during this experiment is consistent with that predicted from equilibrium phase relations and is similar in chemical composition, mineralogy and paragenesis to that reported for oceanic serpentinites.     

Grain boundary diffusion in enstatite

We have investigated grain boundary diffusion rates in enstatite by heating single crystals of quartz packed in powdered San Carlos olivine (Mg_0.90Fe_0.10)₂SiO₄ at controlled oxygen fugacities in the range 10^?5.7 to 10^?8.7?atm and temperatures from 1350° to 1450?°C for times from 5 to 100?h at 1?atm total pressure. Following the experiments, the thickness of the coherent polycrystalline reaction rim of pyroxene that had formed between the quartz and olivine was measured using backscatter scanning imaging in the electron microprobe. Quantitative microprobe analysis indicated that the composition of this reaction phase is (Mg_0.92Fe_0.08)₂Si₂O₆. The rate of growth of the pyroxene increases with increasing temperature, is independent of the oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by ionic diffusion through the pyroxene rim. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the olivine-pyroxene interface, and is therefore controlled by the diffusion of silicon and oxygen. The parabolic rate constants determined from the experiments were analyzed in terms of the oxide activity gradient across the rim to yield mean effective diffusivities for the rate-limiting ionic species, assuming bulk transport through the pyroxene layer. These effective diffusivities are faster than the lattice diffusivities for the slowest species (silicon) calculated from creep experiments, but slower than measured lattice diffusivities for oxygen in enstatite. Thus, silicon grain boundary diffusion is most likely to be the rate-limiting process in the growth of the pyroxene rims. Also, as oxygen transport through the pyroxene rims must be faster than silicon transport, diffusion of oxygen along the grain boundaries must be faster than through the lattice. The grain boundary diffusivity for silicon in orthopyroxenite is then given by D¯gbSiδ=(3.3±3.0)×10^?9f0.0O₂e^?400±65/RT?m³s^?1, where the activation energy for diffusion is in kJ/mol, and δ is the grain boundary width in m. Calculated growth rates for enstatite under these conditions are significantly slower than predicted by an extrapolation from similar experiments performed at 1000?°C under high pressure (hydrous) conditions by Yund and Tullis (1992), perhaps due to water-enhancement of diffusion in their experiments.     

Jadeite, albite and nepheline as inclusions in spinel of chromitite from Hess Deep, equatorial Pacific: their genesis and implications for serpentinite diapir formation

Polymineralic inclusions which consist of a few grains of diopside, enstatite, jadeite, nepheline, albite, pargasite, phlogopites and olivine were found in chromian spinel in a chromitite pod and in troctolite from Hess Deep, equatorial Pacific. The inclusion mineral suite in chromitite is characterized by Na-Al silicates, such as jadeite, nepheline and albite. Jadeite and nepheline commonly coexist with enstatite, and tend to occur as interstitial grains between subhedral enstatite (or other minerals) and host spinel. Albite, diopside and enstatite occur as equant inclusions. The mafic minerals in the inclusions have similar chemistry to those found in the troctolite and dunite. The modes of occurrence and mineral chemistry of the inclusions are controlled by magmatic precipitation, and subsequent reequilibration due to decrease of temperature in the uppermost mantle. The mafic minerals in spinel inclusions were crystallized from a melt enriched in Cr and some incompatible components formed by melt-mantle interaction process mixed to various extent with subsequently supplied more primary melt. Albite and nepheline could also be formed at the magmatic stage. Jadeite was formed by a subsolidus reaction of albite and nepheline at low temperatures (250–300 °C) at slightly less than 3 kbar. This requires a remarkable temperature decrease, at least locally, of the uppermost mantle and crust. The Hess Deep rocks were formed in the uppermost mantle beneath a spreading-ridge axis at more than 1000 °C, and were transposed outwards from the axis by corner flow. At the off-ridge conditions, the rocks were cooled and serpentinized by circulation of sea water at the mantle depth to form jadeite in chromitite. The serpentinized portion could have risen as a kind of serpentinite diapir through the thin crust up to the ocean floor. Received: 24 January 1997 / Accepted: 6 November 1997     

Exsolutions of Diopside and Magnetite in Olivine from Mantle Dunite, Luobusa Ophiolite, Tibet, China

The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chromite （1%-4%） ＋ diopside （〈1%）. Two types of olivine are found in thin sections： one （Fo = 94） is coarse-grained, elongated with development of kink bands, wavy extinction and irregular margins; and the other （Fo = 96） is fine-grained and poly-angied. Some of the olivine grains contain minor Ca, Cr and Ni. Besides the exsolutions in olivine, three micron-size inclusions are also discovered. Analyzed through energy dispersive system （EDS） with unitary analytical method, the average compositions of the inclusions are： Na20, 3.12%-3.84%; MgO, 19.51%-23.79%; Al2O3, 9.33%-11.31%; SiO2, 44.89%-46.29%; CaO, 11.46%-12.90%; Cr2O3, 0.74%-2.29%; FeO, 4.26%- 5.27%, which is quite similar to those of amphibole. Diopside is anhedral f＇dling between olivines, or as micro-inclusions oriented in olivines. Chromite appears euhedral distributed between olivines, sometimes with apparent compositional zone. From core to rim of the chromite, Fe content increases and Cr decreases; and A! and Mg drop greatly on the rim. There is always incomplete magnetite zone around the chromite. Compared with the nodular chromite in the same section, the euhedral chromite has higher Fe3O4 and lower MgCr2O4 and MgAI2O4 end member contents, which means it formed under higher oxygen fugacity environment. With a geothermometer estimation, the equilibrium crystalline temperature is 820℃-960℃ for olivine and nodular chromite, 630℃-770℃ for olivine and euhedral chromite, and 350℃-550℃ for olivine and exsoluted magnetite, showing that the exsolutions occurred late at low temperature. Thus we propose that previously depleted mantle harzburgite reacted with the melt containing Na, Al and Ca, and produced an olivine solid solution added with Na^＋, Al^3＋, Ca^2＋, Fe^3＋, Cr^3＋. With temperature d     

Thermochemistry of synthetic clinopyroxenes on the join CaMgSi2O6-Mg2Si2O6

Enthalpies of solution of synthetic clinopyroxenes on the join CaMgSi₂O₆-Mg₂Si₂O₆ have been measured in a melt of composition Pb₂B₂O₅ at 970 K. Most of the measurements were made on samples crystallized at 1600°–1700°C and 30 kbar pressure, which covered the range 0–78 mole per cent Mg₂Si₂O₆, and whose X-ray patterns could be satisfactorily indexed on the diopside (C2/c) structure. For the reaction: Mg₂Si₂O₆→-Mg₂Si₂O₆ enstatite diopside the present data, in conjunction with previous and new measurements on Mg₂Si₂O₆ enstatite, determine ΔH° ~ 2 kcal and W_H (regular solution parameter) ~ 7 kcal. These values are in good agreement with those deduced by Saxena and Nehru (1975) from a study of high temperature, high pressure phase equilibrium data under the assumption that the excess entropy of mixing is small, but, in light of the recent theoretical treatment of Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), the meanings of these parameters may be ambiguous.Heat of solution measurements on Ca-rich binary diopsides made by annealing glasses at 1358°C in air gave slighter higher values than the higher temperature high pressure samples. This may be evidence for some (Ca, Mg) disorder of the sort postulated by Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), although no differences in heat of solution dependent on synthesis temperature in the range 1350°–1700°C could be found in stoichiometric CaMgSi₂O₆.