Chemical diffusion of fluorine in jadeite melt at high pressure

The chemical diffusion of fluorine in jadeite melt has been investigated from 10 to 15 kbars and 1200 to 1400°C using diffusion couples of Jadeite melt and fluorine-bearing jadeite melt (6.3 wt.% F). The diffusion profile data indicate that the diffusion process is concentration-independent, binary, F-O interdiffusion. The F-O interdiffusion coefficient ranges from 1.3 × 10^?7 to 7.1 × 10^?7 cm²/sec and is much larger than those obtained by Kushiro (1983) for Si-Ge and Al-Ga interdimision in jadeitic melts. The Arrhenius activation energy of diffusion is in the range of 36 to 39 kcal/mole as compared with 19 kcal/mole for fluorine tracer diffusion in a lime-aluminosilicate melt. The diffusivity and activation energy of F-O interdiffusion vary slightly with pressure, but the pressure dependence of F-O, Al-Ga and Si-Ge interdiffusion may be related to the relative volumes of the interdiffusing species for each pair. The magnitude of chemical diffusivity of fluorine is comparable to that of the chemical diffusivity of water in obsidian melts. The diffusivities of various cations are significantly increased by the addition of fluorine or water to a silicate melt. This fact, combined with the high diffusivity of fluorine, suggests that the F^? ion is the principal diffusing species in dry aluminosilicate melts and that dissolved fluorine will accelerate chemical equilibration in dry igneous melts.     

Phase Relations of Basalts in their Melting Ranges at PH2O = 5 kb. Part II. Melt Compositions

This paper describes the melting relations of three basalts,a Picture Gorge tholeiite, the 1921 Kilauea olivine tholeiite,and the 1801 Hualalai alkali basalt, at 5 kb water pressure,680–1045 °C, at the oxygen fugacities of the quartz-fayalite-magnetite(QFM) and hematite-magnetite (HM) buffer. All melts producedwithin the hornblende stability field are strongly quartzo-feldspathic.All are quartz-normative, including those from the alkali basalt,and all but two of the melts are corundum-normative. Melt compositionshows very little dependence on oxygen fugacity within the hornblendestability field, as MgO and FeO contents are very low. Whenhornblende begins to melt extensively (1000°–1045°C), the TiO₂, FeO, and MgO contents of the melt increaseabruptly. In this range, melts formed on the HM buffer havemuch higher Mg/Fe ratios and lower TiO₂ than melts formed onthe QFM buffer. Melt composition is also quite insensitive to changes in basaltcomposition, within the hornblende stability field. The chiefexception is the Na/Ca ratio, which varies directly with Na/Cain the starting basalt. When projected into the Ab-An-Or-Qzquaternary system, all melts produced follow a rather narrowspiral path through the tetrahedron; they descend from the Ancorner, moving toward Qz at constant Ab/Or, moving toward Oronly when plagioclase± quartz begin to precipitate. The melting behavior of hornblende, plagioclase, and augitein these experiments has been examined closely, with the followingresults: successive partial melts may differ from each otherby compositional increments which are very different in compositionfrom the minerals contributing to the melt in the temperatureinterval under consideration. These increments can almost neverbe expressed solely in terms of members of the one or two mineralsolid solutions from which they are actually derived. In a fewcases the increments cannot be expressed in terms of any reasonablecombination of minerals. This pattern contrasts markedly withthat observed in fractional crystallization, in which the differencebetween successive melts must always correspond to present orpossible phenocryst minerals. The contrast implies that magmaseries generated by any kind of melting process, equilibriumor fractional, should be recognizably different from seriesgenerated by fractional crystallization, if minerals like hornblendeor pyroxene are involved.     

Concentrations and behavior of oxygen and oxide ion in melts of composition CaO · MgO · xSiO2

The concentrations and behavior of oxygen and oxide ion were studied in silicate melts of composition CaO · MgO · xSiO₂ (1.25 ≤ x ≤ 3) in the temperature range 1425 to 1575°C by cyclic voltammetry and chronopotentiometry. Electroreduction of oxygen is a reversible, 2 electron process involving dissociated oxygen atoms. The Henry's Law constant for O₂ in molten diopside (CaO · MgO · 2SiO₂) is 0.023 ± 0.004 mole/l atm at 1450°C. The diffusion coefficient for molecular oxygen in diopside melt is 4.5 ± .5 × 10^?6 cm²/sec at 1450°C and the activation energy of diffusion is 80 ± 2 kcal/mole. Oxide ions produced by electroreduction of oxygen, rapidly dissociate silicate polymers, causing the concentration of free oxide ions in diopside melt to be buffered at a low level (4.7 ± .8 × 10^?5 mole/l). The concentration of free oxide ion increases at higher proportions of metal oxides but remains at this value in more silicic melts. The rate of formation of oxide ions by polymerization in diopside melt is 0.021 ± .007 mole/l sec. Thermodynamic parameters (the standard free energy, enthalpy and entropy) for the oxidation of Ni, Co, and Zn in diopside melt in equilibrium with gaseous oxygen agree with those for solid oxide systems. The platinum reference electrode in molten diopside is a reversible, oxygen electrode.     

Structural controls and mechanisms of diffusion in natural silicate melts

The diffusion properties of Na, Cs, Ba, Fe and Eu ions have been determined experimentally for a pantellerite melt and of these ions plus Li, Mn and Co in pitchstone melt, using the radiotracer residual-activity method, and narrow platinum capillaries, over the temperature range 1,200–1,400° C. In addition, Eu diffusion in a basaltic and an andesitic melt was determined. Diffusion of all cations follows an Arrhenius relationship, activation energy values being high for diffusion in the pantellerite melt (e.g. Eu: 100 kcal mol^–1) except in the case of Na (24.3 kcal mol^–1). Activation energies of diffusion in the pitchstone melt are similar to values recorded earlier for andesitic and basaltic melts.The new data are used, along with previously published data for diffusion in other composition melts, to examine the compositional and structural controls on diffusion. The range of diffusivities shows a marked change with melt composition; over two orders of magnitude for a basaltic melt, and nearly four orders for a pantellerite melt (both at 1,300° C). Diffusivity of all cations (except Li and Na) correlates positively with the proportion of network modifying cations. In the case of Li and Na the correlation is negative but the diffusivity of these ions correlates positively with the proportion of Na or of Na + K ions in the bulk melt. Diffusion behaviour in the pantellerite melt departs from the relationships shown by the data for other melt compositions, which could be partly explained by trivalent ions (such as Fe) occupying network forming positions. The diffusivity of alkali metal ions is strongly dependent on ionic radius, but this is not the case with the divalent and trivalent ions; diffusivity of these ions remains relatively constant with change in radius but decreases with increase in ionic charge.A compensation diagram shows four distinct but parallel trends for the majority of the cations in four melt types but the data for Li and Na plot on a separate trend. This and the other relationships are used to elucidate possible mechanisms of diffusion. Exchange mechanisms appear to be common, with the preservation of local charge balance. Li and Na diffuse by a distinct mechanism which involves exchange of similar or identical ions. The diffusion behaviour of the smaller alkali metal ions is sufficiently distinct from all other cations to indicate that diffusion could be an important factor in the geochemical fractionation of the alkali elements.s     

Solubility of sulfur in some magmas at 1 atmosphere

In order to understand the distribution of sulfur in igneous rooks, we determined the solubility of sulfur in volcanic rock melts (tholeiite basalt, hawaiite and rhyodacite from Hawaii) at various gas compositions and at 1250° and 1300°C and 1 atm total pressure. The solubility of sulfur in the melt passes through a minimum with change in oxygen partial pressure, if other factors are held constant. For the basaltic liquid at 1200°C, most sulfur in the melt is as dissolved sulfide (S^?2) at oxygen partial pressures below 10^?8 atm and as dissolved sulfate at oxygen partial pressures above 10^?8 atm. Based on the present solubility data, 5 per cent is inferred for volcanic gas at 1 atm total pressure in equilibrium with subaerially extruded Hawaiian tholeiite basalt (Pele's hair with 180 ppm S) at 1200°C and 10^?8 atm P_O2.     

Melts of garnet lherzolite: experiments, models and comparison to melts of pyroxenite and carbonated lherzolite

Phase equilibrium experiments on a compositionally modified olivine leucitite from the Tibetan plateau have been carried out from 2.2 to 2.8 GPa and 1,380–1,480 °C. The experiments-produced liquids multiply saturated with spinel and garnet lherzolite phase assemblages (olivine, orthopyroxene, clinopyroxene and spinel ± garnet) under nominally anhydrous conditions. These SiO₂-undersaturated liquids and published experimental data are utilized to develop a predictive model for garnet lherzolite melting of compositionally variable mantle under anhydrous conditions over the pressure range of 1.9–6 GPa. The model estimates the major element compositions of garnet-saturated melts for a range of mantle lherzolite compositions and predicts the conditions of the spinel to garnet lherzolite phase transition for natural peridotite compositions at above-solidus temperatures and pressures. We compare our predicted garnet lherzolite melts to those of pyroxenite and carbonated lherzolite and develop criteria for distinguishing among melts of these different source types. We also use the model in conjunction with a published predictive model for plagioclase and spinel lherzolite to characterize the differences in major element composition for melts in the plagioclase, spinel and garnet facies and develop tests to distinguish between melts of these three lherzolite facies based on major elements. The model is applied to understand the source materials and conditions of melting for high-K lavas erupted in the Tibetan plateau, basanite–nephelinite lavas erupted early in the evolution of Kilauea volcano, Hawaii, as well as younger tholeiitic to alkali lavas from Kilauea.     

Solubility of carbon dioxide in melts of andesite,tholeiite, and olivine nephelinite composition to 30 kbar pressure

Carbon dioxide solubilities in H₂O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO₂ solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO₂ solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO₂ solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO₂ contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H₂O also affects the CO₂ solubility (20–30% more CO₂ dissolves in hydrous than in H₂O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO₂/(CO₂+H₂O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO₂ and H₂O are present a vapor phase must exist. Because the solubility of CO₂ in silicate melts is lower than that of H₂O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H₂O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H₂O+CO₂ parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.     

Quantitative Untersuchungen mit der Elektronen-Mikrosonde an Pyroxenen aus Basalten und Peridotit-Einschlüssen

The chemical composition of the pyroxenes and olivines of 12 basaltic rocks and 5 lherzolite nodules was determined quantitatively by electron micro-probe analysis. The composition of the pyroxenes depends on the type of basalt in which they occur. Tholeiitic basalts with normative quartz contain three pyroxenes: orthorombic pyroxenes, pigeonites and augites. All pyroxene phases are zoned and do not show any exsolution. Their Ti and Al contents (Ca-Tschermaks and Ti-augite molecules) are small. All pyroxene phases were formed under disequilibrium with each other and with the melt because of rapid quenching. The sequence of crystallization: orthopyroxene—pigeonite—augite could be established by their Cr content.The alkali olivine basalts undersatured in SiO₂ and the olivine nephelinites are characterized by Ti and Al-rich clinopyroxenes. The distribution of Ti and Al in the pyroxenes of the alkali olivine basalts shows a differentiation trend from the cores of the phenocrysts to their outer zones and to the crystals of the ground mass. Thereby the Ca-Tschermaks molecule is being replaced more and more by the Ti-augite molecule. The Ti content of the pyroxenes of the olivine nephelinites decreases in the last stage of differentiation because simultaneously increasing amounts of titaniferous magnetite crystallize.The pyroxenes of lherzolite peridotite nodules are characterized by high Al and low Ti contents which differ according to the type of basalt (alkali olivine basalt or olivine nephelinite) in which the nodules occur. The homogeneous distribution of the elements within the single grains indicates crystallization under equlibrium conditions. The conditions of their formation are comparable to those of Al-pyroxene peridotites in the upper mantle. The composition of pyroxenes of early accumulates of alkali basaltic melts differ from those of peridotite nodules. Therefore lherzolite nodules can be taken as residues of deeper peridotite masses.     

Formation of plagioclase-bearing peridotite and plagioclase-bearing wehrlite and gabbro suite through reactive crystallization: an experimental study

Plagioclase-bearing peridotites are commonly associated with gabbroic rocks sampled around the Moho Transition Zone. Based on mineral chemistry, texture, and spatial relations, the formation of plagioclase-bearing peridotites has been attributed to impregnation of basalt into residual peridotites. We conducted reactive dissolution and crystallization experiments to test this hypothesis by reacting a primitive mid-ocean ridge basalt with a melt-impregnated lherzolite at 1,300 °C and 1 GPa and then cooling to 1,050 °C as pressure decreased to 0.7 GPa. Crystallization during cooling produced lithologic sequences of gabbro–wehrlite or gabbro–wehrlite–peridotite, depending on reaction time. Wehrlitic and peridotitic sections contain significant amounts of plagioclase interstitial to olivine and clinopyroxene and plagioclase compositions are spatially homogeneous. Clinopyroxene in the wehrlite–peridotite section is reprecipitated from the melt and exhibits poikilitic texture with small rounded olivine chadacrysts. Mineral composition in olivine and clinopyroxene varies spatially, both at the scale of the sample and within individual grains. Olivine grains that crystallized close to the melt–peridotite interface are enriched in iron due to their proximity to the basaltic melt reservoir. Consistent with many field studies, we observed gradual spatial variation in olivine and clinopyroxene composition across a lithologically sharp boundary between the gabbro and wehrlite–peridotite. Plagioclase compositions show no obvious dependence on distance from the melt–rock interface and were precipitated from late-stage trapped melts. Compositional trends of olivine, pyroxene, and plagioclase are consistent with previous experimental results and natural observations of the Moho Transition Zone. Different lithological sequences form based primarily on the melt–rock ratio, composition of the melt and host peridotite, and thermochemical conditions, but are expected to grade from gabbro to wehrlite or troctolite to peridotite. Plagioclase-bearing peridotite represents the low melt–rock ratio end member where pyroxene is only partially replaced by olivine and melt, whereas dunite is expected to form where melts overwhelm and consume all other phases. This study confirms that under nominally anhydrous conditions, the gabbro–wehrlite–plagioclase-peridotite sequence can be formed by reaction between basalt and lherzolite and subsequent crystallization at intermediate to low pressures. Melt–rock reaction is a fundamental process in the formation of new crust at the shallowest part of the melting column where pyroxene-undersaturated melts percolate through depleted peridotite.     

Physicochemical conditions of magma formation at the base of the Siberian plume: Insight from the investigation of melt inclusions in the meymechites and alkali picrites of the Maimecha-Kotui province

Based on the compositions of melt inclusions and coexisting minerals from meymechites and alkali picrites, the temperatures and pressures of the ascending material of the Siberian plume were estimated at the level of the lithosphere-asthenosphere boundary. The melts trapped in olivine show high contents of titanium and other incompatible elements. The rocks crystallized under high oxygen fugacity conditions. The calculated compositions of primary magmas are similar to the compositions of near-solidus melts derived from a dry fertile lherzolite at 7 GPa. The estimated potential temperature is close to 1650°C, which is much higher than the potential temperature of plumes that generate the primary basaltic magmas of mid-ocean ridges. The obtained data show that, during the activity of the giant magma-generating system of the Siberian trap province, hot peridotite masses ascended probably from the core-mantle boundary up to the base of the continental lithosphere. Our results are at odds with the suggestion that the basalt flows of the Siberian and other large igneous provinces are not related to mantle plumes.     

Ultramafic inclusions in basaltic rocks from Hawaii

Ultramafic inclusions and the enclosing basaltic rocks were collected from a number of localities in the Hawaiian Islands; these and other specimens were studied by standard pétrographic techniques and with an electron microprobe. Emphasis was on determination of mineral assemblages, mineral compositions, and variations in composition. Sixty-eight inclusions and thirteen basaltic rocks are described, with partial chemical analyses (Ti, Al, Cr, Fe, Mn, Ni, Mg, Ca, Na, K) of olivines, orthopyroxenes, clinopyroxenes, and some feldspars and other minerals. Inclusions range from dunite to anorthosite, and basaltic hosts range from olivine nephelinite to olivine tholeiite. The inclusions are separable into three categories, which correlate with three groups basaltic hosts: Lherzolite inclusions are relatively poor in Fe, and the component minerals have limited ranges of composition. In Hawaii, lherzolite inclusions occur preferentially in extremely undersaturated hosts (olivine nephelinite, nepheline basanite, and ankaratrite). Other varieties of inclusions (dunite, wehrlite, feldspathic peridotite, pyroxenite) are relatively rich in Fe, and the component minerals have wider ranges of composition. These inclusions, together with gabbro, occur preferentially in hosts which are but moderately undersaturated (alkaline olivine basalt, hawaiite, and ankaramite). The sparse inclusions in nearly-saturated basalt (olivine tholeiite) are petrographically distinct from those in the other two categories. These correlations suggest that the inclusions and the enclosing basaltic rocks are genetically related. As the three suites of inclusions differ chemically, mineralogically, physically, and texturally, more than one origin is probable.     

胜利油田火山岩类、盆地演化及其CO2-Au成藏成矿效应

将胜利油田盆地内火山岩类分为石英拉斑玄武岩、橄榄拉斑玄武岩和碱性橄榄玄武岩3类。其中,碱性橄榄玄武岩多分布于盆地边部、出现较晚并受深断裂控制,其成分中明显更富碱、富轻稀土、富大离子亲石元素而贫铬、镍等相容元素和挥发分,深度大而熔融程度不高,应源于富集地幔。二氧化碳气藏与碱性橄榄玄武岩有空间、时间和成因上的关系;二氧化碳气藏区的火山岩中含有高含量的金。二氧化碳和金是盆地和火山岩类演化一定阶段的产物,源于富集地幔的岩浆去气是其形成的主要机制。     

Silica enrichment of Group II xenoliths by evolved alkali basalt from Jeju Island, South Korea: implication for modification of intraplate deep-seated rocks

Group II xenoliths, corresponding to the lithology of dunite, wehrlite to olivine clinopyroxenite and olivine websterite to websterite, occur in Pleisto-Holocene alkali basalts from Jeju Island, South Korea. The large grain size (up to 5?mm), moderate mg# [=100?×?Mg/(Mg?+?Fe_total) atomic ratio] of olivine (79–82) and pyroxenes (77–83), and absence of metamorphic textural features indicate that they are cumulates of igneous origin. Based on textural features, mineral equilibria and major and trace element variations, it can be inferred that the studied xenoliths were crystallized from basaltic melts enriched in incompatible trace elements and belong to the Jeju Pleisto-Holocene magma system. They appear to have been emplaced near the present Moho, an estimated 5–8?kbars beneath Jeju Island. Consolidation of cumulates was followed by infiltration of silica-enriched metasomatic melt, producing secondary orthopyroxenes at the expense of olivine. The metasomatic agent appears to have been a silica-enriched residual melt evolved from an initially slightly silica-undersaturated alkali basalt to silica-saturated compositions by fractional crystallization under relatively high pressure conditions. The result of this study indicates that relatively young olivine-bearing cumulates could have been metasomatized by a silica-enriched melt within underplates, suggesting that silica enrichment can occur in intraplate Moho-related rocks as well as in the upper mantle of the subarc area.     

Deep differentiation of alkali ultramafic magmas: Formation of carbonatite melts

The study of melt microinclusions in olivine megacrysts from meimechites and alkali picrites of the Maimecha–Kotui alkali ultramafic and carbonatite province (Polar Siberia) revealed that the melt compositions corrected for loss of olivine due to post-entrapment crystallization of olivine on inclusion walls (differentiates of primary meimechite magma) match well to the composition of nephelinites and olivine melilitites belonging to carbonatite magmatic series. Modeling of fractional crystallization of meimechite magmas results in the high-alkali melt compositions corresponding to the silicate–carbonate liquid immiscibility field. The appearance of volatile-rich melts at the base of magma-generating plume systems at early stages of partial melting can be explained by extraction of incompatible elements including volatiles, by near-solidus melts at low degrees of partial melting, and meimechites are an example of such magmas. Subsequent accumulation of CO₂ in the residual melt results in generation of carbonate magma.     

Dissolution Rates of Upper Mantle Minerals in an Alkali Basalt Melt at High Pressure: An Experimental Study and Implications for Ultramafic Xenolith Survival

The dissolution rates of the major upper mantle minerals olivine,orthopyroxene, clinopyroxene, spinel, and garnet have been determinedin an alkali basalt melt at superliquidus temperatures and 5,12, and 30 kb. At low pressure where olivine is the liquidusphase of the basalt, olivine has a slower dissolution rate thanclinopyroxene; however, at higher pressure where clinopyroxeneis the liquidus phase, clinopyroxene has a slower dissolutionrate than olivine. The relative rates of dissolution of olivineand clinopyroxene at each pressure are, therefore, governedby their relative stabilities in the melt and hence by the structureof the melt. As the degree of superheating above the liquidusincreases at each pressure, the dissolution rates of olivineand clinopyroxene converge, suggesting that the melt undergoestemperature-induced structural changes. Orthopyroxene has a dissolution rate similar to olivine at highpressure and similar to clinopyroxene at low pressure. Spinelhas the slowest dissolution rate at each pressure. Garnet dissolvesvery rapidly at 12 kb and at a comparable rate of olivine at30 kb. The dissolution rates determined in the experiments varyfrom 9.21 ? 10^–9cm s^–1 for spinel at 5 kbar and1250?C to 3.83 ? 10^–5cm s^–1 for garnet at 30 kband 1500?C. Textures produced during the dissolution experiments are relatedto mineral stability in the melt at each pressure and are independentof the degree of superheating. The mineral phases that are stableon or near the liquidus exhibit no reaction; whereas complexreaction textures and crystallization characterize dissolutionof minerals that are relatively unstable in the melt. Concentration profiles in the melt adjacent to the same crystalfor different experimental durations are identical, indicatingthat dissolution is time-independent and a steady-state process.However, cation diffusion coefficients calculated for single-componentoxides in the melt reveal that dissolution may not be completelycontrolled by diffusion of cations away from the crystal/meltinterface. The apparent diffusivities positively correlate withthe dissolution rate, which suggests that the stability of themineral is an important factor to consider when deriving diffusioncoefficients from these experiments. Other factors that maybe involved are multi-component effects and the nature of thediffusing species in the melt. A simple model has been constructed that predicts the survivalof ultramafic xenoliths in alkali basalt magmas as a functionof xenolith radius, magma ascent time and superheating. Theresults of the model suggest that the relative proportions ofperidotite and pyroxenite xenoliths brought to the surface inalkali basalts are generally representative of their proportionsas constituents of the upper mantle. Further experiments usingdifferent melt compositions are required to extend the model.     

Trace Element Geochemistry of Tertiary Continental Alkali Basalts from the Liuhe—Yizheng Area,Jiangsu Province,China

Reported in this paper are the chemical compositions and trace element (REE,Ba,Rb,Sr,Nb,Zr,Ni,Cr,V,Ga,Y,Sc,Zn,Cu,etc)abundances of Tertiary continental alkali basalts from the Liube-yizheng area,Jiangsu Province,China.The olivine basalt,alkali olivine basalt and basanite are all derived from evolved melts which were once af-fected by different degrees of fractional crystallization of olivine and clinopyroxene(1:2)under high pres-sures.The initial melts were derived from the garnet lherzolite-type mantle source through low-degree par-tial melting.The mantle source has been affected by recent mantle-enrichment events(e.g.mantle metasomatism),resulting in incompatible trace element enrichment and long-term depletion of radiogenic isotopic compositions of Sr and Nd.     

Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion

Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO₂. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10^–6cm²/s and D=1.43×10^–7cm²/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm²/s for the basalt and D=52.5exp(–60,060±4900/RT)cm²/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10^-2 to 10² m over the time interval of 1 to 10⁶ years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.     

Anhydrous melting of peridotite at 0–15 Kb pressure and the genesis of tholeiitic basalts

The anhydrous melting behaviour of two synthetic peridotite compositions has been studied experimentally at temperatures ranging from near the solidus to about 200° C above the solidus within the pressure range 0–15 kb. The peridotite compositions studied are equivalent to Hawaiian pyrolite and a more depleted spinel lherzolite (Tinaquillo peridotite) and in both cases the experimental studies used peridotite –40% olivine compositions. Equilibrium melting results in progressive elimination of phases with increasing temperature. Four main melting fields are recognized; from the solidus these are: olivine (ol)+orthopyroxene (opx)+clinopyroxene (cpx)+Al-rich phase (plagioclase at low pressure, spinel at moderate pressure, garnet at high pressure)+liquid (L); ol+opx+cpx+Cr-spinel+L; ol+opx+Cr-spinel +L: ol±Cr-spinel+L. Microprobe analyses of the residual phases show progressive changes to more refractory compositions with increasing proportion of coexisting melt i.e. increasing Mg/(Mg+Fe) and Cr/(Cr+Al) ratios, decreasing Al₂O₃, CaO in pyroxene.The degree of melting, established by modal analysis, increases rapidly immediately above the solidus (up to 10% melting occurs within 25°–30° C of the solidus), and then increases in roughly linear form with increasing temperature.Equilibrium melt compositions have been calculated by mass balance using the compositions and proportions of residual phases to overcome the problems of iron loss and quench modification of the glass. Compositions from the melting of pyrolite within the spinel peridotite field (i.e. 15 kb) range from alkali olivine basalt (<15% melting) through olivine tholeiite (20–30% melting) and picrite to komatiite (40–60% melting). Melting in the plagioclase peridotite field produces magnesian quartz tholeiite and olivine-poor tholeiite and, at higher degrees of melting (30–40%), basaltic or pyroxenitic komatiite. Melts from Tinaquillo lherzolite are more silica saturated than those from pyrolite for similar degrees of partial melting, and range from olivine tholeiite through tholeiitic picrite to komatiite for melting in the spinel peridotite field.The equilibrium melts are compared with inferred primary magma compositions and integrated with previous melting studies on basalts. The data obtained here and complementary basalt melting studies do not support models of formation of oceanic crust in which the parental magmas of common mid-ocean ridge basalts (MORB) are attributed to segregation from source peridotite at shallow depths ( 25 km) to leave residual harzburgite. Liquids segregating from peridotite at these depths are more silica-rich than common MORB.     

Experimental testing of olivine–melt equilibrium models at high temperatures

Data are presented on the equilibrium compositions of olivine and melts in the products of 101 experiments performed at 1300–1600°C, atmospheric pressure, and controlled oxygen fugacity by means of new equipment at the Vernadsky Institute. It was shown that the available models of the olivine–melt equilibrium describe with insufficient adequacy the natural systems at temperatures over 1400°C. The most adequate is the model by Ford et al. (1983). However, this model overestimates systematically the equilibrium temperature with underestimating by 20–40°C at 1450–1600°C. These data point to the need for developing a new, improved quantitative model of the olivine–melt equilibrium for high-temperature magnesian melts, as well as to the possibility of these studies on the basis of the equipment presented.     

Ultramafic inclusions and high pressure megacrysts from a nephelinite sill,Nandewar Mountains,north-eastern New South Wales,and their bearing on the origin of certain ultramafic inclusions in alkaline volcanic rocks

Ultramafic inclusions and megacrysts are unusually abundant in a nephelinite sill in the Nandewar Mountains in north-eastern New South Wales. The inclusions are divisible into a Cr-diopside group and a Ti-augite group, the former being dominated by Cr-spinel Iherzolites of restricted modal composition, the latter by olivine and titaniferous Al-rich clinopyroxene assemblages which vary widely in their modal proportions. The principal megacryst species are olivine and black, titaniferous Al-rich clinopyroxene; additional but comparatively rare megacrysts include titanphlogopite, kaersutitic amphibole, and deep green, relatively Fe-rich clinopyroxene. The Cr-spinel Iherzolites conform closely in mineralogy and chemistry with the spinel lherzolites which dominate upper mantle xenolith assemblages in alkaline mafic volcanic rocks from other provinces. Megacrysts and Ti-augite inclusion mineral assemblages are consistently more Fe-rich than analogous phases in the Cr-diopside xenoliths and also display more extensive cryptic variation. The available experimental data on the high pressure liquidus or near-liquidus phases in olivine nephelinite and related compositions indicate that the olivine and black clinopyroxene megacrysts were precipitated at pressures in the vicinity of 15–20 kb. The similarity in the nature and compositions of the principal megacryst species to analogous phases in the Tiaugite group of inclusions indicates that the latter also represent cognate cumulates derived from the olivine nephelinite at broadly comparable pressures. High pressure fractionation of the host olivine nephelinite liquid, controlled mainly by the separation of olivine and aluminous clinopyroxene, produced only comparatively minor compositional changes in the derivative liquid. The hiatus in olivine compositions at approximately Fo_86–88, apparently characteristic of the olivines in coexisting Cr-diopside and Ti-augite inclusions, is assessed in terms of the compositions of olivine in equilibrium with alkali basaltic liquids at high pressures.