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1.
Partition coefficients for a range of Rare Earth Elements (REEs), Y, Sc, Al and Zr were determined between forsteritic olivine (nearly end-member Mg2SiO4) and ten melt compositions in the system CaO-MgO-Al2O3-SiO2 (CMAS) at 1 bar and 1400 °C, with concentrations of the trace elements in the olivine and the melt measured by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The REEs and Sc were added at levels sufficient to ensure that concentrations in the olivine were well above the detection limits. The REE partition coefficients decrease with increasing silica in the melt, indicating strong bonding between REEO1.5 and SiO2 in the melt. The variation of as a function of ionic radius is well described by the Brice equation for each composition, although a small proportion of this variation is due to the increase in the strength of the REEO1.5-SiO2 interactions in the melt with ionic radius. Scandium behaves very similarly to the REEs, but a global fit of the data from all ten melt compositions suggests that deviates somewhat from the parabolas established by the REE and Y, implying that Sc may substitute into olivine differently to that of the REEs. In contrast to the behaviour of the large trivalent cations, the concentration of Al in olivine is proportional to the square root of its concentration in the melt, indicating a coupled substitution in olivine with a high degree of short-range order. The lack of any correlation of REE partition coefficients with Al in olivine or melt suggests that the REE substitution in olivine is charge-balanced by cation vacancies. The partition coefficient of the tetravalent trace element Zr, which is highly incompatible in olivine, depends on the CaO content of the melt.  相似文献   

2.
The chemical compositions of melt inclusions in a primitive and an evolved basalt recovered from the mid-Atlantic ridge south of the Kane Fracture Zone (23°–24°N) are determined. The melt inclusions are primitive in composition (0.633–0.747 molar Mg/(Mg+Fe2+), 1.01–0.68 wt% TiO2) and are comparable to other proposed parental magmas except in having higher Al2O3 and lower CaO. The primitive melt inclusion compositions indicate that the most primitive magmas erupted in this region are not near primary magma compositions. Olivine and plagioclase microphenocrysts are close to exchange equilibrium with their respective basalt glasses, whose compositions are displaced toward olivine from 1 atm three phase saturation. The most primitive melt inclusion compositions are close to exchange equilibrium with the anorthitic cores of zoned plagioclases (An78.3-An83.1; the hosts for the melt inclusions in plagioclase) and with olivines more forsteritic (Fo89-Fo91) than the olivine microphenocrysts (the hosts for the melt inclusions in olivine). Xenocrystic olivine analyzed is Fo89 but contains no melt inclusions. These observations indicate that olivines have exchanged components with the melt after melt inclusion entrapment, whereas plagioclase compositions have remained the same since melt inclusion entrapment. Common denominator element ratio diagrams and oxide versus oxide variation diagrams show that the melt inclusion compositions, which represent liquids higher along the liquid line of descent, are related to the glass compositions by the fractionation of olivine, plagioclase and clinopyroxene (absent from the mincral assemblage), probably occurring at elevated pressures. A model is proposed whereby clinopyroxene segregates from the melt at elevated pressures (to account for its absence in the erupted lavas that have the chemical imprint of clinopyroxene fractionation). Zoned plagioclases in the erupted lavas are thought to be survivors of decompressional melting during magma ascent. Since similar primitive melt inclusions occur in olivine microphenocrysts and in the cores of zoned plagioclases, any model must account for all phases present.  相似文献   

3.
Olivine is abundant in Earth’s upper mantle and ubiquitous in basaltic lavas, but rarely occurs in eclogite. Partial melts of eclogite are, therefore, not in equilibrium with olivine, and will react with peridotite as they migrate through the upper mantle. If such melts erupt at Earth’s surface, their compositions will be highly modified and they may be olivine-saturated. We investigated experimentally the reaction between olivine and siliceous eclogite partial melt, and determined element partitioning between olivine and the melt produced by this reaction. Our results demonstrate that mixing of reacted eclogite partial melt with primitive basalt is capable of producing the positive correlation between melt SiO2 content and olivine Ni content observed in some Hawaiian lavas. Experiments were carried out by equilibrating eclogite partial melt or basalt with San Carlos olivine at 1 bar and 1,201–1,350°C. Our results show that eclogite partial melts equilibrated with mantle olivine retain their high SiO2, low FeO and MgO characteristics. Further, olivine-melt partition coefficients for Ni measured in these experiments are significantly larger than for basalt. Mixing of these melts with primitive Hawaiian tholeiitic lavas results in crystallization of high-Ni olivines similar to those in Makapuu-stage Koolau lavas, even though the mixed magmas have only moderate Ni contents. This results from a hyperbolic increase of the Ni partition coefficient with increasing polymerization of the mixed melt. Note that while eclogite partial melt in contact with peridotite will equilibrate with pyroxene as well as olivine, this will have the effect of buffering the activity of SiO2 in the reacted melt at a higher level. Therefore, an eclogite partial melt equilibrated with harzburgite will have higher SiO2 than one equilibrated with dunite, enhancing the effects observed in our experiments. Our results demonstrate that an olivine-free “hybrid” pyroxenite source is not required to explain the presence of high-Ni olivines in Hawaiian lavas and, therefore, indicate that the proportion of eclogite in the Hawaiian plume is less than has been estimated in recent studies.  相似文献   

4.
Olivine/melt partitioning of ΣFe, Fe2+, Mg2+, Ca2+, Mn2+, Co2+, and Ni2+ has been determined in the systems CaO-MgO-FeO-Fe2O3-SiO2 (FD) and CaO-MgO-FeO-Fe2O3-Al2O3-SiO2 (FDA3) as a function of oxygen fugacity (fO2) at 0.1 MPa pressure. Total iron oxide content of the starting materials was ∼20 wt%. The fO2 was to used to control the Fe3+/ΣFe (ΣFe: total iron) of the melts. The Fe3+/ΣFe and structural roles of Fe2+ and Fe3+ were determined with 57Fe resonant absorption Mössbauer spectroscopy. Changes in melt polymerization, NBO/T, as a function of fO2 was estimated from the Mössbauer data and existing melt structure information. It varies by ∼100% in melts coexisting with olivine in the FDA3 system and by about 300% in the FD system in the Fe3+/ΣFe range of the experiments (0.805-0.092). The partition coefficients ( in olivine/wt% in melt) are systematic functions of fO2 and, therefore, NBO/T of the melt. There is a -minimum in the FDA3 system at NBO/T-values corresponding to intermediate Fe3+/ΣFe (0.34-0.44). In the Al-free system, FD, where the NBO/T values of melts range between ∼1 and ∼2.9, the partition coefficients are positively correlated with NBO/T (decreasing Fe3+/ΣFe). These relationships are explained by consideration of solution behavior in the melts governed by Qn-unit distribution and structural changes of the divalent cations in the melts (coordination number, complexing with Fe3+, and distortion of the polyhedra).  相似文献   

5.
Relationships between mineral/silicate melt partition coefficients and melt structure have been examined by combining Ca and Mn olivine/melt partitioning data with available melt structure information. Compositions were chosen so that melts with olivine on their liquidii range in degree of polymerization, NBO/T, from ∼0.5 to ∼2.5 under near isothermal conditions (1350-1400°C). Olivine/melt Ca-Mn exchange coefficients, Ca(olivine)/CaO(melt)/MnO(olivine)/MnO(melt) (KD Ca-Mnolivine/melt), as a function of melt NBO/T have a parabolic shape with a minimum KD Ca-Mnolivine/melt-value at NBO/T near 1. Notably, published KD Fe2+-Mgolivine/melt versus NBO/T functions are also parabolic with a maximum in KD Fe2+-Mgolivine/melt near 1 (Kushiro and Mysen, 2002).The olivine/melt partitioning data are modeled in terms of structural units (Qn-species) in the melt. The NBO/T-value corresponding to the minimum KD Ca-Mnolivine/melt is near that where the abundance ratio of Qn-species, XQ3/XQ2, has its largest value. Therefore, the activity coefficient ratio in the melt, γCa2+(melt)/γMn2+(melt), attains a minimum where the abundance ratio of XQ3/XQ2 is at maximum. It is inferred from this relationship that Ca2+ in the melts is dominantly bonded to nonbridging oxygen (Ca-NBO) in Q3-species, whereas Mn2+ is bonded to nonbridging oxygen (Mn-NBO) in less polymerized Qn-species such as Q2.  相似文献   

6.
Molten high-temperature solvents can provide major kinetic advantages in phase equilibrium studies of silicate systems, by markedly enhancing rates of crystal growth and chemical reaction. Experience gained in a study of cation partitioning between ortho-and clinopyroxene at low temperatures and atmospheric pressure suggests that an ideal solvent would combine the following properties: high solubilities for component oxides of silicates, with minimum temperature dependence; no formation of oxide-solvent compounds with melting points above that of the pure solvent; minimal incorporation of solvent components into the crystalline phases of interest; ease of chemical separation of crystalline phases from quenched solvent-rich melt; low volatility and viscosity; density close to that of the crystalline phases; and high surface tension against encapsulation materials, typically platinum. Maximum kinetic benefits of the technique are derived only when the composition of saturated solvent-rich melt is carefully determined as a function of temperature, so that melt-to-crystal ratios in experimental charges can be raised to high values. V2O5 is one solvent suitable for studies involving olivine, pyroxenes, and plagioclase in the system CaO-MgO-Al2O3-SiO2 and its subsystems.  相似文献   

7.
Glass inclusions in olivines of the Renazzo, El Djouf 001, and Acfer 182 CR-type chondrites are chemically divers and can be classified into Al-rich, Al-poor, and Na-rich types. The chemical properties of the glasses are independent of the occurrence of the olivine (isolated or part of an aggregate or chondrule) and its composition. The glasses are silica-saturated (Al-rich) or oversaturated (Al-poor, 24% normative quartz). All glasses have chondritic CaO/Al2O3 ratios, unfractionated CI-normalized abundances of refractory trace elements and are depleted in moderately volatile and volatile elements. Thus the glasses are likely to be of a primitive condensate origin whose chemical composition has been established before chondrule formation and accretion, rather then the product of either crystal fractionation from chondrule melts or part melting of chondrules. Rare Na-rich glasses give evidence for elemental exchange between the glass and a vapor phase. Because they have Al2O3 contents and trace element abundances very similar to those of the Al-rich glasses, they likely were derived from the latter by Ca exchange (for Na) with the nebula. Elemental exchange reactions also have affected practically all olivines (e.g., exchange of Mg of olivine for Fe2+, Mn2+, and Cr3+). Glasses formed contemporaneously with the host olivine. As the most likely process for growing nonskeletal olivines from a vapor we consider the VLS (vapor-liquid-solid) growth process, or liquid-phase epitaxy. Glasses are the possible remnants of the liquid interface between growing crystal and the vapor. Such liquids can form stably or metastably in regions with enhanced oxygen fugacity as compared to that of a nebula of solar composition.  相似文献   

8.
The influence on olivine/melt transition metal (Mn, Co, Ni) partitioning of substitution in the tetrahedral network of silicate melt structure has been examined at ambient pressure in the 1450-1550 °C temperature range. Experiments were conducted in the systems NaAlSiO4-Mg2SiO4- SiO2 and CaAl2Si2O8-Mg2SiO4-SiO2 with about 1 wt% each of MnO, CoO, and NiO added. These compositions were used to evaluate how, in silicate melts, substitution and ionization potential of charge-balancing cations affect activity-composition relations in silicate melts and mineral/melt partitioning.The exchange equilibrium coefficient, , is a positive and linear function of melt Al/(Al + Si) at constant degree of melt polymerization, NBO/T. The is negatively correlated with the ionic radius, r, of the M-cation and also with the ionization potential (Z/r2, Z = electrical charge) of the cation that serves to charge-balance Al3+ in tetrahedral coordination in the melts. The activity coefficient ratio, (γM/γMg)melt, is therefore similarly correlated.These melt composition relationships are governed by the distribution of Al3+ among coexisting Q-species in the peralkaline (depolymerized) melts coexisting with olivine. This distribution controls Q-speciation abundance, which, in turn, controls (γM/γMg)melt and . The relations between melt structure and olivine/melt partitioning behavior lead to the suggestion that in natural magmatic systems mineral/melt partition coefficients are more dependent on melt composition and, therefore, melt structure the more alkali-rich and the more felsic the melt. Moreover, mineral/melt partition coefficients are more sensitive to melt composition the more highly charged or the smaller the ionic radius of the cation of interest.  相似文献   

9.
Closed hopper and complex swallowtail morphologies of olivine microcrysts have been described in the past in both mid-oceanic ridge basalts and subaerial tholeitic volcanoes and indicate fluctuations in magma undercooling. We describe similar morphologies in a Mid-Atlantic ridge pillow basalt (sample RD87DR10), and in addition we estimate the duration of temperature fluctuations required to produce these textures as follows: (1) Pairs of melt inclusions are arranged symmetrically around the centre of hopper crystals and each pair represents a heating–cooling cycle. Using the literature olivine growth rates relevant to the observed morphologies, and measuring the distance between two successive inclusions, we estimate the minimum time elapsed during one convection cycle. (2) The major element composition of melt inclusions (analysed by electron microprobe) was found to be in the range of the boundary layer measured in the glass surrounding the olivines, irrespective of their size. Several major elements demonstrate that this boundary layer results from rapid quenching on the seafloor, and not from crystal growth at depth, implying the inclusions had the same composition as the surrounding magma when they were sealed. Using diffusivity of slow diffusing elements such as Al2O3, we estimate the minimum time required for inclusion formation. These two independent approaches give concordant results: each cooling–heating cycle lasted between a few minutes and 1 h minimum. Thus, these crystals probably recorded thermal convection in small magmatic bodies (a dyke or shallow magma chamber) during the last hour or hours before eruption.  相似文献   

10.
The heat capacity and vibrational entropy of a calcium aluminate and three peraluminous calcium aluminosilicate glasses have been determined from 2 to 300 K by heat-pulse relaxation calorimetry. Together with previous adiabatic data for six other glasses in the system CaO-Al2O3-SiO2, these results have been used to determine partial molar heat capacities and entropies for five species namely, SiO2, CaO and three different sorts of Al2O3 in which Al is 4-, 5- and 6-fold coordinated by oxygen. Given the determining role of oxygen coordination on low-temperature heat capacity, the composition independent entropies found for SiO2 and CaO indicate that short-range order around Si and Ca is not sensitive to aluminum speciation up to the highest fraction of 25% observed for VAl by NMR spectroscopy. Because of the higher room-temperature vibrational entropy of IVAl2O3 (72.8 J/mol K) compared to VAl2O3 (48.5 J/mol K), temperature-induced changes from IVAl to VAl give rise to a small negative contribution of the order of 1 J/mol K to the partial molar configurational heat capacity of Al2O3 in melts. Near 0 K, pure SiO2 glass distinguishes itself by the importance of the calorimetric boson peak. On a g atom basis, the maximum of this peak varies with the composition of calcium aluminosilicate glasses by a factor of about 2. It does not show smooth variations, however, either as a function of SiO2 content, at constant CaO/Al2O3 ratio, or as a function of Al2O3 content, at constant SiO2 content.  相似文献   

11.
An experimental method of melt inclusion synthesis within olivine crystals has been developed to determine the composition of the melt present in a partially molten peridotite assemblage. Trace element doped peridotite was equilibrated with 5 wt% of a C-O-H volatile source at 20 kbar/1175 °C in a piston-cylinder apparatus under buffered oxygen and sulphur fugacity conditions [log(f O2) ∼ IW +1 log unit, log (f S2) ∼ Fe/FeS > +1 log unit]. A single crystal of olivine, which had been cut to a disc shape, was included in the sample capsule. At run conditions the peridotite charge formed olivine, orthopyroxene, clinopyroxene, Fe-Ni sulphide and a volatile-bearing melt. The melt phase is preserved as homogeneous glass inclusions up to 50 μm in size, trapped in situ in the olivine disc. The major element composition of the glass inclusions showed them to be of broadly basaltic character, but with a low Mg/(Mg + ΣFe), which is associated with precipitation of olivine from the melt inclusion onto the walls of the olivine disc during quenching. Thus the equilibrium melt composition has been calculated from the glass inclusion composition by addition of olivine component using the Fe/Mg exchange coefficient of Roeder and Emslie (1970); the desired Mg/(Mg + ΣFe) being determined from the composition of olivine formed at run conditions in the peridotite section of the charge. The melt composition obtained is close to the trend for dry melting established by Falloon and Green (1988), and it is evident that although the reduced volatiles in this case have induced a liquidus depression of some 250 °C, there has been only a small shift in melt composition. Trace element, carbon and hydrogen contents of thirteen melt inclusions have been determined by secondary ion mass spectrometry (SIMS). The trace element signature is consistent with ∼29% melting in equilibrium with a lherzolitic assemblage. The equilibrium melt has a C/H of 0.48 by weight. Carbon solubility in partial melts is thus significant under reducing conditions in the presence of dissolved “water components” and establishes a major melt fluxing role for carbon in the upper mantle. The ubiquitous presence of carbon and hydrogen in basaltic magmas underscores the importance of determining both the position of vapour-present solidi and the composition of melts generated, when developing petrogenetic models. Received: 1 July 1996 / Accepted: 25 June 1997  相似文献   

12.
The effect of sulfur dissolved as sulfide (S2−) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al2O3-SiO2 (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S2− were varied from zero to sulfide saturation, reaching 4100 μg g−1 S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S2− in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M2+, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S2− nor of Mg#ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S2− depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10−3 (±1.3 × 10−3) K per μg g−1 of S2−, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO2 content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10−3. The ratio / is well constrained at 0.611 ± 0.016.  相似文献   

13.
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  相似文献   

14.
Primitive chemical characteristics of high-Mg andesites (HMA) suggest equilibration with mantle wedge peridotite, and they may form through either shallow, wet partial melting of the mantle or re-equilibration of slab melts migrating through the wedge. We have re-examined a well-studied example of HMA from near Mt. Shasta, CA, because petrographic evidence for magma mixing has stimulated a recent debate over whether HMA magmas have a mantle origin. We examined naturally quenched, glassy, olivine-hosted (Fo87–94) melt inclusions from this locality and analyzed the samples by FTIR, LA-ICPMS, and electron probe. Compositions (uncorrected for post-entrapment modification) are highly variable and can be divided into high-CaO (>10 wt%) melts only found in Fo > 91 olivines and low-CaO (<10 wt%) melts in Fo 87–94 olivine hosts. There is evidence for extensive post-entrapment modification in many inclusions. High-CaO inclusions experienced 1.4–3.5 wt% FeOT loss through diffusive re-equilibration with the host olivine and 13–28 wt% post-entrapment olivine crystallization. Low-CaO inclusions experienced 1–16 wt% olivine crystallization with <2 wt% FeOT loss experienced by inclusions in Fo > 90 olivines. Restored low-CaO melt inclusions are HMAs (57–61 wt% SiO2; 4.9–10.9 wt% MgO), whereas high-CaO inclusions are primitive basaltic andesites (PBA) (51–56 wt% SiO2; 9.8–15.1 wt% MgO). HMA and PBA inclusions have distinct trace element characteristics. Importantly, both types of inclusions are volatile-rich, with maximum values in HMA and PBA melt inclusions of 3.5 and 5.6 wt% H2O, 830 and 2,900 ppm S, 1,590 and 2,580 ppm Cl, and 500 and 820 ppm CO2, respectively. PBA melts are comparable to experimental hydrous melts in equilibrium with harzburgite. Two-component mixing between PBA and dacitic magma (59:41) is able to produce a primitive HMA composition, but the predicted mixture shows some small but significant major and trace element discrepancies from published whole-rock analyses from the Shasta locality. An alternative model that involves incorporation of xenocrysts (high-Mg olivine from PBA and pyroxenes from dacite) into a primary (mantle-derived) HMA magma can explain the phenocryst and melt inclusion compositions but is difficult to evaluate quantitatively because of the complex crystal populations. Our results suggest that a spectrum of mantle-derived melts, including both PBA and HMA, may be produced beneath the Shasta region. Compositional similarities between Shasta parental melts and boninites imply similar magma generation processes related to the presence of refractory harzburgite in the shallow mantle.  相似文献   

15.
We propose a theory for crystal-melt trace element partitioning that considers the energetic consequences of crystal-lattice strain, of multi-component major-element silicate liquid mixing, and of trace-element activity coefficients in melts. We demonstrate application of the theory using newly determined partition coefficients for Ca, Mg, Sr, and Ba between pure anorthite and seven CMAS liquid compositions at 1330 °C and 1 atm. By selecting a range of melt compositions in equilibrium with a common crystal composition at equal liquidus temperature and pressure, we have isolated the contribution of melt composition to divalent trace element partitioning in this simple system. The partitioning data are fit to Onuma curves with parameterizations that can be thermodynamically rationalized in terms of the melt major element activity product (aAl2O3)(aSiO2)2 and lattice strain theory modeling. Residuals between observed partition coefficients and the lattice strain plus major oxide melt activity model are then attributed to non-ideality of trace constituents in the liquids. The activity coefficients of the trace species in the melt are found to vary systematically with composition. Accounting for the major and trace element thermodynamics in the melt allows a good fit in which the parameters of the crystal-lattice strain model are independent of melt composition.  相似文献   

16.
Significant zonation in major, minor, trace, and volatile elements has been documented in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (e.g., MgO, FeO, Cr2O3, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H2O, and F, components with a lower concentration in the host olivine than in the melt (e.g., Al2O3, SiO2, Na2O, K2O, TiO2, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions, concurrent with diffusive propagation of the boundary layer toward the inclusion center. Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na2O, K2O) by coupling to slow diffusing components such as SiO2 and Al2O3. Concentrations of H2O and F decrease toward the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects. A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C h?1 from the liquidus down to ~1,000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1,000 °C ranges from 40 s to just over 1 h. Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization. All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.  相似文献   

17.
The origin and the relationships between the high potassic (HKS) and potassic (KS) suites of the Roman Comagmatic Province and the nature of their primary magmas have been intensively debated over the past 35 years. We have addressed these problems by a study of mineralogy (olivine Fo92-87, Cr-spinel and diopside) and melt inclusions in olivine phenocrysts from a scoria sample of Montefiascone (Vulsini area). This rock is considered as one of the most primitive (MgO=13.5 wt%, NiO=340 ppm; Cr=1275 ppm) in the northern part of the Roman Comagmatic Province. The compositions of both the olivine and their melt inclusions are controlled by two main processes. In the case of the olivine Fo<90.5, fractional crystallization (olivine + diopside + minor spinel) was the principal mechanism of the magma evolution. The olivine (Fo92-90.5) and the Cr-spinel (Cr#=100. Cr/(Cr+Al)=63-73) represent a near-primary liquidus assemblage and indicate the mantle origin of their parental magmas. The compositions of melt inclusions in these olivine phenocrysts correspond to those of poorly fractionated H2O-rich ( 1 wt%) primary melts (MgO=8.4-9.7 wt%,FeOtotal=6-7.5 wt%). They evidence a wide compositional range (in wt%: SiO2=46.5-50, K2O=5.3-2.8, P2O5=0.4-0.2, S=0.26-0.12; Cl=0.05-0.03, and CaO/Al2O3= 0.8-1.15), with negative correlations between SiO2 and K2O, Al2O3 and CaO, as well as positive correlations between K2O, and P2O5, S, Cl, with nearly constant ratios between these elements. These results are discussed in terms of segregation of various mantle-derived melts. The high and constant Mg# [100.Mg/(Mg+Fe2+)] 73-75 of studied melts and their variable Si, K, P, Ca, Al, S contents could be explained by the melting of a refractory lithospheric mantle source, heterogeneously enriched in phlogopite and clinopyroxene (veined mantle source).  相似文献   

18.
We have measured the water solubility between 1 atmosphere and 5 kilobars for a calcium aluminosilicate melt of molar composition CaO 0.28, Al2O3 0.06, SiO2 0.66 (An9Wo38Qz53). The water contents were measured via thermogravimetric analysis of isobarically quenched glasses, and range from 0.121 wt% H2O near 1 aim to 9.25 wt% H2O at 5 kilobars. The molar water solubility lies between those of SiO2 and albite melts below around three kilobars, and crosses the albite solubility curve above this pressure. The present results are compared with data in the literature on related calcium aluminosilicate melts. There seems to be little variation of water solubility with composition for calcium aluminosilicate melts, unlike analogous alkali aluminosilicate compositions. Examination of the data suggests that there may be a maximum in molar water solubility along the albite-anorthite join.  相似文献   

19.
ABSTRACT

Silicate melt inclusions (SMIs) are small droplets of magma that become trapped in minerals during crystal growth. SMIs in olivine crystals can provide critical information on the range of melt compositions and processes that occur during melt generation, evolution, transport, and eruption. The Pliocene–Quaternary volcanic rocks in the Qorveh–Bijar volcanic belt of western Iran show porphyritic and microlithic textures, with olivine and clinopyroxene being the dominant minerals. Magnesian olivines in these volcanic rocks contain primary SMIs. The composition and characteristic of olivine-hosted SMI of these rocks are investigated to constrain the source lithology for mafic volcanism. Bulk compositions of the SMIs overlap those of their host rocks and extend to higher CaO/Al2O3 values. The estimated entrapment pressures and temperatures of the studied SMIs are 9.1–10.3 kbar and 1220–1355°C. The calculated mafic parental melt contains 42.36 wt.% SiO2, low total alkalis (3.22 wt.%), and high MgO (16.1 wt.%). Exploratory calculations using pMELTS show that this parental composition underwent variable degrees of fractional crystallization, as reflected by the variable compositions of the SMIs. Several lines of evidence including pyroxene xenocrysts and high FeO/MnO, FC3MS (FeO/CaO – 3*MgO/SiO2), and Zn/Fe ratios (14–21), suggest that a metasomatized pyroxenitic source contributed to the genesis of the parental melt. Amphibole in the SMIs indicates a high volatile content in the parental melt, which we conclude was generated from a metasomatized lithospheric mantle source. The pyroxenite source also contained garnet. Our geochemical results lead us to propose a new petrogenetic model. Specifically, we infer that a dense and unstable portion of the lithosphere underwent localized laminar detachment and downward flow, i.e. lithospheric drip. This drip underwent volatile-enhanced partial melting during descent through the underlying hot asthenosphere and generated the studied volcanic rocks.  相似文献   

20.
Dynamic crystallization experiments in the CaO–MgO–Al2O3–SiO2 (CMAS) system have been used to investigate the change in crystal shape when pre-existing polyhedral olivine crystals are cooled rapidly (1,639–2,182°C/h). Polyhedral olivines are crystallized initially in a first step using a slow cooling rate (2°C/h), then skeletal and dendritic overgrowths develop on the polyhedral crystals during a subsequent fast cooling event. During this second episode small dendritic olivines also nucleate within the liquid phase. Observation of the experimental sample by optical microscopy shows that the polyhedral olivine shape progressively changes to a skeletal and then to a dendritic morphology in the following sequence: polyhedral ⇒ hopper polyhedral ⇒ dendritic polyhedral. This evolutional sequence is discussed in terms of changes in the crystal growth conditions during cooling and a general relation between these olivine dynamic crystallization experiments and the integrated model of crystal growth by Sunagawa (Bull Minér 104:81–87, 1981, Morphology of crystals, Terra Scientific Publishing Company, 1987) is proposed.  相似文献   

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