Phase equilibria in the system CaO-CoO-SiO2 and Gibbs energies of formation of the quaternary oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4

Phase relations in the pseudoternary system CaO-CoO-SiO2 have been established at 1323 K. Three quaternary oxides were found to be stable: CaCoSi2O6 with clinopyroxene (Cpx), Ca2CoSi2O7 with melilite (Mel), and CaCoSiO4 with olivine (Ol) structures. The Gibbs energies of formation of the quaternary oxides from their component binary oxides were measured using solid-state galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte in the temperature range of 1000-1324 K. The results can be summarized as follows: CoO (rs) + CaO (rs) + 2SiO(2) (Qtz) --> CaCoSi2O6 (Cpx), Delta G(f)(0) = -117920 + 11.26T (+/-150) J/mol CoO (rs) + 2CaO (rs) + 2SiO(2) (Qtz) --> Ca2CoSi2O7 (Mel), Delta G(f)(0) = -192690 + 2.38T (+/-130) J/mol CoO (rs) + CaO (rs) + SiO2 (Qtz) --> CaCoSiO2 (Ol), Delta G(f)(0) = -100325 + 2.55T (+/-100) J/mol where rs = rock salt (NaCl) structure and Qtz = quartz. The uncertainty limits correspond to twice the standard error estimate. The experimentally observed miscibility gaps along the joins CaO-CoO and CaCoSiO4-Co2SiO4 were used to calculate the excess free energies of mixing for the solid solutions CaxCo1-xO and (CayCo1-y)CoSiO4:Delta G(E) = X(1 - X)[31975X + 26736 (1 - X)] J/mol and Delta G(E) = 23100 (+/-250) Y(1 - Y) J/mol. A T-X phase diagram for the binary CaO-CoO was computed from the thermodynamic information; the diagram agrees with information available in the literature. The computed miscibility gap along the CaCoSiO4-Co2SiO4 join is associated with a critical temperature of 1389 (+/-15) K. Stability fields for the various solid solutions and the quaternary compounds are depicted on chemical-potential diagrams for SiO2, CaO, and CoO at 1323 K.

Gibbs energy of formation of nickel orthosilicate (Ni2SiO4)

Two solid state galvanic cells:Pt, Ni + Ni2Si04 + Si02/(Y203)Zr02/Ni + + NiO, Pt (1) and Pt, Ni + NizSiOj + Si02/CaF2/Ni + + NiO, Pt (11) have been employed for the determination of the Gibbs' energy of formation of nickel orthosilicate(Ni2Si04) from nickel oxide and quartz. The emf of cell (I) was reversible and reproducible in the temperature range 925 to 1375K whereas emf of cell (11) drifted with time and changed polarity. From the results of cell (I), the Gibbs' energy of formation of nickel silicate is obtained as,2Ni0 (r.s.) + Si02 (quartz) + Ni2Si04 (olivine)Gibbs' energy of formation of the spinel form of Ni2Si04 is obtained by combining the data for olivine obtained in this study with high pressure data on olivine to spinel transition reported in the literature. The complex time dependence of the emf of cell (11) can be rationalised on the basis of formation of calcium silicates from calcium oxide, generally present as an impurity in the calcium fluoride electrolyte, and silica. The emf of cell (11) is shown to be the function of the activity of calcium oxide at the electrolyte/ electrode interface. The results provide strong evidence against the recent suggestion of mixed anionic conduction in calcium fluoride.

Refining sub-solidus phase relations in the systems CaO-RuO2-SiO2 and CaO-RuO2-V2O5

Sub-solidus phase relations in the ternary systems CaO-RuO2-SiO2 and CaO-RuO2-V2O5 have been refined using thermodynamic data on calcium ruthenates, silicates and vanadates. Tie lines are established by considering Gibbs energy change for exchange reactions. Quaternary oxides have not been detected in these systems. Because of the relatively large entropy associated with phase transition of Ca2SiO4 from olivine to alpha' structure at 1120 K, reversal of one tie line is seen in the system CaO-RuO2-SiO2 between 950 and 1230 K. There is no change in sub-solidus phase relation as a function of temperature in the system CaO-RuO2-V2O5. Since vanadium can exist in several lower oxidation states, the computed sub-solidus phase relations are valid only at high oxygen partial pressures. There is fair agreement between the computed phase diagram and the limited experimental information available for CaO-deficient compositions in the literature. (C) 2013 Elsevier Ltd. All rights reserved.

Oxygen isotopes and volatiles in martian meteorites

Oxygen isotopes were measured in mineral separates from martian meteorites using laser fluorination and were found to be remarkably uniform in both δ18O and Δ17O, suggesting that martian magmas did not assimilate aqueously altered crust regardless of any other geochemical variations.

Measurements of Cl, F, H, and S in apatite from martian meteorites were made using the SIMS and NanoSIMS. Martian apatites are typically higher in Cl than terrestrial apatites from mafic and ultramafic rocks, signifying that Mars is inherently higher in Cl than Earth. Apatites from basaltic and olivine-phyric shergottites are as high in water as any terrestrial apatite from mafic and utramafic rocks, implying the possibility that martian magmas may be more similar in water abundance to terrestrial magmas than previously thought. Apatites from lherzolitic shergottites, nakhlites, chassignites, and ALH 84001 (all of which are cumulate rocks) are all lower in water than the basaltic and olivine-phyric shergottites, indicating that the slow-cooling accumulation process allows escape of water from trapped melts where apatite later formed. Sulfur is only high in some apatites from basaltic and olivine-phyric shergottites and low in all other SNCs from this study, which could mean that cumulate SNCs are low in all volatiles and that there are other controlling factors in basaltic and olivine-phyric magmas dictating the inclusion of sulfur into apatite.

Sulfur Kα X-rays were measured in SNC apatites using the electron probe. None of the peaks in the SNC spectra reside in the same position as anhydrite (where sulfur is 100% sulfate) or pyrite (where sulfur is 100% sulfide), but instead all SNC spectra peaks lie in between these two end member peaks, which implies that SNC apatites may be substituting some sulfide, as well as sulfate, into their structure. However, further work is needed to verify this hypothesis.

Chemical and mineralogical characterization of micro-inclusions in diamonds

Secondary-ion mass spectrometry (SIMS), electron probe analysis (EPMA), analytical scanning electron microscopy (SEM) and infrared (IR) spectroscopy were used to determine the chemical composition and the mineralogy of sub-micrometer inclusions in cubic diamonds and in overgrowths (coats) on octahedral diamonds from Zaire, Botswana, and some unknown localities.

The inclusions are sub-micrometer in size. The typical diameter encountered during transmission electron microscope (TEM) examination was 0.1-0.5 µm. The micro-inclusions are sub-rounded and their shape is crystallographically controlled by the diamond. Normally they are not associated with cracks or dislocations and appear to be well isolated within the diamond matrix. The number density of inclusions is highly variable on any scale and may reach 10^(11) inclusions/cm^3 in the most densely populated zones. The total concentration of metal oxides in the diamonds varies between 20 and 1270 ppm (by weight).

SIMS analysis yields the average composition of about 100 inclusions contained in the sputtered volume. Comparison of analyses of different volumes of an individual diamond show roughly uniform composition (typically ±10% relative). The variation among the average compositions of different diamonds is somewhat greater (typically ±30%). Nevertheless, all diamonds exhibit similar characteristics, being rich in water, carbonate, SiO_2, and K_2O, and depleted in MgO. The composition of micro-inclusions in most diamonds vary within the following ranges: SiO_2, 30-53%; K_2O, 12-30%; CaO, 8-19%; FeO, 6-11%; Al_2O_3, 3-6%; MgO, 2-6%; TiO_2, 2-4%; Na_2O, 1-5%; P_2O_5, 1-4%; and Cl, 1-3%. In addition, BaO, 1-4%; SrO, 0.7-1.5%; La_2O_3, 0.1-0.3%; Ce_2O_3, 0.3-0.5%; smaller amounts of other rare-earth elements (REE), as well as Mn, Th, and U were also detected by instrumental neutron activation analysis (INAA). Mg/(Fe+Mg), 0.40-0.62 is low compared with other mantle derived phases; K/ AI ratios of 2-7 are very high, and the chondrite-normalized Ce/Eu ratios of 10-21 are also high, indicating extremely fractionated REE patterns.

SEM analyses indicate that individual inclusions within a single diamond are roughly of similar composition. The average composition of individual inclusions as measured with the SEM is similar to that measured by SIMS. Compositional variations revealed by the SEM are larger than those detected by SIMS and indicate a small variability in the composition of individual inclusions. No compositions of individual inclusions were determined that might correspond to mono-mineralic inclusions.

IR spectra of inclusion- bearing zones exhibit characteristic absorption due to: (1) pure diamonds, (2) nitrogen and hydrogen in the diamond matrix; and (3) mineral phases in the micro-inclusions. Nitrogen concentrations of 500-1100 ppm, typical of the micro-inclusion-bearing zones, are higher than the average nitrogen content of diamonds. Only type IaA centers were detected by IR. A yellow coloration may indicate small concentration of type IB centers.

The absorption due to the micro-inclusions in all diamonds produces similar spectra and indicates the presence of hydrated sheet silicates (most likely, Fe-rich clay minerals), carbonates (most likely calcite), and apatite. Small quantities of molecular CO_2 are also present in most diamonds. Water is probably associated with the silicates but the possibility of its presence as a fluid phase cannot be excluded. Characteristic lines of olivine, pyroxene and garnet were not detected and these phases cannot be significant components of the inclusions. Preliminary quantification of the IR data suggests that water and carbonate account for, on average, 20-40 wt% of the micro-inclusions.

The composition and mineralogy of the micro-inclusions are completely different from those of the more common, larger inclusions of the peridotitic or eclogitic assemblages. Their bulk composition resembles that of potassic magmas, such as kimberlites and lamproites, but is enriched in H_2O, CO_3, K_2O, and incompatible elements, and depleted in MgO.

It is suggested that the composition of the micro-inclusions represents a volatile-rich fluid or a melt trapped by the diamond during its growth. The high content of K, Na, P, and incompatible elements suggests that the trapped material found in the micro-inclusions may represent an effective metasomatizing agent. It may also be possible that fluids of similar composition are responsible for the extreme enrichment of incompatible elements documented in garnet and pyroxene inclusions in diamonds.

The origin of the fluid trapped in the micro-inclusions is still uncertain. It may have been formed by incipient melting of a highly metasomatized mantle rocks. More likely, it is the result of fractional crystallization of a potassic parental magma at depth. In either case, the micro-inclusions document the presence of highly potassic fluids or melts at depths corresponding to the diamond stability field in the upper mantle. The phases presently identified in the inclusions are believed to be the result of closed system reactions at lower pressures.

The Equation of State and Petrogenesis of Komatiite

(1) Equation of State of Komatiite

The equation of state (EOS) of a molten komatiite (27 wt% MgO) was detennined in the 5 to 36 GPa pressure range via shock wave compression from 1550°C and 0 bar. Shock wave velocity, U_S, and particle velocity, U_P, in km/s follow the linear relationship U_S = 3.13(±0.03) + 1.47(±0.03) U_P. Based on a calculated density at 1550°C, 0 bar of 2.745±0.005 glee, this U_S-U_P relationship gives the isentropic bulk modulus K_S = 27.0 ± 0.6 GPa, and its first and second isentropic pressure derivatives, K'_S = 4.9 ± 0.1 and K"_S = -0.109 ± 0.003 GPa^-1.

The calculated liquidus compression curve agrees within error with the static compression results of Agee and Walker [1988a] to 6 GPa. We detennine that olivine (FO₉₄) will be neutrally buoyant in komatiitic melt of the composition we studied near 8.2 GPa. Clinopyroxene would also be neutrally buoyant near this pressure. Liquidus garnet-majorite may be less dense than this komatiitic liquid in the 20-24 GPa interval, however pyropic-garnet and perovskite phases are denser than this komatiitic liquid in their respective liquidus pressure intervals to 36 GPa. Liquidus perovskite may be neutrally buoyant near 70 GPa.

At 40 GPa, the density of shock-compressed molten komatiite would be approximately equal to the calculated density of an equivalent mixture of dense solid oxide components. This observation supports the model of Rigden et al. [1989] for compressibilities of liquid oxide components. Using their theoretical EOS for liquid forsterite and fayalite, we calculate the densities of a spectrum of melts from basaltic through peridotitic that are related to the experimentally studied komatiitic liquid by addition or subtraction of olivine. At low pressure, olivine fractionation lowers the density of basic magmas, but above 14 GPa this trend is reversed. All of these basic to ultrabasic liquids are predicted to have similar densities at 14 GPa, and this density is approximately equal to the bulk (PREM) mantle. This suggests that melts derived from a peridotitic mantle may be inhibited from ascending from depths greater than 400 km.

The EOS of ultrabasic magmas was used to model adiabatic melting in a peridotitic mantle. If komatiites are formed by >15% partial melting of a peridotitic mantle, then komatiites generated by adiabatic melting come from source regions in the lower transition zone (≈500-670 km) or the lower mantle (>670 km). The great depth of incipient melting implied by this model, and the melt density constraint mentioned above, suggest that komatiitic volcanism may be gravitationally hindered. Although komatiitic magmas are thought to separate from their coexisting crystals at a temperature =200°C greater than that for modern MORBs, their ultimate sources are predicted to be diapirs that, if adiabatically decompressed from initially solid mantle, were more than 700°C hotter than the sources of MORBs and derived from great depth.

We considered the evolution of an initially molten mantle, i.e., a magma ocean. Our model considers the thermal structure of the magma ocean, density constraints on crystal segregation, and approximate phase relationships for a nominally chondritic mantle. Crystallization will begin at the core-mantle boundary. Perovskite buoyancy at > 70 GPa may lead to a compositionally stratified lower mantle with iron-enriched mangesiowiistite content increasing with depth. The upper mantle may be depleted in perovskite components. Olivine neutral buoyancy may lead to the formation of a dunite septum in the upper mantle, partitioning the ocean into upper and lower reservoirs, but this septum must be permeable.

(2) Viscosity Measurement with Shock Waves

We have examined in detail the analytical method for measuring shear viscosity from the decay of perturbations on a corrugated shock front The relevance of initial conditions, finite shock amplitude, bulk viscosity, and the sensitivity of the measurements to the shock boundary conditions are discussed. The validity of the viscous perturbation approach is examined by numerically solving the second-order Navier-Stokes equations. These numerical experiments indicate that shock instabilities may occur even when the Kontorovich-D'yakov stability criteria are satisfied. The experimental results for water at 15 GPa are discussed, and it is suggested that the large effective viscosity determined by this method may reflect the existence of ice VII on the Rayleigh path of the Hugoniot This interpretation reconciles the experimental results with estimates and measurements obtained by other means, and is consistent with the relationship of the Hugoniot with the phase diagram for water. Sound waves are generated at 4.8 MHz at in the water experiments at 15 GPa. The existence of anelastic absorption modes near this frequency would also lead to large effective viscosity estimates.

(3) Equation of State of Molybdenum at 1400°C

Shock compression data to 96 GPa for pure molybdenum, initially heated to 1400°C, are presented. Finite strain analysis of the data gives a bulk modulus at 1400°C, K'_S. of 244±2 GPa and its pressure derivative, K'_OS of 4. A fit of shock velocity to particle velocity gives the coefficients of U_S = C_O+S U_P to be C_O = 4.77±0.06 km/s and S = 1.43±0.05. From the zero pressure sound speed, C_O, a bulk modulus of 232±6 GPa is calculated that is consistent with extrapolation of ultrasonic elasticity measurements. The temperature derivative of the bulk modulus at zero pressure, θK_OSθT|_P, is approximately -0.012 GPa/K. A thermodynamic model is used to show that the thermodynamic Grüneisen parameter is proportional to the density and independent of temperature. The Mie-Grüneisen equation of state adequately describes the high temperature behavior of molybdenum under the present range of shock loading conditions.

Regional variations in upper mantle structure beneath North America

Several types of seismological data, including surface wave group and phase velocities, travel times from large explosions, and teleseismic travel time anomalies, have indicated that there are significant regional variations in the upper few hundred kilometers of the mantle beneath continental areas. Body wave travel times and amplitudes from large chemical and nuclear explosions are used in this study to delineate the details of these variations beneath North America.

As a preliminary step in this study, theoretical P wave travel times, apparent velocities, and amplitudes have been calculated for a number of proposed upper mantle models, those of Gutenberg, Jeffreys, Lehman, and Lukk and Nersesov. These quantities have been calculated for both P and S waves for model CIT11GB, which is derived from surface wave dispersion data. First arrival times for all the models except that of Lukk and Nersesov are in close agreement, but the travel time curves for later arrivals are both qualitatively and quantitatively very different. For model CIT11GB, there are two large, overlapping regions of triplication of the travel time curve, produced by regions of rapid velocity increase near depths of 400 and 600 km. Throughout the distance range from 10 to 40 degrees, the later arrivals produced by these discontinuities have larger amplitudes than the first arrivals. The amplitudes of body waves, in fact, are extremely sensitive to small variations in the velocity structure, and provide a powerful tool for studying structural details.

Most of eastern North America, including the Canadian Shield has a Pn velocity of about 8.1 km/sec, with a nearly abrupt increase in compressional velocity by ~ 0.3 km/sec near at a depth varying regionally between 60 and 90 km. Variations in the structure of this part of the mantle are significant even within the Canadian Shield. The low-velocity zone is a minor feature in eastern North America and is subject to pronounced regional variations. It is 30 to 50 km thick, and occurs somewhere in the depth range from 80 to 160 km. The velocity decrease is less than 0.2 km/sec.

Consideration of the absolute amplitudes indicates that the attenuation due to anelasticity is negligible for 2 hz waves in the upper 200 km along the southeastern and southwestern margins of the Canadian Shield. For compressional waves the average Q for this region is > 3000. The amplitudes also indicate that the velocity gradient is at least 2 x 10^-3 both above and below the low-velocity zone, implying that the temperature gradient is < 4.8°C/km if the regions are chemically homogeneous.

In western North America, the low-velocity zone is a pronounced feature, extending to the base of the crust and having minimum velocities of 7.7 to 7.8 km/sec. Beneath the Colorado Plateau and Southern Rocky Mountains provinces, there is a rapid velocity increase of about 0.3 km/sec, similar to that observed in eastern North America, but near a depth of 100 km.

Complicated travel time curves observed on profiles with stations in both eastern and western North America can be explained in detail by a model taking into account the lateral variations in the structure of the low-velocity zone. These variations involve primarily the velocity within the zone and the depth to the top of the zone; the depth to the bottom is, for both regions, between 140 and 160 km.

The depth to the transition zone near 400 km also varies regionally, by about 30-40 km. These differences imply variations of 250 °C in the temperature or 6 % in the iron content of the mantle, if the phase transformation of olivine to the spinel structure is assumed responsible. The structural variations at this depth are not correlated with those at shallower depths, and follow no obvious simple pattern.

The computer programs used in this study are described in the Appendices. The program TTINV (Appendix IV) fits spherically symmetric earth models to observed travel time data. The method, described in Appendix III, resembles conventional least-square fitting, using partial derivatives of the travel time with respect to the model parameters to perturb an initial model. The usual ill-conditioned nature of least-squares techniques is avoided by a technique which minimizes both the travel time residuals and the model perturbations.

Spherically symmetric earth models, however, have been found inadequate to explain most of the observed travel times in this study. TVT4, a computer program that performs ray theory calculations for a laterally inhomogeneous earth model, is described in Appendix II. Appendix I gives a derivation of seismic ray theory for an arbitrarily inhomogeneous earth model.

Petrologia dos diabásios da região de Angra dos Reis, RJ

O tema abordado nesta dissertação de mestrado é a petrogênese dos diabásios do Eocretáceo que integram o Enxame de Diques da Serra do Mar na região de Angra dos Reis (RJ). Estes diques intrudem rochas do Terreno Ocidental e do Arco Magmático Rio Negro, inserindo-se no contexto geodinâmico de fragmentação do Gondwana no Cretáceo Inferior. Essas intrusões são subverticais e orientam-se preferencialmente a N039E. Intrusões retilíneas são as mais observadas em campo. Os diabásios são compostos, essencialmente, por plagioclásio e clinopiroxênios (augita e pigeonita). Quartzo, minerais opacos, apatita e olivina ocorrem como minerais acessórios. A composição mineral secundária é marcada pela presença de biotita, uralita e saussurita. Os diabásios estudados compreendem uma série transicional com afinidade toleítica. Os estudos petrológicos revelam a existência de cinco suítes de alto-TiO2, tendo sido as mesmas discriminadas com base nas razões La/Yb de amostras com o mesmo teor de MgO. Destas, apenas a suíte 2 têm quantidade mínima de amostras para avaliação de processos evolutivos. O resultado da modelagem petrogenética aponta que o processo evolutivo mais provável para a geração dos diabásios da suíte 2 é cristalização fracionada sem mudança na assembleia fracionante. As amostras representativas dos líquidos parentais das cinco suítes apresentam razões La/Nb e La/Yb maiores que a unidade, típicas de derivação de fonte enriquecida, que, em várias províncias basálticas continentais, tem sido associada à fusão exclusiva do manto litosférico subcontinental ou a sua participação em processos de mistura de fontes. A discriminação de fontes mantélicas foi feita exclusivamente com base nos teores de elementos traços de amostras representativas de líquidos parentais das cinco suítes discriminadas na área de estudo. Os modelos indicam que todas as cinco suítes estudadas estão relacionadas a fontes harzburgíticas com granada residual. A suíte 5 da área de estudo não pode ser associada à mesma fonte mantélica geradora das suítes 1, 2, 3 e 4 que, por sua vez, se originaram por diferentes quantidades de fusão parcial (respectivamente, 44%, 35%, 31% e 25%) de uma mesma fonte. Cabe ressaltar que a ocorrência de duas suítes, com razões La/Yb muito distintas, porém geograficamente muito próximas, sugere que processos de heterogeneidade mantélica, tipicamente laterais, devem também ocorrer verticalmente.

Petrogênese das rochas máficas alcalinas do litoral entre São Sebastião (SP) e Parati (RJ)

Lamprófiros e diabásios alcalinos afloram no litoral dos estados de São Paulo e Rio de Janeiro e integram o Enxame de Diques da Serra do Mar (EDSM). Essas rochas ocorrem sob a forma de diques e intrudem o Orógeno Ribeira, de idade Neoproterozóica/Cambro-Ordoviciana, inserindo-se no contexto geodinâmico de abertura do Oceano Atlântico Sul durante o Cretáceo Superior. Essas intrusões são subverticais e orientam-se preferencialmente a NE-SW, seguindo a estruturação das rochas encaixantes. Os lamprófiros são classificados como monchiquitos e camptonitos e exibem, respectivamente, textura hipocristalina e holocristalina. Apresentam também textura panidiomórfica, fenocristais de clinopiroxênio e olivina, imersos em matriz formada essencialmente por esses mesmos minerais, além de biotita, kaersutita e minerais opacos. O camptonito apresenta ainda plagioclásio na matriz. Os diabásios alcalinos são hipocristalinos a holocristalinos, equigranulares a inequigranulares, com fenocristais de olivina e/ou clinopiroxênio e/ou plagioclásio, em uma matriz composta essencialmente por esses minerais. As rochas estudadas caracterizam séries alcalinas miaskíticas, com os lamprófiros sendo tanto sódicos, potássicos e ultrapotássicos e os diabásios alcalinos como predominantemente sódicos. Modelagens petrogenéticas envolvendo possíveis processos evolutivos mostram que é improvável que os lamprófiros sejam cogenéticos por processos evolutivos envolvendo tanto cristalização fracionada, com ou sem assimilação concomitante, quanto hibridização. O mesmo ocorre para os diabásios alcalinos. A discriminação de fontes mantélicas foi feita com base nos teores de elementos traços de amostras representativas de líquidos parentais e indica que esse magmatismo alcalino está relacionado a fontes lherzolíticas com fusão parcial na zona de estabilidade do espinélio, isto é, a poucas profundidades. Os dados litogeoquímicos e isotópicos do sistema Sr-Nd das rochas estudadas sugerem tanto o envolvimento de fontes férteis, associadas ao manto sublitosférico, quanto de fontes enriquecidas, relacionadas ao manto litosférico subcontinental. Modelagens de mistura binária revelam que a petrogênese dos lamprófiros e diabásios alcalinos envolveu uma grande participação de um componente fértil misturado com contribuições menores de um componente enriquecido. Idades TDM (760-557 Ma) obtidas sugerem remobilização do manto litosférico no Neoproterozóico, talvez relacionadas à subducção da Placa São Francisco preteritamente à colisão do Orógeno Ribeira. Altas razões CaO/Al2O3 para os líquidos lamprofíricos menos evoluídos, altos teores de Zr, correlações negativas Zr/Hf e Ti/Eu e associação com carbonatitos indicam condições metassomáticas de alto CO2/H2O. Em escala local, modelos geodinâmicos baseados na astenosfera não isotérmica parecem mais aplicáveis. No entanto, modelos geodinâmicos baseados na astenosfera isotérmica (com o envolvimento de plumas) parecem mais indicados num contexto regional, considerando-se outras províncias alcalinas contemporâneas e correlatas.

Petrografia, litogeoquímica e datação Ar-Ar dos montes submarinos e dos rochedos de Martim Vaz - Cadeia Vitória-Trindade

Este trabalho de mestrado estudou a ilha de Martin Vaz e cinco montes submarinos da Cadeia Vitória-Trindade Columbia, Dogaressa, Davis, Jaseur e Montague. Martin Vaz é um conjunto de ilhas formado pela ilha principal - Martin Vaz, duas ilhotas íngremes e inacessíveis - a Ilha do Norte e a Ilha do Sul além de vários rochedos menores, como o Rochedo Agulha, espalhados a 48 km a leste de Trindade, perfazendo uma área total de 0,3 km. Martin Vaz, assim como os montes submarinos, pertencem a chamada Cadeia Vitória-Trindade, estão inseridos em um contexto tectônico regional cujo trend W-E sugere representar o track da pluma mantélica de Trindade quando da passagem da Placa Sul Americana sobre ela desde o Terciário (CROUGH et al., 1980; OCONNOR & DUNCAN, 1990, GIBSON et at., 1997). A petrografia das amostras de Martin Vaz indica haver basanitos parcialmente alteradas, melanocráticas, textura afanítica, porosas, apresentando vesículas em torno de 1,0-5,0 milímetros. Apresenta fenocristais de piroxênio além de alguns fenocristais de olivina verde-oliva translúcido variando de 1,0-3,0 milímetros. A ilha principal apresenta também diques e necks fonolíticos apresentando matriz microlítica alterada, orientada, de cor verde apresentando minerais ripiformes de cor branca (feldspato alcalino) e outros de cor violácea (titanoaugita) além de pequenos opacos. Pequenos fenocristais de aegerina-augita fortemente pleocroica, alguns apresentando geminação simples, por vezes zonado, apresenta extinção variando de c ∧ α ou X = 23 a 33 (medida de 10 grãos). Biotita laranja amarronzada com textura poiquilítica (1,0 mm), minúsculos cristais euédricos de titanita (raros), além de cristais pseudohexagonais isotrópicos alterados de analcita e carbonatos. As amostras utilizadas neste trabalho de mestrado possuem valor mínimo de 33.91 % SiO2 (TRIM-01D) e máximo de 52,2 (MVA-01) variando de ultrabásicas a básicas. Através da análise dos óxidos SiO2 e MgO é possível distinguir dois grupos de rochas para Martin Vaz: um ultramáfico magnesiano (<42% SiO2 e >7% MgO) e um básico (>45% SiO2) e, para os montes submarinos, dois grupos: um ultramáfico magnesiano (>9% MgO <42% SiO2) e um básico (>45% SiO2 e com valores de MgO em torno de 4%). As análises de Ar-Ar para as quatro amostras de Martin Vaz apresentam idades para o derrame de basanito variando de 320366 Ka (MVA-10) à 623127 Ka (MVA-04). A única amostra datada representando do dique de fonólito é a MVA-05B e obteve idade de 64984 Ka, indicando ser contemporânea ao derrame basanítico.

Serpentinization of peridotites from the southern Mariana forearc

A detailed petrologic and mineralogic study was carried out on serpentinized peridotites dredged from the southern landward slopes of the Mariana Trench, in order to reveal the serpentinization process of these unusual rocks and to identify the sole presence of the mineral lizardite. The constituent minerals of these southern Mariana forearc peridotites are olivine, amphibole and spinel, as well as serpentine, chlorite and talc. Compared with serpentinite seamounts, the serpentinized peridotites from the southern Mariana forearc are characterized by the absence of magnetite and brucite, and the common presence of talc; besides, the serpentine mineral variety is simplex, only lizardite. Combining mineral chemistry and mineral phase relationships, we conclude that (1) the absence of magnetite in the serpentinized peridotites is due to incomplete serpentinization, other than magnetite, the iron end-member in olivine forms Fe-rich brucite and Fe-rich serpentine; (2) brucite is not stable with high silica activity, reacting with later SiO2-rich fluid and then forming lizardite, leading to a lack of brucite in these serpentinized peridotites; (3) the occurrence of talc is the result of later SiO2-rich fluid reactions with lizardite; and (4) the reason for the sole occurrence of lizardite is that the temperature condition of our study area was not high enough for the formation of antigorite (which is stable at > 500 degrees C). Despite the broad overlap of lizardite and chrysotile in growth temperature, differences in the modes of occurrence of lizardite and chrysotile, such as the scarcity of H2O, low porosity and permeability, as well as the actual situation of initial serpentinization in the study area, result in the absolute prevalence of lizardite over chrysotile in the area. (C) 2009 National Natural Science Foundation of China and Chinese Academy of Sciences. Published by Elsevier Limited and Science in China Press. All rights reserved.

Deep Fractionation of Clinopyroxene in the East Pacific Rise 13 degrees N: Evidence from High MgO MORB and Melt Inclusions

Mid-ocean ridge basalts (MORBs) from East Pacific Rise (EPR) 13 degrees N are analysed for major and trace elements, both of which show a continuous evolving trend. Positive MgO-Al2O3 and negative MgO-Sc relationships manifest the cotectic crystallization of plagioclase and olivine, which exist with the presence of plagioclase and olivine phenocrysts and the absence of clinopyroxene phenocrysts. However, the fractionation of clinopyroxene is proven by the positive correlation of MgO and CaO. Thus, MORB samples are believed to show a "clinopyroxene paradox". The highest magnesium-bearing MORB sample E13-3B (MgO = 9.52%) is modelled for isobaric crystallization with COMAGMAT at different pressures. Observed CaO/Al2O3 ratios can be derived from E13-3B only by fractional crystallization at pressure > 4 +/- 1 kbar, which necessitates clinopyroxene crystallization and is not consistent with cotectic crystallization of olivine plus plagioclase in the magma chamber (at pressure similar to 1 kbar). The initial compositions of the melt inclusions, which could represent potential parental magmas, are reconstructed by correcting for post-entrapment crystallization (PEC). The simulated crystallization of initial melt inclusions also produce observed CaO/Al2O3 ratios only at > 4 +/- 1 kbar, in which clinopyroxene takes part in crystallization. It is suggested that MORB magmas have experienced clinopyroxene fractionation in the lower crust, in and below the Moho transition zone. The MORB magmas have experienced transition from clinopyroxene+plagioclase+olivine crystallization at > 4 +/- 1 kbar to mainly olivine+plagioclase crystallization at < 1 kbar, which contributes to the explanation of the "clinopyroxene paradox".

芝麻坊石榴子石二辉橄榄岩多期变质演化及其地幔过程

Many garnet peridotite bodies are enclosed in ultrahigh-pressure (UHP) gneisses and/or migmatites in worldwide UHP terranes formed by subduction of continental crust. On the basis of petrochemical data, a group of garnet peridotites have been derived from depleted mantle and were subsequently metasomatized by melts and/or fluids derived from the subducted continental crust. However, their depletion and enrichment processes and tectonic evolutions are still in conflicts. New evidences for metamorphism of garnet lherzolite from Zhimafang, Donghai County, Sulu UHP terrane are reported. The garnet lherzolite have experienced a prolonged multistage metamorphic history. At least seven stages of recrystallization have been identified based on detailed analysis of reaction textures and mineral compositions. Stage I was a high-pressure and high-temperature enriched garnet lherzolite stage, which is inferred from the presence of high Ca-Cr core of garnet porphyroclast and inclusions of high-Mg clinopyroxene, high-Al-Cr orthopyroxene and high-Mg olivine. Stage II is a high-temperature and low-pressure depleted spinel-hurzbergite or spinel-dunite stage, as indicated by the presence of relict Al-rich spinel, very high-Mg and low-Ni olivine and high-Mg orthopyroxene included in the low-Cr mantle of the porphyroclastic garnet and core of fine-grained neoblastic garnet, clinopyroxene is absent in this stage. Stage III is an hydrous amphibole spinel-lherzolite stage, which recorded events of cooling and metasomatic re-enrichment, this stage is manifested by metasomatic origin of amphibole and phlogopite-bearing porphyroblastic clinopyroxene, and porphyroblastic orthopyroxene. Stage IV is a high-pressure amphibole garnet-lherzolite stage, which is indicated by the formation of low-Cr mantle of the porphyroclastic garnet and amphibole-bearing low-Cr core of neoblastic garnet. Stage V is an UHP metamorphic garnet-lherzolite stage, which is characterized by the formation of high-Cr rim of both porphyroclastic and neoblastic garnet and recrystallization of olivine, clinopyroxene and orthopyroxene in the matrix. During UHP metamorphism, the garnet lherzolite is dehydrated, hornblende decomposed to clinopyroxene and olivine. Stage VI is a high-pressure decompression amphibole garnet-lherzolite stage, indicated by formation of later coarse-grained pargasitic hornblende and phlogopite in the garnet stability field. Stage VII is a low-pressure decompression amphibole-chlorite spinel-lherzolite stage, indicated by replacement of garnet by kelyphite of high-Al orthopyroxene + aluminous spinel + tremolitic amphibole + chlorite + talc. The metamorphic evolutions of Zhimafang garnet lherzolite suggest that it displays progressive mantle wedge convection during the subduction of previous oceanic and subsequent continental slab. We propose that the Zhimafang garnet lherzolite were originated from enriched deep mantle wedge above the previously subducted oceanic slab, subduction of oceanic slab resulted in their convection to shallower back arc and sub-arc setting, decompressional melting transformed the enriched garnet-lherzolite to depleted spinel-hurzbergite or spinel-dunite, the spinel-hurzbergite or spinel dunite was then convected to the hydrous mantle wedge corner driven by corner flow and was cooled and metasomatized by slab-derived melts/fluids, and was transformed to enriched lherzolite. The lherzolites formed a downward mantle wedge layer above successively subducted continental crust. The peridotite subducted together with the underlying continental crust and suffered UHP metamorphism. Finally, the garnet-lherzolite exhumed to the earth surface together with the UHP terrane. Detailed analyses of reaction textures and mineral compositions revealed several stages of metasomatism related to continental subduction and exhumation.

辽河盆地西部凹陷深部流体的地球化学特征与成藏效应

The main research area of this thesis is the Western Depression in the Liaohe Basin. Based on the drilling core observation and mud logging data, the features of the mantle–derived fluids and their effects on oil/gas generation in the Western Depression of the Liaohe Basin,was studied with comprehensive methods of volcanic petrology, sediment petrology, fluid geochemistry, sedimentlogy, and structural geology, and use of polarized light microscope, fluorescence microscope, electron microscope, fluid and melt inclusion test, and isotopic test of nature gas etc. The observation of drill cores in study area and other studies reveal that the main passageway of the volcanic eruption in the Cenozoic was the Xibaqian-Gaosheng fault, and the volcanic rocks of each stage were distributed around it. Mantle-derived fluid which affected on oil/gas generation formed later than the volcanic spew and those fluids entered into the depression through the Taian-Dawa fault and the Central fault. The volatile fraction analysis of the melt inclusion reveals the presence of two kinds of mantle fluids; they are hydrogen-rich fluid and carbon dioxide-rich fluid. These the two kinds of fluids were mainly distributed in olivine and pyroxene respectively. The hydrothermal veins development have multiple stages, from high temperature quartz vein to low temperature calcite vein and analcime vein, in which the fluid inclusion extremity component are methane and carbon dioxide, which indicate that when mantle-derived fluids ascended and entered into the basin, most of these fluids interacted with the organic matter in the basin even though some of these entered into atmosphere. The present isotopic test of the nature gas reveals the high 3He/4He value between the region of the Taian-Dawa fault and the Central fault, which also imply the feature of origin in mantle. This phenomenon indicates that the Mesozoic basement faults and the main Cenozoic faults had connected crust and the mantle during the basin evolution, so the mantle derived fluids could enter the basin along those faults. The main source rocks of the ES3 and ES4 members of the Shahejie Formation began to expel hydrocarbon at the end period of the ES1 member of the Shahejie Formation, and reached its peak during the period of the Dongying Formation deposition. During these periods, the mantle derived-fluids entered the basin constantly along the main faults, and supplied lots of hydrogen for hydrocarbon generation. Though the volcanic rocks and the mantle-derived fluids in the Eastern Depression were more developed than in the Western Depression, the source rocks and the deep fluids were not interacted better than the Western Depression because of the affection of structural evolution. In the Eocene, the Eastern Depression did not deposit the ES4 member of the Shahejie Formation, furthermore, the mantle-fluid formed in the Fangshengpao stage escaped to the atmosphere, which confined the later stage hydrocarbon generation capability.

西秦岭新生代火山岩中的地幔捕虏体和捕虏晶研究

Western Qinling, a conjunction region of the North China Craton, the Yangtze Craton and the Tibetan Plateau, has very complicated history of geologic and tectonic evolution. Previous studies mainly focus on tectonics and petrology of volcanic rocks in the western Qinling. Therefore, little is known about the Cenozoic lithospheric mantle beneath the western Qinling. Mafic, ultramafic and/or alkaline volcanic rocks and their entrained mantle peridotitic xenoliths and xenocrysts are known as samples directly from the lithospheric mantle. Their petrological and geochemical characteristics can reflect the nature and deep processes of the lithospheric mantle. Cenozoic volcanic rocks in the western Qinling contain abundant mantle xenoliths and xenocrysts, which provide us an opportunity to probe the lithospheric mantle beneath this region and a new dimension to insight into geologic evolution. Cenozoic volcanic rocks (7-23 Ma) from the western Qinling are sparsely distributed in the Lixian-Dangchang-Xihe Counties, Gansu Province, China. Volcanic rocks contain plenty of mantle-derived xenoliths, including spinel lherzolites with subordinate wehrlite, dunite, olivine websterite, clinopyroxenite and garnet lherzolite, and few olivine, clinopyroxene and spinel xenocrysts. These peridotitic xenoliths show clear deformed textures and their major minerals show excellent orientation. Thus, these peridotites are typical deformed peridotites. Olivine xenocrysts have clearly-zoned textures. The peridotitic xenoliths can be divided into two groups based on their compositions, namely, the H-type and L-type. The H-type peridotites are characterized by high Fo (>90) in olivines in which fine-grained ones have higher Fo than the coarse grains, low CaO (<20 %) in clinopyroxenes, high Cr# (>40) in spinels and high equilibration temperatures. They may represent the refractory lithospheric mantle. In contrast, the L-type peridotites contain low Fo (<90) olivines (with lower Fo in fine-grained olivines), high CaO (>20 %) clinopyroxenes, low Cr# (<20) spinels and low equilibration temperatures. They experienced low degree of partial melting. The Cenozoic lithospheric mantle beneath the western Qinling was refractory in major element compositions based on the mineral compositions of xenoliths and xenocrysts and experienced complicated deep processes. The lithospheric mantle was modified by shear deformation due to the diapirism of asthenosphere and strong tectonic movements including the collision between North China Craton and Yangze Craton and the uplift of Tibetan Plateau, and then underwent metasomatism with a hydrous, Na, Ti and Cr enriched melt.