ALBERT

Description: In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (〉 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of 〈 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Description: Phase equilibria simulations were performed on naturally quenched basaltic glasses to determine crystallization conditions prior to eruption of magmas at the Mid-Atlantic Ridge (MAR) east of Ascension Island (7°11°S).The results indicate that midocean ridge basalt (MORB) magmas beneath different segments of the MAR have crystallized over a wide range of pressures (100-900MPa). However, each segment seems to have a specific crystallization history. Nearly isobaric crystallization conditions (100-300MPa) were obtained for the geochemically enriched MORB magmas of the central segments, whereas normal (N)-MORB magmas of the bounding segments are characterized by polybaric crystallization conditions (200-900MPa). In addition, our results demonstrate close to anhydrous crystallization conditions of N-MORBs, whereas geochemically enriched MORBs were successfully modeled in the presence of 0.4-1wt% H2O in the parental melts.These estimates are in agreement with direct (Fourier transform IR) measurements of H2O abundances in basaltic glasses and melt inclusions for selected samples. Water contents determined in the parental melts are in the range 0.04-0.09 and 0.30-0.55 wt% H2O for depleted and enriched MORBs, respectively. Our results are in general agreement (within ±200MPa) with previous approaches used to evaluate pressure estimates in MORB. However, the determination of pre-eruptive conditions of MORBs, including temperature and water content in addition to pressure, requires the improvement of magma crystallization models to simulate liquid lines of descent in the presence of small amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation

Description: To investigate the processes that control Ta incorporation in zircon, two types of synthesis experiments were performed: (1) crystallization of zircon from an Li-Mo flux at 1 atm, and (2) crystallization of zircon (with or without coexisting tantalite) from a highly fluxed pegmatitic melt at 200 MPa and nearly water-saturated conditions. The first type of experiment is used to identify the influence of various doping elements (Hf, P, Al, and Mn) on Ta incorporation in zircon. These experiments reveal that P hinders the incorporation of Ta, whereas Al enhances Ta incorporation via charge balancing, and that Ta can be incorporated in the absence of any other doping element via the creation of vacancies in the zircon structure. Hafnium does not affect significantly Ta incorporation. Manganese and lithium do not enter the structure of zircon, except in the presence of P. Experiments with Nb show that the concentration of this element in zircon is nearly one order of magnitude lower than Ta (for similar Ta and Nb concentrations in the flux). The second type of experiments show how Ta is incorporated in zircon in natural granite and pegmatite systems. In those systems, P and Al have elevated concentrations, and P is preferentially incorporated in zircon via Al substitution to maintain charge balance. Below a P/Ta atomic ratio of ~10 in the melt, Ta competes with P for Al, and P is involved in a coupled substitution with Mn for charge balancing. Concentrations up to 3.7 wt% Ta2O5 (0.03 apfu calculated to four atoms of oxygen) were measured in these zircon samples. The partition coefficients of Ta between melt and zircon are around 1 at 800-900 {degrees}C at conditions close to tantalite saturation. These results show that zircon incorporates significant amounts of Ta from the melt in P-poor peraluminous granites with a P/Ta atomic ratio lower than ~10, which may ultimately affect the precipitation of Ta minerals. Such interactions between cations both in melts and in mineral structures are important to constrain in order to understand rare-metal enrichment in granitic systems.

Description: INTRODUCTION: THE OCCURRENCE OF MAGMATIC SULFUR-BEARING MINERALS Almost all magmas contain sulfide- or sulfate-bearing phases. In most natural samples the sulfur-bearing phase is a sulfide, which typically is pyrrhotite (Fe1–xS) or pyrite (FeS2) although chalcopyrite (CuFeS2), pentlandite ((Fe,Ni)9S8), sphalerite (ZnS) or molybdenite (MoS2) may be present as well. Sulfate minerals are rare at magmatic conditions, and anhydrite (CaSO4) is the most common. Other magmatic SO4-bearing minerals include the sodalite group minerals (haüyne simplified formula: (Na,Ca)4–8(Al6Si6(O,S)24)(SO4,Cl)1–2), scapolite minerals (silvialite: (Ca,Na)4Al6Si6O24(SO4,CO3)), and S-bearing apatite (Ca5(PO4)3(F, Cl, OH)). Barite (BaSO4) has been mentioned in rare cases (Marchev 1991). Sulfur-bearing minerals usually constitute a negligible fraction of the mineral assemblage in magmatic rocks and thus can be classified as accessory minerals. The crystallization of sulfide, sulfate, and S-bearing minerals strongly depends on melt composition, temperature and pressure, and the S speciation in melt which, in turn, is strongly dependent on the prevailing oxygen fugacity (Baker and Moretti 2011, this volume; Wilke et al. 2011, this volume). Irrespectively of the low abundance of S-bearing minerals, the evolution of sulfur in magmas may be evaluated from the occurrence of sulfides and sulfates. These minerals are critical for estimating the activity of various sulfur-bearing species in magmas and can be used to constrain the oxygen fugacity and the S concentration in the melt (e.g., pre-eruptive sulfur concentration in melts). The presence of either sulfide or sulfate in silicate melt indicates that the predominant dissolved sulfur species in the melt are S2– or S6+, respectively. Typically one of these species is dominant, but there are conditions where S2– or S6+ are present in subequal proportions (Wilke et al. 2011, this volume). In this...

Description: Crystallization experiments were conducted at 200 MPa to determine the effect of small amounts of H2O on the liquidus temperature of basaltic melts in which plagioclase is the liquidus phase. The H2O concentrations in the quenched glasses, determined by infrared spectroscopy and Karl-Fischer titration, ranged from 0.02 to 4.2 wt% H2O. The dry liquidus temperature at 200 MPa was estimated from experiments at 1 atm (H2O-free) and from the known pressure dependence of plagioclase crystallization temperature. The effect of water (expressed as wt% H2O) on the plagioclase liquidus temperature is nonlinear and diminishing with increasing melt H2O concentrations. According to our new experimental data, it can be empirically predicted with following equation: where CH2O is the water concentration in the melt (wt%), TDRY, and TWET are plagioclase crystallization temperatures in water-free and water-bearing systems, respectively.The relationship between CH2O and liquidus temperature worked out in this study is valid for a range of basaltic compositions, ranging from high-alumina basalts to basaltic andesites. The combination of the empirical equation predicting the liquidus depression of plagioclase with previous models predicting the olivine liquidus curve is useful to determine the liquidus temperature in various H2O-bearing basaltic systems in which either plagioclase or olivine is the liquidus phase.