ALBERT

Notes: Abstract  Complete chemical analyses, including ferric and ferrous iron, H2O contents and δD values for 16 phlogopite and biotite and 2 hornblende separates are presented. Samples were obtained from volcanic rocks from four localities: (1) phlogopite phenocrysts from minette lavas from the western Mexico continental arc, (2) biotite and hornblende phenocrysts from andesite lavas from Mono Basin, California, (3) phlogopite and biotite from clinopyroxenite nodules entrained in potassic lavas from the East African Rift, Uganda, and (4) phlogopite phenocrysts from a wyomingite lava in the Leucite Hills, Wyoming. The Fe2O3 contents in the micas range from 0.8 to 10.5 wt%, corresponding to 0.09 to 1.15 Fe3+ per formula unit (pfu). Water contents vary from 1.6 to 3.0 wt%, corresponding to 1.58 to 3.04 OH pfu, significantly less than would be expected for a site fully occupied by hydroxyl. Cation- and anion-based normalization procedures provide accurate mineral formulae with respect to most cations and anions, but are unable to generate accurate estimates of Fe3+/FeT, and overestimate OH at the expense of O on the hydroxyl site. These inaccuracies are present despite acceptable adjusted totals and stoichiometric calculated site occupancies. The phlogopite and biotite phenocrysts in arc-related lavas from western Mexico and eastern California have the highest Fe3+/FeT ratios (56–87%), reflecting high magmatic oxygen fugacities (ΔNNO = +2 to +5), in contrast to those from Uganda (25–40%) and the Leucite Hills (23%). There is no correlation between the OH content and the Fe3+/FeT ratio in the micas. Values of KMg/Fe2+D (± 2σ errors) were calculated for three phlogopite-olivine pairs (0.12 ± 0.12, 0.26 ± 0.14, 0.09 ± 0.12), two biotite-hornblende pairs (0.73 ± 0.08 and 1.22 ± 0.10) and a single phlogopite-augite pair (1.15 ± 0.12). Values of KF/OHD for two biotite and hornblende pairs could not be determined without significant error because of the extremely low F contents (〈 0.2 wt%) of the four phases. The δD values obtained in this study encompass a large range (−137 to −43‰). The phlogopite and biotite separates from Uganda have δD values of −70 to −49‰, which overlap those believed to represent “primary” mantle. There is a larger range in δD values (−137 to −43‰) for phlogopite phenocrysts from western Mexico minette lavas, although their range in δ18O values (5.2–6.2‰) is consistent with “normal” mantle. It is unlikely, therefore, that the variable δD values reflect heterogeneity in the mantle source region of the minette magmas. Nor can the extremely low δD values reflect degassing of H2 or H2O since almost 100% loss of dissolved water in the magma is required, an unrealistic scenario given the stability of the hydrous phenocrysts. The very low δD values of the Mascota minette phlogopites require that the hydrogen be introduced from an external source (e.g., meteoric water). Whatever the process responsible for the observed hydrogen isotope composition, it had no effect on the δ18O value, f O 2, a H 2O or bulk composition of the host magmas.

Notes: Abstract Step-scanning calorimetric measurements using a Setaram HT1500 calorimeter were performed between 800 and 1400°C on two natural samples: a ugandite from the East African rift and an olivine basalt from the western Mexican arc. Our measurements provide the first in-situ quantitative assessment of enthalpy during melting of initially crystalline natural samples. The distribution of latent heat across the liquidus-solidus intervals of the two samples is distinctly different, reflecting significant variation in the sequence and abundance of mineral phases during melting (clinopyroxene and leucite in the ugandite; olivine, clinopyroxene, and plagioclase in the basalt). Our data further indicate that the common assumption of a uniform distribution of latent heat across the liquidus-solidus interval of a magma is a reasonable approximation for the olivine basalt, but is grossly in error for the ugandite. This is due to cotectic precipitation of leucite and clinopyroxene, leading to a large, disproportionate release of latent heat early in the crystallization sequence. The implication for the thermal history of a crystallizing ugandite magma is that therate of heat loss during conductive cooling will unitially be more rapid than the average rate. The net result will be to produce lower magmatic temperatures after a given cooling interval relative to models assuming a uniform release of latent heat. An additional series of scanning calorimetric experiments were performed at variable rates (1,2 and 3°/min) to evaluate the role of kinetics on the distribution of enthalpy during both melting and crystallization of the ugandite and olivine basalt. The results indicate that clinopyroxene is the most important mineral phase in controlling the shapes of the enthalpy profiles during cooling; this is due to its large enthalpy of fusion and its tendency for sluggish nucleation, followed by rapid crystallization at temperatures that vary with cooling rate. The resolution of the calorimeter (in terms of heat detected per unit time) is also important in determining the shapes of theobserved enthalpy profiles during these rapid scans. Estimates based on the observed calorimetric signal associated with melting of olivine, and the lack of a calorimetric signal during melting of leucite, combined with known enthalpies of fusion for the two phases, indicate detection limits of approximately 0.6–1.2 kJ per 5 min increments.

Notes: Abstract Direct measurements of liquid heat capacity, using a Setaram HT1500 calorimeter in step-scanning mode, have been made in air on six compositions in the Na2O-FeO-Fe2O3-SiO2 system, two in the CaO-FeO-Fe2O3-SiO2 system and four of natural composition (basanite, andesite, dacite, and peralkaline rhyolite). The fitted standard deviations on our heat capacity measurements range from 0.6 to 3.6%. Step-scanning calorimetry is particularly useful when applied to iron-bearing silicate liquids because: (1) measurements are made over a small temperature interval (10K) through which the ferric-ferrous ratio of the liquid remains essentially constant during a single measurement; (2) the sample is held in equilibrium with an atmosphere that can be controlled; (3) heat capacity is measured directly and not derived from the slope of enthalpy measurements with temperature. Liquid compositions in the sodic and calcic systems were chosen because they contain large concentrations of Fe2O3 (up to 19 mol%), and their equilibrium ferric-ferrous ratios were known at every temperature of measurement. These measurement have been combined with heat capacity (Cp) data in the literature on iron-free silicate liquids to fit Cp as a function of composition. A model assuming no excess heat capacity (linear combination of partial molar heat capacities of oxide components) reproduces the liquid data within error (±2.2% on average). The derived partial molar heat capacity of the Fe2O3 component is 240.9 ±7.9 J/g.f.w.-K, with a standard error reduced by more than a factor of two from that in earlier studies. The model equation, based primarily on simple, synthetic compositions, predicts the heat capacity of the four magmatic liquids within 1.8% on average.

Notes: Abstract The molar volumes of 19 hydrous albitic liquids (1.9 to 6.1 wt% H2Ototal) were determined at one bar and 505–765 K. These volume data were derived from density measurements on hydrous glasses at 298 K, followed by measurements of the thermal expansion of each glass from 298 K to its respective glass transition temperature. The technique exploits the fact that the volume of a glass is equal to that of the corresponding liquid at the limiting fictive temperature (T f′), and that T f′ can be approximated as the temperature near the onset of the rapid increase in thermal expansion that occurs in the glass transition interval. The volume data of this study were combined with available volume data for anhydrous, Na2O-Al2O3-SiO2 liquids to derive the partial molar volume (±1) of the H2O component in an albitic melt at ∼565 K and one bar. To extend the determination of to higher temperatures and pressures, the molar volumes of the hydrous albitic liquids determined in this study were combined with those measured by previous authors at 1023–1223 K and 480–840 MPa, leading to the following fitted values (±1) at 1673 K and one bar: (±0.46)×10−3 cm−3/mol-K, and dV¯ H 2 O total /dP=−3.82 (±0.36)×10−4 cm3/mol-bar. The measured molar volumes of this study and those of previous authors can be recovered with a standard deviation of 0.5%, which is within the respective experimental errors. There is a significant difference between the values for derived in this study as a function of temperature and pressure and those obtained from an existing polynomial, primarily caused by the previous absence of accurate density measurements on anhydrous silicate liquids. The coefficients of thermal expansion (=4.72×10−4/K) and isothermal compressibility ( T =1.66×10−5/bar) for the H2O component at 1273 K and 100 MPa, indicate that H2Ototal is the single most expansive and compressible component in silicate liquids. For example, at 1473 K and 70 MPa (conditions of a mid-ocean ridge crustal magma chamber), the presence of just 0.4 wt% H2O will decrease the density of a basaltic liquid by more than one percent. An equivalent decrease in melt density could be achieved by increasing the temperature by 175 degrees or the decreasing pressure by 230 MPa. Therefore, even minor quantities of dissolved water will have a marked effect on the dynamic properties of silicate liquids in the crustal environment.

Notes: Abstract A revised model for the volume and thermal expansivity of K2O-Na2O-CaO-MgO-Al2O3-SiO2 liquids, which can be applied at crustal magmatic temperatures, has been derived from new low temperature (701–1092 K) density measurements on sixteen supercooled liquids, for which high temperature (1421–1896 K) liquid density data are available. These data were combined with similar measurements previously performed by the present author on eight sodium aluminosilicate samples, for which high temperature density measurements are also available. Compositions (in mol%) range from 37 to 75% SiO2, 0 to 27% Al2O3, 0 to 38% MgO, 0 to 43% CaO, 0 to 33% Na2O and 0 to 29% K2O. The strategy employed for the low temperature density measurements is based on the assumption that the volume of a glass is equal to that of the liquid at the limiting fictive temperature, T f ′. The volume of the glass and liquid at T f ′ was obtained from the glass density at 298 K and the glass thermal expansion coefficient from 298 K to T f ′. The low temperature volume data were combined with the existing high temperature measurements to derive a constant thermal expansivity of each liquid over a wide temperature interval (767–1127 degrees) with a fitted 1 error of 0.5 to 5.7%. Calibration of a linear model equation leads to fitted values of V¯ i ±1 (cc/mol) at 1373 K for SiO2 (26.86 ± 0.03), Al2O3 (37.42±0.09), MgO (10.71±0.08), CaO (15.41±0.06), Na2O (26.57±0.06), K2O (42.45 ± 0.09), and fitted values of dV¯ i /dT (10−3 cc/mol-K) for MgO (3.27±0.17), CaO (3.74±0.12), Na2O (7.68±0.10) and K2O (12.08±0.20). The results indicate that neither SiO2 nor Al2O3 contribute to the thermal expansivity of the liquids, and that dV/dT liq is independent of temperature between 701 and 1896 K over a wide range of composition. Between 59 and 78% of the thermal expansivity of the experimental liquids is derived from configurational (vs vibrational) contributions. Measured volumes and thermal expansivities can be recovered with this model with a standard deviation of 0.25% and 5.7%, respectively.