Thermal equation of state of magnesite to 32 GPa and 2073 K

Pressure–volume–temperature relations have been measured to 32 GPa and 2073 K for natural magnesite (Mg_0.975Fe_0.015Mn_0.006Ca_0.004CO₃) using synchrotron X-ray diffraction with a multianvil apparatus at the SPring-8 facility. A least-squares fit of the room-temperature compression data to a third-order Birch–Murnaghan equation of state (EOS) yielded K₀ = 97.1 ± 0.5 GPa and K′ = 5.44 ± 0.07, with fixed V₀ = 279.55 ± 0.02 Å³. Further analysis of the high-temperature compression data yielded the temperature derivative of the bulk modulus (∂K_T/∂T)_P = −0.013 ± 0.001 GPa/K and zero-pressure thermal expansion α = a₀ + a₁T with a₀ = 4.03 (7) × 10⁻⁵ K⁻¹ and a₁ = 0.49 (10) × 10⁻⁸ K⁻². The Anderson–Grüneisen parameter is estimated to be δ_T = 3.3. The analysis of axial compressibility and thermal expansivity indicates that the c-axis is over three times more compressible (K_Tc = 47 ± 1 GPa) than the a-axis (K_Tc = 157 ± 1 GPa), whereas the thermal expansion of the c-axis (a₀ = 6.8 (2) × 10⁻⁵ K⁻¹ and a₁ = 2.2 (4) × 10⁻⁸ K⁻²) is greater than that of the a-axis (a₀ = 2.7 (4) × 10⁻⁵ K⁻¹ and a₁ = −0.2 (2) × 10⁻⁸ K⁻²). The present thermal EOS enables us to accurately calculate the density of magnesite to the deep mantle conditions. Decarbonation of a subducting oceanic crust containing 2 wt.% magnesite would result in a 0.6% density reduction at 30 GPa and 1273 K. Using the new EOS parameters we performed thermodynamic calculations for magnesite decarbonation reactions at pressures to 20 GPa. We also estimated stability of magnesite-bearing assemblages in the lower mantle.     

Thermal equation of state of majorite with MORB composition

In situ synchrotron X-ray diffraction experiments were conducted using the SPEED-1500 multi-anvil press at SPring-8 on majoritic garnet synthesized from natural mid-ocean ridge basalt (MORB), whose chemical composition is close to the average of oceanic crust, at 19 GPa and 2200 K. Pressure-volume-temperature data were collected using a newly developed high-pressure cell assembly to 21 GPa and 1273 K. Data were fit to the high-temperature Birch-Murnaghan equation of state, with fixed values for the ambient cell volume (V₀ = 1574.14(4) Å³) and the pressure derivative of the isothermal bulk modulus (K^′T = 4). This yielded an isothermal bulk modulus of K_T0 = 173(1) GPa, a temperature derivative of the bulk modulus (∂K_T/∂T)_P = −0.022(5) GPa K⁻¹, and a volumetric coefficient of thermal expansivity α = a + bT with values of a = 2.0(3) × 10⁻⁵ K⁻¹ and b = 1.0(5) × 10⁻⁸ K⁻². The derived thermoelastic parameters are very similar to those of pyrope. The density of subducted oceanic crust compared to pyrolitic mantle at the conditions in Earth's transition zone (410-660 km depth) was calculated using these results and previously reported thermoelastic parameters for MORB and pyrolite mineral assembledges. These calculations show that oceanic crust is denser than pyrolitic mantle throughout the mantle transition zone along a normal geotherm, and the density difference is insensitive to temperature at the pressures in lower part of the transition zone.     

Thermal equation of state of magnesiowüstite (Mg0.6Fe0.4)O

Volume measurements for magnesiowüstite (Mg_0.6Fe_0.4)O, were carried out up to pressures of 10.1 GPa in the temperature range 300–1273 K, using energy-dispersive synchrotron X-ray diffraction. These data allow reliable determination of the temperature dependence of the bulk modulus and good constraint on the thermal expansitivity at ambient pressure which was previously not known for magnesiowüstite. From these data, thermal and elastic parameters were derived from various approaches based on the Birch–Murnaghan equation of state (EOS) and on the relevant thermodynamic relations. The results from three different equations of state are remarkably consistent. With (∂K_T/∂P)_T fixed at 4, we obtained K₀=158(2) GPa, (∂K_T/∂T)_P=−0.029(3) GPa K⁻¹, (∂K_T/∂T)_V=−3.9(±2.3)×10⁻³ GPa K⁻¹, and α_T=3.45(18)×10⁻⁵+1.14(28)×10⁻⁸T. The K₀, (∂K_T/∂T)_P, and (∂K_T/∂T)_V values are in agreement with those of Fei et al. (1992) and are similar to previously determined values for MgO. The zero pressure thermal expansitivity of (Mg_0.6Fe_0.4)O is found to be similar to that for MgO (Suzuki, 1975). These results indicate that, for the compositional range x=0–0.4 in (Mg_1−xFe_x)O, the thermal and elastic properties of magnesiowüstite exhibit a dependence on the iron content that is negligibly small, within uncertainties of the experiments. They are consequently insensitive to the Fe–Mg partitioning between (Mg, Fe)SiO₃ perovskite and magnesiowüstite when applied to compositional models of the lower mantle. With the assumption that (Mg_0.6Fe_0.4)O is a Debye-like solid, a modified equation of heat capacity at constant pressure is proposed and thermodynamic properties of geophysically importance are calculated and tabulated at high temperatures.     

High-magnesium primary magmas from Haleakala Volcano, east Maui, Hawaii: petrography, nickel, and major-element constraints

For any given volcanic field the compositions of primary melts provide important constraints on models of magmatic processes and volcanic eruptions. In this paper, based on petrography, olivine and bulk rock compositions, two tholeiitic picrites (samples C122 and C123) from Haleakala Volcano, east Maui are evaluated as possible primary melts. Sample C122 (bulk rock MgO = 16.6%) has a high apparent Mg-Fe exchange coefficient, K_D, between olivine phenocrysts and bulk rock (0.6). However, major-elements and Ni mass-balance calculations show that the olivines in C122 are in equilibrium with the residual melt (matrix) after closed-system equilibrium fractionation of 25 wt.% olivine. Therefore, the Mg/Fe ratio, Ca content, and Ni content of C122 are consistent with the hypothesis that the bulk composition of C122 is close to a primary melt formed by partial melting of a mantle containing olivine with composition around Fo₈₉ to Fo₉₁. The uniform composition and small size (mostly 0.2–0.3 mm) of the olivine, and the glass patches in the matrix suggest fast ascent, and rapid cooling at shallow depth for C122. On the contrary, sample C123, which has an apparent K_D (between the most mafic olivine megacrysts and the bulk rock) close to the equilibrium value (0.27), the multiple planar subgrain boundaries in most of the olivine crystals indicate that it may not be a primary melt unless the deformed olivines are generated at magmatic condition as phenocrysts. If the deformed subgrain boundary texture in olivine could indeed be generated at magmatic condition, then the wide compositional range of olivine crystals in C123 (Fo₇₄ to Fo₉₁) suggests multi-stage crystallization over a wide range of cooling temperatures.The compositions of the two picrites, and a differentiated basalt which does not contain xenocrysts suggest that the Haleakala tholeiites are derived from primary melts with at least 16–17 wt.% MgO. Lavas with such high MgO content are rare in Haleakala and other Hawaiian volcanoes; therefore, most Hawaiian tholeiites must have undergone extensive fractionation histories.     

The thermodynamic properties of the earth's lower mantle

The thermodynamic properties of the lower mantle are determined from the seismic profile, where the primary thermodynamic variables are the bulk modulus K and density ρ. It is shown that the Bullen law (K ∝ P) holds in the lower mantle with a high correlation coefficient for the seismic parametric Earth model (PEM). Using this law produces no ambiguity or trade-off between ρ₀ and K₀, since both K₀ and K′₀ are exactly determined by applying a linear K?ρ relationship to the data. On the other hand, extrapolating the velocity data to zero pressure using a Birch-Murnaghan equation of state (EOS) results in an ambiguous answer because there are three unknown adjustable parameters (ρ₀, K₀, K′₀) in the EOS.From the PEM data, K = 232.4 + 3.19 P (GPa). The PEM yields a hot uncompressed density of 3.999 ± 0.0026 g cm^?3 for material decompressed from all parts of the lower mantle. Even if the hot uncompressed density were uniform for all depths in the lower mantle, the cold uncompressed mantle would be inhomogeneous because the decompression given by the Bullen law crosses isotherms; for example, the temperature is different at different depths. To calculate the density distribution correctly, an isothermal EOS must be used along an isotherm, and temperature corrections must be placed in the thermal pressure P_TH.The thermodynamic parameters of the lower mantle are found by iteration. Values of the three uncompressed anharmonic parameters are first arbitrarily selected: α₀ (hot), the coefficient of thermal expansion; γ₀, the Grüneisen parameter; and δ, the second Grüneisen parameter. Using γ₀ and the measured ρ₀ (hot) and K₀ (hot), the values of θ₀ (Debye temperature) and q = dlnγ/dlnρ are found from the measured seismic velocities. Then from (αK_T)₀ and q the thermal pressure P_TH at all high temperatures is found. Correlating P_TH against T to the geotherm for the lower mantle, P_TH is found at all depths Z. The isothermal pressure, along the 0 K isotherm, at every Z is found by subtracting P_TH from the measured P given by the seismic model. Using the isothermal pressure at depth Z, the solution for the cold uncompressed density ρ_0C and the cold uncompressed bulk modulus, K_T0 is found as a trace in the K_T0?_ρ0C plane. A narrow band of solutions is then found for ρ_0C and K_T0 at all depths.The thermal expansion at all T is found from [ρ_0C ? ρ₀ (hot)/ρ_0C. From Suzuki's formula, the best fit to the thermal expansion determines γ₀ and α₀ (hot). When the values of these two parameters do not agree with the original assumptions, the calculation is repeated until they do agree. In this way all the important thermodynamic parameters are found as a self-consistent set subject only to the assumptions behind the equations used.     

Seasonal variations in pCO2 and its controlling factors in surface seawater of the northern East China Sea

Surface partial pressure of CO₂ (pCO₂), temperature, salinity, nutrients, and chlorophyll a were measured in the East China Sea (ECS; 31°30′–34°00′N to 124°00′–127°30′E) in August 2003 (summer), May 2004 (spring), October 2004 (early fall), and November 2005 (fall). The warm and saline Tsushima Warm Current was observed in the eastern part of the survey area during four cruises, and relatively low salinity waters due to outflow from the Changjiang (Yangtze River) were observed over the western part of the survey area. Surface pCO₂ ranged from 236 to 445 μatm in spring and summer, and from 326 to 517 μatm in fall. Large pCO₂ (values >400 μatm) occurred in the western part of the study area in spring and fall, and in the eastern part in summer. A positive linear correlation existed between surface pCO₂ and temperature in the eastern part of the study area, where the Tsushima Warm Current dominates; this correlation suggests that temperature is the major factor controlling surface pCO₂ distribution in that area. In the western part of the study area, however, the main controlling factor is different and seasonally complex. There is large transport in this region of Changjiang Diluted Water in summer, causing low salinity and low pCO₂ values. The relationship between surface pCO₂ and water stability suggests that the amount of mixing and/or upwelling of CO₂-rich water might be the important process controlling surface pCO₂ levels during spring and fall in this shallow region. Sea–air CO₂ flux, based on the application of a Wanninkhof [1992. Relationship between wind speed and gas exchange over the ocean. Journal of Geophysical Research 97, 7373–7382] formula for gas transfer velocity and a set of monthly averaged satellite wind data, were −5.04±1.59, −2.52±1.81, 1.71±2.87, and 0.39±0.18 mmol m⁻² d⁻¹ in spring, summer, early fall, and fall, respectively, in the northern ECS. The ocean in this study area is therefore a carbon sink in spring and summer, but a weak source or in equilibrium with the atmosphere in fall. If the winter flux value is assumed to have been the mean of autumnal and vernal values, then the northern ECS absorbs about 0.013 Pg C annually. That result suggests that the northern ECS is a net sink for atmospheric CO₂, a result consistent with previous studies.     

Genesis of high-magnesium andesites and associated basalts from Saga–Futagoyama, northwest Kyushu, southwest Japan

High-magnesium andesites associated with basalts erupted after the opening of the Sea of Japan are present at Saga–Futagoyama in northwest Kyushu, southwest Japan. High Mg/(Mg + Fe) [=0.84] of orthopyroxene phenocrysts and bulk rock Mg–Fe–Ni compositions suggest that these high-magnesium andesites were originally primitive melts insignificantly modified in crustal magma chambers. K_D^Ca–Na [= (Ca/Na)_pl/(Ca/Na)_{bulk rock}] ranges from 1.21 to 0.97 and suggests that the high-magnesium andesite magmas would originally have contained H₂O less than 1.8 wt.%. Nb/La does not show a negative correlation with respect to SiO₂. These lines of evidence indicate that hydrous components derived from the subducting slab would not have played a significant role in the genesis of the high-magnesium andesite magmas. Instead, the normative olivine − quartz − [CaTs + Jd] compositions and a negative correlation between Sr/Nd and SiO₂ indicate that the basalt-high-magnesium andesite association would have been formed by multi-stage partial melting of relatively anhydrous source at pressure ranging from 1.5 to 0.5 GPa.     

Rutile saturation in magmas: implications for TiNbTa depletion in island-arc basalts

The TiO₂ contents of rutile-saturated melts ranging from basalt to rhyodacite have been investigated at P = 8–30 kbar and T = 1000–1300°C under hydrous, CO₂-saturated, and volatile-absent conditions. Dissolved TiO₂ is positively correlated with T and not strongly dependent on P_total. For fixed P and T, TiO₂ content decreases markedly as the melts become more felsic. The distribution of TiO₂ between rutile and liquid, expressed as a wt.% concentration ratio, D (rut/liq), is given by: In D = −3.16 + (9373T) + 0.026P − 0.152FM where T is in Kelvins, P in kbar and FM is a melt composition parameter, FM = [Na+K+ 2(Ca+Fe+Mg)]/Al· 1/Si in which the chemical symbols represent cation fractions. The first term expresses the competition of aluminate and titanate anions for charge-compensating cations, and the second term expresses the inverse dependence of dissolved TiO₂ on SiO₂ content. There is no apparent dependence of rutile solubility on water content.For ranges of probable solidus conditions, rutile saturation in basaltic, andesitic, and dacitic liquids requires 7–9, 5–7, and 1–3 wt.% TiO₂, respectively. These concentrations are well in excess of those found in the respective rock types, so depletion in Nb, Ta, and Ti and reduced Nb/U and Nb/Th ratios in volcanic rocks erupted at convergent plate margins cannot be attributed to residual rutile in their source regions. Thus, Nb, Ta and Ti depletion must be an inherent property of the source region.We suggest that the island-arc source region has been depleted in Nb and Ta by a previous episode of melt extraction (MORB), zoning refining, or equilibration with a percolating melt or fluid. Such a process markedly depletes the LILE and HFSE element concentrations in the residuum, but ratios such as Nb/U, Nb/Th and U/Th remain relatively constant due to similar solid-melt partition coefficients. The depletion of Nb relative to Th in the source regions of island-arc magmas occurs during hybridization of the source by rutile-saturated (Nb/Ta-depleted) melts or aqueous fluids. If the hybridizing agent is a melt, a relatively felsic composition, produced under low T (900°) hydrous conditions, is required.     

Sedimentological constraints on hydrometeor-enhanced particle deposition: 1992 Eruptions of Crater Peak, Alaska

Water is a dominant component of volcanic clouds and has fundamental control on very fine particle deposition. Particle size characteristics of distal tephra-fall (100s km from source volcano) have a higher proportion of very fine particles compared to predictions based on single particle settling rates. In this study, sedimentological analyses of fallout from for the 18 August and 16–17 September 1992 eruptions of Crater Peak, Alaska, are combined with satellite observations, and cloud trajectory and microphysics modeling to investigate meteorological influences on particle sedimentation. Total grain size distributions of tephra fallout were reconstructed for both Crater Peak eruptions and indicate a predominance of fine particles < 125 μm. Polymodal analysis of the deposits has identified a particle subpopulation with mode ~ 15–18 μm involved in particle aggregation. Accounting for the magmatic water source only, calculated ice water content of the 3.7 hour old September 1992 Spurr cloud was ~ 4.5 × 10^− 2 g m^− 3 (based on an estimated cloud thickness of ~ 1000 m from trajectory modeling). Hydrometeor formation on particles in the volcanic cloud and subsequent sublimation may induce a cloud base instability that leads to rapid bulk (en masse) sedimentation of very fine particles through a mammatus-like mechanism.     

Equation of state of gold and its application to the phase boundaries near 660 km depth in Earth’s mantle

The pressure-volume-temperature equation of state (EOS) of gold is fundamental to high-pressure science because of its widespread use as an internal pressure standard. In particular, the EOS of gold has been used in recent in situ multi-anvil press studies for determination of phase boundaries related to the 660-km seismic discontinuity. These studies show that the boundaries are lower by 2 GPa than expected from the depth of the 660-km discontinuity. Here we report a new P-V-T EOS of gold based on the inversion of quasi-hydrostatic compression and shock wave data using the Mie-Grüneisen relation and the Birch-Murnaghan-Debye equation. The previously poorly constrained pressure derivative of isothermal bulk modulus and the volume dependence of Grüneisen parameter (q=d lnγ/d ln V) are determined by including both phonon and electron effects implicitly: K′_0T=5.0±0.2 and q=1.0±0.1. This combined with other accurately measured parameters enables us to calculate pressure at a given volume and temperature. At 660-km depth conditions, this new EOS yields 1.0±0.2 GPa higher pressure than Anderson et al.’s EOS which has been used in the multi-anvil experiments. However, after the correction, there still exists a 1.5-GPa discrepancy between the post-spinel boundary measured by multi-anvil studies and the 660-km discontinuity. Other potential error sources, such as thermocouple emf dependence on pressure or systematic errors in spectroradiometry, should be investigated. Theoretical and experimental studies to better understand electronic and anharmonic effects in gold at high P-T are also needed.     

The solubility mechanisms of volatiles in silicate melts and their relations to crystal-andesite liquid equilibria

The anionic structure of magmatic liquids has been estimated at 1 atm and at pressures corresponding to those of the upper mantle. These estimates are based predominantly on spectroscopic data on binary metal oxide-silica and ternary metal oxide-silica-alumina melts. Structural information on melt compositions in aluminate-silica joins has been used to provide detailed information on the role of Al³⁺ in natural magma at atmospheric and high pressure.Regardless of pressure, andesitic melts may be described as combinations of chain, sheet, and three-dimensional network units. Nearly all Al³⁺ in the magmatic liquid resides in the three-dimensional network units. This Al³⁺ is locally charge-balanced with Na⁺, K⁺, Ca²⁺, and Mg²⁺. In the latter two cases, Al³⁺ and Si⁴⁺ are ordered, whereas for Na⁺ and K⁺, Si⁴⁺ and Al³⁺ are randomly mixed. Solution of water in natural magma results in the formation of new nonbridging oxygens in addition to OH groups attached to Si⁴⁺ and metal cations.On the basis of determined solution mechanisms of CO₂ and H₂O in silicate melts, thermodynamic properties of HO+CO₂, fluids and hydrous silicate melts and melting phase relations in peridotite-H₂O-CO₂, systems, it is found that natural andesitic magma in equilibrium with spinel Iherzolite in the upper mantle (10–20 kbar) must contain at least 5–7 wt.% H₂O. Andesitic magma with 5–7 wt.% H₂O in solution may be described as a mixture of Al-free three-dimensional units, sheets, and chains with a small proportion (less than 10%) of monomers.     

The use of MRS in the determination of hydraulic transmissivity: The case of alluvial aquifers

Magnetic Resonance Sounding (MRS) is nowadays accepted as a new geophysical method that can be used for a reliable determination of the ground water content distribution in the top 150 m. A great effort has also been made in MRS development to deduce the hydraulic transmissivity, based on empiric relationships of the permeability with a factor F which is calculated with NMR parameters measured at laboratory scale. To use this relationship under field conditions a calibration coefficient C_T = T_pt / F has to be previously established, which demands the knowledge of the transmissivity T_pt evaluated in the pumping test. The transmissivity can then be calculated at any other site of the same aquifer using the relation T_mrs = C_TF. The C_T values reported suggest a certain relationship with the lithology, but with a great dispersion and contradictory results. MRS surveys carried out in alluvial aquifers in Spain have shown that the value of C_T evaluated at one site may not be valid at another place of the same aquifer, because of the great heterogeneity of this kind of geological environment. The demand of a pumping test at each site where a MRS is measured invalidates the method actually used for MRS transmissivity evaluation. More than 50 MRS have been used to propose a new methodology. The aquifers visited cover a great range of transmissivities (from 2 × 10^− 6 to 9 × 10^− 3 m²/s). The MRS signal amplitude varies between 20 and 1400 nV, the signal/noise ratio is in the range from 0.6 to 42, and the value of the decay time constant varies from 200 to 800 ms. It has been demonstrated that when the transmissivity increases, the value of F decreases, and C_T increases, except for certain groups of MRS taken at the same aquifer or part of one aquifer, for which F increases with T_pt, keeping C_T constant. A function C_T(F) of the type C_T = mF^− n has been obtained that allows the transmissivity evaluation without the need of T_pt. Considering that both values of transmissivity, T_pt and T_mrs, are subjected to deviations due to the experimental errors as well as due to evaluation errors, the prediction achieved by the proposed equation is rather good. To perform a better evaluation of the values of the coefficients m and n it is necessary to have a greater number of MR soundings of good quality and with a trustworthy inversion at locations where a really comparable and good performed pumping test is available, covering a sufficient range of transmissivities. Though the data we have used do not always fulfil these conditions, the result is promising. Once a trustable function is available, the forecast of the transmissivity using MRS will not need the existence of any pumping test in the area. The general extension of this methodology demands the availability of MRS taken at all kinds of geological and hydrogeological environments, which is impossible without the existence of a universal MRS data base.     

A scaling law for K′0 for silicates with constant mean atomic mass

It is shown that Birch's formula for the isothermal pressure derivative of the isothermal bulk modulus, K′, can be used to generate reasonable values of K′₀ for a sequence of silicates with various ambient densities and constant mean atomic mass, m¯. The theory predicts values in fairly good agreement with experimental results, although there is a regrettable spread of experimental values of K′₀ for each solid. This first-order approximation theory for scaling between K′₀ and ?₀ is analogous to the law of corresponding states which scales K₀ and ?₀.     

Viscosity of a Teide phonolite in the welding interval

The viscosity of a natural phonolitic composition with variable amounts of H₂O has been experimentally determined. The starting materials were crystal-free phonolitic glasses from Montaña Blanca, situated within the Las Cañadas caldera of Teide. Dry phonolitic melt viscosities were determined using concentric cylinder viscometry in the low viscosity range. The glassy quench products of these runs were then hydrated by high pressure synthesis in a piston–cylinder apparatus to generate a suite of samples with water contents ranging from 0.02 to 3.75 wt%. Samples thus hydrated were quenched rapidly and prepared (cut and polished) for the determination of water contents by infrared spectroscopy before and after experimental viscometry. The viscosities of the melts (dry and hydrated) were determined at 1 bar using a micropenetration technique. Samples were stable under the measurement conditions up to 3.75 wt% H₂O. Homogeneity of water content was confirmed by infrared spectroscopy and total water contents were calculated using absorptivity coefficients for compositions extremely close to that investigated here. The variation of viscosity as a function of water content and temperature can be described in the high viscosity interval of relevance to many welding processes by the non-Arrhenian expression:

(1)

log₁₀ η=−5.900−0.286 ln (H₂O)+(10775.4−394.8(H₂O))/(T−148.7+21.65 ln (H₂O))

whereas the high viscosity range alone is adequately described by the Arrhenian expression

(2)

log₁₀ η=−10.622−0.738 ln (H₂O)+(17114.3−590.4(H₂O))×1/T

where η is the viscosity in Pa s, H₂O is the water content in wt% and T is the temperature in K.These results are particularly useful for the scaling of conditions extant during the welding of phonolitic products of Montaña Blanca. The welding of glassy phonolitic rocks is enhanced by the lower viscosity of these melts with respect to calcalkaline rhyolites. The ratio of viscosities of phonolitic to calcalkaline rhyolitic melts is a complex function of temperature and water content and reaches up to 10^4.5 at 0.1 wt% H₂O and 500°C. Abundant evidence of welding and remobilisation of pyroclastic and spatter products of Teide system volcanism are consistent with these experimental observations.     

Rare earth element systematics of hydrous liquids from partial melting of basaltic eclogite a re-evaluation

The origin of orogenic andesitic magmas is tested by calculations of REE fractionation in hydrous melts derived from partial melting of subducted ocean basalt in eclogite facies. New data on the subsolidus phase proportions of basaltic eclogite, the enrichment of LREE in altered ocean basalts, and experimentally determined REE partition coefficients (K_D's) between garnet and melt have been included in trace element fractionation equations. Non-modal melting of phases combined with variation inK_D's during melting is a unique feature of these calculations.Variation ofK_D, melting proportions, initial proportion of subsolidus phases, degree of melting, and initial REE concentrations yield a wide range of input parameters that produce REE profiles in partial melts of basaltic eclogite matching REE profiles of some orogenic andesites. The positive correlation of REE concentration with silica content for many andesitic suites can be accounted for by non-modal melting if quartz (or a similar phase with low REEK_D values) melts at a high melting proportion and garnet melts at a low melting proportion during the first stages of fusion. However, no mineralogic fractionation scheme can account for REE/silica systematics if REEK_D values are linearly decreasing with increasing melting. Earlier workers who have used similar calculations to discredit the eclogite fractionation model have set overly strict, and sometimes incorrect, constraints concerning the range in REEK_D values for garnet, the subsolidus proportions of phases in basaltic eclogite, and the relative concentrations of REE in subducted ocean crust undergoing partial melting.     

δCa evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite

To improve understanding of Ca isotope transport during water-rock interaction on the continents, we measured dissolved δ⁴⁴Ca values along a 236 km flow path in the Madison aquifer, South Dakota, where fluids have chemically evolved according to dolomite and anhydrite dissolution, calcite precipitation, and Ca-for-Na ion-exchange over a timescale spanning ~ 15 kyr. We used a reactive transport model employing rate data constrained from major ion mass-balances to evaluate the extent to which calcite precipitation and ion-exchange fractionate Ca isotopes. Elevated δ⁴⁴Ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and Ca-for-Na ion-exchange, respectively. However, for the bulk of the flow path, δ⁴⁴Ca values evolve by mixing between anhydrite and dolomite dissolution, with no fractionation during calcite precipitation under saturated conditions. We attribute the absence of Ca isotope fractionation to the long timescale of water-rock interaction and slow rate of calcite precipitation, which have enabled fluids to chemically and isotopically equilibrate with calcite. We therefore conclude that the equilibrium Ca isotope fractionation factor between calcite and water (Δ_cal–w) is very close to zero. To the extent that the Madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium, this study suggests that groundwater contributions to δ⁴⁴Ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination.     

Studies on turbulent diffusion processes and evaluation of diffusivity values from hydrodynamic observations in Corpus Christi Bay

The physical process of dispersion which can be attributed to turbulence (turbulent diffusion) or shear (shear-augmented diffusion) within the flow field is very important as it ultimately governs the distribution of constituents of interest within the environment. A series of diffusion experiments were conducted in Corpus Christi Bay, TX with the purpose of characterizing turbulent diffusion through dispersion coefficients or turbulent diffusivity, K_i (i=x, y, z) dependent on the degree of randomness or turbulence intensity, I.Measured with a boat-mounted acoustic doppler current profiler (ADCP), the Eulerian velocity time-series of fluid particles in random motion, u_i was used in the evaluation of the Eulerian time-scale of turbulence, T^E based on the velocity correlation function, R^E with T^E being related to the Lagrangian time-scale T^L through a scaling parameter, β(=T^L/T^E). Surface currents were obtained with high frequency (HF) Radar equipment deployed over the study area from which the horizontal velocity gradients were determined.Within the spatial scale of the experiment (1000 m), the observed low horizontal gradients (10⁻⁴ s⁻¹) allowed for the generation of velocity time-series from an ADCP mounted on a moving platform. A numerical scheme for evaluating turbulent diffusivity values was developed on the basis of Eulerian current measurements and calibrated through the statistics of an evolving dye patch for the scaling parameter β which in this scheme was found to be in the range 1–3.     

Static compression of hydrous silicate melt and the effect of water on planetary differentiation

High pressure experiments using the sink/float method have bracketed the density of hydrous iron-rich ultrabasic silicate melt from 1.35 to 10.0 GPa at temperatures from 1400 to 1860 °C. The silicate melt composition was a 50–50 mixture of natural komatiite and synthetic fayalite. Water was added in the form of brucite Mg(OH)₂ and was present in the experimental run products at 2 wt.% and 5 wt.% levels as confirmed by microprobe analyses of total oxygen. Buoyancy marker spheres were olivines and garnets of known composition and density. The density of the silicate melt with 5 wt.% water at 2 GPa and 1500 °C is 0.192 g cm^? 3 less than the anhydrous form of this melt at the same P and T. This density difference gives a partial molar volume of water in silicate melt of ～ 7 cm³ mol^? 1, which is similar to previous studies at high pressure. The komatiite–fayalite liquids with 0 and 2 wt.% H₂O, have extrapolated density crossovers with equilibrium liquidus olivine at 8 and 9 GPa respectively, but there is no crossover for the liquid with 5 wt.% H₂O. These results are consistent with the hypothesis that dense hydrous melts could be gravitationally stable atop the 410 km discontinuity in the Earth. The results also support the notion that equilibrium liquidus olivine could float in an FeO-rich hydrous martian magma ocean. Extrapolation of the data suggests that FeO-rich hydrous melt could be negatively buoyant in the Earth's D″-region or atop the core–mantle-boundary (CMB), although experiments at higher pressure are needed to confirm this prediction.     

Hydraulic properties of peat soils along a bulk density gradient—A meta study

Our understanding of hydraulic properties of peat soils is limited compared with that of mineral substrates. In this study, we aimed to deduce possible alterations of hydraulic properties of peat soils following degradation resulting from peat drainage and aeration. A data set of peat hydraulic properties (188 soil water retention curves [SWRCs], 71 unsaturated hydraulic conductivity curves [UHCs], and 256 saturated hydraulic conductivity [K_s] values) was assembled from the literature; the obtained data originated from peat samples with an organic matter (OM) content ranging from 23 to 97 wt% (weight percent; and according variation in bulk density) representing various degrees of peat degradation. The Mualem‐van Genuchten model was employed to describe the SWRCs and UHCs. The results show that the hydraulic parameters of peat soils vary over a wide range confirming the pronounced diversity of peat. Peat decomposition significantly modifies all hydraulic parameters. A bulk density of approximately 0.2 g cm^?3 was identified as a critical threshold point; above and below this value, macroporosity and hydraulic parameters follow different functions with bulk density. Pedotransfer functions based on physical peat properties (e.g., bulk density and soil depth) separately computed for bog and fen peat have significantly lower mean square errors than functions obtained from the complete data set, which indicates that not only the status of peat decomposition but also the peat‐forming plants have a large effect on hydraulic properties. The SWRCs of samples with a bulk density of less than 0.2 g cm^?3 could be grouped into two to five classes for each peat type (botanical composition). The remaining SWRCs originating from samples with a bulk density of larger than 0.2 g cm^?3 could be classified into one group. The Mualem‐van Genuchten parameter values of α can be used to estimate K_s if no K_s data are available. In conclusion, the derived pedotransfer functions provide a solid instrument to derive hydraulic parameter values from easily measurable quantities; however, additional research is required to reduce uncertainty.     

Iron-magnesium order-disorder in an orthopyroxene crystal from the Johnstown meteorite

Equilibrium reversals of Fe²⁺Mg distribution between the M1 and M2 sites of an orthopyroxene from the Johnstown meteorite were achieved at several temperatures between 700 and 1000°C. One single crystal was used for the whole thermal treatment and for collecting all the X-ray data after quenching. The intracrystalline ion exchange for the bulk chemical composition: (Mg_1.453Fe_0.441Cr_0.024Ca_0.054Mn_0.015Fe_0.005Ti_0.003Al_0.005)(Si_1.960Al_0.040)O₆ is given by: ln K_D = −3027(±39)/T(K) + 0.872(±0.013)> where K_D is the distribution coefficient for the reaction: Fe_M2²⁺ + Mg_M1 = Mg_M2 + Fe_M1²⁺.A transmission electron microscopy (TEM) study of part of the crystal showed the presence of very thin augite lamellae and Guinier-Preston zones indicating a relatively rapid cooling of the host rock at temperatures close to 1000°C. The new temperature scale yields a relatively high quenching temperature of 379 (±8)°C for the pyroxene which appears consistent with a rapid cooling (estimated few degrees per hundred years) of a magmatic cumulate excavated by an impact on its parental body.