A Fluid-Dynamical Study of Crystal Settling in Convecting Magmas

Thermal convection in magma chambers is believed to be almostalways highly time-dependent, or ‘turbulent’, andpredicted convective velocities are commonly orders of magnitudelarger than settling velocities for typical crystals calculatedfrom Stokes' Law. To understand crystal settling in magma chamberswe have therefore undertaken a theoretical and experimentalstudy of particle settling in a turbulently convecting fluid. The regime of interest is where the ratio, S, of the Stokes'Law settling velocity, v_s, to the root mean square verticalcomponent of convective velocity, W, at mid-depth in the fluidis less than unity. Although v_s < W, settling is still possiblebecause convective velocities are height-dependent and mustdecrease to zero at the boundaries of the fluid. Particles immediatelyadjacent to the bottom boundary settle out with their full Stokes'settling velocities. At the same time, convection is vigorousenough to ensure that the distribution of particles in the fluidis uniform. It follows that the number of particles in suspensiondecays with time according to an exponential law, and the decayconstant is simply the ratio of v_s to h, the depth of the fluid.Experiments confirm this relationship, at least for low particleconcentrations, provided S < 0.5 and there is no re-entrainmentof particles from the floor of the tank. We apply this relationship to crystals in magma chambers andso calculate residence times for typical crystals. We find thatfor basaltic magmas the predicted residence times are smallcompared with the many thousands of years that a chamber takesto solidify if cooling is dominated by conduction through thecountry rock. We therefore conclude that crystal settling maybe an efficient differentiation mechanism. Significant magmaticevolution may, however, take place on time-scales that are competitivewith these residence times. If the settling of crystals is the rate-limiting step duringthe crystallization of a magma chamber it is expected that asteady state will be achieved at which the rate of supply ofcrystals into the convecting magma by crystallization balancesthe rate at which crystals settle out. We show how this ideacan explain both the lack of hydraulic equivalence in cumulaterocks and the commonly observed discrepancy between the relativeproportions of phenocrysts of various phases in fractionatedbasaltic lavas and the calculated relative proportions of thesemineral phases in the fractionating assemblage. Finally, anattempt is made to calculate the steady-state crystal contentof convecting magma chambers. Comparison of the predicted crystalcontents with the observed phenocryst contents of typical basalticlavas suggests that magma chambers may often cool more rapidlythan would be expected for conduction through the country rockalone.     

Crystal size distribution in Jurassic Ferrar flows and sills (Victoria Land,Antarctica): evidence for processes of cooling,nucleation, and crystallisation

 Jurassic Ferrar rocks in Victoria Land (Antarctica) occur predominantly as basaltic or andesitic flows and sills. Both show characteristic petrographical and chemical variations, which can be related to in-situ differentiation processes. Such characteristics have been investigated at one flow (“Colonnade flow”) and one sill (“Thumb Point sill”) in the Prince Albert Mountains (Central Victoria Land) based on a statistical grain size analysis and the application of the crystal size distribution theory. A third magma body (“HiTi-unit”), which in previous literature was described as a flow, does not show clear similarities to either the flow or sill. Sill and flow are in-situ differentiated with accumulation of silicic residual melt in the latest cooled parts. For the flow this part is located in the lower half and for the sill in the upper third of their thickness. Thumb Point sill additionally shows an accumulation zone of olivine in the lower third. The position of the residual melt accumulation zone is an indicator for an origin as flow or sill. The HiTi-unit, by contrast, exhibits, only moderate petrographical and chemical variations. Growth and nucleation rates have been determined using, with some modifications, the CSD theory introduced by Marsh (1988). Growth rates of plagioclase for the flow vary from 10⁻¹¹ to 10⁻¹⁰ cm/s and are comparable with literature values for basaltic lava lakes on Hawaii. Nucleation rates vary from 10⁻⁴ to 10⁻³ cm⁻³s⁻¹, which are generally smaller than for Hawaiian basalts. Growth and nucleation rates for the sill cover a large range from 10⁻¹³ to 10⁻¹¹ cm/s and 10⁻⁹ to 10⁻³ cm⁻³s⁻¹, respectively. Systematic variations of these parameters with vertical position were obtained for the sill with its extensive differentiation history. Nucleation and growth rates are dependant on the mode of cooling. Nevertheless, small but significant differences between the flow and sill exist. Growth and nucleation rates of HiTi-unit (10⁻¹² to 10⁻¹¹ cm/s and 10⁻⁶ to 10⁻⁵ cm⁻³s⁻¹) are intermediate between the flow and sill and thus do not allow a distinction of emplacement mode. Received: 6 December 1995 / Accepted: 3 May 1996     

Erratum to: Crystal growth during dike injection of MOR basaltic melts: evidence from preservation of local Sr disequilibria in plagioclase

Profiles of a total of 23 plagioclase crystals erupted within the 1982–1991 and 1993 flows of the Coaxial segment of the Juan de Fuca ridge, the 1996 flow of the North Gorda ridge, and from the Western Volcanic Zone of the ultra-slow spreading Gakkel Ridge, have been studied for variations in major and trace element concentrations. We derive equilibration times for the relatively rapidly diffusing Sr in mid-ocean ridge basalt (MORB) plagioclase crystals of the order of months to a few years in each case. All crystals preserve diffusive disequilibria of strontium and barium. Crystal residence times at MORB magmatic temperatures are thus significantly shorter, of the order of days to a few months at most, precluding prolonged crystal storage in axial magma chambers and instead pointing to rapid crystal growth (up to ~10⁻⁸ cm s⁻¹) and cooling (up to ~1°C h⁻¹) shortly prior to eruption of these samples. Growth of these crystals is therefore inferred to occur almost entirely within oceanic layer 2 during dike injection. Crystals that grew at lower crustal levels or earlier in the differentiation sequence appear to have been excluded from the erupted magmas, as might occur if most of the gabbroic rocks in oceanic layer 3 formed an interlocking crystal framework, with viscosities that are too high to carry earlier formed crystals with the melt. The vertical extent of eruptible, crystal-poor melt lenses within the gabbroic zone is constrained to ~1 m or less by considering the width of local equilibrium growth zones, equilibration times, and crystal settling velocities. This lengthscale is consistent with field evidence from ophiolites. Finally, crystal aggregates within the Gakkel ridge sample studied here are the result of synneusis within the propagating dike during melt ascent.     

Slowly moving thermal/mineral waters in deep crystalline basement

Crystalline basement can contain notable quantities of thermal/mineral waters. Knowledge about their movement and it characteristics (fluxes, velocities, trajectories) is of great relevance for subjects like waste disposal or geothermal resources. Geothermal methods enable to quantify these flow characteristics. The use and potential of several methods is demonstrated at three sites, all from Hercynian basement in Western Europe. The results show rather uniform characteristics: Darcy flow velocities on the order of 10⁻¹¹–10⁻¹⁰ m s⁻¹; the domain of flow ranges down to 5–7 km depth.     

Ultrabasic magmas and high-degree melting of the mantle

As the degree of melting of mantle peridotite increases, the liquids that are formed become more basic and less viscous, and the spacing between residual crystals increases. The settling velocities of residual crystals in partial melts consequently will increase by several orders of magnitude, from 9.4 × 10^–4 cm/s to 4.3 × 10^–1 cm/s for a 1 cm olivine grain, as the proportion of liquid increases from 15 to 60%.To produce an ultrabasic komatiitic magma from a source with commonly assumed mantle composition requires 50 to 80% melting. Before this degree of melting can be reached, a highly fluid picritic magma produced by 30 to 50% melting will segregate from the source. Ultrabasic magmas probably form by a sequential melting process and are derived from a residuum composed of refractory minerals and trapped liquid left by previous episodes of partial melting and magma extraction. Trace element concentrations in ultrabasic komatiite lavas are consistent with this theory.     

Spatial structure of hydrography and flow in a Chilean fjord,Estuario Reloncaví

Underway current velocity profiles were combined with temperature and salinity profiles at fixed stations to describe tidal and subtidal flow patterns in the middle of the northernmost Chilean fjord, Estuario Reloncaví. This is the first study involving current velocity measurements in this fjord. Reloncaví fjord is 55 km long, 2 km wide, and on average is 170 m deep. Measurements concentrated around a marked bend of the coastline, where an 8-km along-fjord transect was sampled during a semidiurnal tidal cycle in March 2002 and a 2-km cross-fjord transect was occupied, also during a semidiurnal cycle, in May 2004. The fjord hydrography showed a relatively thin (<5 m deep), continuously stratified, buoyant layer with stratification values >4 kg m⁻³ per meter of depth. Below this thin layer, the water was relatively homogeneous. Semidiurnal tidal currents had low amplitudes (<10 cm s⁻¹) that allowed the persistence of a surface front throughout the tidal cycle. The front oscillated with a period of ca. 2.5 h and showed excursions of 2 km. The front oscillations could have been produced by a lateral seiche that corresponds to the natural period of oscillation across the fjord. This front could have also caused large (2 h) phase lags in the semidiurnal tidal currents, from one end of the transect to the other, within the buoyant layer. Tidal phases were relatively uniform underneath this buoyant layer. Subtidal flows showed a 3-layer pattern consisting of a surface layer (8 m thick, of 5 cm s⁻¹ surface outflow), an intermediate layer (70 m thick, of 3 cm s⁻¹ net inflow), and a bottom layer (below 80 m depth, of 3 cm s⁻¹ net outflow). The surface outflow and, to a certain extent, the inflow layer were related to the buoyant water interacting with the ambient oceanic water. The inflowing layer and the bottom outflow were attributed to nonlinear effects associated with a tidal wave that reflects at the fjord's head. The weak subtidal currents followed the morphology of the bend and caused downwelling on the inside and upwelling on the outside part of the bend.     

Variation in surface turbulence and the gas transfer velocity over a tidal cycle in a macro-tidal estuary

The gradient flux technique, which measures the gas transfer velocity (k), and new observational techniques that probe turbulence in the aqueous surface boundary layers were conducted over a tidal cycle in the Plum Island Sound, Massachusetts. Efforts were aimed at testing new methods in an estuarine system and to determine if turbulence created by tidal velocity can be responsible for the short-term variability ink. Measurements were made during a low wind day, at a site with tidal excursions of 2.7 m and a range in tidal velocity of nearly 1 m s⁻¹. Estimates ofk using the gradient flux technique were made simultaneously with the Controlled Flux Technique (CFT), infrared imagery, and high-resolution turbulence measurements, which measure the surface renewal rate, turbulent scales, and the turbulent dissipation rate, respectively. All measurements were conducted from a small mobile catamaran that minimizes air- and water-side flow distortions. Infrared imagery showed considerable variability in the turbulent scales that affect air-water gas exchange. These measurements were consistent with variation in the surface renewal rate (range 0.02 to 2 s⁻¹), the turbulent dissipation rate (range 10⁻⁷ to 10⁻⁵ W kg⁻¹), andk (range 2.2 to 12.0 cm hr⁻¹). During this low wind day, all variables were shown to correlate with tidal speed. Taken collectively our results indicate the promise of these methods for determining short-term variability in gas transfer and near surface turbulence in estuaries and demonstrate that turbulent transport associated with tidal velocity is a potentially important factor with respect to gas exchange in coastal systems.     

Reactions and reaction rates in the regional aquifer beneath the Pajarito Plateau,north-central New Mexico,USA

Reactions and reaction rates within aquifers are fundamental components of critical hydrological processes. However, reactions simulated in laboratory experiments typically demonstrate rates that are much faster than those observed in the field. Therefore, it is necessary to conduct more reaction rate analyses in natural settings. This study of geochemical reactions in the regional aquifer in the Pajarito Plateau near Los Alamos, New Mexico combines modeling with petrographic assessment to further knowledge and understanding of complex natural hydrologic systems. Groundwater geochemistry shows marked evolution along assumed flow paths. The flow path chosen for this study was evaluated using inverse mass balance modeling to calculate the mass transfer. X-ray diffraction and field emission gun scanning electron microscopy were used to identify possible reactants and products. Considering the mineralogy of the aquifer and saturation indices for the regional water refined initial interpretations. Calculations yielded dissolution rates for plagioclase on the order of 10⁻¹⁵ mol s⁻¹ m⁻² and for K-feldspar on the order of 10⁻¹⁷ mol s⁻¹ m⁻², orders of magnitude slower than laboratory rates. While these rates agree with other aquifer studies, they must be considered in the light of the uncertainty associated with geometric surface area estimates, ¹⁴C ages, and aquifer properties.     

Variations in long term wind speed during different decades in Arabian Sea and Bay of Bengal

A study has been carried out by comparing the extreme wind speeds estimated based on NCEP/NCAR reanalysis data for 100 years return period using Fischer Tippet-1 (commonly known as Gumbel) and Weibull distributions for three locations (off Goa, Visakhapatnam and Machilipatnam) in the north Indian Ocean. The wind dataset for Goa is compared with that from ERA-40 data. For higher wind speeds (12–20m s⁻¹), NCEP wind speed has higher percentage of occurrence than that of ERA-40. Analysis has shown slight upward trend in the annual maximum wind for location off Machilipatnam with an increase of 1.2 cm s⁻¹ per year and a decreasing trend of −1.3 cm s⁻¹ per year in the case of Goa. The Weibull distribution with shape parameter 2 fits the annual maximum wind data better than FT-1 distribution.     

The effect of experiment geometry on the mechanism and rate of dissolution of quartz in basanite at 0.5 GPa and 1350 °C

Mineral dissolution is an important factor in many magmatic processes such as melting, assimilation and magma mixing. Since it is not possible to determine dissolution rates or mechanisms from natural samples, experimental measurements are very useful. However, the geometry of the crystal–melt system can have a large effect on the measured rate, depending on whether the contaminated melt formed during dissolution is gravitationally stable or unstable. This study examines the effects of the crystal–melt geometry on the dissolution rate and mechanism. The experiments were performed using basanite melt and cylinders and spheres prepared from a single crystal of natural quartz. All of the experiments were performed in the piston cylinder apparatus at 0.5 GPa and 1350 °C. Four crystal–melt geometries were used: (1) quartz cylinders on top of a column of melt; (2) quartz cylinders beneath a column of basanite melt; (3) quartz cylinders in the middle of column of melt; (4) quartz spheres on top of a column of basanite melt. These geometries allow an examination of non-convective, convective and mixed non-convective/convective dissolution. Sphere experiments were included, as this has been the most commonly used geometry in previous experimental studies. In all of the experiments quartz dissolves directly into the basanite without formation of cristobalite or tridymite. Quartz on top of a column of melt dissolves at a rate almost proportional to the square root of time and forms a silica-rich compositional boundary layer that is gravitationally stable. All of the samples show well-defined compositional gradients in the boundary layer; however, the melt at the interface varies in composition with time and plots of concentration as a function of distance normalized to time show that the diffusion rate of SiO₂ increases with time. These data suggest that the rate-controlling step during quartz dissolution is interface reaction rather than cation diffusion. Quartz on the bottom of a column of basanite dissolves much more quickly than in the quartz-on-top experiments and the dissolution rate is linear, due to the periodic gravitational instability and resultant convection of the boundary layer. Even though interface kinetics are the rate-controlling step in quartz dissolution, convection causes an increase in dissolution rate because it replenishes the boundary layer with new, silica-undersaturated melt, which dissolves the quartz more quickly than the contaminated melt. These data suggest that the interface reaction rate is controlled by the degree of undersaturation of the solvent melt in the dissolving component. Both quartz-in-middle and quartz sphere experiments dissolve at a rate intermediate between the two extremes and both show a power law rate. Both dissolve by a combination of convective and non-convective dissolution but the sphere experiments are affected by an additional factor. During the experiment the sphere can sink through the capsule causing forced convection which adds another complication to the interpretation of the dissolution rate data. The results of this study indicate that the choice of experiment geometry plays a major role in determining the observed dissolution rate. Mineral spheres, which have been widely used in the past, are not ideal for dissolution studies. Instead, dissolution rates and mechanisms are best determined in the absence of convection. These experiments have an additional advantage in that for diffusion-controlled dissolution, they allow determination of cation diffusivity. Received: 2 March 2000 / Accepted: 11 April 2000     

Magmatic graphite in dolomite carbonatite at Pogranichnoe,North Transbaikalia,Russia

A recently discovered dolomite carbonatite at Pogranichnoe, North Transbaikalia, Russia, dated at 624 ± 3 Ma, contains xenoliths of calcite-bearing dolomite carbonatite with graphite spherulites. Apatite and aegirine are the other rock-forming minerals. Chemically the carbonatites are ferrocarbonatite and ferruginous calciocarbonatite. The graphite forms <1 mm up to 1.5 mm diameter spherulites, with Raman spectra similar to published spectra of microcrystalline, amorphous carbon and disordered graphite, with G and D bands at 1,580−1,600 cm⁻¹ and at around 1,350 cm⁻¹. Alteration has formed Fe-bearing calcite to Ca-bearing siderite compositions not previously reported in nature around the graphite along cracks and fractures. Mineral and stable isotope geothermometers and melt inclusion measurements for the carbonatite all give temperatures of 700°–900°. It is concluded that the graphite precipitated from the ferrocarbonatite magma. There are three candidates to control the precipitation of graphite (a) a redox reaction with Fe^II in the magma, (b) potential presence of organics in the magma (c) seeding of, or dissolution in, the magma of graphite/diamond from the mantle, and further work is required to identify the most important mechanism(s). Graphite in carbonatite is rare, with no substantial published accounts since the 1960s but graphite at other localities seems also to have precipitated from carbonatite magma. The precipitation of reduced carbon from carbonatite provides further evidence that diamond formation in carbonate melts at high mantle pressures is feasible.     

The cosmic vacuum and the rotation of galaxies

The rotational effect of the cosmic vacuum is investigated. The induced rotation of elliptical galaxies due to the anti-gravity of the vacuum is found to be 10⁻²¹ s⁻¹ for real elliptical galaxies. The effect of the vacuum rotation of the entire Universe is discussed, and can be described by the invariant ω _ν = ω ₀ ∼ $ \sqrt {G\rho v} $ \sqrt {G\rho v} . The corresponding numerical angular velocity of the Universe is 10⁻¹⁹ s⁻¹, in good agreement with modern data on the temperature fluctuations of the cosmic background radiation.     

Geochemical constraints on the origin of the Permian Baimazhai mafic–ultramafic intrusion,SW China

The ∼260 Ma Baimazhai mafic–ultramafic intrusion is considered to be part of the Emeishan large igneous province and consists of orthopyroxenite surrounded by websterite and gabbro. The intrusion is variably mineralized with a massive sulfide ore body (∼20 vol.%) in the core of the intrusion. Silicate rocks have Ni/Cu ratios ranging from 0.3 to 46 with majority less than 7 and are rich in LREE relative to HREE and show Nb and Ta anomalies in primitive mantle-normalized trace element patterns, with low Nb/Th (1.0–4.5) and Nb/La (0.3–1.0) ratios. Their ɛ Nd(t) values range from −3.3 to −8.4. Uniform Pd/Pt (0.7–3.5) and Cu/Pd (100,000–400,000) ratios throughout the intrusion indicate that all the sulfides in the rocks were formed in a single sulfide-saturation event. Modeling suggests that the Baimazhai rocks were formed when an Mg-rich magma became crustally contaminated in a deep-seated staging chamber. Crustal contamination (up to ∼35%) drove the magma to S-saturation and forced orthopyroxene (Opx) onto the liquidus. The crystal-bearing magma forced out of the staging chamber was migrated by flow differentiation and consequently, the denser sulfide melt and the Opx crystals became centrally disposed in the flowing magma to form the Baimazhai intrusion.Electronic Supplementary Material Supplementary material is available to authorised users in the online version of this article at .     

Light-cued emergence and re-entry events in a strongly tidal estuary

Acoustic backscatter from an active sonar system (TAPS-6) over a range of six frequencies between 265 kHz and 3 MHz revealed characteristics of emergence and reentry events within 1 h of sunset and sunrise, respectively, at a site 10 m deep in the Damariscotta River estuary, Maine. Emergence traps indicated that the mysid shrimpNeomysis americana was the dominant migrator. Daily fluctuation in irradiance influenced the timing of dusk emergence. Local variability in irradiance apparently caused populations to emerge occasionally before sunset or to leave the surface after the beginning of nautical twilight near dawn. Emergence before sunset was marked by slower-than-average ascent, and departure from the surface after initiation of nautical twilight was marked by faster-than-average descent. This pattern would be expected for populations avoiding visual predators by concealment in dark water. Mean ascent (0.29 ± 0.03 cm s⁻¹ [±1 SE]) and descent (−0.26 ± 0.02 cm s⁻¹) velocities showed little difference in magnitude, suggesting that a similar mechanism controls both. Ascent initiation times for the first such event of the night were consistent with a cue based on relative rate of change in light intensity and inconsistent with either the progress of isolumes or with absolute rate of change in light intensity.     

Numerical modeling of the development of a preferentially leached layer on feldspar surfaces

Compositional depth profiles in the leached layer of feldspar surfaces are usually interpreted by using analytical solutions which introduce oversimplifying assumptions. Here we present a general multicomponent interdiffusion numerical model for simulating cation release from a preferentially leached layer on feldspar surfaces in acid solutions. The numerical model takes into account interdiffusion, dissolution of the solid phase (represented by a moving boundary problem), and adsorption in the leached layer. Effective diffusion coefficients of ions vary with concentration along the leached layer. Governing equations of ions diffusion in the leached layer are solved numerically with a finite element method implemented in a multicomponent reactive transport code, CORE^3D, previously verified against analytical solutions of compositional depth profiles. The numerical model is tested with published X-ray photoelectron spectroscopy (XPS) data on early development of compositional profiles of labradorite leached in pH 2 HCl solutions. Model parameters are estimated by fitting depth profiles of Ca and Al measured at 12, 26, 48, 72, and 143 h. The best fit is achieved with tracer diffusion coefficients of 4 × 10⁻¹⁸, 8 × 10⁻¹⁷, 3.4 × 10⁻¹⁷, and 7 × 10⁻¹⁸ cm²/s for H, Na, Ca, and Al, respectively, which fall within the range of values reported in the literature. Our estimate of the retreat velocity corresponding to the dissolution rate is 3 × 10⁻¹³ cm/s. Results of sensitivity runs show that computed compositional profiles are sensitive to most model parameters.     

Diurnal variation in rates of calcification and carbonate sediment dissolution in Florida Bay

Water quality and criculation in Florida Bay (a shallow, subtropical estuary in south Florida) are highly dependent upon the development and evolution of carbonate mud banks distributed throughout the Bay. Predicting the effect of natural and anthropogenic perturbations on carbonate sedimentation requires an understanding of annual, seasonal, and daily variations in the biogenic and inorganic processes affecting carbonate sediment precipitation and dissolution. In this study, net calcification rates were measured over diurnal cycles on 27 d during summer and winter from 1999 to 2003 on mud banks and four representative substrate types located within basins between mud banks. Substrate types that were measured in basins include seagrass beds of sparse and intermediate densityThalassia sp., mud bottom, and hard bottom communities. Changes in total alkalinity were used as a proxy for calcification and dissolution. On 22 d (81%), diurnal variation in rates of net calcification was observed. The highest rates of net carbonate sediment production (or lowest rates of net dissolution) generally occurred during daylight hours and ranged from 2.900 to −0.410 g CaCO₃ m⁻²d⁻¹. The lowest rates of carbonate sediment production (or net sediment dissolution) occurred at night and ranged from 0.210 to −1.900 g CaCO₃ m⁻² night⁻¹. During typical diurnal cycles, dissolution during the night consumed an average of 29% of sediment produced during the day on banks and 68% of sediment produced during the day in basins. Net sediment dissolution also occurred during daylight, but only when there was total cloud cover, high turbidity, or hypersalinity. Diurnal variation in calcification and dissolution in surface waters and surface sediments of Florida Bay is linked to cycling of carbon dioxide through photosynthesis and respiration. Estimation of long-term sediment accumulation rates from diurnal rates of carbonate sediment production measured in this study indicates an overall average accumulation rate for Florida Bay of 8.7 cm 1000 yr⁻¹ and suggests that sediment dissolution plays a more important role than sediment transport in loss of sediment from Florida Bay.     

Iron Diffusion in Single-Crystal Diopside

 Iron tracer diffusion experiments in diopside have been performed using natural and synthetic single crystals of diopside, and stable iron tracers enriched in ⁵⁴Fe, at temperatures in the range 950–1100 °C, total pressure 1 atm, for times up to 29 days. Iron isotope diffusion profiles were determined with an ion microprobe. For experiments performed at log pO₂ = −13, in directions parallel to the c axis and the b axis of two natural, low iron (Fe ∼ 1.8 at %) diopsides, the data obey a single Arrhenius relationship of the form D = 6.22_−5.9 ^+49.6×10⁻¹⁵ exp(−161.5 ± 35.0 kJ mol⁻¹/RT) m² s⁻¹. A single datum for iron diffusion in iron-free, single-crystal diopside at 1050 °C, is approximately 1 order of magnitude slower than in the natural crystals. The pO₂ dependence of iron diffusion in natural crystals at 1050 °C (power exponent = 0.229 ± 0.036) indicates a vacancy mechanism; this is consistent with the results of unpublished atomistic simulation studies. There is no evidence of anisotropy for iron diffusion in diopside. Received: 16 March 1999 / Accepted: 10 April 2000     

Dissolution Kinetics of Calcite in 0.1 M NaCl Solution at Room Temperature: An Atomic Force Microscopic (AFM) Study

Atomic force microscopy (AFM) was used to study the rates of migration of the (10¯1 4) plane of a single-crystal of calcite dissolving in 0.1 M NaCl aqueous solutions at room temperature. The solution pH and P_{CO 2} controlled in the ranges 4.4 < pH < 12.2 and 0 < P_{CO 2} < 10^-3.5 atm (ambient), respectively. Measured step velocities were compared with the mineral dissolution rates determined from the calcium fluxes. The step velocity is defined as the average of the velocities of the obtuse and acute steps. Rates of step motion increased gradually from 1.4(±0.2) at pH 5.3 to 2.4(±0.3) nm s^-1 at pH 8.2, whereas the rates inverted and decreased to the minimum value of 0.69(±0.18) nm s^-1 at pH 10.8. For pH > 10.8, only the velocity of the obtuse steps increased as pH increased, whereas that of acute steps gradually decreased.The dissolution rate of the mineral can be calculated from the measured step velocities and average slope, which is proportional to the concentration of exposed monomolecular steps on the surface. The average slope of the dissolving mineral, measured at pH 5.6 and 9.7, was 0.026 (±0.015). Using this slope, we calculate bulk dissolution rates for 5.3 < pH < 12.2 of 4.9(±3.0) × 10^-11 to 1.8(±1.0) × 10^-10 mol cm^-2 s^-1. The obtained dissolution rate can be expressed by the following empirical equation:R_dss = 10^{-4.66(±0.13)}[H⁺] + 10^{-3.87(±0.06)}[HCO₃ ^-] + 10^{-7.99(plusmn; 0.08)}[OH^-]We propose that calcite dissolution in these solutions is controlled by elementary reactions that are similar to those that control the dissolution of other amphoteric solids, such as oxides. The mechanisms include the proton-enhanced hydration and detachment of calcium-carbonate ion pairs. The detachments are enhanced by the presence of adsorbed nucleophiles, such as hydroxyl and bicarbonate ions, and by protons adsorbed to key oxygens. A molecular model is proposed that illustrates these processes.     

Changes in the circulation of Tampa Bay due to Hurricane Frances as recorded by ADCP measurements and reproduced with a numerical Ocean model

Hurricane Frances is shown to greatly alter the hydrodynamics within Tampa Bay, Florida, and the exchange of water with the Gulf of Mexico in both observational data and a realistic numerical circulation model of the Tampa Bay estuary. Hurricane Frances hit Tampa Bay on September 5, 2004 with surface winds peaking twice near 22 m s⁻¹. There were three stages to the hydrodynamic effect of Frances on Tampa Bay. The first stage included the approach of Frances up to the first wind peak. The winds were to the south and southeast. During this stage sea level was maintained below mean sea level (MSL) and the residual current (demeaned, detided) was weak. The second stage began as the winds turned to the east and northeast, as the eye passed near the bay, and ended as the second wind peak appeared. During this stage the residual currents were strongly positive (into the bay), raising sea level to 1.2 m above MSL at St. Petersburg. The measured residual circulation peaked at over +0.7 m s⁻¹ near the surface. The model shows this velocity peak yielded a maximum volume flux into the bay of +44,227 m³ s⁻¹, displacing a total volume of 1.5 billion m³ in just a few hours, about 42% of the bay volume. In the third stage a strong negative flow developed as the wind and sea level relaxed to near normal levels. The ADCP measured a peak outflow of −0.8 m s⁻¹ during this time. Model results indicate a maximum flux of −37,575 m³ s⁻¹, and that it took about 50 h to drain the extra volume driven into the bay by Hurricane Frances.