Interactions between gravity currents and convective dissolution

Geological storage of carbon dioxide (CO₂) is a promising technology for reducing atmospheric emissions. The large discrepancy in the time- and length-scales between up-dip migration of buoyant supercritical CO₂ and the sinking fingers of dissolved CO₂ poses a challenge for numerical simulations aimed at describing the fate of the plume. Hence, several investigators have suggested methods to simplify the problem, but to date there has been no reference solution with which these simplified models can be compared. We investigate the full problem of Darcy-based two-phase flow with gravity-current propagation and miscible convective mixing, using high-resolution numerical simulations. We build on recent developments of the Automatic Differentiation - General Purpose Research Simulator (AD-GPRS) at Stanford. The results show a CO₂ plume that travels for 5000 years reaching a final distance of 14 km up-dip from the injection site. It takes another 2000 years before the CO₂ is completely trapped as residual (40%) and dissolved (60%) CO₂. Dissolution causes a significant reduction of the plume speed. While fingers of dissolved CO₂ appear under the propagating gravity current, the resident brine does not become fully saturated with CO₂ anywhere under the plume. The overall mass transfer of CO₂ into the brine under the plume remains practically constant for several thousands of years. These results can be used as a benchmark for verification, or improvements, of simplified (reduced-dimensionality, upscaled) models. Our results indicate that simplified models need to account for: (i) reduced dissolution due to interaction with the plume, and (ii) gradual reduction of the local dissolution rate after the fingers begin to interact with the bottom of the aquifer.     

The effects of volcanic ash on COSPEC measurements

Data from a series of laboratory experiments show the relationships between measured correlation spectrometer (COSPEC) sulfur-dioxide (SO₂) burdens, automatic gain control (AGC) deflections, and visible wavelength opacities in ash-laden plumes. The data show that the COSPEC reliably measures (within a 10% accuracy) SO₂ burdens up to AGC deflections of 2 V and visible wavelength opacities of 50%. Beyond these limits, the under measurement of the SO₂ burden is not well constrained. During typical COSPEC runs, these limits are rarely violated. The 10% error introduced by measuring ash-laden plumes is acceptable because the error is small relative to other error sources associated with the technique, especially plume velocity; and the error is correctable which allows for a wider range of plume conditions to be measured.These results imply that the densest SO₂ concentrations near the volcanic source can be measured. This is important so that SO₂ is not lost from the volcanic plume due to physical and chemical processes and that measurements are conducted under maximum signal to noise ratios.     

Influence of capillary-pressure models on CO2 solubility trapping

The typical shape of a capillary-pressure curve is either convex (e.g., Brooks–Corey model) or S-shaped (e.g., van Genuchten model). It is not universally agreed which model reflects natural rocks better. The difference between the two models lies in the representation of the capillary entry pressure. This difference does not lead to significantly different simulation results for modeling CO₂ sequestration in aquifers without considering CO₂ dissolution. However, we observe that the van-Genuchten-type capillary-pressure model accelerates CO₂ solubility trapping significantly compared with the Brooks–Corey-type model. We also show that the simulation results are very sensitive to the slope of the van-Genuchten-type curve around the entry-pressure region. For the representative examples we study, the differences can be so large as to have complete dissolution of the CO₂ plume versus persistence of over 50% of the plume over a 5000-year period.The cause of such sensitivity to the capillary-pressure model is studied. Particularly, we focus on how the entry pressure is represented in each model. We examine the mass-transfer processes under gravity-capillary equilibrium, molecular diffusion, convective mixing, and in the presence of small-scale heterogeneities. Laboratory measurement of capillary-pressure curves and some important implementation issues of capillary-pressure models in numerical simulators are also discussed. Most CO₂ sequestration simulations in the literature employ one of the two capillary-pressure models. It is important to recognize that these two representations lead to very different predictions of long-term CO₂ sequestration.     

Chemical reaction rates and entrainment within the Endeavour Ridge hydrothermal plume

The aging of the hydrothermal plume over the Endeavour segment of the Juan de Fuca Ridge was estimated by measuring the²²²Rn³He ratio in the plume as it dispersed. Despite uncertainties in the source function of hydrothermal input, it wa determined that the relative sequence of removal from the plume isH₂ > Δc >²²²Rn>CH₄ Mn, whereΔc is a measure of particle concentration and the mean life of²²²Rn is 5.5 days. H₂ is removed from the plume within hours of input while Mn is not removed within the two-week timescale of the radon-helium clock.Entrainment of bottom water within the buoyant plume may introduce additional chemical signatures into the spreading effluent layer over that which would be introduced by hydrothermal discharge alone. This is particularly significant for those chemical species which are not greatly enriched in the vent fluids relative to bottom water concentration and which display a nutrient-like profile in the deep ocean. Thus we found that significant fractions of the Si and²²⁶Ra anomalies in the plume were not of hydrothermal origin but were derived from entrained bottom water which has a higher concentration of these elements than ambient water at plume height.     

Apparent downwind depletion of volcanic SO<Subscript>2</Subscript> flux—lessons from Masaya Volcano,Nicaragua

A series of 707 measurements at Masaya in 2005, 2006, and 2007 reveals that SO₂ emissions 15km downwind of the active vent appear to be ~33% to ~50% less than those measured only 5km from the vent. Measurements from this and previous studies indicate that dry deposition of sulfur from the plume and conversion of SO₂ to sulfate aerosols within the plume each may amount to a maximum of 10% loss, and are not sufficient to account for the larger apparent loss measured. However, the SO₂ measurement site 15km downwind is located on a ridge over which local trade winds, and the entrained plume, accelerate. Greater wind speeds cause localized dilution of the plume along the axis of propagation. The lower concentrations of SO₂ measured on the ridge therefore lead to calculations of lower fluxes when calculated at the same plume speed as measurements from only 5km downwind, and is responsible for the apparent loss of SO₂. Due to the importance of SO₂ emission rates with respect to hazard mitigation, petrologic studies, and sulfur budget calculations, measured fluxes of SO₂ must be as accurate as possible. Future campaigns to measure SO₂ flux at Masaya and similar volcanoes will require individual plume speed measurements to be taken at each flux measurement site to compensate for dilution and subsequent calculation of lower fluxes. This study highlights the importance of a comprehensive understanding of a volcano’s interaction with its surroundings, especially for low, boundary layer volcanoes.     

Major Ion and Trace Metal Geochemistry of an Acidic Septic-System Plume in Silt

Four years of detailed ground-water monitoring at a newly installed, seasonal-use, domestic septic system located on poorly buffered (CaCO₃ equivalent content ≤ 1.6 wt.%) lacustrine silt, has revealed the development of an acidic ground-water plume. Acid, generated by the partial oxidation of effluent NH₄⁺ dissolved organic carbon (DOC), and possibly sulfide minerals present in the sediment, has resulted in a distal plume core zone with pH values in the range of 4.4 to 5.0. The acidic zone, where NH₄⁺ does, however, persist (> 2 mg/1, as N) and where DOC remains elevated (6–13 mg/1), is associated with high average concentrations of the trace metals Fe (4.7 mg/1), Al (1.9 mg/1), and Mn (3.6 mg/1). Attenuation of nitrogen along the plume core flowpath is indicated by a decrease in the N/ Cl⁻ ratio from an effluent value of 1.7, to a plume value of only 0.5 after 4 m of subsurface flow. Increased SO₄²⁻ levels observed in the zone of N depletion suggest that attenuation can be at least partly attributed to reduction of plume NO₃⁻ by oxidation of reduced S present in the sediment. PO₄³⁻ has not migrated significantly beyond the infiltration bed gravel layer, demonstrating that PO₄³⁻ mobility is limited in these sediments (retardation factor > 10).     

Modeling the response of primary production and sedimentation to variable nitrate loading in the Mississippi River plume

Increases in nitrate loading to the Mississippi River watershed during the last 50 years are considered responsible for the increase in hypoxic zone size in Louisiana-Texas shelf bottom waters. There is currently a national mandate to decrease the size of the hypoxic zone to 5000 km² by 2015, mostly by a 30% reduction in annual nitrogen discharge into the Gulf of Mexico. We developed an ecosystem model for the Mississippi River plume to investigate the response of organic matter production and sedimentation to variable nitrate loading. The nitrogen-based model consisted of nine compartments (nitrate, ammonium, labile dissolved organic nitrogen, bacteria, small phytoplankton, diatoms, micro- and mesozooplankton, and detritus), and was developed for the spring season, when sedimentation of organic matter from plume surface waters is considered important in the development of shelf hypoxia. The model was forced by physical parameters specified along the river-ocean salinity gradient, including residence time, light attenuation by dissolved and particulate matter, mixed layer depth, and dilution. The model was developed using measurements of biological biomasses and nutrient concentrations across the salinity gradient, and model validation was performed with an independent dataset of primary production measurements for different riverine NO₃ loads. Based on simulations over the range of observed springtime NO₃ loads, small phytoplankton contributed on average 80% to primary production for intermediate to high salinities (>15), and the main contributors to modeled sedimentation at these salinities were diatom sinking, microzooplankton egestion, and small phytoplankton mortality. We investigated the impact of limiting factors on the relationship between NO₃ loading and ecosystem rates. Model results showed that primary production was primarily limited by physical dilution of NO₃, followed by abiotic light attenuation, light attenuation due to mixing, and diatom sinking. Sedimentation was mainly limited by the first three of these factors. Neither zooplankton grazing or plume residence times acted as limiting factors of ecosystem rates. Regarding nutrient reductions to the watershed, simulations showed that about half of the percent decrease in NO₃ load was reflected in decreased plume sedimentation. For example, a 30% decrease in NO₃ load resulted in a 19% decrease in average plume primary production and a 14% decrease in sedimentation. Finally, our model results indicated that the fraction of primary production exported from surface waters is highly variable with salinity (7–87%), a finding which has important implications for predictive models of hypoxic zone size that assume a constant value for this ratio.     

Hydrological flow paths controlling stream chemistry in Japanese forested watersheds

Water sources and flow paths contributing to stream chemistry were evaluated in four Japanese forested watersheds with steep topography (slopes ≥30°). Stream chemistry during periods without rainfall and during events with less than 100 mm of precipitation was similar to seepage water chemistry, but markedly different from that of soil water which had higher concentrations of NO⁻₃ and Ca²⁺ and lower concentrations of Na⁺ and HCO⁻₃. Also, stream Cl⁻ concentrations in a Cl⁻‐treated watershed did not increase either during events with less than 100 mm of total rainfall or at baseflow conditions, even three years after the Cl⁻ treatment. These results suggest that groundwater within bedrock fissures of Paleozoic strata had a long residence time and was a major contributor to steam water under baseflow conditions and even during small precipitation events (≤100 mm). In contrast, for large precipitation events (≥100 mm), stream chemistry became more similar to soil water chemistry, especially within the steepest watershed. Also, for large precipitation events, stream Cl⁻ concentrations in the Cl⁻‐treated watershed increased markedly. These results suggest that soil water was a major contributor to stream waters only during these large events. Copyright © 1999 John Wiley & Sons, Ltd.     

Impact of capillary hysteresis and trapping on vertically integrated models for CO2 storage

Vertically integrated models are frequently applied to study subsurface flow related to CO₂ storage scenarios in saline aquifers. In this paper, we study the impact of capillary-pressure hysteresis and CO₂ trapping on the integrated constitutive parameter functions. Our results show that for the initial drainage and a subsequent imbibition, trapping is the dominant contributor to hysteresis in integrated models. We also find that for advective processes like injection and plume migration in a sloped aquifer the correct treatment of the hysteretic nature of the capillary fringe is likely of secondary importance. However, for diffusive/dispersive processes such as a redistribution of the CO₂ plume due to buoyancy and capillary forces, the hysteretic nature of the capillary fringe may significantly impact the final distribution of the fluids and the timescale of the redistribution.     

Automated,high time-resolution measurements of SO<Subscript>2</Subscript> flux at Soufrière Hills Volcano,Montserrat

We report here the first results from an automated, telemetered UV scanning spectrometer system for monitoring SO ₂ emission rates at Soufrière Hills Volcano, Montserrat. Two spectrometers receive light by way of a motor-driven stepping prism and telescope in order to make vertical scans of the volcanic plume. Spectral data from these spectrometers, situated 2,800 m apart and 4,500 m from the volcano, are relayed back to the observatory every 4–5 s via radio modems. A full scan of the plume is accomplished every 1–6 min by the (time-synchronised) spectrometers and a SO ₂ emission rate is calculated using the SO ₂ slant concentrations, scan angles and plume speeds estimated from the wind speed from a telemetered weather station near to the volcano. The plume's position and dimensions are calculated using the angular data from the two spectrometers. The plume height varies significantly diurnally and seasonally and is important in order to minimise the error on SO ₂ emission rates. The new scanning system (Scanspec) provides SO ₂ emission rates from 08:00 to 16:00 h local time every day. Preliminary results highlight a number of features of the SO ₂ time series and plume dynamics and give our first indications of the errors and limits of detection of this system. SO ₂ emission rates vary widely on all time scales (minutes, days, months). This new system has already provided the first real and consistent indication that SO ₂ emission rates vary on a minutes to hours basis, which can be correlated with volcanic activity (for example, rockfall and pyroclastic flow activity). It is anticipated that this system at Soufrière Hills will yield information on shallow processes occurring on short time scales (periods of minutes to hours) as well as deep processes relating to magma supply rates, which will be associated with longer wavelength SO ₂ signals of weeks to months.     

Radiative transfer corrections for accurate spectroscopic measurements of volcanic gas emissions

There is widespread use of passive remote sensing techniques to quantify trace gas column densities in volcanic plumes utilizing scattered sunlight as a light source. Examples include passive DOAS, COSPEC, and the SO₂ camera. In order to calculate trace gas concentrations or volcanic emission fluxes, knowledge about the optical path through the plume is necessary. In the past, a straight photon path through the plume has always been assumed although it was known that this is not always true. Here we present the results of model studies conducted specifically to quantify the effects of realistic radiative transfer in and around volcanic plumes on ground-based remote sensing measurements of SO₂. The results show that measurements conducted without additional information on average photon paths can be inaccurate under certain conditions, with possible errors spanning more than an order of magnitude. Both over and underestimation of the true column density can occur. Actual errors depend on parameters such as distance between instrument and plume, plume SO₂ concentration, plume aerosol load, as well as aerosol conditions in the ambient atmosphere. As an example, a measurement conducted with an SO₂ camera is discussed, the results of which can only be correctly interpreted if realistic radiative transfer is considered. Finally, a method is presented which for the first time allows the retrieval of actual average photon paths in spectroscopic (i.e. DOAS) measurements of adequate resolution. By allowing for a wavelength dependent column density during the evaluation of DOAS measurements, we show how radiative transfer effects can be corrected using information inherently available in the measured spectra, thus greatly enhancing the accuracy of DOAS measurements of volcanic emissions.     

A new technique to estimate volcanic gas composition: plume measurements with a portable multi-sensor system

A portable multi-sensor system was developed to measure volcanic plumes in order to estimate the chemical composition and temperature of volcanic gases. The multi-sensor system consists of a humidity–temperature sensor, SO₂ electrochemical sensor, CO₂ IR analyzer, pump and flow control units, pressure sensor, data logger, and batteries; the whole system is light (∼5 kg) and small enough to carry in a medium-size backpack. Volcanic plume is a mixture of atmosphere and volcanic gas; therefore volcanic gas composition and temperature can be estimated by subtracting the atmospheric gas background from the plume data. In order to obtain the contrasting data of the plume and the atmosphere, measurements were repeated in and out of the plume. The multi-sensor technique was applied to measure the plume of Tarumae, Tokachi, and Meakan volcanoes, Hokkaido, Japan. Repeated measurements at each volcano gave a consistent composition with ±10–30% errors, depending on the stability of the background atmospheric conditions. Fumarolic gas samples were also collected at the Tokachi volcano by a conventional method, and we found a good agreement (the difference <10%) between the composition estimated by the multi-sensor technique and conventional method. Those results demonstrated that concentration ratios of major volcanic gas species (i.e., H₂O, CO₂, and SO₂) and temperature can be estimated by the new technique without any complicated chemical analyses even for gases emitted from an inaccessible open vent. Estimation of a more detailed gas composition can be also achieved by the combination of alkaline filter techniques to measure Cl/F/S ratios in the plume and other sensors for H₂S and H₂.     

A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

CO₂ injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO₂ into the brine. The resulting neutralization will drive further dissolution of both CO₂ and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO₂), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H₂O–CO₂–Na–Cl–CaCO₃ system, so as to model CO₂ injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO₂ plume because the brine below the plume tends to reach high CO₂ concentrations quite rapidly. We conclude that carbonate dissolution needs not to be feared.     

Natural 222Rn as a tracer of mixing and volatilization in a shallow aquifer during a CO2 injection experiment

This study aims to evaluate the application of ²²²Rn in groundwater as a tracer for monitoring CO₂ plume migration in a shallow groundwater system, which is important to detect potential CO₂ leakage in the carbon capture and storage (CCS) project. For this research, an artificial CO₂-infused water injection experiment was performed in a shallow aquifer by monitoring hydrogeochemical parameters, including ²²²Rn. Radon in groundwater can be a useful tracer because of its sensitivity to sudden changes in subsurface environment. To monitor the CO₂ plume migration, the data were analysed based on (a) the influence of mixing processes on the distribution of ²²²Rn induced by the artificial injection experiment and (b) the influence of a carrier gas role by CO₂ on the variation of ²²²Rn. The spatio-temporal distributions of radon concentrations were successfully explained in association with horizontal and vertical mixing processes by the CO₂-infused water injection. Additionally, the mixing ratios of each monitoring well were calculated, quantitatively confirming the influence of these mixing processes on the distribution of radon concentrations. Moreover, one monitoring well showed a high positive relationship between ²²²Rn and Total dissolved inorganic carbon (TIC) by the carrier gas effect of CO₂ through volatilization from the CO₂ plume. It indicated the applicability of ²²²Rn as a sensitive tracer to directly monitor CO₂ leakage. When with a little effect of carrier gas, natural ²²²Rn in groundwater can be used to compute mixing ratio of CO₂-infused water indicative of CO₂ migration pathways. CO₂ carrier gas effect can possibly increase ²²²Rn concentration in groundwater and, if fully verified with more field tests, will pose a great potential to be used as a natural tracer for CO₂.     

Detailed PSC formation in a two-dimensional chemical transport model of the stratosphere

A new two-dimensional zonal model of the stratosphere, based on a formulation in an isentropic framework, with complete chemistry has been coupled with a high resolution detailed microphysical model for polar stratospheric clouds (PSCs). The 2D model chemistry includes all presently known heterogeneous processes on sulfate aerosols and PSCs. The coupling of these two models, with inherently different time scales, is discussed. It is demonstrated that in order to obtain a realistic interrelationship between NO_y and N₂O an accurate simulation of the sedimentation by PSC particles is necessary. A good agreement of model PSC presence and observations is found for the Antarctic polar winter without the need to impose additional artificial temperature variations in the model. The calculated occurrence of polar stratospheric clouds and resulting heterogeneous chemistry during the Antarctic winter are discussed. Sensitivity of the polar stratospheric chemical composition and cloud formation for different perturbations is investigated by studying the effects of transport across the polar vortex boundary and heterogeneous processing by an enhanced sulfate aerosol load. The importance of including sedimentation for all cases is also discussed.     

Modeling of aircraft exhaust emissions and infrared spectra for remote measurement of nitrogen oxides

Infrared (IR) molecular spectroscopy is proposed to perform remote measurements of NO_x concentrations in the exhaust plume and wake of aircraft. The computer model NIRATAM is applied to simulate the physical and chemical properties of the exhaust plume and to generate low resolution IR spectra and synthetical thermal images of the aircraft in its natural surroundings. High-resolution IR spectra of the plume, including atmospheric absorption and emission, are simulated using the molecular line-by-line radiation model FASCODE2. Simulated IR spectra of a Boeing 747–400 at cruising altitude for different axial and radial positions in the jet region of the exhaust plume are presented. A number of spectral lines of NO can be identified that can be discriminated from lines of other exhaust gases and the natural atmospheric background in the region around 5.2 µm. These lines can be used to determine NO concentration profiles in the plume. The possibility of measuring nitrogen dioxide NO₂ is also discussed briefly, although measurements turn out to be substantially less likely than those of NO. This feasibility study compiles fundamental data for the optical and radiometric design of an airborne Fourier transform spectrometer and the preparation of in-flight measurements for monitoring of aircraft pollutants.     

Determination of two‐dimensional laboratory‐scale dispersivities

A tracer test was conducted in a laboratory chamber representing a two‐dimensional aquifer to investigate the longitudinal dispersivity (α_L) and the ratio (α_T/α_L) of transverse to longitudinal dispersivity of sandy aquifer materials. Dispersive parameters were obtained by matching the observed chloride plumes at 9 hours and 16 hours after tracer injection with those simulated by a flow and transport model. The best match was found for α_L = 0·2 ? 0·25 cm and α_T/α_L = 0·2. The ratio of α_T/α_L = 0·2 was within the range of laboratory values reported in the literature. Sensitivity analysis revealed that the tracer plume concentration and shape were more sensitive to variations in longitudinal dispersivity than to the ratio of transverse to longitudinal dispersivity. This result contrasted with findings of others, showing that the dispersivity ratio greatly affects contaminant plume shape. However, our experimental boundary conditions restricted expansion of the plume normal to the direction of flow and thus affected the parameter estimation. Copyright © 2004 John Wiley & Sons, Ltd.     

Factors controlling the major ion chemistry of streams in the blue ridge and valley and ridge physiographic provinces of Virginia and Maryland

The factors controlling the chemistry of 69 low-order streams in the Blue Ridge and Valley and Ridge physiographic provinces of Virginia and Maryland were studied over a 13-month period. Principal component analysis was used to examine regional patterns in stream chemistry and to examine the degree to which the chemistry of low-order streams is controlled by the bedrock upon which they flow. Streams clustered into regionally isolated groups, strongly related to bedrock type, with SO^2?₄ and HCO^?₃ the chemical variables of most importance. Sulphate concentrations appear to be strongly controlled by climate and hydrology, and sorption in the soils within the watershed. Much of the atmospherically derived SO^2?₄ accumulates in watersheds during the growing season and is later flushed out. Weathering reactions were found to be particularly important in the production of HCO^?₃, accounting for 91 per cent on an annual basis, and export of divalent cations from these watersheds, accounting for 48–50 per cent on an annual basis. About half of non-anthropogenic Na⁺ was derived from weathering of silicates, whereas nearly all K⁺ was identified with leaching by SO^2?₄. Water chemistry was strongly related to the rock type in the watershed and the weatherability of the component minerals. Rock type is not a randomly distributed function; instead, it is controlled by geologic factors that result in clusters of similar rock types in a given region. When planning large synoptic studies, it is extremely important to consider that a sampling scheme based on random sampling of a non-randomly distributed function May, not provide the most accurate representation of the variables of interest. Instead, a hierarchical sampling scheme May, be indicated. Our results also suggest that, although one sample in time May, be sufficient to characterize the primary geochemical factors controlling stream chemistry throughout the year, it May, not be sufficient to detect subtle, flow-related alterations in chemistry.     

Variation of electrical conductivity in enstatite with oxygen partial pressure: Comparison of observed and predicted behavior

Oxygen partial pressure influences the electrical conductivity of enstatite because it affects the point-defect concentrations in enstatite. The behavior of the defect concentrations with P_O2 are obtained for open and partially closed conditions. On the basis of the defect variations, models for the effect of oxygen pressure on the conductivity can be constructed. The first-order models, which assume one defect type transporting all the charge, predict log(P_O2) vs. log(conductivity) slopes that are not in agreement with slopes derived from measurements on natural single crystals of enstatite. The disagreement could result from: (1) more defect species being present than the assumed charge-neutrality condition gives, or (2) the charge is transported by two or more defect types. The data suggesting the latter is the cause of the disagreement, and hence the experimentally derived activation energies must be treated carefully.     

Dynamical geochemistry of the Hawaiian plume

This paper presents a simple dynamical model for melting and trace element distribution in the Hawaiian mantle plume. I model the plume as a partially molten stagnation point flow against the oceanic lithosphere, and obtain solutions for the temperature, melt migration rate, and trace element concentration within it. Trace element concentrations in the melt exceed simple batch melting predictions by up to 70%. The magnitude of this effect depends strongly on the solid-melt partition coefficientK. Trace elements with differentK therefore experience a “dynamical fractionation” within the plume, and incompatible trace element ratios such asLa/Ce always exceed the batch melting predictions. I suggest a simple model for plume-lithosphere interaction in which melts from these two sources mix in proportions determined by thermodynamic constraints. The model can explain the composition of basalts from Haleakala if the degree of melting of the lithosphereF₁ decreases with time from roughly 10% for tholeiites to 2% for alkalic basalts. These values are considerably higher than previous estimates ofF₁ < 1%, and imply correspondingly smaller and more realistic values ( 10 km) for the thickness of the melted part of the lithosphere. Partial melting of additional depleted sources such as the asthenosphere is therefore not required by the Haleakala data. Estimates ofF₁ are highly sensitive to the values chosen for the partition coefficients, however, and should therefore be interpreted with caution.