Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

The usability of bottom ash as an engineering material when amended with different matrices

This study aims at investigating the utilization of bottom ash obtained from four different power stations as a construction fill and landfill bottom liner. For the matrix material, commercial powdered bentonite, construction lime and natural clay were used. Compaction tests (Standard Proctor and vibratory hammer) were carried out on the different ratios of bottom ash and matrix material. The optimum water content ranged from 40 to 45% yielding a dry density mostly ca 1 Mg m⁻³. Uniaxial compressive strength of mixtures ranges from 0.1 to 0.5 kgf cm⁻² which showed a 3–20-fold increase when tested on 28-day cured specimens. Triaxial compression tests yield varying rates of shear strength which also showed as high as an 11-fold increase for cured specimens. The hydraulic conductivity of those mixtures was mostly ca 10⁻⁴ cm s⁻¹, which is not considered to be low enough for landfill lining. Leaching tests using deionized water were also performed to investigate the possible effect of leachate produced from the mixtures on the environment. In conclusion a light density and environmentally friendly mixture is determined and proposed as construction filler.     

Dissolution kinetics of experimentally shocked silicate minerals

The effect of lattice strain on mineral dissolution rates was examined by comparing the dissolution rates of shocked and unshocked minerals. Labradorite, oligoclase and hornblende were explosively shocked at mean pressures ranging from 4 to 22 GPa. The labradorite was examined with transmission electron microscopy to estimate the density of dislocations produced by the shock-loading experiment. Subsamples of the labradorite were then thermally annealed to remove some of the dislocations, and to evaluate the importance of such thermal pre-treatment in preparing mineral surfaces for experiments. The dissolution rates of these minerals were measured in batch experiments at pH-values of 2.7 and 4.0.

Shock-loading did not produce extremely high dislocation densities in the labradorite. The density of dislocations in the unshocked labradorite is ≤ 10¹⁰ m⁻². After shocking, the density increases to 10¹²-10¹³ m⁻². The distribution of dislocations is heterogeneous, and the amount of deformation does not increase substantially with shock pressure. These results are highly atypical of shock-modified minerals, where relatively low shock pressures usually induce high ( 10¹⁵ m⁻²) densities of dislocations. Thermal annealing for 1 hr. at 900°C in a dry furnace removes many dislocations from the shocked labradorite.

The difference in observed dissolution rates between shocked and unshocked minerals appears to have a weak correlation with the increase in the density of dislocations on the mineral surface. The unshocked and shocked oligoclase and hornblende samples exhibit limited dissolution enhancement at pH 4.0. Increasing the density of dislocations by several orders of magnitude with shock-loading causes a relatively small increase in dissolution rates for these silicate minerals. These results suggest that the surface dislocations produced by the shock treatment are not the primary sites for dissolution reactions.     

A comparison of mud- and sand-dominated meanders in a downstream coarsening reach of the mixed bedrock-alluvial Klip River, eastern Free State, South Africa

Along a 28 km reach of the Klip River, eastern Free State, South Africa, mud- and sand-dominated meanders have developed in close proximity within a floodplain wetland up to 1.5 km wide, providing an unusual opportunity to compare their characteristics under similar hydrological conditions. Throughout the reach, the channel bed is grounded on sandstone/shale bedrock although the banks are alluvial, and most river activity occurs during summer high flows. The reach can be divided into three geomorphological zones: Zone 1 (0–11 km), a muddy proximal part with a single meandering channel (w/d < 10) and near-permanent standing water in oxbows and backswamps; Zone 2 (11–17.5 km), a transitional mud-to-sand part with one main channel (w/d  20–30), a number of sinuous palaeochannels and oxbows, and only limited standing water; and Zone 3 (17.5–28 km), a sandy distal part with a single meandering channel (w/d  15–30), scroll bars and oxbows, and little standing water. Each zone also has a distinctive sedimentology: Zone 1 is characterised by an  3–4 m thick succession of basal sand and minor granules overlain by dominantly muddy sediment deposited primarily by oblique accretion in meander bends; Zone 2 is characterised by < 4 m of interbedded sand and mud deposited primarily by lateral point-bar accretion, although a history of avulsions also attests to the importance of abandoned-channel accretion; and Zone 3 is characterised by < 3 m of dominantly sand deposited primarily by lateral point-bar accretion. This unusual downstream sediment coarsening trend, and the associated changes in channel and floodplain character, are independent of sediment inputs from tributaries, and result from a downstream increase in bankfull unit stream power from < 3.5 W m^− 2 (Zone 1) to  4–10 W m^− 2 (Zone 3). Mud is deposited primarily in low-energy Zone 1 but is conveyed in suspension more effectively through higher energy Zones 2 and 3, only forming drapes over sandy lateral accretion deposits during waning flood stages. The downstream increase in unit stream power is controlled in part by a slight downstream increase in floodplain gradient that may be related to a subtle variation in the erosional resistance of the bedrock underlying the channel bed. These findings add to previous work on meandering rivers by demonstrating that mud-dominated meanders can occur in long-term erosional settings where the channel bed is grounded on bedrock, and that downstream fining trends may be reversed locally.     

Late Quaternary basin evolution of the Gulf of Corinth: Sequence stratigraphy, sedimentation, fault–slip and subsidence rates

The Gulf of Corinth is a graben, which has undergone extension during the Late Quaternary. The subsidence rate is rapid in the currently marine part whereas uplift now affects a large part of the initially subsiding area in the North Peloponnese. In this paper, we document the rates of subsidence/uplift and extension based on new subsurface data, including seismic data and long piston coring in the deepest part of the Gulf. Continuous seismic profiling data (air gun) have shown that four (at least) major oblique prograding sequences can be traced below the northern margin of the central Gulf of Corinth. These sequences have been developed successively during low sea level stands, suggesting continuous and gradual subsidence of the northern margin by 300 m during the Late Quaternary (last 250 ka). Subsidence rates of 0.7–1.0 m kyr^− 1 were calculated from the relative depth of successive topset to foreset transitions. The differential total vertical displacement between the northern and the southern margins of the Corinth graben is estimated at about 2.0–2.3 m kyr^− 1.

Sequence stratigraphic interpretation of seismic profiles from the basin suggests that the upper sediments (0.6 s twtt thick) in the depocenter were accumulated during the last 250 ka at a mean rate of 2.2–2.4 m kyr^− 1. Long piston coring in the central Gulf of Corinth basin enabled the recovery of lacustrine sediments, buried beneath 12–13.5 m of Holocene marine sediments. The lacustrine sequence consists of varve-like muddy layers interbedded with silty and fine sand turbidites. AMS dating determined the age of the marine–lacustrine interface (reflector Z) at about 13 ka BP. Maximum sedimentation rates of 2.4–2.9 m kyr^− 1 were calculated for the Holocene marine and the last glacial, lacustrine sequences, thus verifying the respective rates obtained by the sequence stratigraphic interpretation. Recent accumulation rates obtained by the ²¹⁰Pb-radiometric method on short sediment box cores coincide with the above sedimentation rates. Vertical fault slip rates were measured by using fault offsets of correlated reflector Z. The maximum subsidence rate of the depocenter (3.6 m kyr^− 1) exceeds the maximum sedimentation rate by 1.8 m kyr^− 1, which, consequently, corresponds to the rate of deepening of the basin's floor. The above rates indicate that the 2.2 km maximum sediment thickness as well as the 870 m maximum depth of the basin may have formed during the last 1 Ma, assuming uniform mean sedimentation rate throughout the evolution of the basin.     

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area.

Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6×10⁻¹⁷ mol m⁻² s⁻¹ for biotite. Faster weathering rates of 1.8 to 3.6×10⁻¹⁶ mol m⁻² s⁻¹ are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering.     

Gum rosin (colophony): A suitable material for thermomechanical modelling of the lithosphere

We investigate the use of a ductile material with temperature-sensitive viscosity for thermomechanical modelling of the lithosphere. First, we consider the scaling of mechanical and thermal properties. For a normal field of gravity, the balance of stresses and body forces sets the stress scale, in proportion to the linear dimensions and the densities. The equation of thermal conduction sets the time scale. The activation enthalpy for creep sets the temperature scale; but the thermal expansivity provides an additional constraint on this temperature scale.

Gum rosin appears to be a suitable material for lithospheric modelling. We have measured its flow properties, at various temperatures, in a specially designed rotary viscometer with unusually low machine friction. The rosin is almost Newtonian. Strain rate depends upon stress to the power n, where 1.0 <n < 1.14. The viscosity varies over 5 orders of magnitude, from about 10² Pa s at 80°C, to about 10⁷ Pa s at 40°C. The activation enthalphy is thus about 250 kJ/mol. Measured with a needle probe, the thermal conductivity is 0.113 ± 0.001 W m⁻¹K⁻¹; the thermal diffusivity, (6±3) ×10⁻⁷ m² s⁻¹. Calculated from X-ray profiles, the thermal expansivity is about 3 × 10⁻⁴ K⁻¹. These thermal and mechanical properties make gum rosin suitable for thermomechanical models, where linear dimensions scale down by a factor of 10⁶; time, by 10¹¹; viscosity, by 10¹⁷; and temperature change, by 10¹.     

Dissolved load of the Loire River: chemical and isotopic characterization

The Loire River, with one of the largest watersheds in France, has been monitored just outside the city of Orleans since 1994. Physico-chemical parameters and major and trace elements were measured between 2-day and 1-week intervals according to the river flow. The sampling site represents 34% of the total Loire watershed with 76% silicate rocks and 24% carbonate rocks.

Elements are transported mainly in the dissolved phase with the ratio of total dissolved salts (TDS) to suspended matter (SM) ranging between 1.6 and 17.4. Chemical weathering of rocks and soils are thus the dominant mechanisms in the Loire waters composition. The highest TDS/SM ratios are due to dissolved anthropogenic inputs. The database shows no link between NO₃⁻ content and river flow. The Na⁺, K⁺, Mg²⁺, SO₄²⁻, and Cl⁻ concentrations are seen to decrease with increasing discharge, in agreement with a mixing process involving at least two components: the first component (during low flow) is concentrated and may be related with input from the groundwater and sewage station water, the second component (during high flow) is more dilute and is in agreement with bedrock weathering and rainwater inputs. A geochemical behaviour pattern is also observed for HCO₃⁻ and Ca²⁺ species, their concentrations increase with increasing discharge up to 300 m³/s, after which, they decrease with increasing discharge. The Sr isotopic composition of the dissolved load is controlled by at least five components — a series of natural components represented by (a) waters draining the silicate and carbonate bedrock, (b) groundwater, and (c) rainwaters, and two kinds of anthropogenic components.

The aim of this study is to describe the mixing model in order to estimate the contribution of each component. Finally, specific export rates in the upper Loire watershed were evaluated close to 12 t year⁻¹ km⁻² for the silicate rate and 47 t year⁻¹ km⁻² for the carbonate rate.     

A soil acidification study using the PROFILE model on two contrasting regions in Switzerland

The steady-state soil chemistry model PROFILE was used to calculate the chemical status of forest soils under present deposition loads for two areas with dissimilar ecosystem properties. Two regions in Switzerland, with contrasting bedrock geology were selected to be investigated in detail: 88 locations in the Jura Mountains, representative for carbonate bedrock and 91 locations in the Ticino Area dominated by metamorphic crystalline host rocks. Weathering rates calculated for the key regions cover the tremendous range between 0.013 and 25 keq ha⁻¹ yr⁻¹. In the Ticino Area, the effect of increased abundance of relatively fast weathering silicates (epidote, hornblende and plagioclase) on the weathering rate is apparently masked by the total effects of the physical conditions applied and by the variation in the deposition load. In the Jura Mountains, generally high weathering rates occur with about 50% of the sites yielding rates above 1 keq ha⁻¹ yr⁻¹. In many of the sites investigated, however, carbonates have already been dissolved completely in the soil horizons of interest resulting in very low weathering rates. The critical load of actual acidity was calculated according to: CL_Acidity=R_Weathering−ANC_Leaching, where alkalinity leaching is estimated by keeping the base cation to aluminum molar ratio at the critical limit of 1 at steady-state. The minimum critical load calculated was 0.2 keq ha⁻¹ yr⁻¹ and the maximum was 6.2 keq ha⁻¹ yr⁻¹. Comparing the cumulative frequency distributions of critical loads of actual acidity for forest soils in the individual areas it can be seen that the differences between the key regions are less substantial than with the weathering rates. Critical loads of acidity for the Ticino Area range from 1 to 3.9 keq ha⁻¹ yr⁻¹. Sites yielding the lowest critical loads of acidity are observed in the Jura Mountains. Among these apparent sensitive soils are soils with intermediate or high weathering rates, although it has depleted topsoil layers. Within the context of this model application, it becomes apparent that the sensitivity of these soils with respect to acidification is also governed by the alkalinity leaching term and not only by the susceptibility of its minerals to weathering.     

Overconsolidation effects of ground freezing

Temporary ground freezing is a valuable technique for stabilizing soft soils during construction. It imparts large increases in strength and bearing capacity to most soils. However, freezing can cause significant changes in soil structure and density which can lead to adverse settlement during thaw.

Settlement of clay soils after freezing and thawing is the result of the suction forces that draw pore water to the freezing front. These suction forces cause an increase in the effective stress on the clay beneath the freezing front, and thus cause an overconsolidation of the clay. As these suction forces often exceed 1 atm, their direct measurement is not easy.

A technique for indirectly determining the maximum suction occurring during freezing is presented which utilizes the apparent memory that clay soils have for maximum past (preconsolidation) pressures. Suctions as large as 532 kN m⁻² were observed after freezing and thawing a clay soil which was initially consolidated to 128 kN m⁻².

The volume changes resulting from the freezing and thawing of clays were related to the plastic limit and were observed in the laboratory to be as high as 25%. If provisions are not made to account for these volume changes in a ground freezing project, considerable damage to structures can occur from settlement and the resulting stresses.     

Geothermal studies in the Hyderabad granitic region and the crustal thermal structure of the Southern Indian Shield

Based on temperature measurements in three boreholes (one specially drilled for the purpose) and thermal conductivity determinations, heat flow density values were determined for three sites in the Archaean Hyderabad granitic batholith. A mean heat flow density value of 40± 1 (s.d.) mW m⁻² has been obtained. The heat generation in its rocks (5.57 μW m⁻³) is significantly higher than in average crustal rocks. It has been proposed that the Hyderabad batholith has a layered structure with a thin ( ≈ 1 km) surface layer of high radioactivity. These results together with the already reported data have been used to estimate the conductive steady-state temperature within and at the base of the crust of the Southern Indian Shield, yielding values of the same order as found in the Western Australian Shield.     

Electrokinetic retention, migration and remediation of nitrates in silty loam soil under hydraulic gradients

Contamination of groundwater by nitrates leaching from intensive agricultural and livestock operations have become a major concern for surrounding communities that use groundwater as their water supply. High levels of nitrate in drinking water poses a significant risk to human health, i.e., methaemoglobinaemia (“blue baby” syndrome).

The traditional pump-and-treat method is ineffective in medium to fine-textured agricultural soils due to the low hydraulic conductivity. This paper presents the results of a laboratory experiment investigating the feasibility of using electrokinetic treatment in retaining, accumulating, moving and remediating nitrates in a silty loam soil under hydraulic gradients.

A hydraulic gradient of 1.25 was applied to the horizontal soil columns to simulate a groundwater movement system. The study was performed in two stages. During the first stage of the experiment, the anode located at the inflow end of the columns was able to retard the movement of nitrates even under a hydraulic gradient of 1.25. After 15 days of flow, the effluent nitrate concentration in the control column rose to 90 mg l⁻¹ while no nitrates were detected in the effluent from columns subjected to the electrokinetic treatment.

After 15 days, the polarity of the electrodes was switched and this second stage lasted another 20 days. The cathode near the inflow end promoted the conversion of nitrates entering the column to other forms. The anode near the outflow end promoted the migration and accumulation of negatively charged nitrate ions towards the outflow end. By the 12th day, the nitrate concentrations in the electrokinetically treated columns were brought down to <5 mg NO₃-N l⁻¹. Electrokinetic treatment retarded nitrate movement against a hydraulic gradient of 1.25 and effectively restored a medium-textured soil contaminated with NO₃-N.

The NO₂-N level remained below 1 mg l⁻¹ throughout the experiment. The hydraulic conductivity varied between 1.0E–7 and 3.6E–7 m s⁻¹. The current requirement varied between 3 and 6 mA.     

The role of buried bedrock valleys on the development of karstic aquifers in flat-lying carbonate bedrock: insights from Guelph, Ontario, Canada

A spatial relationship between high capacity municipal production wells (>5,000 m³/day), completed in a deep bedrock aquifer, and a buried bedrock valley was recognized in the city of Guelph, southwestern Ontario, Canada. Most production wells are completed in a discrete zone, ～60 m below ground surface, within flat-lying dolostones of the Silurian Amabel Formation. Thick overburden and limited subsurface data make characterization of the karstic aquifer difficult. This study integrates hydrogeologic data with models of karst formation, deriving a conceptual model of porosity development as it relates to valley incision. Bedrock valley incision likely occurred prior to the early Wisconsinan age (>60–75 ka). Incision created steep hydraulic gradients within the flat-lying bedrock, and provided the driving force required to integrate regional groundwater flow into karst conduits that drained at the base of the valley. Dissolution in production zone dolostones was favoured over dissolution in shallower bedrock due to abundant bedding plane partings and fossiliferous facies with high intercrystalline porosity. Burial of the valley during subsequent ice advances reduced the valley’s hydraulic influence and the efficacy of the flow system to cause dissolution. The high capacity municipal wells near the buried bedrock valley tap into the now dormant karst aquifer system.     

青藏高原南缘某机场场区深厚覆盖层工程地质特征

青藏高原南缘某拟建机场场区发育第四系深厚覆盖层,对该工程建设具有较大的制约作用.钻孔资料显示,该深厚覆盖层普遍分布于整个场区,厚度均在30 m以上,最大孔深105 m仍未揭穿.纵向上深厚覆盖层由上而下可划分为4层:全新世泥石流堆积层(Qsef4)、全新世冲洪积堆积层(Qal+pl4)、全新世湖相堆积层(Ql4)和晚更新...     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

Geochemistry and petrology of Tertiary volcanic rocks and related ultramafic xenoliths from the central and eastern Oman Mountains

The Tertiary volcanic rocks of the central and the eastern parts of the Oman Mountains consist mainly of basanites with abundant upper mantle ultramafic xenoliths. The lavas are alkaline (42–43 wt.% SiO₂; 3.5–5.5 wt.% Na₂O + K₂O). They include primitive (11–14 wt.% MgO) features with strong OIB-like geochemical signatures. Trace element and Sr–Nd isotope data for the basanites suggest mixing of melts derived from variable degrees of melting of both garnet- and spinel lherzolite-facies mantle source. The associated xenolith suite consists mainly of spinel and Cr-bearing diopside wehrlite, lherzolite and dunite with predominantly granuloblastic textures. No significant difference in chemistry was found between the basanites and xenoliths from the central and eastern Oman Mountains, which indicate a similar mantle source. Calculated oxygen fugacity indicates equilibration of the xenoliths at − 0.43 to − 2.2 log units above the fayalite–magnetite–quartz (FMQ) buffer. Mantle xenolith equilibration temperatures range from 910–1045 + 50 °C at weakly constrained pressures between 13 and 21 kbar. Xenolith data and geophysical studies indicate that the Moho is located at a depth of  40 km. A geotherm substantially hotter (90 mW m^− 2) than the crust–mantle boundary (45 mW m^− 2) is indicated and probably relates to tectonothermal events associated with the local and regional Tertiary magmatism. The petrogenesis of the Omani Tertiary basanites is explained by partial melting of an asthenospheric mantle protolith during an extension phase predating opening of the Gulf of Aden and plume-related alkaline volcanic rocks.     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Upper Mississippi embayment shallow seismic velocities measured in situ

Vertical seismic compressional- and shear-wave (P-and S-wave) profiles were collected from three shallow boreholes in sediment of the upper Mississippi embayment. The site of the 60-m hole at Shelby Forest, Tennessee, is on bluffs forming the eastern edge of the Mississippi alluvial plain. The bluffs are composed of Pleistocene loess, Pliocene-Pleistocene alluvial clay and sand deposits, and Tertiary deltaic-marine sediment. The 36-m hole at Marked Tree, Arkansas, and the 27-m hole at Risco, Missouri, are in Holocene Mississippi river floodplain sand, silt, and gravel deposits. At each site, impulsive P- and S-waves were generated by man-made sources at the surface while a three-component geophone was locked downhole at 0.91-m intervals.

Consistent with their very similar geology, the two floodplain locations have nearly identical S-wave velocity (V_S) profiles. The lowest V_S values are about 130 m s⁻¹, and the highest values are about 300 m s⁻¹ at these sites. The shear-wave velocity profile at Shelby Forest is very similar within the Pleistocene loess (12 m thick); in deeper, older material, V_S exceeds 400 m s⁻¹.

At Marked Tree, and at Risco, the compressional-wave velocity (V_P) values above the water table are as low as about 230 m s⁻¹, and rise to about 1.9 km s⁻¹ below the water table. At Shelby Forest, V_P values in the unsaturated loess are as low as 302 m s⁻¹. V_P values below the water table are about 1.8 km s⁻¹. For the two floodplain sites, the V_P/V_S ratio increases rapidly across the water table depth. For the Shelby Forest site, the largest increase in the V_P/V_S ratio occurs at 20-m depth, the boundary between the Pliocene-Pleistocene clay and sand deposits and the Eocene shallow-marine clay and silt deposits.

Until recently, seismic velocity data for the embayment basin came from eartquake studies, crustal-scale seismic refraction and reflection profiles, sonic logs, and from analysis of dispersed earthquake surface waves. Since 1991, seismic data for shallow sediment obtained from reflection, refraction, crosshole and downhole techniques have been obtained for sites at the northern end of the embayment basin. The present borehole data, however, are measured from sites representative of large areas in the Mississippi embayment. Therefore, they fill a gap in information needed for modeling the response of the embayment to destructive seismic shaking.     

Late quaternary floodplain sedimentation along the Pomme de Terre River,southern Missouri

New cross sections and dates from along the Pomme de Terre River clarify the complex local history of valley development and floodplain sedimentation. The observed history begins with a series of ancient bedrock strath terraces that record past bedrock valley positions at 15.5 to more than 58 m above the modern bedrock floor. Each strath is capped by 1–2 m of channel gravel and sand permeated by red clay. Sometime previous to ca. 140,000 yr B.P., a much lower bedrock valley only about 5–6 m above the modern level was excavated. By 140,000 yr B.P., accumulation of red and gray mottled silty clay had commenced, and had reached to 8.5 m above the modern floodplain before 48,900 ± 900 ¹⁴C yr B.P. Sometime between ca. 49,000 and 45,000 ¹⁴C yr B.P., erosion caused abandonment of an oxbow meander, and lowered the bedrock valley to about its present depth. Younger yellowish-red and gray mottled silty clay alluvium then began accumulating. This mid-Wisconsinan fill reached to 2.5 m above the modern floodplain sometime before 31,800 ± 1340 ¹⁴C yr B.P., at which time another erosional phase was in progress. A late Wisconsinan olive clay accumulated between 27,480 ± 1950 and ca. 23,000 ¹⁴C yr B.P., followed by approximate stability until 13,550 ± 400 ¹⁴C yr B.P. After stability, an erosional episode began, but by 10,200 ± 330 ¹⁴C yr B.P., deposition of a distinctive brown clayey silt was underway. This early Holocene fill reached to about the same level as the mid-Wisconsinan fill by 8100 ± 140 ¹⁴C yr B.P. Erosion occurred between this date and 7490 ± 170 ¹⁴C yr B.P., but the former floodplain level was rapidly reattained, and was apparently stable until ca. 5000 ¹⁴C yr B.P. Finally, erosional unconformities and 17 dates from the brown clayey silt, and from younger grayish-brown silty sand underlying the modern floodplain, record subsequent episodes of floodplain erosion at ca. 5000, 2900, 1500 and 350 ¹⁴C yr B.P. The timing of Pomme de Terre floodplain sedimentary regimes, characterized by net aggradation, erosion, or stability, may have been controlled by climate. In particular, both periods of stability appear to have been coeval to times of strongly zonal upper atmospheric circulation. Intensified zonal circulation would have resulted in less frequent large floods and an increased dominance by floods of small to moderate size. In contrast, there are no obvious parallels to be drawn between this local alluvial history and sea level or glacial outwash induced baselevel changes.     

Dating bedrock gorge incision in the French Western Alps (Ecrins-Pelvoux massif) using cosmogenic 10Be

We report in-situ produced ¹⁰Be data from the Gorge du Diable (French Western Alps) to date and quantify bedrock gorge incision into a glacial hanging valley. We sampled gorge sidewalls and the active channel bed to derive both long-term and present-day incision rates. ¹⁰Be ages of sidewall profiles reveal rapid incision through the late Holocene (ca 5 ka) at rates ranging from 6.5 to 13 mm yr⁻¹. Present-day incision rates are significantly lower and vary from 0.5 to 3 mm yr⁻¹ within the gorge. Our data imply either delayed initiation of gorge incision after final ice retreat from internal Alpine valleys at ca 12 ka, or post-glacial surface reburial of the gorge. Our results suggest that fluvial incision rates >1 cm yr⁻¹ into crystalline bedrock may be encountered in transient landscape features induced by glacial-interglacial transitions.