The thermal structure and thickness of continental roots

We compare heat flow data from the Precambrian shields in North America and in South Africa. We also review data available in other less well-sampled Shield regions. Variations in crustal heat production account for most of the variability of the heat flow. Because of this variability, it is difficult to define a single average crustal model representative of a whole tectonic province. The average heat flow values of different Archean provinces in Canada, South Africa, Australia and India differ by significant amounts. This is also true for Proterozoic provinces. For example, the heat flow is significantly higher in the Proterozoic Namaqua–Natal Belt of South Africa than in the Grenville Province of the Canadian Shield (61 vs. 41 mW m⁻² on average). These observations indicate that it is not possible to define single value of the average heat flow for all provinces of the same crustal age. Large amplitude short wavelength variations of the heat flow suggest that most of the difference between Proterozoic and Archean heat flow is of crustal origin. In eastern Canada, there is no good correlation between the local values of heat flow and heat production. In the Archean, Proterozoic and Paleozoic provinces of eastern Canada, heat flow values through rocks with the same heat production are not significantly different. There is therefore no evidence for variations of the mantle heat flow beneath these different provinces. After removing the local crustal heat production from the surface heat flow, the mantle (Moho) heat flow was estimated to be between 10–15 mW m⁻² in the Archean, Proterozoic and Paleozoic provinces of eastern Canada. Estimates of the mantle heat flow in the Kaapvaal craton of South Africa may be slightly higher (≈17 mW m⁻²). Large-scale variations of bulk crustal heat production are well-documented in Canada and imply significant differences of deep lithospheric thermal structure. In thick lithosphere, surficial heat flow measurements record a time average of heat production in the lithospheric mantle and are not in equilibrium with the instantaneous heat production. The low mantle heat flow and current estimates of heat production in the lithospheric mantle do not support a mechanical (conductive) lithosphere thinner than 200 km and thicker than 330 km. Temperature anomalies with surrounding oceanic mantle extend to the convective boundary layer below the conductive layer, and hence to depths greater than these estimates. Mechanical and thermal stability of the lithosphere require the mantle part of the lithosphere to be chemically buoyant and depleted in radiogenic elements. Both characteristics are achieved simultaneously by partial melting and melt extraction.     

The distribution of radiogenic heat production as a function of depth in the Sierra Nevada Batholith, California

Geochemical analyses and geobarometric determinations have been combined to create a depth vs. radiogenic heat production database for the Sierra Nevada batholith, California. This database shows that mean heat production values first increase, then decrease, with increasing depth. Heat production is 2 μW/m³ within the 3-km-thick volcanic pile at the top of the batholith, below which it increases to an average value of 3.5 μW/m³ at 5.5 km depth, then decreases to 0.5–1 μW/m³ at 15 km depth and remains at these values through the entire crust below 15 km. Below the crust, from depths of 40–125 km, the batholith's root and mantle wedge that coevolved beneath the batholith appears to have an average radiogenic heat production rate of 0.14 μW/m³. This is higher than the rates from most published xenolith studies, but reasonable given the presence of crustal components in the arc root assemblages. The pattern of radiogenic heat production interpreted from the depth vs. heat production database is not consistent with the downward-decreasing exponential distribution predicted from modeling of surface heat flow data. The interpreted distribution predicts a reasonable range of geothermal gradients and shows that essentially all of the present day surface heat flow from the Sierra Nevada could be generated within the 35 km thick crust. This requires a very low heat flux from the mantle, which is consistent with a model of cessation of Sierran magmatism during Laramide flat-slab subduction, followed by conductive cooling of the upper mantle for 70 m.y. The heat production variation with depth is principally due to large variations in uranium and thorium concentration; potassium is less variable in concentration within the Sierran crust, and produces relatively little of the heat in high heat production rocks. Because silica content is relatively constant through the upper 30 km of the Sierran batholith, while U, Th, and K concentrations are highly variable, radiogenic heat production does not vary directly with silica content.     

Low temperature Phanerozoic history of the Northern Yilgarn Craton, Western Australia

The Phanerozoic cooling history of the Western Australian Shield has been investigated using apatite fission track (AFT) thermochronology. AFT ages from the northern part of the Archaean Yilgarn Craton, Western Australia, primarily range between 200 and 280 Ma, with mean confined horizontal track lengths varying between 11.5 and 14.3 μm. Time–temperature modelling of the AFT data together with geological information suggest the onset of a regional cooling episode in the Late Carboniferous/Early Permian, which continued into Late Jurassic/Early Cretaceous time. Present-day heat flow measurements on the Western Australian Shield fall in the range of 40–50 mW m⁻². If the present day geothermal gradient of  18 ± 2 °C km⁻¹ is representative of average Phanerozoic gradients, then this implies a minimum of  50 °C of Late Palaeozoic to Mesozoic cooling. Assuming that cooling resulted from denudation, the data suggest the removal of at least 3 km of rock section from the northern Yilgarn Craton over this interval. The Perth Basin, located west of the Yilgarn Craton, contains up to 15 km of mostly Permian to Lower Cretaceous clastic sediment. However, published U–Pb data of detrital zircons from Permian and Lower Triassic basin strata show relatively few or no grains of Archaean age. This suggests that the recorded cooling can probably be attributed to the removal of a sedimentary cover rather than by denudation of material from the underlying craton itself. The onset of cooling is linked to tectonism related to either the waning stages of the Alice Springs Orogeny or to the early stages of Gondwana breakup.     

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.     

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.     

Water movement within lac du bonnet batholith as revealed by detailed thermal studies of three closely-spaced boreholes

Successive temperature logs have been obtained over a period of two years in three closely-spaced boreholes in the Lac du Bonnet batholith of the Superior Province of the Canadian Shield. Two of the boreholes, of depth 450 m and 830 m, intersect a dipping fracture zone at 435–450 m. In both holes water is flowing from near the surface to the fracture zone at approximately 1.5–1.9·10⁻⁵ m³ s⁻¹, the flow being inferred from analysis of the temperature logs. Below 25 m, temperatures in these two holes are 0.22–0.28 K lower than those in the third, 145 m, hole.The temperature data have been combined with over 200 thermal conductivity measurements on core samples to produce heat flow values. In the deepest hole heat flow above the fracture zone is 16% higher than that below the zone. This indicates that water is flowing up the fracture zone. The flow rate is approximately 0.3 g s⁻¹ m⁻¹, and the flow has existed for thousands of years.Observation of thermal effects of water flow in massive, relatively unfractured plutons in a region having little topographic relief causes one to be concerned about the reliability of heat flow values measured in similar environments.The regional heat flow is taken to be 50 mW m⁻² after correction for glaciation effects. The average value of 24 determinations of radioactive heat generation in granitic core samples is 5.23 ± 1.11 μW m⁻³, which is more than three times higher than expected for such a heat flow in the Superior Province. This implies that the layer of high radioactive heat generation is thin, being not more than 4 km and probably about 1.3 km thick.     

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.     

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.     

Continental margin magmatism and migmatisation in the west-central Fennoscandian Shield

The Ljusdal Batholith (LjB) is a major component of the central Svecofennian Domain in Sweden. It is separated from the Bothnian Basin to the north by the 1.82–1.80 Ga crustal-scale Hassela Shear Zone (HSZ). The LjB has emplacement ages of 1.86–1.84 Ga, is mainly alkali-calcic, metaluminous, has _Nd values between − 0.3 and + 1.2 and was formed in a magmatic arc setting.

During the Svecokarelian orogeny the LjB was affected by at least three fold episodes. Large-scale folded screens of migmatised metasedimentary rocks occur in the eastern part of the batholith, and to the north of the HSZ, there is a 50 km wide diatexite belt. The Transition Belt (TrB), consisting of 1.88–1.85 Ga granitoids, is located at the northwestern extension of this belt. A calc-alkaline and peraluminous composition combined with negative _Nd values (− 1.7 to − 0.8) indicates a large proportion of metasediments in the source for these granitoids.

U–Pb SIMS data on zircon rims from migmatites and leucogranites to the north and east of LjB yield ages of 1.87–1.86 Ga, i.e. coeval with the granitoids of the LjB and the TrB. There is thus a close relationship between the LjB, the TrB and the migmatites in both space and time. Syn-migmatitic shearing along the HSZ indicates that a proto-HSZ was initiated already at c. 1.86 Ga, and the location of the proto-HSZ is inferred to be controlled by two older nuclei present in the lower parts of the crust. As crustal-scale shear zone systems are known to act as ascent pathways for sheet-like flow in active orogenies the TrB may represents accumulations of melts that were attracted and extracted by the proto-HSZ and intruded in a block that was not pervasively affected by subsequent shear along the HSZ.

An active continental margin setting for the LjB implies subduction at c. 1.86 Ga, and provides a heat source for both the migmatites and the TrB.

A later migmatisation at 1.82 Ga has been recorded to the south of the HSZ. Within the LjB the 1.82 Ga stromatic migmatites are folded by F₂ folds, and the fabric is truncated by 1.80 Ga pegmatites.     

Temperature independent thermal expansivities of sodium aluminosilicate melts between 713 and 1835 K

The thermal expansivities of eight sodium aluminosilicate liquids were derived from the slope of new volume data at low temperatures (713−1072 K) combined with the high temperature (1300−1835 K) volume measurements of Stein et al. (1986) on the same liquids. Melt compositions range from 47−71 wt% SiO₂, 0−31 wt% A1203, and 17−33 wt% Na₂O; the volume of albite supercooled liquid at 1092 K was also determined. The low temperature volumes were derived from measurements of the glass density of each sample at 298 K, followed by measurements of the glass thermal expansion coefficient from 298 K to the respective glass transition interval. This technique takes advantage of the fact that the volume of a glass is equal to the volume of the corresponding liquid at the limiting fictive temperature (T′_f), and that T′_f can be approximated as the onset of the rapid rise in thermal expansion at the glass transition in a heating curve (Moynihan, 1995). No assumptions were made regarding the equivalence of enthalpy and volume relaxation through the glass transition. The propagated error on the volume of each supercooled liquid at T′_f is 0.25%. Combination of these low temperature data with the high temperature measurements of Stein et al. (1986) allowed a constant thermal expansivity of each liquid to be derived over a wide temperature interval (763−1001 degrees) with a fitted 1σ error of 0.6–4.6%; in every case, no temperature dependence to dV/dT^liq could be resolved. Calibration of a linear model equation leads to fitted values ± 1σ (units of cm³/mole) for (26.91 ± .04), (37.49 ± .12), (26.48 ± .06) at 1373 K, and (7.64 ± .08 × 10^-3 cm³/mole-K). The results indicate that neither Si02 nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT^liq is independent of temperature between 713–1835 K over a wide range of liquid composition. Calculated volumes based on this model recover both low and high temperature measurements with a standard deviation <0.25%, whereas values of dV/dT^liq can be predicted within 5.6%.     

The South Patagonian batholith: 150 my of granite magmatism on a plate margin

A new database of 70 U–Pb zircon ages (mostly determined by SHRIMP) indicates that the South Patagonian batholith resulted from the amalgamation of subduction-related plutons from the Late Jurassic to the Neogene. Construction of the batholith began with a voluminous, previously undetected, Late Jurassic bimodal body mainly composed of leucogranite with some gabbro, emplaced along its present eastern margin within a restricted time span (157 to 145 Ma). This episode is, at least in part, coeval with voluminous rhyolitic ignimbrites of the Tobífera Formation, deposited in the deep Rocas Verdes Basin east of the batholith; this was the last of several southwestward-migrating silicic volcanic episodes in Patagonia that commenced in an Early Jurassic extensional tectonic regime. The quasi-oceanic mafic floor of the basin was also contemporaneous with this Late Jurassic batholithic event, as indicated by mutually cross-cutting field relationships. Changes in subduction parameters then triggered the generation of earliest Cretaceous plutons (Cretaceous 1: 144–137 Ma) west of the Late Jurassic ones, a westward shift that culminated at 136–127 Ma (Cretaceous 2) along the present western margin of the batholith. Most mid- to Late Cretaceous (Cretaceous 3: 126–75 Ma) and Paleogene (67–40 Ma) granitoids are represented by geographically restricted plutons, mainly emplaced between the previously established margins of the batholith, and mostly in the far south; no associated volcanic rocks of similar age are known at present in this area. During the final Neogene stage of plutonism (25–15 Ma) a recurrence of coeval volcanism is recognized within and east of the batholith. Typical εNdt values for the granitoids vary from strongly negative (− 5) in the Late Jurassic, to progressively higher values for Cretaceous 1 (− 4), Cretaceous 2 (− 0.7), Cretaceous 3 (+ 2) and the Paleogene (+ 5), followed by lower and more variable ones in the Neogene (− 1 to + 5). These variations may reflect different modes of pluton emplacement: large crustal magma chambers developed in the early stages (Late Jurassic to Cretaceous 1), leading to widespread emplacement of plutons with a crustal signature, whereas the Cretaceous 2, Cretaceous 3 and Palaeogene parts of the batholith resulted from incremental assembly of small plutons generated at greater depths and with higher εNdt. This does not in itself justify the idea of a reduction in crustal character due to progressive exhaustion of fusible material in the crust through which the magmas passed.     

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.     

Seismic, gravity and petrological evidence for partial melt beneath the thickened Central Andean crust (21–23°S)

On the basis of seismic refraction investigations and gravimetric data we have modelled the crustal structure of the southern Central Andes (21–23°S). A pronounced variation in crustal parameters is seen in N-S- and W-E-crossing seismic profiles over the entire Andean orogene, characterized by a crustal thickness of up to 70 km under the magmatic arc and backarc, strongly reduced seismic velocities and a Bouguer minimum of −450 mGal. Anomalously low velocities of 5.9–6.0 km/s in the deeper crust of the Western Cordillera and Altiplano regions lead to an over-compensation of the Bouguer minima resulting in values of crustal densities higher than estimates based purely on seismic velocity measurements. In an attempt to reconcile these differences, the behavior of crystalline rocks based on published laboratory data was studied under varying pressure and temperature conditions up to the range of partial melting. If the temperature is increased above the melting point, a rapid decrease in seismic velocity is accompanied by a slow decrease in density. For the Central Andes, a good fit of the observed and calculated Bouguer anomalies is obtained if the densities of the rocks from the low-velocity zone (LVZ) beneath the Western Cordillera and the Altiplano are varied. Model calculations lead to a velocity-density relation for partial molten rocks that allows the melt proportions of rocks to be estimated. Model calculations indicate that 15–20 vol.% of basaltic to andesitic melt at depth is necessary to explain the LVZ and Bouguer anomaly beneath the arc and parts of the backarc. High heat flow values (100 mW/m²) support the idea that large areas of the deeper Andean crust are strongly weakened by the presence of partially molten rocks, resulting in reduced seismic velocities, with the Western Cordillera, the active volcanic arc of the Andean mountain range, acting as a ductile buffer between the two more rigid crustal blocks of the forearc and backarc regions.     

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.     

Influence of volcanic activity on spring water chemistry at Popocatepetl Volcano, Mexico

The results of the 7 years (1994–2000) of monthly monitoring of spring water before and during eruptions show response to volcanic activity. Low salinity and temperature characterize most of the springs, which are located on the flanks of Popocatepetl Volcano. The pH ranges from 5.8 to 7.8 and temperature from 3 to 36 °C. Oxygen and hydrogen isotopic data show that the water is of meteoric origin, but SO₄²⁻, Cl⁻, F⁻, HCO₃⁻, B, and SO₄²⁻/Cl⁻ variations precede main eruptive activity, which is considered linked to influx of magmatic gases and acid fluids that react with sublimates and host rock and mix with the large water system. Na⁺, Ca²⁺, SiO₂ and Mg²⁺ concentrations in the water also increased before eruptive activity. The computed partial pressure of CO₂ in equilibrium with spring waters shows values higher than air-saturated water (ASW), with the highest values up to 0.73 bar of pCO₂. Boron is detected in the water only preceding the larger eruptions. When present, boron concentration is normally under health standard limits, but in two cases the concentration was slightly above. Other components are within health standard limits, except for F⁻ in one spring.     

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).     

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

Geotechnical characterisation of Obudu damsite, Obudu, south-eastern Nigeria

The Obudu dam is being built across Abeb river in Obudu area of the Cross River State (Nigeria). The earthfill dam will be approximately 18 m high with a crest length of 385 m. The dam site is located within part of the Obudu crystalline basement plateau which is a region of low seismicity. The terrain is smoothly undulating and low lying and was known to be composed of unclassified basement and decomposed bedrock (overburden). The present study was carried out to assess the suitability of the chosen dam axis based on the determination of the nature and geotechnical characteristics of the overburden and bedrock. The investigation included geophysical surveys, bearing capacity tests (cone penetrometer and standard penetration), classification and grain size distribution as well as tests for compaction, consolidation and compressive strength. The results show that the bedrock is heterogeneous, including gneisses sillimanite, biotite and granite types), dolerite, quartzite and pegmatite with an overall moderate strength (about 76.04 MN m⁻² average) and fair rock mass rating (RMR). The bedrock along the dam axis is apparently lacking in major fractures which could lead to short circuiting of the future impoundment. The overburden (soil) comprises silt (MH, ML), silty clay (CL) and silty sand (SM) with a combined thickness of about 2–20 m, increasing away from the valley floor towards the shoulders. Generally the overburden is of suitable compressive strength (150–300 KN m⁻²), low to medium plasticity and swelling potential and low permeability (up to 1.41 × 10⁻⁷ ms⁻¹) which would ensure a tight reservoir. The material settlement is expected to be small and slow. Accordingly, excavation of up to 5 m, decreasing towards the valley shoulders has been suggested to expose the recommended bearing medium: fresh/competent bedrock and overburden in the valley floor and flanks, respectively. While a detailed investigation of burrow areas was not part of the present study, a few potential sites in the dam axis and reservoir areas have been suggested based on the evaluation of material properties.     

Overbank and channelfill deposits of the modern Yellow River delta

The Huanghe is noted for its high transport rate of silt and clay, which may reach depth-averaged values of 200 kg m⁻³ during peak discharge. The sediment load transported through the river on entering the delta plain, amounts to 10¹² kg per year. In contrast to most other large deltas only one distributary channel is active at any one time. The high sediment load causes the rivermouth to prograde at a yearly rate of 1–4 km into the shallow (less than 20 m deep) Bohai gulf. The vertical aggradation of the channel belt and mouth bar complex is also rapid (decimetres per year on average), so that after a normal average of twelve years increasing channel instability and avulsion create the start of a new delta lobe.

A series of satellite images covering the last fifteen years has provided insight in the evolution of the river pattern as well as the progradation of the delta front. A newly developed distributary passes from a multichannel to a single, straight channel system, and ends with the formation of meanders. The protruding mature delta lobe shows a radiating pattern of crevasse channels.

Overbank/ crevasse deposits are made of vertically stacked dm-scale waning flow sequences, structurally characterized by (from bottom to top) small scour-and-fills, even (parallel) lamination, and climbing-ripple crosslamination. Accumulation rates on crevasse splays can be predicted on the basis of estimated river sediment discharge. It can be concluded that each sequence has been deposited within a few hours, and that tidal waterlevel fluctuations may have played a role in the generation of a single sequence.