On the effects of preferential or barrier flow features on solute plumes in permeable porous media

Despite that discrete flow features (DFFs, e.g. fractures and faults) are common features in the subsurface, few studies have explored the influence of DFFs on solute plumes in otherwise permeable rocks (e.g. sandstone, limestone), compared to low-permeability rock settings (e.g. granite and basalt). DFFs can provide preferential flow pathways (i.e. ‘preferential flow features’; PFFs), or can act to impede flow (i.e. ‘barrier flow features’; BFFs). This research uses a simple analytical expression and numerical modelling to explore how a single DFF influences the steady-state distributions of solute plumes in permeable aquifers. The analysis quantifies the displacement and widening (or narrowing) of a steady-state solute plume as it crosses a DFF in idealised, 1 × 1 m moderately permeable rock aquifers. Previous research is extended by accounting for DFFs as 2D flow features, and including BFF situations. A range of matrix-DFF permeability ratios (0.01 to 100) and DFF apertures (0.25 mm to 2 cm), typical of sedimentary aquifers containing medium-to-large fractures, are considered. The results indicate that for the conceptual models considered here, PFFs typically have a more significant influence on plume distributions than BFFs, and the impact of DFFs on solute plumes generally increases with increasing aperture. For example, displacement of peak solute concentration caused by DFFs exceeds 20 cm in some PFF cases, compared to a maximum of 0.64 cm in BFF cases. PFFs widen plumes up to 9.7 times, compared to a maximum plume widening of 2.0 times in BFF cases. Plumes crossing a PFF are less symmetrical, and peak solute concentrations beneath PFFs are up to two orders of magnitude lower than plumes in BFF cases. This study extends current knowledge of the attenuating influence of DFFs in otherwise permeable rocks on solute plume characteristics, through evaluation of 2D flow effects in DFFs for a variety of DFF apertures, and by considering BFF situations.     

Nanoscale porosity in SAFOD core samples (San Andreas Fault)

With transmission electron microscopy (TEM) we observed nanometer-sized pores in four ultracataclastic and fractured core samples recovered from different depths of the main bore hole of the San Andreas Fault Observatory at Depth (SAFOD). Cutting of foils with a focused ion beam technique (FIB) allowed identifying porosity down to the nm scale. Between 40 and 50% of all pores could be identified as in-situ pores without any damage related to sample preparation. The total porosity estimated from TEM micrographs (1–5%) is comparable to the connected fault rock porosity (2.8–6.7%) estimated by pressure-induced injection of mercury. Permeability estimates for cataclastic fault rocks are 10^? 21–10^? 19 m² and 10^? 17 m² for the fractured fault rock. Porosity and permeability are independent of sample depth. TEM images reveal that the porosity is intimately linked to fault rock composition and associated with deformation. The TEM-estimated porosity of the samples increases with increasing clay content. The highest porosity was estimated in the vicinity of an active fault trace. The largest pores with an equivalent radius > 200 nm occur around large quartz and feldspar grains or grain-fragments while the smallest pores (equivalent radius < 50 nm) are typically observed in the extremely fine-grained matrix (grain size < 1 μm). Based on pore morphology we distinguish different pore types varying with fault rock fabric and alteration. The pores were probably filled with formation water and/or hydrothermal fluids at elevated pore fluid pressure, preventing pore collapse. The pore geometry derived from TEM observations and BET (Brunauer, Emmett and Teller) gas adsorption/desorption hysteresis curves indicates pore blocking effects in the fine-grained matrix. Observations of isolated pores in TEM micrographs and high pore body to pore throat ratios inferred from mercury injection suggest elevated pore fluid pressure in the low permeability cataclasites, reducing shear strength of the fault.     

Age estimation of the deposition of the cretaceous Upper Sandstones and a later remagnetization event,from Hirna area,SE Ethiopia

Outcrops of the Cretaceous Upper sandstone formation some 375 km to the East of Addis Ababa on the motor Highway to Harar was paleomagnetically investigated. About seventy core samples were collected at various stratigraphic levels from 250–300 meters thick sedimentary formation. After standard sample preparations in the laboratory the resulting specimens were subjected to routine paleomagnetic demagnetization protocol. In the first steps of demagnetizations process the recent and viscous magnetizations were removed by heating until a temperature of level of 300 °C. Further demagnetization of the samples resulted in the isolation of the final magnetization with stable line segments that is directed towards the origin, which is interpreted as Characteristic Remanent Magnetization (ChRM). Rock – magnetic experiments have identified goethite (αFeOOH), hematite (αFe₂O₃), detritial hematite, and magnetite as the magnetic mineral phases carrying the remanence. The ChRM identified resulted in an average value of (D_s = 0.5°, I_s = ?0.7°, α₉₅ = 4.3°, N = 34) for the red sandstones while an average value of (D_s = 335.8°, I_s = ?31.8°, α₉₅ = 4.7°, N = 14) for the limestone intercalations. The former ChRM in the red sandstone is determined to be secondary while the latter ChRM is known to be primary. Comparison of these directional results and their pole equivalents with the African plate Apparent Polar Wander Path curve established by Besse and Courtillot (2003) give ages of between 115–130 Million years for the limestone intercalation and ages of 30 million years for red sandstone unit. These are interpreted respectively as estimates of the age of deposition and a later remagnetization respectively.     

First results on determination of cosmogenic 36Cl in limestone from the Yenicekale Complex in the Hittite capital of Hattusha (Turkey)

We have measured ³⁶Cl in three rock surfaces of the Yenicekale building complex in Hattusha (Bo?azköy, Turkey). Hattusha was the capital of Hittite Empire which lasted from about 1650/1600 to 1200 BC. At Yenicekale, Hittite masons flattened the summit of an outcropping limestone knoll to form an artificial platform as the foundation for a building. Next they built a circuit wall along the lateral precipices of the flattened bedrock platform. We took one sample from the limestone bedrock platform and two samples from limestone building blocks of the circuit wall for cosmogenic ³⁶Cl analysis. Calculated exposure ages are 20 ± 1 ka for the sample from the bedrock platform and 24 ± 1 ka and 52 ± 2 ka for the circuit wall blocks. These exposure ages are significantly older than the age expected based on the estimated time of construction between 3.2 ka and 3.7 ka. We conclude that the sampled surfaces contain significant inherited cosmogenic ³⁶Cl. We cannot directly determine exposure ages for the building complex based on these three samples. On the other hand we may use the measured concentrations to determine how much of the rock was removed from the platform during flattening. To this end we modeled the variation of ³⁶Cl production with depth at Yenicekale using the results from the bedrock sample. We conclude that the Hittite masons removed only around 3 m from top of the limestone block. This means that the volume of rock removed from the bedrock platform is significantly less than the volume in the circuit wall atop the platform. They did not gain enough rock from this flattening to make the building. In agreement with this, the first results of our detailed microfacies analysis indicate that many of the building blocks are not of the same facies as the underlying limestone and must have been quarried elsewhere. Although we were not able to exposure date the Yenicekale complex due to the presence of inherited ³⁶Cl, our data suggest that Hittite masons excavated (most of) the building stones not at Yenicekale, but in quarries outside of Hattusha and then transported them to the construction site. These quarries have not yet been identified.     

Elastic anisotropy of ferromagnesian post-perovskite in Earth's D” layer

We report experimental observation of a sizable elastic anisotropy in a polycrystalline sample of ferromagnesian silicate in post-perovskite (ppv) structure. Using a novel composite X-ray transparent gasket to contain and synthesize ppv in a panoramic diamond-anvil cell along with oblique X-ray diffraction geometry, we observed the anisotropic lattice strain and {1 0 0} or {1 1 0} slip-plane texture in the sample at 140 GPa. We deduced the elasticity tensor (c_ij), orientation-dependent compressional wave velocities, polarization-dependent shear-wave velocities, and the velocity anisotropy of the silicate ppv. Our results are consistent with calculations and indicate that with sufficient preferred orientation, the elastic anisotropy of this phase can produce large shear-wave splitting.     

Thermal conditions of the central Sinai Microplate inferred from new surface heat-flow values and continuous borehole temperature logging in central and southern Israel

This paper reports ten new surface heat-flow density (qs) values for central and southern Israel (central Sinai Microplate), whose crystalline crust and lithosphere formed as part of the Neoproterozoic Arabian-Nubian Shield. Heat flow was calculated in Mesozoic sediments using the classical approach of heat-flow determination by implementing in the analysis high-precision continuous temperature logs obtained in air- and/or water-filled boreholes. Thermal conductivity (TC) measured for a large suite of rock samples of lithotypes making up the sequence was assigned to temperature gradients in intervals for which the lithology was known. The heat-flow values obtained for different depth intervals in a borehole as well as the average values for the individual borehole locations cover a narrow range, attesting heat-conduction conditions. A steady-state thermal model along an E–W crustal cross section through the area shows that the observed systematic spatial distribution of the qs values, which range between 50 and 62 mW m⁻², can primarily be explained by variations in the thickness of the upper crust and in the ratio between sedimentary and crystalline rocks therein. Given the time lapse of thermal heat transfer through the lithosphere, the qs data monitor the crustal thermal conditions prior to rift- and plume-related lithospheric thermal perturbations that have started in the larger area ca. 30 Ma ago. Observed and modeled qs display the best fit for a pre-Oligocene lithosphere–asthenosphere boundary (LAB) at ∼150 km, which would be at the upper end of LAB depths determined from stable areas of the Arabian Shield (150–120 km) not affected by the young, deep-seated thermal processes that have caused a further uprise of the LAB. Our data imply or predict that the surface heat flow of the Sinai Microplate generally tends to increase along N–S and W–E traverses, from ∼45–50 mW m⁻² to ∼55–60 mW m⁻². Surface heat flows on the order of 55–60 mW m⁻² may be common in the northern Arabian Shield, where it exhibits typical lithosphere structure and composition and is unaffected by young heating processes, compared to values of ≤45 mW m⁻² recently determined in the southern Arabian Plate for the Arabian Platform.     

Sensitivity of ground-motion scenarios to earthquake source parameters in the Tehran metropolitan area,Iran

The northern Tehran fault (NTF) is a principal active fault of the Alborz mountain belt in the northern Iran. The fault is located north of the highly populated Metropolitan Area of Tehran. Historical records and paleoseismological studies have shown that the NTF poses a high seismic risk for the Tehran region and the surrounding cities (e.g. Karaj). A series of ground-motion simulations are carried out using a hybrid kinematic-stochastic model to calculate broadband (0.1–20 Hz) ground-motion time histories for deterministic earthquake scenarios (M7.2) on the NTF. We will describe the source characteristics of the target event to develop a list of scenario earthquakes that are probably similar to a large earthquake on the NTF. The effect of varying different rupture parameters such as rupture velocity and rise time on the resulting broadband strong motions has been investigated to evaluate the range of uncertainty in seismic scenarios. The most significant parameters in terms of ground-shaking level are the rise time and the value of the rupture velocity. For the worst-case scenario, the maximum expected horizontal acceleration, and velocity at rock sites in Tehran range between 128 and 1315 cm/s/s and 11–191 cm/s, respectively. For the lowest scenario, the corresponding values range between 102 and 776 cm/s/s and 12 to 81 cm/s. Nonlinear soil effects may change these results but are not accounted for in this study. The largest variability of ground motion is observed in neighborhood of asperity and also in the direction of rupture propagation. The calculated standard deviation of all ground-motion scenarios is less than 30% of the mean. The capability of the simulation method to synthesize expected ground motions and the appropriateness of the key parameters used in the simulations are confirmed by comparing the synthetic peak ground motions (PGA, PGV and response spectra) with empirical ground-motion prediction equations.     

Sources of in-situ 36Cl in basaltic rocks. Implications for calibration of production rates

In-situ cosmogenic ³⁶Cl production rates from spallation of Ca and K determined in several previously published calibration studies differ by up to 50%. In this study we compare whole rock ³⁶Cl exposure ages with ³⁶Cl exposure ages evaluated in Ca-rich plagioclase in the same 10 ± 3 ka lava sample taken from Mt. Etna (Sicily, 38° N). The exposure age of the sample was determined by K–Ar and corroborated by cosmogenic ³He measurements on cogenetic pyroxene phenocrysts. Sequential dissolution experiments showed that high Cl concentrations in plagioclase grains could be reduced from 450 ppm to less than 3 ppm after 16% dissolution. ³⁶Cl exposure ages calculated from the successive dissolution steps of this leached plagioclase sample are in good agreement with K–Ar and ³He age. Stepwise dissolution of whole rock grains, on the other hand, is not as effective in reducing high Cl concentrations as it is for the plagioclase. 330 ppm Cl still remains after 85% dissolution. The ³⁶Cl exposure ages derived are systematically about 30% higher than the ages calculated from the plagioclase. We could exclude contamination by atmospheric ³⁶Cl as an explanation for this overestimate. Magmatic ³⁶Cl was estimated by measuring a totally shielded sample, but was found to account for only an insignificant amount of ³⁶Cl in the case of the 10 ka whole rock sample. We suspect that the overestimate of the whole rock exposure age is due to the difficulty in accurately assessing all the factors which control production of ³⁶Cl by low-energy neutron capture on ³⁵Cl, particularly variable water content and variable snow cover. We conclude that some of the published ³⁶Cl spallation production rates might be overestimated due to high Cl concentrations in the calibration samples. The use of rigorously pretreated mineral separates reduces Cl concentrations, allowing better estimates of the spallation production rates.In the Appendix of this paper we document in detail the equations used. These equations are also incorporated into a ³⁶Cl calculation spreadsheet made available in the supplementary data.     

Radiogenic heat production in the lithosphere of Sulu ultrahigh-pressure metamorphic belt

The Chinese Continental Scientific Drilling (CCSD) project is located at the Sulu ultrahigh-pressure metamorphic (UHPM) belt. It offers a unique opportunity for studying the radiogenic heat production of both shallower and deeper rocks. Based on the concentrations of radiogenic elements U, Th and K on 349 samples from main hole of CCSD (CCSD MH), pilot holes and exposures, we determined radiogenic heat productions of all major rock types in the Sulu UHPM belt. Results show the mean values of orthogneiss and paragneiss are respectively 1.65 ± 0.81 and 1.24 ± 0.61 µW m^? 3. Due to different composition and grade of retrogressive metamorphism, the eclogites display significant scatter in radiogenic heat production, ranging from 0.01 to 2.85 µW m^? 3, with a mean of 0.44 ± 0.55 µW m^? 3. The radiogenic heat production in ultramafic rocks also varies within a large range of 0.02 to 1.76 µW m^? 3, and the average turns out to be 0.18 ± 0.31 µW m^? 3. Based on the measurements and crustal petrologic model, the vertical distribution model of heat production in Sulu crust is established. The resulting mean heat production (0.76 µW m^? 3) contributes 24 mW m^? 2 to the surface heat flow. 1-D thermal model indicates that the temperature at the Moho reaches above 750 °C, and the thermal thickness of the lithosphere is ~ 75 km, in good agreement with the geophysical results. The high teat flow (~ 75 mW m^? 2) together with thin lithosphere presents strong support for the extension events during the late Cretaceous and Cenozoic.     

A long-term rock uplift rate for eastern Crete and geodynamic implications for the Hellenic subduction zone

The island of Crete in the forearc of the Hellenic subduction zone has a rugged topography with local relief exceeding 2 km. Based on the elevation of marine shorelines, rates of rock uplift during the Late Holocene were previously estimated to range between 1 and 4 mm/a in different parts of the island. These rates may, however, not be representative for longer timescales, because subduction earthquakes with up to 9 m of vertical coseismic displacement have affected Crete in the Late Holocene. Here we use a well preserved sequence of marine terraces near Kato Zakros in eastern Crete to determine the rate of rock uplift over the last ∼600 ka. Field investigations and topographic profiles document a flight of more than 13 marine bedrock terraces that were carved into limestones of the Tripolitza unit. Preliminary age constraints for the terraces were obtained by ¹⁰Be exposure dating of rare quartz-bearing sandstone clasts, which are present on some terraces. The ¹⁰Be ages of these samples, which have been corrected for an inherited nuclide component, yielded exposure ages between ∼100 ka and zero. Combined with geomorphologic evidence the two oldest ¹⁰Be ages suggest that the terraces T₄ and T₅, with shoreline angles at an elevation of ∼68 and ∼76 m above sea level, respectively, formed during the marine isotope stage 5e about 120 ka ago. The correlation of the higher terraces (T₆ to T₁₃) with regional sea-level highstands indicates sustained rock uplift at a rate of ∼0.5 m/ka since at least ∼600 ka. As normal faulting has dominated the tectonics of Crete during the last several million years, upper crustal shortening can be ruled out as a cause for rock uplift. We argue that the sustained uplift of the island results from the continuous underplating of sediments, which are transferred from the subducting African plate to the base of the crust beneath Crete.     

Th–U–total Pb geochronology of authigenic monazite in the Adelaide rift complex,South Australia,and implications for the age of the type Sturtian and Marinoan glacial deposits

The Adelaide rift complex in South Australia contains the type sections for Sturtian and Marinoan glacial deposits. The litho- and chemo-stratigraphy of these deposits play a central role in evaluating global Neoproterozoic ice age hypotheses and Rodinia supercontinent reconstructions, but reliable depositional age constraints have been extremely limited. We report results of in situ Th–U–total Pb (electron microprobe) dating of detrital and authigenic monazite in two samples from the Umberatana Group (Sturtian Holowilena Ironstone and pre-Marinoan Enorama Shale) in the Central Flinders Ranges. Several texturally and chemically distinct detrital and authigenic populations are recognized. Detrital dates range from 1600 Ma to 760 Ma and most relate to well-known orogenic or igneous events in surrounding cratonic regions. Authigenic monazite grew in three or more pulses ranging from 680 Ma to 500 Ma. The date of 680 ± 23 Ma (2σ) for the earliest generation of authigenic monazite in sandstone from the Enorama Shale (1) provides an estimate for the age of the base of the Trezona carbon isotopic anomaly just beneath the Marinoan glacial deposits, (2) provides an absolute minimum age constraint on the underlying Sturtian glacial deposits, and (3) supports proposed correlations between type Marinoan deposits and precisely dated glacial deposits in Namibia and China, which bracket the presumed Marinoan equivalents between 655 and 635 Ma. This age is inconsistent with a Re–Os isochron age of 643 ± 2.4 Ma (2σ) on shales near the bottom of the Sturtian–Marinoan interglacial succession, stratigraphically > 3000 m below the Enorama Shale sample, and militate against the hypothesis that the type Marinoan is correlative with the 580 Ma Gaskiers glaciation. Monazite growth near 600 Ma and again at about 500 Ma probably represent hydrothermal fluid-flow events, the latter of which also corresponds to the well-known Delamerian Orogeny during which the Adelaide sediments were folded into their present structural pattern.     

Critical phenomena in thermal conductivity: Implications for lower mantle dynamics

Microscopic mechanisms for heat transport in dense minerals (phonon scattering and photon attenuation) exhibit aspects of threshold behavior, discussed qualitatively here. For all minerals examined so-far using laser-flash analysis, the lattice component of the thermal conductivity of the mantle asymptotes to a constant above a critical temperature of ∼1500 K. Radiative transfer calculated from absorption spectra has thresholds in both grain-size and Fe content, and a rather complex dependence on temperature. These critical phenomena impact convection of the lower mantle, because the lattice contribution tends to destabilize the cold boundary layers, whereas radiative transfer mostly promotes stability in the lower mantle, unless the grains are large and Fe-rich, which makes convection chaotic and time-dependent. The specific behavior suggests that flow in the lower mantle is sluggish, whereas flow in the upper mantle-transition zone is time-dependent. The decrease in k_rad as Fe/(Fe + Mg) increases beyond ∼0.1 may be connected with formation of lower mantle, thermo-chemical plumes through positive feedback.     

Stability of massive ground ice bodies in University Valley,McMurdo Dry Valleys of Antarctica: Using stable O–H isotope as tracers of sublimation in hyper-arid regions

To date, studies of the stability of subsurface ice in the McMurdo Dry Valleys of Antarctica have been mainly based on climate-based vapor diffusion models. In University Valley (1800 m), a small glacier is found at the base of the head of the valley, and adjacent to the glacier, a buried body of massive ice was uncovered beneath 20–40 cm of loose cryotic sediments and sandstone boulders. This study assesses the origin and stability of the buried body of massive ice by measuring the geochemistry and stable O–H isotope composition of the ice and applies a sublimation and molecular diffusion model that accounts for the observed trends. The results indicate that the buried massive ice body represents an extension of the adjacent glacier that was buried by a rock avalanche during a cold climate period. The contrasting δ¹⁸O profiles and regression slope values between the uppermost 6 cm of the buried massive ice (upward convex δ¹⁸O profile and S_D-18O = 5.1) and that below it (progressive increase in δ¹⁸O and S_D-18O = 6.4) suggest independent post-depositional processes affected the isotope composition of the ice. The upward convex δ¹⁸O profile in the uppermost 6 cm is consistent with the ice undergoing sublimation. Using a sublimation and molecular diffusion model, and assuming that diffusion occurred through solid ice, the sublimation rate needed to fit the measured δ¹⁸O profile is 0.2 ? 10^? 3 mm yr^? 1, a value that is more similar to net ice removal rates derived from ³He data from cobbles in Beacon Valley till (7.0 ? 10^? 3 mm yr^? 1) than sublimation rates computed based on current climate (0.1–0.2 mm yr^?1). We suggest that the climate-based sublimation rates are offset due to potential ice recharge mechanisms or to missing parameters, particularly the nature and thermo-physical properties of the overlying sediments (i.e., temperature, humidity, pore structure and ice content, grain size).     

Optical dating of a hyperconcentrated flow deposit on a Yellow River terrace in Hukou,Shaanxi, China

A sand layer, interpreted as a hyperconcentrated flow deposit, was found interbedded between loess on a Yellow River terrace in Hukou, Shaanxi, China. The site is known as the Longwangchan Palaeolithic site. The deposits from the terrace were dated using optically stimulated luminescence (OSL). Two samples from the sand layer were dated to 30 ± 2 and 33 ± 3 ka using coarse-grained (CG) quartz, and to 82 ± 7 and 94 ± 5 ka using fine-grained (FG) quartz, respectively. The CG quartz OSL ages are believed to be reliable on the basis of the OSL ages of the bracketing loess samples. The overestimation of the FG quartz OSL ages of the sand samples is explained in terms of hyperconcentrated flow processes during sediment transport and deposition. The large difference between the CG and FG quartz OSL ages of the sand samples helps to better understand the formation of the hyperconcentrated flow deposit. The hyperconcentrated flow deposit in this study indicates an extreme river flood occurring at ～30 ka in this area. In addition, the stone artifacts found in the lower loess layer overlying the bedrock of the terrace were dated to ～47 ka.     

CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

Preconcentration of trace multi-elements in water samples using Dowex 50W-x8 and Chelex-100 resins prior to their determination using inductively coupled plasma atomic emission spectrometry (ICP-OES)

This work presents a solid phase extraction (SPE) method for simultaneous preconcentration of trace elements in water samples prior to their ICP-OES determination. Dowex 50W-x8 and Chelex-100 resins were used as SPE sorbent materials for preconcentration of trace Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn. The optimum sample pH, eluent concentration and sample flow rates were found to 6, 3.0 mol L⁻¹ and 3.0 mL min⁻¹, respectively. In terms of multi-element preconcentration capabilities, Dowex 50W-x8 appeared to be a better sorbent. The recoveries for all the tested analytes were >95%. However, Chelex-100 showed a better performance in terms of recovery (>95%) towards Cu, Fe and Zn. Under optimized conditions using Dowex 50W-x8, the relative standard deviations for different metals were <3%. The limits of detection and limits of quantification ranged from 0.01–0.39 μg L⁻¹ and 0.05–0.1.3 μg L⁻¹, respectively. The accuracy of the preconcentration method was confirmed by spike recovery test and the analysis of certified reference materials. The SPE method was applied for preconcentration of the analyte ions in tap water, bottled water and wastewater samples.     

A linearized approach to flow resistance uncertainty in a 2-D finite volume model of flood flow

A linearized approach to quantifying predictive uncertainty in a 2-D model of shallow water flow in response to uncertainty in friction parameterization is presented. The resulting uncertain finite volume (UFV) method is tested against Monte Carlo simulations for uncertain models over channel only, floodplain only and channel and floodplain meshes. The results show that the UFV model performs well in predicting mean and standard deviations of water depths, for problems with two independent Manning's n values, with standard deviations of up to 0.02 m^1/3 s⁻¹ with a mean value of 0.03 m^1/3 s⁻¹. For depth averaged velocities, mean values are well represented, but standard deviations are poorly predicted by UFV. UFV also performs well when modelling flow over an uneven fractal topography and for a distributed (11 degrees of freedom) parameterization. A computation time advantage of >50 when compared to the Monte Carlo method is observed.     

Three-dimensional numerical analysis of magma transport through a pre-existing fracture in the crust

Magmas are transported through pre-existing fractures in many repeatedly erupting volcanoes. The study of this special process of magma transport is fundamentally important to understand the mechanisms and conditions of volcanic eruptions. In this paper, we numerically simulate the magma propagation process through a pre-existing vertical fracture in the crust by using the combined finite difference method (FDM), finite element method (FEM) and discontinuous deformation analysis (DDA) approach. FDM is used to analyze magma flow in the pre-existing fracture, FEM is used to calculate the opening of the fracture during magma intrusion, and DDA is used to deal with the contact of the closed fracture surfaces. Both two-dimensional (2D) and three-dimensional (3D) examples are presented. Parametric studies are carried out to investigate the influence of various physical and geometric parameters on the magma transport in the pre-existing fracture. We have considered magma chamber depth ranging from 7 km to 10 km under the crust surface, magma viscosity ranging from 2 × 10⁻² to 2 × 10⁻⁷ MPa s, and the density difference between the magma and host rock ranging from 300 to 700 kg/m³. The numerical results indicate that (1) the fluid pressure p varies gradually along the depth, (2) the shape of the magma body during propagation is like a torch bar and its width ranges from 2 m to 4 m approximately in the 3D case and 10 m to 50 m in the 2D case for the same physical parameters used, (3) the crust surface around the pre-existing fracture begins to increase on both sides of the fracture, forms a trough between them, then gradually uplifts during the transport of the magma, and finally takes the shape of a crater when the magma reaches the surface. We have also examined the influence of physical and geometric parameters on the minimum overpressure for magma transport in the 3D case. The numerical results show that our numerical technique presented in this paper is an effective tool for simulating magma transport process through pre-existing fractures in the crust.     

Luminescence dating of baked earth and sediments from the Qujialing archaeological site,China

The Qujialing site is a representative Neolithic archaeological site in the middle reaches of the Yangtze River, China. Absence of suitable material for radiocarbon dating in this region makes the timing of the similar sites difficult. Here we applied optically stimulated luminescence (OSL–SAR) and thermoluminescence (TL–SAR) techniques to date the archaeological and natural deposits from the Qujialing site with known age, testing the techniques on samples at archaeological sites in this region. The results showed that the luminescence properties of quartz from sediment and baked earth samples are very similar. The quartz OSL ages obtained for a sediment sample and a baked earth sample from the cultural layer are 5.4 ± 0.3 and 5.1 ± 0.3 ka, respectively. The quartz TL age of the baked earth sample is 5.6 ± 0.5 ka. These dates are consistent with the calibrated radiocarbon ages (4.9 ± 0.1 and 5.1 ± 0.1 ka cal BP (±1σ)) of the two charcoal samples from the cultural layer at a nearby locality, and are also in agreement with the age of Qujialing culture period. The results indicate that the OSL dating techniques can be applied to date similar archaeological sites in the middle reaches of the Yangtze River, China.     

Astrochronology of the late Jurassic Kimmeridge Clay (Dorset,England) and implications for Earth system processes

The Late Jurassic Kimmeridge Clay Formation (KCF) is an economically important, organic-rich source rock of Kimmeridgian–Early Tithonian age. The main rock types of the KCF in Dorset, UK, include grey to black laminated shale, marl, coccolithic limestone, and dolostone, which occur with an obvious cyclicity at astronomical timescales. In this study, we examine two high-resolution borehole records (Swanworth Quarry 1 and Metherhills 1) obtained as part of a Rapid Global Geological Events (RGGE) sediment drilling project. Datasets examined were total organic carbon (TOC), and borehole wall microconductivity by Formation Microscanner (FMS). Our intent is to assess the rhythmicity of the KCF with respect to the astronomical timescale, and to discuss the results with respect to other key Late Jurassic geological processes. Power spectra of the untuned data reveal a hierarchy of cycles throughout the KCF with ～ 167 m, ～ 40 m, 9.1 m, 3.8 m and 1.6 m wavelengths. Tuning the ～ 40 m cycles to the 405-kyr eccentricity cycle shows the presence of all the astronomical parameters: eccentricity, obliquity, and precession index. In particular, ～ 100-kyr and 405-kyr eccentricity cycles are strongly expressed in both records. The 405-kyr eccentricity cycle corresponds to relative sea-level changes inferred from sequence stratigraphy. Intervals with elevated TOC are associated with strong obliquity forcing. The 405-kyr-tuned duration of the lower KCF (Kimmeridgian Stage) is 3.47 Myr, and the upper KCF (early part of the Tithonian Stage, elegans to fittoni ammonite zones) is 3.32 Myr. Two other chronologies test the consistency of this age model by tuning ～ 8–10 m cycles to 100-kyr (short eccentricity), and ～ 3–5 m cycles to 36-kyr (Jurassic obliquity). The ‘obliquity-tuned’ chronology resolves an accumulation history for the KCF with a variation that strongly resembles that of Earth's orbital eccentricity predicted for 147.2 Ma to 153.8 Ma. There is evidence for significant non-deposition (up to 1 million years) in the lowermost KCF (baylei–mutabilis zones), which would indicate a Kimmeridgian/Oxfordian boundary age of 154.8 Ma. This absolute calibration allows assignment of precise numerical ages to zonal boundaries, sequence surfaces, and polarity chrons of the lower M-sequence.