Do organic ligands affect calcite dissolution rates?

Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO₂ sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA⁴⁻, succinate, d-glucosaminate, l-glutamate, d-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA⁴⁻. The presence of 0.05 mol/kg citrate and EDTA⁴⁻ increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.     

Using Mg Isotopes to Trace Cyanobacterially Mediated Magnesium Carbonate Precipitation in Alkaline Lakes

This study assesses the potential use of Mg isotopes to trace Mg carbonate precipitation in natural waters. Salda Lake (SW Turkey) was chosen for this study because it is one of the few modern environments where hydrous Mg carbonates are the dominant precipitating minerals. Stromatolites, consisting mainly of hydromagnesite, are abundant in this lake. The Mg isotope composition of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments were measured. Because Salda Lake is located in a closed basin, mass balance requires that the Mg isotopic offset between Lake Salda water and precipitated hydromagnesite be comparable to the corresponding offset between Salda Lake and its water inputs. This is consistent with observations; a ??²⁶Mg offset of 0.8?C1.4??? is observed between Salda Lake water and it is the incoming streams and groundwaters, and precipitated hydromagnesite has a ??²⁶Mg 0.9?C1.1??? more negative than its corresponding fluid phase. This isotopic offset also matches closely that measured in the laboratory during both biotic and abiotic hydrous Mg carbonate precipitation by cyanobacteria (Mavromatis, V., Pearce, C., Shirokova, L. S., Bundeleva, I. A., Pokrovsky, O. S., Benezeth, P. and Oelkers, E.H.: Magnesium isotope fractionation during inorganic and cyanobacteria-induced hydrous magnesium carbonate precipitation, Geochim. Cosmochim. Acta, 2012a. 76, 161?C174). Batch reactor experiments performed in the presence of Salda Lake cyanobacteria and stromatolites resulted in the precipitation of dypingite (Mg₅(CO₃)₄(OH)₂·5(H₂O)) and hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O) with morphological features similar to those of natural samples. Concurrent abiotic control experiments did not exhibit carbonate precipitation demonstrating the critical role of cyanobacteria in the precipitation process.     

Sequentially sampled gas hydrate water,coupled with pore water and bottom water isotopic and ionic signatures at the Kukuy mud volcano,Lake Baikal: ambiguous deep-rooted source of hydrate-forming water

The isotopic and ionic composition of pure gas hydrate (GH) water was examined for GHs recovered in three gravity cores (165–193 cm length) from the Kukuy K-9 mud volcano (MV) in Lake Baikal. A massive GH sample from core St6GC4 (143–165 cm core depth interval) was dissociated progressively over 6 h in a closed glass chamber, and 11 sequentially collected fractions of dissociated GH water analyzed. Their hydrogen and oxygen isotopic compositions, and the concentrations of Cl^– and HCO₃ ^– remained essentially constant over time, except that the fraction collected during the first 50 minutes deviated partly from this pattern. Fraction #1 had a substantially higher Cl^– concentration, similar to that of pore water sampled immediately above (135–142 cm core depth) the main GH-bearing interval in that core. Like the subsequent fractions, however, the HCO₃ ^– concentration was markedly lower than that of pore water. For the GH water fractions #2 to #11, an essentially constant HCO₃ ^–/Cl^– ratio of 305 differed markedly from downcore pore water HCO₃ ^–/Cl^– ratios of 63–99. Evidently, contamination of the extracted GH water by ambient pore water probably adhered to the massive GH sample was satisfactorily restricted to the initial phase of GH dissociation. The hydrogen and oxygen isotopic composition of hydrate-forming water was estimated using the measured isotopic composition of extracted GH water combined with known isotopic fractionation factors between GH and GH-forming water. Estimated δD of ?126 to ?133‰ and δ¹⁸O of ?15.7 to ?16.7‰ differed partly from the corresponding signatures of ambient pore water (δD of ?123‰, δ¹⁸O of ?15.6‰) and of lake bottom water (δD of ?121‰, δ¹⁸O of ?15.8‰) at the St6GC4 coring site, suggesting that the GH was not formed from those waters. Observations of breccias in that core point to a possible deep-rooted water source, consistent with published thermal measurements for the neighboring Kukuy K-2 MV. By contrast, the pore waters of core St6GC4 and also of the neighboring cores GC2 and GC3 from the Kukuy K-9 MV show neither isotopic nor ionic evidence of such a source (e.g., elevated sulfate concentration). These findings constrain GH formation to earlier times, but a deep-rooted source of hydrate-forming water remains ambiguous. A possible long-term dampening of key deep-water source signatures deserves further attention, notably in terms of diffusion and/or advection, as well as anaerobic oxidation of methane.     

Differential melt scaling for oblique impacts on terrestrial planets

Analytical estimates of melt volumes produced by a given projectile and contained in a given impact crater are derived as a function of impact velocity, impact angle, planetary gravity, target and projectile densities, and specific internal energy of melting. Applications to impact events and impact craters on the Earth, Moon, and Mars are demonstrated and discussed. The most probable oblique impact (45°) produces ～1.6 times less melt volume than a vertical impact, and ～1.6 and 3.7 times more melt volume than impacts with 30° and 15° trajectories, respectively. The melt volume for a particular crater diameter increases with planetary gravity, so a crater on Earth should have more melt than similar-size craters on Mars and the Moon. The melt volume for a particular projectile diameter does not depend on gravity, but has a strong dependence on impact velocity, so the melt generated by a given projectile on the Moon is significantly larger than on Mars. Higher surface temperatures and geothermal gradients increase melt production, as do lower energies of melting. Collectively, the results imply thinner central melt sheets and a smaller proportion of melt particles in impact breccias on the Moon and Mars than on Earth. These effects are illustrated in a comparison of the Chicxulub crater on Earth, linked to the Cretaceous–Tertiary mass extinction, Gusev crater on Mars, where the Mars Exploration Rover Spirit landed, and Tsiolkovsky crater on the Moon. The results are comparable to those obtained from field and spacecraft observations, other analytical expressions, and hydrocode simulations.     

Interface and embedded joint methods for modeling dynamic fracture opening by explosive products

Two computational approaches are proposed in the paper to model dynamic fracture opening by explosive products. The first method assumes that the fractures may be modeled using flow elements embedded along the mesh lines. This method models crack opening in a straightforward way by splitting the nodes of the computational grid. It can account for crack branching; however, the crack directions are constrained by existing mesh faces, which may lead to mesh dependence. Also, the stress in flow elements is calculated explicitly separate from the surrounding solid elements that can impose additional limits on the time step stability condition for explicit integration. The second approach uses embedded flow elements to model the cracks. Typical thickness of the cracks is much smaller than the element size. Therefore, gas pressure in the cracks is assumed to be in stress equilibrium with the element stress. To achieve this, the crack thickness and the state of the gas is updated simultaneously with the state of the solid element which contains the crack. Therefore, the time step is controlled by the explicit solver applied for the solid and does not depend on the thickness of the crack. The main disadvantage of the second approach is due to the complexity of modeling multiple intersecting cracks, which go through the same element. We discuss the areas of possible applications of these 2 methods and the ways to improve and enhance them for future practical applications.     

A semi-analytical approach to a nonlinear stress–strain analysis of buried steel pipelines crossing active faults

In the present paper a semi-analytical methodology for a nonlinear stress–strain analysis of buried steel pipelines at active fault crossings is presented and verified. The developed model introduces a number of critical refinements to the existing methodologies which extend the application area of analytical models in pipeline design. In particular, a strike-slip and normal-slip fault crossings can be analyzed taking into account material and large displacement nonlinearities, nonlinear pipe–soil interaction. The proposed model is verified against the results by other authors and numerical results, obtained with the finite element method.     

Intense diurnal surface currents in the Bay of La Paz,Mexico

Currents in the northern Bay of La Paz were examined using an 8-month Acoustic Doppler Current Profiler (ADCP) record collected in the upper 185 m of the water column during 2007. Flow variability was dominated by tidal motions, which accounted for 43% (33% diurnal, 10% semidiurnal) of the total kinetic energy. The tidal motions had a pronounced vertical structure dominated within a shallow (∼30 m thick) surface layer by intense counterclockwise (CCW) rotary S₁ diurnal radiational currents that were highly coherent with the counterclockwise seabreeze. Motions within the semidiurnal frequency band were primarily associated with significant counterclockwise S₂ radiational tidal currents, which were also coherent with the seabreeze. Both S₁ and S₂ tidal ellipses in the upper layer were aligned perpendicular to the bay entrance with mean semi-major axes of 55 and 20 cm/s, respectively. Below the surface layer, tidal currents decayed rapidly to relatively weak, clockwise rotary barotropic motions. In contrast to those for radiational harmonics, tidal ellipses of the gravitational constituents (M₂, K₁ and O₁) were oriented cross-bay. Energy within the diurnal frequency band in the surface layer was dominated by a coherent component (barotropic, phase-locked baroclinic and radiational), which accounted for roughly 65% (59% from S₁ alone) of the total diurnal kinetic energy. Of the remaining diurnal band energy, 18% was associated with an incoherent baroclinic component and 17% with a background noise component. Below 30 m depth, the corresponding estimates are 40%, 32% and 28%, respectively. The persistent, surface-intensified CCW rotary currents observed at the mooring site are assumed to be forced by strong CCW seabreeze winds in the presence of a “slippery” low-density surface layer. This response may be further augmented by topographic narrowing at the bay entrance and by the close proximity of the diurnal and inertial frequency bands in the region.     

Distribution and morphology of mud volcanoes and other fluid flow-related lake-bed structures in Lake Baikal, Russia

New high-resolution multibeam bathymetry data recorded in 2009 in the deepest lake in the World, Lake Baikal, Siberia, enabled a better understanding of the morphology of ten known lake-bed structures—the Bolshoy, Malenki, Malyutka and Stari mud volcanoes in the South Baikal Basin, the K1–4 structures in the Selenga delta, and the Novosibirsk and St. Petersburg structures in the Central Baikal Basin—and also the discovery of 29 new lake-bed structures. These new structures are the S1, Tolstiy, mTSG and S2 in the South Baikal Basin, the P1–P4, P6–P19 and K5–K8 in the Selenga delta accommodation zone, and the C1, C3 and C4 edifices in the Central Baikal Basin. In all, 39 positive relief structures were identified and their large-scale distribution mapped. Based on their typical shape, the observation of high-reflectivity areas on side-scan sonar data records, and evidence of feeder channels on subsurface data, these structures can be classified as mud volcanoes. This has already been confirmed in other publications for the Bolshoy, Malenki and K2 structures, by the recovery of mud breccias in sediment cores. Most structures occur on or near faults and have orientations parallel with the major faults and main stress orientations in the basins, suggesting a strong structural control on the formation of the mud volcanoes. Their slopes are generally steeper than 5°, consistent with interpretation as mud cones formed by high-viscosity, stiff mud plugs. Only few structures appear to be characterised by a crater, in which case this apparent crater seems to be formed by the coalescence of several single cones, leaving a depression in the centre. Some structures have a moat, which has probably an erosional origin. Furthermore, three depressions have been found, named P5, P20 and C2, which are suggested to be pockmarks.     

Adaptive volume penalization for ocean modeling

The development of various volume penalization techniques for use in modeling topographical features in the ocean is the focus of this paper. Due to the complicated geometry inherent in ocean boundaries, the stair-step representation used in the majority of current global ocean circulation models causes accuracy and numerical stability problems. Brinkman penalization is the basis for the methods developed here and is a numerical technique used to enforce no-slip boundary conditions through the addition of a term to the governing equations. The second aspect to this proposed approach is that all governing equations are solved on a nonuniform, adaptive grid through the use of the adaptive wavelet collocation method. This method solves the governing equations on temporally and spatially varying meshes, which allows higher effective resolution to be obtained with less computational cost. When penalization methods are coupled with the adaptive wavelet collocation method, the flow near the boundary can be well-resolved. It is especially useful for simulations of boundary currents and tsunamis, where flow near the boundary is important. This paper will give a thorough analysis of these methods applied to the shallow water equations, as well as some preliminary work applying these methods to volume penalization for bathymetry representation for use in either the nonhydrostatic or hydrostatic primitive equations.     

Surface chemistry and reactivity of plant phytoliths in aqueous solutions

In order to better understand the reactivity of plant phytoliths in soil solutions, we determined the solubility, surface properties (electrophoretic mobilities and surface charge) and dissolution kinetics of phytoliths extracted from fresh biomass of representative plant species (larch tree and elm, horsetail, fern, and four grasses) containing significant amount of biogenic silica. The solubility product of larch, horsetail, elm and fern phytoliths is close to that of amorphous silica and soil bamboo phytoliths. Electrophoretic measurements yield isoelectric point pH_IEP = 0.9, 1.1, 2.0 and 2.2 for four grasses, elm, larch and horsetail phytoliths respectively, which is very close to that of quartz or amorphous silica. Surface acid–base titrations allowed generation of a 2-pK surface complexation model (SCM) for larch, elm and horsetail phytoliths. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 1 ≤ pH ≤ 8, were found to be very similar among the species, and close to those of soil bamboo phytoliths. Mechanistic treatment of all plant phytoliths dissolution rates provided three-parameters equation sufficient to describe phytoliths reactivity in aqueous solutions:$R(\text{mol}/{\text{cm}}^2/\text{s})=6?{10}^{?16}?a_{\text{H+}}+5.0?{10}^{?18}+3.5?{10}^{?13}?a_{\text{OH}?}^{0.33}$Alternatively, the dissolution rate dependence on pH can be modeled within the concept of surface coordination theory assuming the rate proportional to concentration of > SiOH₂⁺, > SiOH⁰ and > SiO^? species. In the range of Al concentration from 20 to 5000 ppm in the phytoliths, we have not observed any correlation between their Al content and solubility, surface acid–base properties and dissolution kinetics.It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ～ 3. Mass-normalized dissolution rates are similar among all four types of plant species studied and these rates are an order of magnitude higher than those of typical soil clay minerals. The minimal half life time of larch and horsetail phytoliths in the interstitial soil solution ranges from 10–12 years at pH = 2–3 to < 1 year at pH above 6, comparable with mean residence time of phytoliths in soil from natural observations.