The effect of dissolved barium on biogeochemical processes at cold seeps

A numerical model was applied to investigate and quantify the biogeochemical processes fueled by the expulsion of barium and methane-rich fluids in the sediments of a giant cold-seep area in the Derugin Basin (Sea of Okhotsk). Geochemical profiles of dissolved Ba²⁺, Sr²⁺, Ca²⁺, SO₄²⁻, HS⁻, DIC, I⁻ and of calcium carbonate (CaCO₃) were fitted numerically to constrain the transport processes and the kinetics of biogeochemical reactions. The model results indicate that the anaerobic oxidation of methane (AOM) is the major process proceeding at a depth-integrated rate of 4.9 μmol cm⁻² a⁻¹, followed by calcium carbonate and strontian barite precipitation/dissolution processes having a total depth-integrated rate of 2.1 μmol cm⁻² a⁻¹. At the low seepage rate prevailing at our study site (0.14 cm a⁻¹) all of the rising barium is consumed by precipitation of barite in the sedimentary column and no benthic barium flux is produced. Numerical experiments were run to investigate the response of this diagenetic environment to variations of hydrological and biogeochemical conditions. Our results show that relatively low rates of fluid flow (<∼5 cm a⁻¹) promote the dispersed precipitation of up to 26 wt% of barite and calcium carbonate throughout the uppermost few meters of the sedimentary column. Distinct and persistent events (several hundreds of years long) of more vigorous fluid flow (from 20-110 cm a⁻¹), instead, result in the formation of barite-carbonate crusts near the sediment surface. Competition between barium and methane for sulfate controls the mineralogy of these sediment precipitates such that at low dissolved methane/barium ratios (<4-11) barite precipitation dominates, while at higher methane/barium ratios sulfate availability is limited by AOM and calcium carbonate prevails. When seepage rates exceed 110 cm a⁻¹, barite precipitation occurs at the seafloor and is so rapid that barite chimneys form in the water column. In the Derugin Basin, spectacular barite constructions up to 20 m high, which cover an area of roughly 22 km² and contain in excess of 5 million tons of barite, are built through this process. In these conditions, our model calculates a flux of barium to the water column of at least 20 μmol cm⁻² a⁻¹. We estimate that a minimum of 0.44 × 10⁶ mol a⁻¹ are added to the bottom waters of the Derugin Basin by cold seep processes, likely affecting the barium cycle in the Sea of Okhotsk.     

Feldspathic clast populations in polymict ureilites: Stalking the missing basalts from the ureilite parent body

Polymict ureilites DaG 164/165, DaG 319, DaG 665, and EET 83309 are regolith breccias composed mainly of monomict ureilite-like material, but containing ∼2 vol% of feldspathic components. We characterized 171 feldspathic clasts in these meteorites in terms of texture, mineralogy, and mineral compositions. Based on this characterization we identified three populations of clasts, each of which appears to represent a common igneous (generally basaltic) lithology and whose mafic minerals show a normal igneous fractionation trend of near-constant Fe/Mn ratio over a range of Fe/Mg ratios that extend to much higher values than those in monomict ureilites. The melts represented by these populations are unlikely to be impact melts, because the ubiquitous presence of carbon in polymict ureilites (the regolith of the ureilite parent body) implies that impact melts would have crystallized under conditions of carbon redox control and therefore have highly magnesian mafic mineral compositions with constant Mn/Mg ratio. Therefore, these melts appear to be indigenous products of igneous differentiation on the ureilite parent body (UPB), complementary to the olivine-pigeonite residues represented by the majority of monomict ureilites.The most abundant population is characterized by albitic plagioclase in association with pyroxenes, phosphates, ilmenite, silica, and incompatible-element enriched glass. Model calculations suggest that it formed by extensive fractional crystallization of the earliest melt(s) of precursor materials from which the most magnesian (shallowest) olivine-pigeonite ureilites formed. A less abundant population, characterized by labradoritic plagioclase, may have formed from melts complementary to more ferroan olivine-pigeonite ureilites, and derived from deeper in the UPB. The third population, characterized by the presence of olivine and augite, could only have formed from melts produced at greater depths in the UPB than the olivine-pigeonite ureilites. Many other feldspathic clasts cannot be positively associated with any of these three populations, because their mafic mineral compositions exhibit carbon redox control. However, they may be products of early crystallization of basaltic melts produced on the UPB, before carbon was exhausted by reduction.Partial melting on the ureilite parent body was a fractional (or incremental) process. Melts were produced early in UPB history, and most likely extracted rapidly, thus preserving primitive chemical and oxygen isotopic signatures in the residues.     

The post-glacial landscape evolution of the North German Basin: morphology, neotectonics and crustal deformation

The recent evolution of the north German Basin (NGB), which is presently a low-seismic area, was partly affected by glacial loading and unloading of the ice masses. Major stresses acting within the NGB are induced by the North-Atlantic ridge push, the ongoing Alpine collision, and the post-glacial rebound of Fennoscandia. Present-day horizontal stresses within the NGB are directed generally NW–SE, but fan and bend north of 52°N towards NNE. Major basement faults are directed NW–SE, minor faults NE–SW and NNE–SSW, and are clearly detectable in geomorphological and satellite lineaments. Furthermore, the drainage pattern and the distribution of lakes in northern Germany follow exactly block boundaries and, hence, mark zones of present-day subsidence. The understanding of the post-glacial morphology and reactivation of faults requires a view into the very heterogeneous crust and upper mantle below the NGB. The re-adjustment of the individual fault blocks during post-glacial relaxation of the lithosphere leads to differential, crust-dependent uplift and, probably, to the formation of Urstrom valleys. The Urstrom valleys and terminal moraines in northern Germany appear to parallel the major tectonic lineaments and lithospheric “block” boundaries. The lithospheric memory is expressed in the post-glacial landscape evolution of the NGB.     

Numerical modeling of toxic nonaqueous phase liquid removal from contaminated groundwater systems: mesh effect and discretization error estimation

Numerical modeling has now become an indispensable tool for investigating the fundamental mechanisms of toxic nonaqueous phase liquid (NAPL) removal from contaminated groundwater systems. Because the domain of a contaminated groundwater system may involve irregular shapes in geometry, it is necessary to use general quadrilateral elements, in which two neighbor sides are no longer perpendicular to each other. This can cause numerical errors on the computational simulation results due to mesh discretization effect. After the dimensionless governing equations of NAPL dissolution problems are briefly described, the propagation theory of the mesh discretization error associated with a NAPL dissolution system is first presented for a rectangular domain and then extended to a trapezoidal domain. This leads to the establishment of the finger‐amplitude growing theory that is associated with both the corner effect that takes place just at the entrance of the flow in a trapezoidal domain and the mesh discretization effect that occurs in the whole NAPL dissolution system of the trapezoidal domain. This theory can be used to make the approximate error estimation of the corresponding computational simulation results. The related theoretical analysis and numerical results have demonstrated the following: (1) both the corner effect and the mesh discretization effect can be quantitatively viewed as a kind of small perturbation, which can grow in unstable NAPL dissolution systems, so that they can have some considerable effects on the computational results of such systems; (2) the proposed finger‐amplitude growing theory associated with the corner effect at the entrance of a trapezoidal domain is useful for correctly explaining why the finger at either the top or bottom boundary grows much faster than that within the interior of the trapezoidal domain; (3) the proposed finger‐amplitude growing theory associated with the mesh discretization error in the NAPL dissolution system of a trapezoidal domain can be used for quantitatively assessing the correctness of computational simulations of NAPL dissolution front instability problems in trapezoidal domains, so that we can ensure that the computational simulation results are controlled by the physics of the NAPL dissolution system, rather than by the numerical artifacts. Copyright © 2014 John Wiley & Sons, Ltd.