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.     

The influence of coupled physical swelling and chemical reactions on deformable geomaterials

Coupled thermo‐hydro‐mechanical‐chemical modelling has attracted attention in past decades due to many contemporary geotechnical engineering applications (e.g., waste disposal, carbon capture and storage). However, molecular‐scale interactions within geomaterials (e.g., swelling and dissolution/precipitation) have a significant influence on the mechanical behaviour, yet are rarely incorporated into existing Thermal‐Hydro‐Mechanical‐Chemical (THMC) frameworks. This paper presents a new coupled hydro‐mechanical‐chemical constitutive model to bridge molecular‐scale interactions with macro‐physical deformation by combining the swelling and dissolution/precipitation through an extension of the new mixture‐coupling theory. Entropy analysis of the geomaterial system provides dissipation energy, and Helmholtz free energy gives the relationship between solids and fluids. Numerical simulation is used to compare with the selected recognized models, which demonstrates that the swelling and dissolution/precipitation processes may have a significant influence on the mechanical deformation of the geomaterials.     

A framework of Holocene and Late Pleistocene environmental change in eastern Iran inferred from the dating of periods of alluvial fan abandonment,river terracing,and lake deposition

We review studies of the Holocene and Late Pleistocene stratigraphy of eastern Iran to infer past changes in the environment within this presently arid region. We build a scenario of widespread, and presumably climatically driven, evolution of the landscape through the Holocene. Six sites, covering a 10° range in latitude, indicate a regional abandonment of alluvial fan surfaces at ～10 ± 3 ka, with the younger (～9 ka) end of this age range supported by several of the best-constrained studies. Incision of rivers into the fan surfaces has occurred in discrete stages in the early to mid-Holocene (～9–7 ka) leading to the formation of flights of river terraces. Detailed records of lakebed deposition in the presently arid interior of Iran are rare, though the available data indicate lake highstand conditions at <7.8 ka at South Golbaf in SE Iran and at < 8.7 ± 1.1 ka at the Nimbluk plain in NE Iran. The major periods of Holocene landscape development hence correlate with a period of time where water was more abundant than at present, with incision of rivers into thick alluvial deposits possibly occurring due to a combination of decreased sediment supply and high levels of precipitation, and with the formation of inset river terraces possibly responding to century-scale fluctuations in precipitation. No major geomorphic changes are identified within the later part of the Holocene, from which we infer that increased aridity has slowed evolution of the landscape. A decrease in precipitation in the mid-Holocene may have had a detrimental effect on bronze age societies in eastern Iran as has been inferred elsewhere in the eastern Mediterranean region. The pre-Holocene environmental changes in eastern Iran are less well constrained, though there are suggestions of alluvial fan abandonment at 40–60 ka, at ～80 ka, and at ～120 ka.     

The supergene origin of ruthenian hexaferrum in Ni‐laterites

For two decades, the nature of Fe‐rich, oxygen‐bearing, Ru–Os compounds found in the supergene environment has been debated. Ru–Os–Fe‐oxides and nano‐intergrowths of ruthenium with magnetite have been proposed. We applied FE‐SEM, EMPA, μ‐Raman spectroscopy and synchrotron tts‐μXRD to Ru–Os–Fe compounds recovered from Ni‐laterites from the Dominican Republic. The results demonstrate that a significant portion of Fe exists in a common structure with the Ru–Os alloy, that is, ruthenian hexaferrum. This mineral occurs both as nanoparticles and as micrometric patches within a matrix of Fe‐oxide(s). Our data suggest that supergene ruthenian hexaferrum with a (Ru_0.4(Os,Ir)_0.1Fe_0.5)_?1.0 stoichiometry represents the most advanced weathering product of primary laurite within Ni‐laterites from the Dominican Republic.     

Correction to: New insights into the rainfall variability in the tropical Andes on seasonal and interannual time scales

Climate Dynamics - The original version of the article contained errors in Fig.     

A 2000‐year lipid biomarker record preserved in a stalagmite from north‐west Scotland

Previous studies on lipid biomarkers preserved in Chinese stalagmites have indicated that ratios of low‐molecular‐weight (LMW) to high‐molecular‐weight (HMW) n‐alkanes, n‐alkan‐2‐ones, n‐alkanols and n‐alkanoic acids can be used as an index of vegetation versus microbial organic matter input to the system and, by extension, a marker of climatic changes, with increases in the proportion of LMW compounds coinciding with colder periods. Here we test whether this hypothesis is equally applicable to a different geographical region (north‐west Scotland), by examining a stalagmite record of the past 200 years, and a wider range of lipid markers. We also test the applicability of other lipid proxies in this context, including the use of n‐alkane ratios, to interpret vegetation changes, and unsaturated alkanoic acid ratios as climatic indicators. The results show that lipid proxies preserved in stalagmites, and especially those related to vegetation, are potentially extremely useful in palaeoenvironmental research. Of particular value is the use of C₂₇/C₃₁ n‐alkane ratios as a proxy for vegetation change, clearly indicating variations between herbaceous and arboreal cover. This proxy has now been successfully applied to samples from diverse environments, and can be considered sufficiently robust to be of use in analysing future stalagmite records. It will be of particular value in areas where reliable pollen records are not available, as is often the case with deeper cave deposits. However, the division between LMW and HMW aliphatic compounds is not a clear‐cut case of microbial versus plant activity, with the changes in LMW compounds relating more closely to those in their HMW analogues than in specific bacterial biomarkers. The use of unsaturated alkanoic acid ratios here gives conflicting results, with the observed variation through time depending on the isomer measured. The discrepancies between the findings of this study and previous work are likely to be due to the varying controls on the lipids (original organic matter input, and compound degradation), which in turn will be affected by whether the main climatic limiting factor on the soil is temperature or precipitation. This suggests that lipid proxies preserved in stalagmites must be interpreted with care, particularly in the case of bacterial compounds which may be derived from within the cave or from the soil. However, many of these issues can be resolved by the use of multi‐proxy studies. Copyright © 2011 John Wiley & Sons, Ltd.