Mineral dissolution kinetics as a function of distance from equilibrium – New experimental results

We revisit a fundamental question in mineral dissolution kinetics, namely: is the function of dissolution rate versus the distance from equilibrium continuous, or does the “switch” between two different reaction mechanisms cause a discontinuity, i.e., a kinetic bifurcation? Based on new insight from experimental results, including direct observations of retreating crystal surfaces with vertical scanning interferometry (VSI), we present evidence that a discontinuity does indeed exist. Through a carefully designed near-equilibrium albite dissolution experiment, we show how a non-steady-state dissolution rate observed on a crystal surface reflects reactivity inherited from earlier episodes of undersaturation. This outcome forces us to re-think the common practice of extrapolating overall dissolution rates measured far-from-equilibrium to near-equilibrium conditions.     

Chondritic Mg isotope composition of the Earth

The processes of planetary accretion and differentiation have potentially been recorded as variations in the stable isotope ratios of the major elements between planetary objects. However, the magnitude of observed isotopic variations for several elements (Mg, Fe, Si) is at the limit of what current analytical precision and accuracy are able to resolve. Here, we present a comprehensive data set of Mg isotope ratios measured in ocean island and mid-ocean ridge basalts, peridotites and chondrites. The precision and accuracy were verified by isotopic standard addition for two samples, one carbonaceous chondrite (Murchison) and one continental flood basalt (BCR-1). In contrast with some previous studies, our data from terrestrial and chondritic materials have invariant Mg isotope ratios within the uncertainty of the method (0.1‰ for the ²⁶Mg/²⁴Mg ratio, 2SD). Although isotopic variations of less than about 0.1‰ could still be present, the data demonstrate that, at this level of uncertainty, the bulk silicate Earth and chondritic Mg reservoir have a homogeneous δ²⁶Mg = −0.23‰ (²⁶Mg/²⁴Mg ratio of the sample relative to the DSM3 standard set to zero by definition). This implies that neither planetary accretion processes nor partial mantle melting and subsequent shallow-level differentiation have fractionated Mg isotope ratios. These observations imply in particular that the formation of the Earth cannot stem from preferential sorting of chondrite constituents that would have been fractionated in their Mg isotope composition. It also implies that unlike oxygen isotopes, there was no zonation in Mg isotopes in the inner solar system.     

Description of an aerodynamic levitation apparatus with applications in Earth sciences

Background  

In aerodynamic levitation, solids and liquids are floated in a vertical gas stream. In combination with CO₂-laser heating, containerless melting at high temperature of oxides and silicates is possible. We apply aerodynamic levitation to bulk rocks in preparation for microchemical analyses, and for evaporation and reduction experiments.     

The myth of community and sustainable grassland management in China

Within national and international domestic academic circles, there are increasing calls for enhanced involvement of communities in formulating and implementing grassland management arrangements. In contrast to the current national policy of contracting grasslands to households, many scholars call for support for collective grassland use arrangements. Several reasons are given for increased recognition and support for community-based management of grasslands, including lower costs of exclusion and dispute resolution, economies of scale in herding and marketing, mitigation of environmental risk, and ensuring equitable access to grassland resources. One conclusion from this literature is that devolving authority for designing and implementing grassland management systems to communities would lead to more sustainable grassland use, a position that I term as the ‘myth of community.’ This paper presents the results of a study of grazing systems in two communities in Hongyuan County, Sichuan Province. Each community uses its grasslands collectively. However, the study found evidence of severe overgrazing, especially in winter pastures, suggesting that community-based management of grasslands is not necessarily sustainable. The paper discusses three potential policy innovations required to support sustainable grazing systems in China’s grassland areas: overcoming constraints in labor and land markets, and payments for environmental services that reward sustainable stocking levels.     

A water movement study in Lianzhou Bay,Guangxi Province,China

This study investigates the physical conditions (water depth, current speed, salinity, temperature) in Lianzhou Bay, a shallow coastal bay in southern China, during two expeditions in the dry and wet seasons of 2011. Based on these expedition data, basic hydrodynamic parameters like Brunt-Väisälä Frequency, Richardson Number, Rossby radius, and Resonance Period are calculated. The results show that Lianzhou Bay is characterized by comparatively small quantity of freshwater input and weak stratification. Strong tides, which are spatially uniform within the bay, cause turbulent mixing. Residence time of the water is shorter in winter due to a stronger coastal current in that season. Consideration of the water movement may help to reduce the harmful ecological impact of aquaculture waste water discharge.     

Early-Morning Flow Transition in a Valley in Low-Mountain Terrain Under Clear-Sky Conditions

We investigate the evolution of the early-morning boundary layer in a low-mountain valley in south-western Germany during COPS (convective and orographically induced precipitation study) in summer 2007. The term low-mountain refers to a mountainous region with a relief of gentle slopes and with an absolute altitude that remains under a specified height (usually 1,500 m a.s.l.). A subset of 23 fair weather days from the campaign was selected to study the transition of the boundary-layer flow in the early morning. The typical valley atmosphere in the morning hours was characterized by a stable temperature stratification and a pronounced valley wind system. During the reversal period—called the low wind period—of the valley wind system (duration of 1–2 h), the horizontal flow was very weak and the conditions for free convection were fulfilled close to the ground. Ground-based sodar observations of the vertical wind show enhanced values of upward motion, and the corresponding statistical properties differ from those observed under windless convective conditions over flat terrain. Large-eddy simulations of the boundary-layer transition in the valley were conducted, and statistical properties of the simulated flow agree with the observed quantities. Spatially coherent turbulence structures are present in the temporal as well as in the ensemble mean analysis. Thus, the complex orography induces coherent convective structures at predictable, specific locations during the early-morning low wind situations. These coherent updrafts, found in both the sodar observations and the simulation, lead to a flux counter to the gradient of the stably stratified valley atmosphere and reach up to the heights of the surrounding ridges. Furthermore, the energy balance in the surface layer during the low wind periods is closed. However, it becomes unclosed after the onset of the valley wind. The partition into the sensible and the latent heat fluxes indicates that missing flux components of sensible heat are the main reason for the unclosed energy balance in the considered situations. This result supports previously published investigations on the energy balance closure.     

Extended regional climate model projections for Europe until the mid-twentyfirst century: combining ENSEMBLES and CMIP3

This study aims at sharpening the existing knowledge of expected seasonal mean climate change and its uncertainty over Europe for the two key climate variables air temperature and precipitation amount until the mid-twentyfirst century. For this purpose, we assess and compensate the global climate model (GCM) sampling bias of the ENSEMBLES regional climate model (RCM) projections by combining them with the full set of the CMIP3 GCM ensemble. We first apply a cross-validation in order to assess the skill of different statistical data reconstruction methods in reproducing ensemble mean and standard deviation. We then select the most appropriate reconstruction method in order to fill the missing values of the ENSEMBLES simulation matrix and further extend the matrix by all available CMIP3 GCM simulations forced by the A1B emission scenario. Cross-validation identifies a randomized scaling approach as superior in reconstructing the ensemble spread. Errors in ensemble mean and standard deviation are mostly less than 0.1 K and 1.0 % for air temperature and precipitation amount, respectively. Reconstruction of the missing values reveals that expected seasonal mean climate change of the ENSEMBLES RCM projections is not significantly biased and that the associated uncertainty is not underestimated due to sampling of only a few driving GCMs. In contrast, the spread of the extended simulation matrix is partly significantly lower, sharpening our knowledge about future climate change over Europe by reducing uncertainty in some regions. Furthermore, this study gives substantial weight to recent climate change impact studies based on the ENSEMBLES projections, since it confirms the robustness of the climate forcing of these studies concerning GCM sampling.     

Catchment precipitation processes in the San Francisco valley in southern Ecuador: combined approach using high-resolution radar images and in situ observations

The precise estimation of precipitation quantities in tropical mountain regions is in great demand by ecological and hydrological studies, due to the heterogeneity of the rainfall distribution and the lack of meteorological station data. This study uses radar images and ground station data to provide the required high-resolution precipitation maps. Also wind data are taken into account, due to its influence on the precipitation formation and to demonstrate the relation between synoptic wind, topography and the precipitation distribution inside small mountain valleys. The study analyses the rainfall distribution and amounts of 4 days inside the San Francisco Valley, a small catchment in the tropical Andes of southern Ecuador, representing different seasons and the typical atmospheric flows, which are correlated to the annual precipitation map. The results show that the rainfall distribution and amounts are generally defined by the wind direction and velocity, besides the topographic location in relation to the main barriers and pathways. The dominant wind direction causes a division of the catchment in a wetter eastern and a dryer western part. Moreover, the annual seasons are reversed; the main rainy season for the eastern part occurs between June and August, while the western part reaches the precipitation maximum between January and March. This may have influence on the species composition at the different slopes and the annual hydrological cycle inside the catchment.     

An iterative version of the adaptive Gaussian mixture filter

The adaptive Gaussian mixture filter (AGM) was introduced as a robust filter technique for large-scale applications and an alternative to the well-known ensemble Kalman filter (EnKF). It consists of two analysis steps, one linear update and one weighting/resampling step. The bias of AGM is determined by two parameters, one adaptive weight parameter (forcing the weights to be more uniform to avoid filter collapse) and one predetermined bandwidth parameter which decides the size of the linear update. It has been shown that if the adaptive parameter approaches one and the bandwidth parameter decreases, as an increasing function of the sample size, the filter can achieve asymptotic optimality. For large-scale applications with a limited sample size, the filter solution may be far from optimal as the adaptive parameter gets close to zero depending on how well the samples from the prior distribution match the data. The bandwidth parameter must often be selected significantly different from zero in order to make large enough linear updates to match the data, at the expense of bias in the estimates. In the iterative AGM we introduce here, we take advantage of the fact that the history matching problem is usually estimation of parameters and initial conditions. If the prior distribution of initial conditions and parameters is close to the posterior distribution, it is possible to match the historical data with a small bandwidth parameter and an adaptive weight parameter that gets close to one. Hence, the bias of the filter solution is small. In order to obtain this scenario, we iteratively run the AGM throughout the data history with a very small bandwidth to create a new prior distribution from the updated samples after each iteration. After a few iterations, nearly all samples from the previous iteration match the data, and the above scenario is achieved. A simple toy problem shows that it is possible to reconstruct the true posterior distribution using the iterative version of the AGM. Then a 2D synthetic reservoir is revisited to demonstrate the potential of the new method on large-scale problems.     

Element signatures of subduction-zone fluids. An experimental study of the element partitioning (Dfluid/rock) of natural partly altered igneous rocks from the ODP drilling site 1,256

The trace element signatures of fluids were investigated by leaching experiments on natural samples of partly altered mafic igneous rocks recovered from the drilling site 1,256 of ODP Leg 206 on the Cocos plate (Central America). Experiments with ultrapure water were performed at 400 °C/0.4 GPa and 500 °C/0.7 GPa. Both fluids and residual solids were examined to obtain the partition coefficients (D^fluid/rock) of various trace elements. Element partition coefficients (D^fluid/rock) obtained at 500 °C/0.7 GPa are significantly lower compared to results obtained at 400 °C/0.4 GPa, which is in contrast to observations at higher pressures (2.2–6 GPa) and temperatures between 700 and 1,400 °C (Kessel et al. in Earth Planet Sci Lett 237: 873–892, 2005a; Spandler et al. in Chem Geol 239: 228–249, 2007). This finding may indicate a considerable pressure effect on the leaching processes and strongly divergent fluid–rock interactions in the upper part of a subduction zone at 0.4–0.7 GPa compared to deeper subduction areas with higher pressures. Furthermore, this may be interpreted as one of the earliest fractionation processes during the subduction of crustal material.