Fe–Mg Interdiffusion in (Mg,Fe)O

We have performed a series of interdiffusion experiments on magnesiowüstite samples at room pressure, temperatures from 1,320° to 1,400°C, and oxygen fugacities from 10^?1.0 Pa to 10^?4.3 Pa, using mixed CO/CO₂ or H₂/CO₂ gases. The interdiffusion couples were composed of a single-crystal of MgO lightly pressed against a single-crystal of (Mg_1-x Fe _x )_1-δO with 0.07<x<0.27. The interdiffusion coefficient was calculated using the Boltzmann–Matano analysis as a function of iron content, oxygen fugacity, temperature, and water fugacity. For the entire range of conditions tested and for compositions with 0.01<x<0.27, the interdiffusion coefficient varies as $$\tilde D\, =\,2.9\times10^{ - 6}\,f_{{\text{O}}_2 }^{0.19}\,x^{0.73}\,{\text{e}}^{ - (209,000\, -\,96,000\,x)/RT}\,\,{\text{m}}^{\text{2}} {\text{s}}^{ -1} $$ These dependencies on oxygen fugacity and composition are reasonably consistent with interdiffusion mediated by unassociated cation vacancies. For the limited range of water activity that could be investigated using mixed gases at room pressure, no effect of water on interdiffusion could be observed. The dependence of the interdiffusion coefficient on iron content decreased with increasing iron concentration at constant oxygen fugacity and temperature. There is a close agreement between our activation energy for interdiffusion extrapolated to zero iron content (x=0) and that of previous researchers who used electrical conductivity experiments to determine vacancy diffusivities in lightly doped MgO.     

A STATISTICAL APPROACH TO THE PROBLEM OF MISSING SPATIAL DATA USING A FIRST-ORDER MARKOV MODEL*

Geographical data sets sometimes contain missing observations that need to be estimated. A statistical approach to the problem is discussed for multivariate normal spatial data sets satisfying the first-order spatial Markov property with constant mean, where the information at neighboring or contiguous observed sites is used to estimate the missing values. The completed data are used to estimate the parameters of the distribution. The procedure is iterative. The approach is a special case of the Orchard and Woodbury missing information principle. The paper concludes with an illustrative empirical example using rainfall data from an area of Kansas and Nebraska. The quality of the estimates for different sites are compared.     

Incorporation of argon, krypton and xenon into clathrates on Mars

Calculations of the trapping of heavy noble gases within multiple guest clathrates under Mars-like conditions show that a substantial fraction of the martian Xe, perhaps even the vast majority, could be in clathrates. In addition, the Xe/Kr ratio in the clathrates would probably be much higher than in the atmosphere, so the formation or dissociation of a relatively small amount of clathrate could measurably change the atmospheric ratio. Relatively crude (factor of 2) measurements of the seasonal variability in that ratio by in situ spacecraft would be sensitive to ∼10% of the seasonal atmospheric CO₂ variability being a result of clathrates, rather than pure CO₂ frost. In addition, sequestration of Xe in clathrates remains a viable mechanism for explaining the variable Xe/Kr ratios seen in different suites of martian meteorites.     

Denitrification coupled to pyrite oxidation and changes in groundwater quality in a shallow sandy aquifer

This study focuses on denitrification in a sandy aquifer using geochemical analyses of both sediment and groundwater, combined with groundwater age dating (³H/³He). The study sites are located underneath cultivated fields and an adjacent forested area at Oostrum, The Netherlands. Shallow groundwater in the region has high nitrate concentrations (up to 8 mM) due to intense fertilizer application. Nitrate removal from the groundwater below cultivated fields correlates with sulfate production, and the release of dissolved Fe²⁺ and pyrite-associated trace metals (e.g. As, Ni, Co and Zn). These results, and the presence of pyrite in the sediment matrix within the nitrate removal zone, indicate that denitrification coupled to pyrite oxidation is a major process in the aquifer. Significant nitrate loss coupled to sulfate production is further confirmed by comparing historical estimates of regional sulfate and nitrate loadings to age-dated groundwater sulfate and nitrate concentrations, for the period 1950-2000. However, the observed increases in sulfate concentration are about 50% lower than would be expected from complete oxidation of pyrite to sulfate, possibly due to the accumulation of intermediate oxidation state sulfur compounds, such as elemental sulfur. Pollutant concentrations (NO₃, Cl, As, Co and Ni) measured in the groundwater beneath the agricultural areas in 1996 and 2006 show systematic decreases most likely due to declining fertilizer use.     

Numerical Simulation of a Solar Active Region. I: Bastille Day Flare

We present three-dimensional unsteady modeling and numerical simulations of a coronal active region, carried out within the compressible single-fluid MHD approximation. We focus on AR 9077 on 14 July 2000, and the triggering of the X5.7 GOES X-ray class “Bastille Day” flare. We simulate only the lower corona, although we include a virtual photosphere and chromosphere below. The boundary conditions at the base of this layer are set using temperature maps from line intensities and line-of-sight magnetograms (SOHO/MDI). From the latter, we generate vector magnetograms using the force-free approximation; these vector magnetograms are then used to produce the boundary condition on the velocity field using a minimum energy principle (Longcope, Astrophys. J. 612, 1181, 2004). The reconnection process is modeled through a dynamical hyper-resistivity which is activated when the current exceeds a critical value (Klimas et al., J. Geophys. Res. 109, 2218, 2004). Comparing the time series of X-ray fluxes recorded by GOES with modeled time series of various mean physical variables such as current density, Poynting energy flux, or radiative loss inside the active region, we can demonstrate that the model properly captures the evolution of an active region over a day and, in particular, is able to explain the initiation of the flare at the observed time.     

Evaluation of a simple,inexpensive, in situ sampler for measuring time‐weighted average concentrations of suspended sediment in rivers and streams

The accurate measurement of suspended sediment (<200 μm) in aquatic environments is essential to understand and effectively manage changes to sediment, nutrient, and contaminant concentrations on both temporal and spatial scales. Commonly used sampling techniques for suspended sediment either lack the ability to accurately measure sediment concentration (e.g., passive sediment samplers) or are too expensive to deploy in sufficient number to provide landscape‐scale information (e.g., automated discrete samplers). Here, we evaluate a time‐integrated suspended sediment sampling technique, the pumped active suspended sediment (PASS) sampler, which collects a sample that can be used for the accurate measurement of time‐weighted average (TWA) suspended sediment concentration and sediment particle size distribution. The sampler was evaluated against an established passive time‐integrated suspended sediment sampling technique (i.e., Phillips sampler) and the standard discrete sampling method (i.e., manual discrete sampling). The PASS sampler collected a sample representative of TWA suspended sediment concentration and particle size distribution of a control sediment under laboratory conditions. Field application of the PASS sampler showed that it collected a representative TWA suspended sediment concentration and particle size distribution during high flow events in an urban stream. The particle size distribution of sediment collected by the PASS and Phillips samplers were comparable and the TWA suspended sediment concentration of the samples collected using the PASS and discrete sampling techniques agreed well, differing by only 4% and 6% for two different high flow events. We should note that the current configuration of the PASS sampler does not provide a flow‐weighted measurement and, therefore, is not suitable for the determination of sediment loads. The PASS sampler is a simple, inexpensive, and robust in situ sampling technique for the accurate measurement of TWA suspended sediment concentration and particle size distribution.     

The Influence of Place on the Willingness to Pay for Ecosystem Services

Sense of place, including an individual’s attitudes toward specific geographic settings, is generally predicted to influence willingness to engage in place-protective behaviors. Relatively little research, however, has empirically examined the influence of people’s attitudes toward a place on their willingness to pay for environmental protection. Using the example of a payment for ecosystem services (PES) initiative in the McKenzie River watershed, Oregon, USA, we found that place attitudes were a significant predictor of respondents’ willingness to pay for a program designed to benefit drinking water quality. These results suggest that connecting conservation actions to landscapes that are meaningful to people may increase their financial support for PES and other conservation programs. While program managers have little or no influence over stakeholders’ political ideology, gender, or income, managers may be able to influence prospective PES buyers’ awareness and attitudes through targeted communications, thereby potentially increasing support for place-based conservation efforts.     

Fracturing and fluid‐flow during post‐rift subsidence in carbonates of the Jandaíra Formation,Potiguar Basin,NE Brazil

Pervasive fracture networks are common in many reservoir‐scale carbonate bodies even in the absence of large deformation and exert a major impact on their mechanical and flow behaviour. The Upper Cretaceous Jandaíra Formation is a few hundred meters thick succession of shallow water carbonates deposited during the early post‐rift stage of the Potiguar rift (NE Brazil). The Jandaíra Formation in the present onshore domain experienced <1.5 km thermal subsidence and, following Tertiary exhumation, forms outcrops over an area of >1000 km². The carbonates have a gentle, <5?, dip to the NE and are affected by few regional, low displacement faults or folds. Despite their simple tectonic history, carbonates display ubiquitous open fractures, sub‐vertical veins, and sub‐vertical as well as sub‐horizontal stylolites. Combining structural analysis, drone imaging, isotope studies and mathematical modelling, we reconstruct the fracturing history of the Jandaíra Formation during and following subsidence and analyse the impact fractures had on coeval fluid flow. We find that Jandaíra carbonates, fully cemented after early diagenesis, experienced negligible deformation during the first few hundreds of meters of subsidence but were pervasively fractured when they reached depths >400–500 m. Deformation was accommodated by a dense network of sub‐vertical mode I and hybrid fractures associated with sub‐vertical stylolites developed in a stress field characterised by a sub‐horizontal σ₁ and sub‐vertical σ₂. The development of a network of hybrid fractures, rarely reported in the literature, activated the circulation of waters charged in the mountainous region, flowing along the porous Açu sandstone underlying the Jandaíra carbonates and rising to the surface through the fractured carbonates. With persisting subsidence, carbonates reached depths of 800–900 m entering a depth interval characterised by a sub‐vertical σ₁. At this stage, sub‐horizontal stylolites developed liberating calcite which sealed the sub‐vertical open fractures transforming them in veins and preventing further flow. During Tertiary exhumation, several of the pre‐existing veins and stylolites opened and became longer, and new fractures were created typically with the same directions of the older features. The simplicity of our model suggests that most rocks in passive margin settings might have followed a similar evolution and thus display similar structures.