Kinetic analysis of cation exchange in birnessite using time-resolved synchrotron X-ray diffraction

In this study, we applied time-resolved synchrotron X-ray diffraction (TRXRD) to develop kinetic models that test a proposed two-stage reaction pathway for cation exchange in birnessite. These represent the first rate equations calculated for cation exchange in layered manganates. Our previous work has shown that the substitution of K, Cs, and Ba for interlayer Na in synthetic triclinic birnessite induces measurable changes in unit-cell parameters. New kinetic modeling of this crystallographic data supports our previously postulated two-stage reaction pathway for cation exchange, and we can correlate the kinetic steps with changes in crystal structure. In addition, the initial rates of cation exchange, R (ų min⁻¹), were determined from changes in unit-cell volume to follow these rate laws: R = 1.75[]^0.56, R = 41.1[]^1.10, R = 1.15[]^0.50. Thus, the exchange rates for Na in triclinic birnessite decreased in the order: Cs ? K > Ba. These results are likely a function of hydration energy differences of the cations and the preference of the solution phase for the more readily hydrated cation.     

Dust in the Wind: Long Range Transport of Dust in the Atmosphere and Its Implications for Global Public and Ecosystem Health

Movement of soil particles in atmospheres is a normal planetary process. Images of Martian dust devils (wind-spouts) and dust storms captured by NASA's Pathfinder have demonstrated the significant role that storm activity plays in creating the red atmospheric haze of Mars. On Earth, desert soils moving in the atmosphere are responsible for the orange hues in brilliant sunrises and sunsets. In severe dust storm events, millions of tons of soil may be moved across great expanses of land and ocean. An emerging scientific interest in the process of soil transport in the Earth's atmosphere is in the field of public and ecosystem health. This article will address the benefits and the potential hazards associated with exposure to particle fallout as clouds of desert dust traverse the globe. This revised version was published online in September 2006 with corrections to the Cover Date.     

Bleaching of the post‐IR IRSL signal: new insights for feldspar luminescence dating

Post‐infrared (pIR) stimulated luminescence dating of sedimentary feldspar largely avoids the effects of anomalous fading that affect conventional infrared stimulated luminescence (IRSL) dating. However, optical resetting of pIR signals is more difficult than resetting the conventional IRSL signal, which may undermine the crucial assumption that pIR signals were effectively bleached upon deposition and burial of sediment grains. In this study, we quantify the bleaching properties of several pIR signals on various samples using laboratory‐simulated bleaching in full sunlight and water‐attenuated sunlight. Our data show that bleaching is most efficient under full spectrum conditions for all pIR signals and that pIR signals measured at elevated temperature are increasingly harder to bleach than IR and pIR signals measured at low temperature (e.g. IR at 50°C). All bleaching curves exhibit a very slow and steady decrease, indicating that a fixed un‐bleachable residual level cannot be reached within the 11 days of solar simulator exposure undertaken here. We show that the magnitude of a laboratory‐determined residual dose depends on the adopted bleaching protocol and cannot be used as a proxy for the dose that remains in the sample at the time of burial (remnant dose). Our data emphasize the importance of finding a balance between sufficient signal stability and a minimized contribution of a remnant dose when using pIR procedures for feldspar luminescence dating.     

Mineralogical sources of the buffer capacity in a granite catchment determined by strontium isotopes

The role of different minerals in base cation release and thus the increase of buffering capacity of groundwater against acid deposition is controversially discussed in the literature. The ⁸⁷Sr/⁸⁶Sr ratios and base cation concentration were investigated in whole rock leachates, mineral separates, precipitation, soil solution, groundwater and stream water samples in the Lehstenbach catchment (Germany) to identify the weathering sequence of the granite bedrock. Three different approaches were followed in parallel. It was assumed that the contribution of different minerals to base cation supply of the groundwater with increasing weathering intensity would be observed by investigating (1) unweathered rock leachates, deep groundwater and shallow groundwater, (2) groundwater samples from new groundwater wells, reflecting the initial weathering of the drilled bedrock, and groundwater from wells that were drilled in 1988, (3) stream water during baseflow, dominated by deep groundwater, and stream water during high flow, being predominantly shallow groundwater. Whereas the first approach yielded consistent patterns, there was some evidence that groundwater from the new wells initially reflected contamination by the filter gravel rather than cation release in an initial stage of weathering. Time series samples of stream water and groundwater solute concentrations and isotope ratios turned out to reflect varying fractions of soil water and precipitation water at baseflow and high flow conditions rather than varying contributions of different minerals that prevail at different stages of granite weathering.     

Hydrogeologic controls on summer stream temperatures in the McKenzie River basin,Oregon

Stream temperature is a complex function of energy inputs including solar radiation and latent and sensible heat transfer. In streams where groundwater inputs are significant, energy input through advection can also be an important control on stream temperature. For an individual stream reach, models of stream temperature can take advantage of direct measurement or estimation of these energy inputs for a given river channel environment. Understanding spatial patterns of stream temperature at a landscape scale requires predicting how this environment varies through space, and under different atmospheric conditions. At the landscape scale, air temperature is often used as a surrogate for the dominant controls on stream temperature. In this study we show that, in regions where groundwater inputs are key controls and the degree of groundwater input varies in space, air temperature alone is unlikely to explain within-landscape stream temperature patterns. We illustrate how a geologic template can offer insight into landscape-scale patterns of stream temperature and its predictability from air temperature relationships. We focus on variation in stream temperature within headwater streams within the McKenzie River basin in western Oregon. In this region, as in other areas of the Pacific Northwest, fish sensitivity to summer stream temperatures continues to be a pressing environmental issue. We show that, within the McKenzie, streams which are sourced from deeper groundwater reservoirs versus shallow subsurface flow systems have distinct summer temperature regimes. Groundwater streams are colder, less variable and less sensitive to air temperature variation. We use these results from the western Oregon Cascade hydroclimatic regime to illustrate a conceptual framework for developing regional-scale indicators of stream temperature variation that considers the underlying geologic controls on spatial variation, and the relative roles played by energy and water inputs. Copyright © 2007 John Wiley & Sons, Ltd.     

Delgada Fan: Preliminary interpretation of channel development

The Delgada Fan, an irregularly shaped turbidite deposit extending more than 350 km offshore from northern California, consists of two large leveed-valley units each fed by a separate complex of coalescing submarine canyons and slope gullies. Although the leveed-valley units head within 25 km of each other, both appear to have developed independently during fan growth. The larger southern leveed-valley system has not developed middle-fan distributary channels and appears to illustrate a period of progressive valley abandonment. Although the lower-fan area is underlain by sandy sediments, little sand has been recovered in piston cores from the leveed-valley unit. Margin setting represents fan and/or source area     

Re–Os isotope and platinum-group element geochemistry of the Pobei Ni–Cu sulfide-bearing mafic–ultramafic complex in the northeastern part of the Tarim Craton

A number of mafic–ultramafic intrusions that host Ni–Cu sulfide mineralization occur in the northeastern Tarim Craton and the eastern Tianshan Orogenic Belt (NW China). The sulfide-mineralized Pobei mafic–ultramafic complex is located in the northeastern part of the Tarim Craton. The complex is composed of gabbro and olivine gabbro, cut by dunite, wehrlite, and melatroctolite of the Poyi and Poshi intrusions. Disseminated Ni–Cu sulfide mineralization is present towards the base of the ultramafic bodies. The sulfide mineralization is typically low grade (<0.5 wt.% Ni and <2 wt.% S) with low platinum-group element (PGE) concentrations (<24.5 ppb Pt and <69 ppb Pd); the abundance of Cu in 100 % sulfide is 1–8 wt.%, and Ni abundance in 100 % sulfide is typically >4 wt.%. Samples from the Pobei complex have εNd (at 280 Ma) values up to +8.1, consistent with the derivation of the magma from an asthenospheric mantle source. Fo 89.5 mol.% olivine from the ultramafic bodies is consistent with a primitive parental magma. Sulfide-bearing dunite and wehrlite have high Cu/Pd ratios ranging from 24,000 to 218,000, indicating a magma that evolved under conditions of sulfide saturation. The grades of Ni, Cu, and PGE in 100 % sulfide show a strong positive correlation. A model for these variations is proposed where the mantle source of the Pobei magma retained ~0.033 wt.% sulfide during the production of a PGE-depleted parental magma. The parental magma migrated from the mantle to the crust and underwent further S saturation to generate the observed mineralization along with its high Cu/Pd ratio at an R-factor varying from 100 to 1,200. The mineralization at Poshi and Poyi has very high γOs (at 280 Ma) values (+30 to +292) that are negatively correlated with the abundance of Os in 100 % sulfide (5.81–271 ppb) and positively correlated with the Re/Os ratios; this indicates that sulfide saturation was triggered by the assimilation of crustal sulfide with both high γOs and Re/Os ratios. When compared to other Permian mafic–ultramafic intrusions with sulfide mineralization in the East Tianshan, the Poyi and Poshi ultramafic bodies were formed from more primitive magmas, and this helps to explain why the sulfide mineralization has high Ni tenor.     

A Local Example of Land‐Use Change: Southern Illinois—1807, 1938, and 1993*

This article provides an analysis of a wetland site in southern Illinois from presettlement to the present. The study area is part of the Cache River‐Cypress Creek Wetland, which has international importance, as recognized by the Ramsar Convention on Wetlands. Land‐cover data for 1807, 1938, and 1993 were created and analyzed with a geographic information system (GIS). Land‐use change by topographic setting (uplands, transitional, and bottomlands) and soil productivity was quantified and studied. Interviews with local experts informed this analysis. Results illustrate the complexity of environmental change and its driving forces. First, notable forest and swamp acreage was converted to cropland between 1807 and 1938 and, to a lesser degree, from 1938 to 1993. Second, there were land‐use variations by topographic region. Between 1807 and 1938, the largest transformation occurred in the uplands, with substantial acreage converted from forest to cropland. Between 1938 and 1993, however, agriculture decreased in the upland areas as hilly areas reverted to forest cover. At the same time, agriculture expanded in the bottomlands as this land was drained for farming. Third, there are interesting patterns within these categories of land‐use change, as soil productivity is an indicator of what lands were taken out of cropland and converted back to grassland and forest.     

Wetland economic valuation approaches and prospects in China

Ecosystem services valuation seeks to increase the social relevance of ecosystem characteristics, the underlying biological mechanisms that support services, by making the contribution of ecosystems to human well-being explicit. Economic valuation can help management by clarifying the full range of benefits and costs of proposed management actions. In the past two decades, economic valuation of wetland ecosystem services has become one of the most significant scientific priorities for wetland protection. In this paper, we provide an overview of ecosystem services, and summarize the main interdisciplinary approaches to measure and value wetland ecosystem services. We identified four main methodological gaps preventing progress on wetland valuation of ecosystem services in China, which are: 1) confusion on terminology like intermediate and final ecosystem services, 2) lack of ecological production functions to link ecosystem characteristics to final ecosystem services, 3) static valuation making it difficult to evaluate the trade-offs and synergies among ecosystem services, and 4) lack of clear guidance on relating ecological compensation programs to conservation targets. Overcoming these gaps is important to inform wetland compensation mechanisms and conservation policies. We propose future research on wetland ecosystem services in China should be focused on: 1) defining final ecosystem services based on beneficiary preferences and underlying biophysical mechanisms, 2) establishing wetland monitoring programs at specific sites to collect data on final ecosystem service indicators and ecosystem characteristic metrics to create ecological production functions for economic valuation and rescaling techniques, and 3) incorporating wetland ecosystem service values into decision-making processes to inform wetland management.