Stoichiometry of smectite dissolution reaction

The dissolution stoichiometry of smectite-rich bentonites SAz-1, STx-1 and SWy-1 was studied at 50°C and pH 2 and 3 using flow-through reactors. In addition to smectite, these samples contain considerable amounts of silica phases (quartz, cristobalite and/or amorphous silica). As a result, the molar Al/Si ratios of the bulk samples are significantly lower than those of the pure smectite.Smectite dissolution was highly incongruent during the first few hundred to few thousand hours of the experiments. Release rates of Si, Mg, Ca and Na underwent a distinct transition from an initial period of rapid release to significantly lower release rate at steady state. A reversed trend was observed for release of Al, which gradually increased from very low starting release rate to higher release rate at steady state. At steady state the ratio of released Al to released Si was found to be constant and independent of the experimental conditions. We suggest that this ratio represents the Al/Si ratio of the smectite itself, and it is not influenced by the presence of accessory phases in the sample.The rapid release of calcium, sodium and magnesium from the interlayer sites is explained by ion-exchange reactions, whereas the fast release of silicon is explained by dissolution of amorphous silica. We interpret the initial slow release of Al as the result of inhibition of smectite dissolution due to coating or cementation of the smectite aggregates by amorphous silica. As the silica is dissolved, the aggregates fall apart and more smectite surfaces are exposed, resulting in an increase in the smectite dissolution rate. Thereafter, the system approaches steady state, in which the major tetrahedral and octahedral cations of smectite are released congruently.     

RCP 8.5��A scenario of comparatively high greenhouse gas emissions

This paper summarizes the main characteristics of the RCP8.5 scenario. The RCP8.5 combines assumptions about high population and relatively slow income growth with modest rates of technological change and energy intensity improvements, leading in the long term to high energy demand and GHG emissions in absence of climate change policies. Compared to the total set of Representative Concentration Pathways (RCPs), RCP8.5 thus corresponds to the pathway with the highest greenhouse gas emissions. Using the IIASA Integrated Assessment Framework and the MESSAGE model for the development of the RCP8.5, we focus in this paper on two important extensions compared to earlier scenarios: 1) the development of spatially explicit air pollution projections, and 2) enhancements in the land-use and land-cover change projections. In addition, we explore scenario variants that use RCP8.5 as a baseline, and assume different degrees of greenhouse gas mitigation policies to reduce radiative forcing. Based on our modeling framework, we find it technically possible to limit forcing from RCP8.5 to lower levels comparable to the other RCPs (2.6 to 6 W/m²). Our scenario analysis further indicates that climate policy-induced changes of global energy supply and demand may lead to significant co-benefits for other policy priorities, such as local air pollution.     

A parameterization for modelling the meteorological effects of tall forests — A case study of a large clearing

A parameterization scheme has been developed to describe the effects of a tall forest on the mean structure of the atmospheric boundary layer (ABL). The main advantage of the scheme is that dynamical and thermodynamical effects of a forest surface can be simulated satisfactorily using only a coarse-grid resolution within numerical models. Thereby, the canopy layer is parameterized as a quasi-subgrid phenomenon. This makes it possible to study meteorological phenomena within the ABL in a very economical way (with respect to computational time) whereby, nevertheless, more detailed information concerning the forest surface is taken into account than could be done using the same grid resolution and quite simple assumptions describing the canopy, e.g., the effective roughness.The applicability in numerical models is shown by using a slightly modified two-dimensional version of the mesoscale model FITNAH. For comparison, simulations with a high numerical grid resolution within the canopy have been carried out.Model results reproduce the known meteorological phenomena in forested areas, e.g., a stable thermal stratification near the surface during the day, and at night, a neutral — or slightly unstable condition — and, in general, reduced windspeed within the canopy layer.Diurnal variations and spatial distributions of temperature and humidity are found to be similar for both cases. Also, a thermally-induced local circulation system in the vicinity of a large clearing has been simulated satisfactorily.A comparison of the calculated results verifies that the parameterization scheme is quite suitable for simulating the effects of plant canopies on the distributions of meteorological variables in the ABL.     

Can Water Vapour Raman Lidar Resolve Profiles of Turbulent Variables in the Convective Boundary Layer?

High-resolution water vapour measurements made by the Atmospheric Radiation Measurement (ARM) Raman lidar operated at the Southern Great Plains Climate Research Facility site near Lamont, Oklahoma, U.S.A. are presented. Using a 2-h measurement period for the convective boundary layer (CBL) on 13 September 2005, with temporal and spatial resolutions of 10 s and 75 m, respectively, spectral and autocovariance analyses of water vapour mixing ratio time series are performed. It is demonstrated that the major part of the inertial subrange was detected and that the integral scale was significantly larger than the time resolution. Consequently, the major part of the turbulent fluctuations was resolved. Different methods to retrieve noise error profiles yield consistent results and compare well with noise profiles estimated using Poisson statistics of the Raman lidar signals. Integral scale, mixing-ratio variance, skewness, and kurtosis profiles were determined including error bars with respect to statistical and sampling errors. The integral scale ranges between 70 and 130 s at the top of the CBL. Within the CBL, up to the third order, noise errors are significantly smaller than sampling errors and the absolute values of turbulent variables, respectively. The mixing-ratio variance profile rises monotonically from ≈0.07 to ≈3.7 g² kg⁻² in the entrainment zone. The skewness is nearly zero up to 0.6 z/z _i , becomes −1 around 0.7–0.8 z/z _i , crosses zero at about 0.95 z/z _i , and reaches about 1.7 at 1.1 z/z _i (here, z is the height and z _i is the CBL depth). The noise errors are too large to derive fourth-order moments with sufficient accuracy. Consequently, to the best of our knowledge, the ARM Raman lidar is the first water vapour Raman lidar with demonstrated capability to retrieve profiles of turbulent variables up to the third order during daytime throughout the atmospheric CBL.     

Middle to Late Pleistocene lake‐level fluctuations of Lake El'gygytgyn,far‐east Russian Arctic

Lake El'gygytgyn, located in central Chukotka, Russian Arctic, was the subject of an international drilling project that resulted in the recovery of the longest continuous palaeoclimatic and palaeoenvironmental record for the terrestrial Arctic covering the last 3.6 million years. Here, we present the reconstruction of the lake‐level fluctuations of Lake El'gygytgyn since Marine Isotope Stage (MIS) 7 based on lithological and palynological as well as chronological studies of shallow‐water sediment cores and subaerial lake terraces. Reconstructed lake levels show an abrupt rise during glacial–interglacial terminations (MIS 6/5 and MIS 2/1) and during the MIS 4/3 stadial–interstadial transition. The most prominent lowstands occurred during glacial periods associated with a permanent lake‐ice cover (namely MIS 6, MIS 4 and MIS 2). Major triggering mechanisms of the lake‐level fluctuations at Lake El'gygytgyn are predominantly changes in air temperature and precipitation. Regional summer temperatures control the volume of meltwater supply as well as the duration of the lake‐ice cover (permanent or seasonal). The duration of the lake‐ice cover, in turn, enables or hampers near‐shore sediment transport, thus leading to long‐term lake‐level oscillations on glacial–interglacial time scales by blocking or opening the lake outflow, respectively. During periods of seasonal ice cover the lake level was additionally influenced by changes in precipitation. The discovered mechanism of climatologically driven level fluctuations of Lake El'gygytgyn are probably valid for large hydrologically open lakes in the Arctic in general, thus helping to understand arctic palaeohydrology and providing missing information for climate modelling.     

Stable Sulfur Isotopic Evidence for Historical Changes of Sulfur Cycling in Estuarine Sediments from Northern Florida

Data on abundance and isotopic composition of porewater and sedimentary sulfur species are reported for relatively uncontaminated and highly contaminated fine-grained anoxic sediments of St. Andrew Bay, Florida. A strong contrast in amount and composition of sedimentary organic matter at the two sites allows a comparative study of the historical effects of increased organic loading on sulfur cycling and sulfur isotopic fractionation. In the contaminated sediments, an increase in organic loading caused increased sedimentary carbon/sulfur ratios and resulted in higher rates of bacterial sulfate reduction, but a lower efficiency of sulfide oxidation. These differences are well reflected in the isotopic composition of dissolved sulfate, sulfide, and sedimentary pyrite. Concentration and isotopic profiles of dissolved sulfate, organic carbon, and total sulfur suggest that the anaerobic decomposition of organic matter is most active in the upper 8cm but proceeds at very slow rates below this depth. The rapid formation of more than 90% of pyrite in the uppermost 2 cm which corresponds to about 3 years of sediment deposition allows the use of pyrite isotopic composition for tracing changing diagenetic conditions. Sediment profiles of the sulfur isotopic composition of pyrite reflect present-day higher rates of bacterial sulfate reduction and lower rates of sulfide oxidation, and record a profound change in the diagenetic cycling of sulfur in the contaminated sediments coincident with urban and industrial development of the St. Andrew Bay area.