Complexation of cadmium to sulfur and oxygen functional groups in an organic soil

Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd) to soil organic matter (SOM) was determined in an organic (49% organic C) soil as a function of reaction time, pH and Cd concentration. In experiments conducted at native Cd concentrations in soil (0.23 μg g⁻¹ dry soil), halides (Cl, Br) were used as competing ligands to functional groups in SOM. The concentration of Cd in the aqueous phase was determined by isotope-dilution (ID) inductively-coupled-plasma-mass-spectrometry (ICP-MS), and the activity of Cd²⁺ was calculated from the well-established Cd-halide constants. At higher Cd loading (500-54,000 μg g⁻¹), the Cd²⁺ activity was directly determined by an ion-selective electrode (ISE). On the basis of results from extended X-ray absorption fine structure (EXAFS) spectroscopy, a model with one thiolate group (RS⁻) was used to describe the complexation (Cd²⁺ + RS⁻ ? CdSR⁺; log K_CdSR) at native Cd concentrations. The concentration of thiols (RSH; 0.047 mol kg⁻¹ C) was independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. Log K_CdSR values of 11.2-11.6 (pK_a for RSH = 9.96), determined in the pH range 3.1-4.6, compare favorably with stability constants for the association between Cd and well-defined thiolates like glutathione. In the concentration range 500-54,000 μg Cd g⁻¹, a model consisting of one thiolate and one carboxylate (RCOO⁻) gave the best fit to data, indicating an increasing role for RCOOH groups as RSH groups become saturated. The determined log K_CdOOCR of 3.2 (Cd²⁺ +  RCOO⁻ ? CdOOCR⁺; log K_CdOOCR; pK_a for RCOOH = 4.5) is in accordance with stability constants determined for the association between Cd and well-defined carboxylates. Given a concentration of reduced sulfur groups of 0.2% or higher in NOM, we conclude that the complexation to organic RSH groups may control the speciation of Cd in soils, and most likely also in surface waters, with a total concentration less than 5 mg Cd g⁻¹ organic C.     

Modelling daily temperature extremes: recent climate and future changes over Europe

Probability distributions of daily maximum and minimum temperatures in a suite of ten RCMs are investigated for (1) biases compared to observations in the present day climate and (2) climate change signals compared to the simulated present day climate. The simulated inter-model differences and climate changes are also compared to the observed natural variability as reflected in some very long instrumental records. All models have been forced with driving conditions from the same global model and run for both a control period and a future scenario period following the A2 emission scenario from IPCC. We find that the bias in the fifth percentile of daily minimum temperatures in winter and at the 95th percentile of daily maximum temperature during summer is smaller than 3 (±5°C) when averaged over most (all) European sub-regions. The simulated changes in extreme temperatures both in summer and winter are larger than changes in the median for large areas. Differences between models are larger for the extremes than for mean temperatures. A comparison with historical data shows that the spread in model predicted changes in extreme temperatures is larger than the natural variability during the last centuries.     

Temporal Variability in Ecological Stoichiometry and Material Exchange in a Tidally Dominated Estuary (North Inlet,South Carolina) and the Impact on Community Nutrient Status

Across the coastal zone, rates of carbon and nutrient exchange are defined by the spatiotemporal heterogeneity of individual estuarine systems. Elemental stoichiometry provides a mechanism for simplifying overlapping physical, chemical, and biological drivers into proxies that can be used to compare and monitor estuarine biogeochemistry. To this end, the seasonal and tidal variability of estuarine stoichiometry was examined over an annual cycle in North Inlet (NI), South Carolina. Surface samples for dissolved and particulate carbon (C), nitrogen (N), and phosphorus (P) were collected every 20 days (August 2014 to August 2015) over a semi-diurnal tidal cycle. Dissolved nutrient flux estimates of an individual tidal creek were also made. Overall, the results demonstrated the dominance of seasonal versus tidal forcing on water column C:N:P stoichiometry. This seasonal behavior mediated the relative exchange of N and P into and out of the tidal creek and influenced the nutrient status index (NSI) of NI plankton communities. These communities were largely N deficient with the magnitude of this deficiency impacted by assumptions of inorganic versus organic plankton P demand and nutrient supply. Persistent N deficiency appeared to help drive the net import of N, while temporary P surplus likely drives its seasonal export. Combined, these results indicate that material delivery must be considered on seasonal time frames, as net annual fluxes do not reflect the short-term deliveries of C and nutrients into nearshore ecosystems.     

On Empirical Correlations for Normalised Shear Strengths from Fall Cone and Direct Simple Shear Tests in Soft Swedish Clays

Empirical correlations provide valuable information in early design stages, and they help to validate or discard single values from site investigations. This paper presents a multivariate database from commercial projects consisting of evaluated shear strengths obtained from direct simple shear tests and fall cone tests (which are calibrated to the field vane test), including index tests. The multivariate database is used to investigate the performance of common transformation models and to test the recommended correction for fall cone tests. It is found that the measured normalised shear strength evaluated from direct simple shear tests and fall cone tests is correlated to the liquid limit and that the results conform to Swedish and Norwegian recommendations. However, the scatter is large, more for fall cone tests than for direct simple shear tests, which is thought to depend mainly on sample disturbance. It can however be concluded that the trend of normalised shear strengths increases with increasing plasticity.

     

Late‐Summer Peak in Sediment Accumulation in Two Lakes with Contrasting Watersheds,Alaska

The timing of clastic sedimentation in two glacial‐fed lakes with contrasting watersheds was monitored using sequencing sediment traps for two consecutive years at Allison Lake (Chugach Range, Alaska) and four months at Shainin Lake (Brooks Range, Alaska). Shainin Lake is a weakly stratified lake fed by distant glaciers, whereas Allison Lake is more strongly stratified and fed predominantly by proximal glaciers. At Shainin Lake, sediment accumulation started in late June and reached its maximum in mid‐August, just before lake mixing and during a period of low river discharge. The grain size of the sediment reaching the sediment trap in Shainin Lake was homogenous throughout the summer. At Allison Lake, pulsed sedimentation of coarse particles during late summer and early fall storms were superimposed on the fine‐grained sedimentation pattern similar to that observed at Shainin Lake. These storms triggered underflows that were observed in the thermal structure of the lake and deposited abundant sediment. The sequencing sediment traps reveal a lag between fluvial discharge and sediment deposition at both lakes, implying limitations to interpreting intra‐annual sedimentary features in terms of inflow discharge.     

Effects of climate change and nutrient concentrations on carbon sources for zooplankton in a Tibetan Plateau lake over the past millennium

Journal of Paleolimnology - Autochthonous and allochthonous organic carbon (OC) are important carbon sources for zooplankton in lakes, and changes in the abundance and proportions of those sources...     

Simultaneous radio and X-ray observations of Galactic Centre low-mass X-ray binaries

We have performed simultaneous X-ray and radio observations of 13 Galactic Centre low-mass X-ray binaries in 1998 April using the Wide Field Cameras on board BeppoSAX and the Australia Telescope Compact Array, the latter simultaneously at 4.8 and 8.64 GHz. We detect two Z sources, GX 17+2 and GX 5−1, and the unusual 'hybrid' source GX 13+1. Upper limits, which are significantly deeper than previous non-detections, are placed on the radio emission from two more Z sources and seven atoll sources. Hardness–intensity diagrams constructed from the Wide Field Camera data reveal GX 17+2 and GX 5−1 to have been on the lower part of the horizontal branch and/or the upper part of the normal branch at the time of the observations, and the two non-detected Z sources, GX 340+0 and GX 349+2, to have been on the lower part of the normal branch. This is consistent with the previous empirically determined relation between radio and X-ray emission from Z sources, in which radio emission is strongest on the horizontal branch and weakest on the flaring branch. For the first time we have information on the X-ray state of atoll sources, which are clearly radio-quiet relative to the Z sources, during periods of observed radio upper limits. We place limits on the linear polarization from the three detected sources, and use accurate radio astrometry of GX 17+2 to confirm that it is probably not associated with the optical star NP Ser. Additionally we place strong upper limits on the radio emission from the X-ray binary 2S 0921−630, disagreeing with suggestions that it is a Z-source viewed edge-on.     

Coupled 1D–3D hydrodynamic modelling,with application to the Pearl River Delta

Within the hydrodynamic modelling community, it is common practice to apply different modelling systems for coastal waters and river systems. Whereas for coastal waters 3D finite difference or finite element grids are commonly used, river systems are generally modelled using 1D networks. Each of these systems is tailored towards specific applications. Three-dimensional coastal water models are designed to model the horizontal and vertical variability in coastal waters and are less well suited for representing the complex geometry and cross-sectional areas of river networks. On the other hand, 1D river network models are designed to accurately represent complex river network geometries and complex structures like weirs, barrages and dams. A disadvantage, however, is that they are unable to resolve complex spatial flow variability. In real life, however, coastal oceans and rivers interact. In deltaic estuaries, both tidal intrusion of seawater into the upstream river network and river discharge into open waters play a role. This is frequently approached by modelling the systems independently, with off-line coupling of the lateral boundary forcing. This implies that the river and the coastal model run sequentially, providing lateral discharge (1D) and water level (3D) forcing to each other without the possibility of direct feedback or interaction between these processes. An additional disadvantage is that due to the time aggregation usually applied to exchanged quantities, mass conservation is difficult to ensure. In this paper, we propose an approach that couples a 3D hydrodynamic modelling system for coastal waters (Delft3D) with a 1D modelling system for river hydraulics (SOBEK) online. This implies that contrary to off-line coupling, the hydrodynamic quantities are exchanged between the 1D and 3D domains during runtime to resolve the real-time exchange and interaction between the coastal waters and river network. This allows for accurate and mass conserving modelling of complex coastal waters and river network systems, whilst the advantages of both systems are maintained and used in an optimal and computationally efficient way. The coupled 1D–3D system is used to model the flows in the Pearl River Delta (Guangdong, China), which are determined by the interaction of the upstream network of the Pearl River and the open waters of the South China Sea. The highly complex upstream river network is modelled in 1D, simulating river discharges for the dry and wet monsoon periods. The 3D coastal model simulates the flow due to the external (ocean) periodic tidal forcing, the salinity distribution for both dry and wet seasons, as well as residual water levels (sea level anomalies) originating from the South China Sea. The model is calibrated and its performance extensively assessed against field measurements, resulting in a mean root mean square (RMS) error of below 6% for water levels over the entire Pearl River Delta. The model also represents both the discharge distribution over the river network and salinity transport processes with good accuracy, resolving the discharge distribution over the main branches of the river network within 5% of reported annual mean values and RMS errors for salinity in the range of 2 ppt (dry season) to 5 ppt (wet season).     

Modelling the uptake and release of carbon dioxide in the Baltic Sea surface water

We present and analyse a fully coupled physical–biogeochemical model of the uptake and release of carbon dioxide in the Baltic Sea. The modelling includes the interaction between physical (stratification, temperature, salinity, penetration of solar radiation, and ice), chemical (total alkalinity, pH, dissolved inorganic carbon, oxygen, and nutrients), and biological processes (plankton and dissolved organic carbon (DOC)). These processes have been built into an advanced process-oriented coupled basin ocean model that has been extensively explored and validated for the Baltic Sea.