Investigating the effect of ballasting by CaCO3 in Emiliania huxleyi, II: Decomposition of particulate organic matter

The quantitative relationship between organic carbon and mineral contents of particles sinking below 1800 m in the ocean indicates that organisms with mineral shells such as coccolithophores are of special importance for transporting carbon into the deep sea. Several hypotheses about the mechanism behind this relationship between minerals and organic matter have been raised, such as mineral protection of organic matter or enhanced sinking rates through ballast addition. We examined organic matter decomposition of calcifying and non-calcifying Emiliania huxleyi cultures in an experiment that allowed aggregation and settling in rotating tanks. Biogenic components such as particulate carbon, particulate nitrogen, particulate volume, pigments, transparent exopolymer particles (TEP), and particulate amino acids in suspended particles and aggregates were followed over a period of 30 d. The overall pattern of decrease in organic matter, the amount of recalcitrant organic matter left after 30 d, and the compositional changes within particulate organic matter indicated that cells without a shell are more subject to loss than calcified cells. It is suggested that biogenic calcite helps in the preservation of particulate organic matter (POM) by offering structural support for organic molecules. Over the course of the experiment, half the particulate organic carbon in both calcifying and non-calcifying cultures was partitioned into aggregates and remained so until the end of the experiment. The partial protection of particulate organic matter from solubilization by biominerals and by aggregation that was observed in our experiment may help explain the robustness of the relationship between organic and mineral matter fluxes in the deep ocean.     

Development of a soil moisture‐based distributed hydrologic model for determining hydrologically based critical source areas

A simple grid cell‐based distributed hydrologic model was developed to provide spatial information on hydrologic components for determining hydrologically based critical source areas. The model represents the critical process (soil moisture variation) to run‐off generation accounting for both local and global water balance. In this way, it simulates both infiltration excess run‐off and saturation excess run‐off. The model was tested by multisite and multivariable evaluation on the 50‐km² Little River Experimental Watershed I in Georgia, U.S. and 2 smaller nested subwatersheds. Water balance, hydrograph, and soil moisture were simulated and compared to observed data. For streamflow calibration, the daily Nash‐Sutcliffe coefficient was 0.78 at the watershed outlet and 0.56 and 0.75 at the 2 nested subwatersheds. For the validation period, the Nash‐Sutcliffe coefficients were 0.79 at the watershed outlet and 0.85 and 0.83 at the 2 subwatersheds. The per cent bias was less than 15% for all sites. For soil moisture, the model also predicted the rising and declining trends at 4 of the 5 measurement sites. The spatial distribution of surface run‐off simulated by the model was mainly controlled by local characteristics (precipitation, soil properties, and land cover) on dry days and by global watershed characteristics (relative position within the watershed and hydrologic connectivity) on wet days when saturation excess run‐off was simulated. The spatial details of run‐off generation and travel time along flow paths provided by the model are helpful for watershed managers to further identify critical source areas of non‐point source pollution and develop best management practices.     

Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ³⁴S_SO4 and δ¹⁸O_SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ¹⁸O_H2O and initial δ¹⁸O_SO4, all strains show ³⁴S enrichment, whereas only six strains show significant ¹⁸O enrichment. The remaining six show no (or minimal) change in δ¹⁸O_SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO₃²⁻), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.     

Development of a distributed hydrological model to facilitate watershed management

To facilitate precise and cost-effective watershed management, a simple yet spatially and temporally distributed hydrological model (DHM-WM) was developed. The DHM-WM is based on the Mishra-Singh version of the curve number method, with several modifications: The spatial distribution of soil moisture was considered in moisture updating; the travel time of surface runoff was calculated on a grid cell basis for routing; a simple tile flow module was included as an option. The DHM-WM was tested on a tile-drained agricultural watershed in Indiana, USA. The model with the tile flow module performed well in the study area, providing a balanced water budget and reasonable flow partitioning. The daily coefficient of determination and Nash-Sutcliffe coefficient were 0.58 and 0.56, for the calibration period, and 0.63 and 0.62 for the validation period. The DHM-WM also provides detailed information about the source areas of flow components, the travel time and pathways of surface runoff.

EDITOR A. Castellarin; ASSOCIATE EDITOR F.-J. Chang     

Kinetics of peptide hydrolysis and amino acid decomposition at high temperature

Dipeptide hydrolysis and amino acid decomposition appear to follow a first-order rate law. The hydrolysis rate increases exponentially with increasing temperature in aqueous solution at both 265 atm and water steam pressures over the temperature range of 100 to 220 degrees C. Dipeptide hydrolysis has a lower apparent activation energy at 265 atm (44.1 KJ/mol) than at water steam pressure (98.9 KJ/mol). At lower temperatures (<200-220 degrees C), the rate of peptide bond hydrolysis is faster at 265 atm than at water steam pressure. At higher temperatures (>200-220 degrees C), however, peptide bond hydrolysis is slower at 265 atm than at water steam pressure. In aqueous solution, amino acid decomposition rates also increase exponentially with increasing temperature. Amino acid decomposition rates are much higher at 265 atm than at water steam pressure over the entire temperature range investigated.     

Are carbonate barrier islands mobile? Insights from a mid to late-Holocene system,Al Ruwais,northern Qatar

Barrier islands are important landforms in many coastal systems around the globe. Studies of modern barrier island systems are mostly limited to those of siliciclastic realms, where the islands are recognized as mobile features that form on transgressive coastlines and migrate landward as sea-level rises. Barrier islands of the ‘Great Pearl Bank’ along the United Arab Emirates coast are the best-known carbonate examples. These Holocene islands, however, are interpreted to be anchored by older deposits and immobile. The mid-Holocene to late-Holocene depositional system at Al Ruwais, northern Qatar, provides an example of a mobile carbonate barrier island system, perhaps more similar to siliciclastic equivalents. Sedimentological and petrographic analyses, as well as ¹⁴C-dating of shells and biogenic remains from vibracored sediments and surface deposits, show that after 7000 years ago a barrier system with a narrow back-barrier lagoon formed along what is now an exposed coastal zone, while, contemporaneously, a laterally-extensive coral reef was forming immediately offshore. After 1400 years ago the barrier system was forced to step ca 3 km seaward in response to a sea-level fall of less than 2 m, where it re-established itself directly on the mid-Holocene reef. Since that time, the barrier has retreated landward as much as 1000 m to its current position, exposing previously-deposited back-barrier lagoonal sediment at the open-coast shoreline. In modern neritic warm-water carbonate settings mobile barrier island systems are rare. Their construction and migration may be inhibited by reef formation, early cementation, and the relative inefficiency of sourcing beach sediments from open carbonate shelves. Carbonate barrier island systems likely formed more commonly during geological periods when ramps and unrimmed shelves predominated and in calcite seas, when meteoric cementation was minimized as a result of initial calcitic allochem mineralogy. As with their siliciclastic analogues, however, recognition of the influence of these transient landforms in the rock record is challenging.     

Exploring the effects of data quality,data worth,and redundancy of CO2 gas pressure and saturation data on reservoir characterization through PEST inversion

This study examined the impacts of reservoir properties on carbon dioxide (CO₂) migration after subsurface injection and evaluated the possibility of characterizing reservoir properties using CO₂ monitoring data such as spatial–temporal distributions of gas pressure, which can be reasonably monitored in practice. The injection reservoir was assumed to be located 1,400–1,500 m below the ground surface such that CO₂ remained in the supercritical state. The reservoir was assumed to contain layers with alternating conductive and resistive properties, which is analogous to actual geological formations such as the Mount Simon Sandstone unit. The CO₂ injection simulation used a cylindrical grid setting in which the injection well was situated at the center of the domain, which extended out 8,000 m from the injection well. The CO₂ migration was simulated using the latest version of the simulator, subsurface transport over multiple phases (the water–salt–CO₂–energy module), developed by Pacific Northwest National Laboratory. A nonlinear parameter estimation and optimization modeling software package, Parameter ESTimation (PEST), is adopted for automated reservoir parameter estimation. The effects of data quality, data worth, and data redundancy were explored regarding the detectability of reservoir parameters using gas pressure monitoring data, by comparing PEST inversion results using data with different levels of noises, various numbers of monitoring wells and locations, and different data collection spacing and temporal sampling intervals. This study yielded insight into the use of CO₂ monitoring data for reservoir characterization and how to design the monitoring system to optimize data worth and reduce data redundancy. The feasibility of using CO₂ saturation data for improving reservoir characterization was also discussed.     

Cadmium accumulation by the blue crab, callinectes sapidus: Involvement of hemocyanin and characterization of cadmium-binding proteins

The accumulation of cadmium from seawater by the blue crab, Callinectes sapidus, was studied as a function of metal concentration and exposure time, with special emphasis on cadmium-binding proteins. Cadmium was found, in decreasing order of magnitude, in gills, digestive gland and hemolymph. When exposed to 0·5 ppm cadmium for 2–24h, virtually all of the cadmium in the cytosolic fraction of the gill was associated with a low molecular weight (LMW) cadmium-binding protein (MW 8000). However, after 48h of exposure only 50% of the cadmium in the cytosol was bound to this protein. The rest wasfound to be associated with proteins of a molecular weight of 300 000 and 60 000. This pattern of cadmium distribution did not change over a 12-day depuration period. Similar results were obtained upon exposure to 0·1 ppm cadmium. The pattern of cadmium accumulation in the cytosolic fraction of the digestive gland was in marked contrast to that observed for the gill. Initially, the cadmium was distributed over three low molecular weight fractions. During depuration the distribution of cadmium changed and all of the metal became bound to a low molecular weight protein (MW 9000). The cadmium concentrations in the gill and digestive gland remained essentially constant during depuration (12 days). The LMW cadmium-binding proteins were purified by a combination of gelpermeation and ion-exchange chromatography. Their molecular weight, spectral properties and amino acid composition are characteristic of the vertebrate metallothioneins. During exposure to cadmium the metal rapidly appeared in the hemolymph, mainly associated with hemocyanin. During depuration cadmium was transferred from the hemolymph to the digestive gland, demonstrating that hemocyanin acts as a carrier in trace metal transport.     

Flood Events in the Rhine Basin: Genesis,Influences and Mitigation

The paper analyses the hydrological regime of the Rhine catchment,the genesis of recent floods,and recommends some research and practical activities to mitigate flood damage. The catchment of the Rhine River can be divided into four main subcatchments: the alpine region with the Aare River as its main tributary and downstream the lower mountain regions of the tributaries Neckar, Main and Moselle. These four basins generate very different hydrographs. Due to the geographical conditions, the average discharge maximums shift from summer to winter downstream the Rhine. Moreover, the spatial and temporalprecipitation patterns of each river have a strong influence on the individual flood events. Some recent extraordinary floods are used to illustrate the parameters that have influenced these events.A strong relationship between recent climate change observationsand the occurrence of flood levels cannot be proven. However, the consequences of human interventions and the resulting changes to the river system (the Rhine and its tributaries) for the hydrograph can be quantified precisely.The influences of different land-use and climatic scenarios on flood conditions in the Rhine basin have not yet been separately identified. Thus, the Dutch-German project LAHoR was established. The primary aim of this project is to giveadvice for the ``Action Plan on Flood Defence' of the International Commission for the Protection of the Rhine (IKSR). In this plan a multidisciplinary approach to mitigating floods is suggested.It is anticipated that the plan willgenerate synergistic effects between flood prevention, water management, regional planning, agriculture, forestry and ecological demands.     

Snow model sensitivity analysis to understand spatial and temporal snow dynamics in a high‐elevation catchment

In this paper, we addressed a sensitivity analysis of the snow module of the GEOtop2.0 model at point and catchment scale in a small high‐elevation catchment in the Eastern Italian Alps (catchment size: 61 km²). Simulated snow depth and snow water equivalent at the point scale were compared with measured data at four locations from 2009 to 2013. At the catchment scale, simulated snow‐covered area (SCA) was compared with binary snow cover maps derived from moderate‐resolution imaging spectroradiometer (MODIS) and Landsat satellite imagery. Sensitivity analyses were used to assess the effect of different model parameterizations on model performance at both scales and the effect of different thresholds of simulated snow depth on the agreement with MODIS data. Our results at point scale indicated that modifying only the “snow correction factor” resulted in substantial improvements of the snow model and effectively compensated inaccurate winter precipitation by enhancing snow accumulation. SCA inaccuracies at catchment scale during accumulation and melt period were affected little by different snow depth thresholds when using calibrated winter precipitation from point scale. However, inaccuracies were strongly controlled by topographic characteristics and model parameterizations driving snow albedo (“snow ageing coefficient” and “extinction of snow albedo”) during accumulation and melt period. Although highest accuracies (overall accuracy = 1 in 86% of the catchment area) were observed during winter, lower accuracies (overall accuracy < 0.7) occurred during the early accumulation and melt period (in 29% and 23%, respectively), mostly present in areas with grassland and forest, slopes of 20–40°, areas exposed NW or areas with a topographic roughness index of ?0.25 to 0 m. These findings may give recommendations for defining more effective model parameterization strategies and guide future work, in which simulated and MODIS SCA may be combined to generate improved products for SCA monitoring in Alpine catchments.