Quantifying seasonal export and retention of nutrients in West European lowland rivers at catchment scale

To set accurate critical values for the protection of lakes and coastal areas, it is crucial to know the seasonal variation of nutrient exports from rivers. This article presents an improved method for estimating export and in‐stream nutrient retention and its seasonal variation. For 13 lowland river catchments in Western Europe, inputs to surface water and exports were calculated on a monthly basis. The catchments varied in size (21 to 486 km²), while annual in‐stream retention ranged from 23 to 84% for N and 39 to 72% for P. A novel calculation method is presented that quantifies monthly exports from lowland rivers based on an annual load to the river system. Inputs in the calculation are annual emission to the surface waters, average monthly river discharge, average monthly water temperature and fraction of surface water area in the catchment. The method accounts for both seasonal variation of emission to the surface water and seasonal in‐stream retention. The agreement between calculated values and calibration data was high (N: r² = 0·93; p < 0·001 and P: r² = 0·81; p < 0·001). Validation of the model also showed good results with model efficiencies for the separate catchments ranging from 31 to 95% (average 76%). This indicates that exports of nitrogen and phosphorus on a monthly basis can be calculated with few input data for a range of West European lowland rivers. Further analysis showed that retention in summer is higher than that in winter, resulting in lower summer nutrient concentrations than that calculated with an average annual input. This implies that accurate evaluation of critical thresholds for eutrophication effects must account for seasonal variation in hydrology and nutrient loading. Our quantification method thus may improve the modelling of eutrophication effects in standing waters. Copyright © 2011 John Wiley & Sons, Ltd.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Optically stimulated luminescence age of the Old Cedar midden, St. Joseph Peninsula State Park, Florida

We report optically stimulated luminescence (OSL) dating results from the Old Cedar midden in St. Joseph Peninsula State Park, located between the Gulf of Mexico and St. Joseph Bay near Port St. Joe, FL, USA. The Old Cedar site (8GU85) is located on top of a relict beach ridge which is actively eroding into St. Joseph Bay. Old Cedar is noted for its conch shell tool assemblage, otherwise rare at northwest Florida archaeological sites, and is believed to have been utilized during the Late Woodland Weeden Island and possibly the Fort Walton periods [Benchley, E.D., Bense, J.A., 2001. Archaeology and history of St. Joseph Peninsula State Park: Phase I investigations. Report of Investigations, No. 89, University of West Florida Archaeology Institute]. After removing surficial erosion deposits, we extracted OSL core samples from both the midden layer and the underlying beach ridge. The resulting OSL age is compared with the age of another beach ridge on St. Joseph Peninsula. We hope that this study will aid in the investigation and conservation of Old Cedar specifically and other Weeden Island sites in the St. Joseph Bay area.     

Finite-frequency sensitivity of body waves to anisotropy based upon adjoint methods

We investigate the sensitivity of finite-frequency body-wave observables to mantle anisotropy based upon kernels calculated by combining adjoint methods and spectral-element modelling of seismic wave propagation. Anisotropy is described by 21 density-normalized elastic parameters naturally involved in asymptotic wave propagation in weakly anisotropic media. In a 1-D reference model, body-wave sensitivity to anisotropy is characterized by 'banana–doughnut' kernels which exhibit large, path-dependent variations and even sign changes. P -wave traveltimes appear much more sensitive to certain azimuthally anisotropic parameters than to the usual isotropic parameters, suggesting that isotropic P -wave tomography could be significantly biased by coherent anisotropic structures, such as slabs. Because of shear-wave splitting, the common cross-correlation traveltime anomaly is not an appropriate observable for S waves propagating in anisotropic media. We propose two new observables for shear waves. The first observable is a generalized cross-correlation traveltime anomaly, and the second a generalized 'splitting intensity'. Like P waves, S waves analysed based upon these observables are generally sensitive to a large number of the 21 anisotropic parameters and show significant path-dependent variations. The specific path-geometry of SKS waves results in favourable properties for imaging based upon the splitting intensity, because it is sensitive to a smaller number of anisotropic parameters, and the region which is sampled is mainly limited to the upper mantle beneath the receiver.