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Estuaries worldwide act as "filters" of land-derived nitrogen (N) loads, yet differences in coastal environmental settings can affect the N filter function. We investigated microbial N retention (nitrification, ammonium assimilation) and N removal (denitrification, anammox) processes in the aphotic benthic system (bottom boundary layer (BBL) and sediment) of two Baltic Sea estuaries differing in riverine N loads, trophic state, geomorphology, and sediment type. In the BBL, rates of nitrification (5–227 nmol N L -1 d -1) and ammonium assimilation (9–704 nmol N L -1 d -1) were not enhanced in the eutrophied Vistula Estuary compared to the oligotrophic Öre Estuary. No anammox was detected in the sediment of either estuary, while denitrification rates were twice as high in the eutrophied (352±123 µ mol N m -2 d -1) as in the oligotrophic estuary. Particulate organic matter (POM) was mainly of phytoplankton origin in the benthic systems of both estuaries. It seemed to control heterotrophic denitrification and ammonium assimilation as well as autotrophic nitrification by functioning as a substrate source of N and organic carbon. Our data suggest that in stratified estuaries, POM is an essential link between riverine N loads and benthic N turnover and may furthermore function as a temporary N reservoir. During long particle residence times or alongshore transport pathways, increased time is available for the recycling of N until its eventual removal, allowing effective coastal filtering even at low process rates. Understanding the key controls and microbial N processes in the coastal N filter therefore requires to also consider the effects of geomorphological and hydrological features. [ABSTRACT FROM AUTHOR]

Estuaries worldwide are known to act as filters of land-derived N loads, yet their variable environmental settings can affect microbial nitrogen (N) retention and removal and thus the coastal filter function. We investigated microbial N-retention (nitrification, ammonium assimilation) and N-removal (denitrification, anammox) in the aphotic benthic systems (here defined as: bottom boundary layer [BBL] and sediment) of two Baltic Sea estuaries that differ in riverine N loads, trophic state, bottom topography, and sediment type. Contrary to our expectations, nitrification rates (5-227 nmol L-1 d-1) in the BBL neither differed between the eutrophied Vistula estuary and the oligotrophic Öre estuary, nor between seasons. Ammonium assimilation rates were slightly higher in the oligotrophic Öre estuary in spring but did not differ between estuaries in summer (9-704 nmol L-1 d-1). In the sediment, no anammox was found in either estuary and denitrification rates were higher in the eutrophied (349 ± 117 µmol N m-2 d-1) than in the oligotrophic estuary (138 ± 47 µmol N m-2 d-1). Irrespective of their differences, in both estuaries the quality of the mainly phytoplankton-derived particulate organic matter (POM) - evaluated by means of C : N and POC : Chl.a ratios - seemed to control N-cycling processes through the availability of particulate organic N and C as substrate sources. Our data suggest, that in stratified estuaries, phytoplankton-derived POM is an essential link between riverine N loads and benthic N cycling and may function as a temporary N reservoir via long particle residence time or coastal parallel transport. Even at low process rates, effective coastal filtering would thus be achieved by the increased time available for the recycling of N via microbial retention processes until its permanent removal via denitrification. [ABSTRACT FROM AUTHOR]

Iron (Fe) plays a key role in sedimentary diagenetic processes in coastal systems, participating in various redox reactions and influencing the burial of organic carbon. Large amounts of Fe enter the marine environment from boreal river catchments associated with dissolved organic matter (DOM) and as colloidal Fe oxyhydroxides, principally ferrihydrite. However, the fate of this Fe pool in estuarine sediments has not been extensively studied. Here we show that flocculation processes along a salinity gradient in an estuary of the northern Baltic Sea efficiently transfer Fe and OM from the dissolved phase into particulate material that accumulates in the sediments. Flocculation of Fe and OM is partially decoupled. This is likely due to the presence of discrete colloidal ferrihydrite in the freshwater Fe pool, which responds differently from DOM to estuarine mixing. Further decoupling of Fe from OM occurs during sedimentation. While we observe a clear decline with distance offshore in the proportion of terrestrial material in the sedimentary particulate organic matter (POM) pool, the distribution of flocculated Fe in sediments is modulated by focusing effects. Labile Fe phases are most abundant at a deep site in the inner basin of the estuary, consistent with input from flocculation and subsequent focusing. The majority of the labile Fe pool is present as Fe (II), including both acid-volatile sulfur (AVS)-bound Fe and unsulfidized phases. The ubiquitous presence of unsulfidized Fe (II) throughout the sediment column suggests Fe (II)-OM complexes derived from reduction of flocculated Fe (III)-OM, while other Fe (II) phases are likely derived from the reduction of flocculated ferrihydrite. Depth-integrated rates of Fe (II) accumulation (AVS-Fe + unsulfidized Fe (II) + pyrite) for the period 1970-2015 are greater in the inner basin of the estuary with respect to a site further offshore, confirming higher rates of Fe reduction in near-shore areas. Mössbauer 57Fe spectroscopy shows that refractory Fe is composed largely of superparamagnetic Fe (III), high-spin Fe (II) in silicates, and, at one station, also oxide minerals derived from past industrial activities. Our results highlight that the cycling of Fe in boreal estuarine environments is complex, and that the partial decoupling of Fe from OM during flocculation and sedimentation is key to understanding the role of Fe in sedimentary diagenetic processes in coastal areas. [ABSTRACT FROM AUTHOR]

Iron (Fe) plays a key role in sedimentary diagenetic processes in coastal systems, participating in various redox reactions and influencing the burial of organic carbon. Large amounts of Fe enter the marine environment from boreal river catchments associated with dissolved organic matter (DOM). However, the fate of this Fe pool in estuarine sediments has not been extensively studied. Here we show that flocculation of DOM along salinity gradients in an estuary of the northern Baltic Sea efficiently transfers Fe from the dissolved phase into particulate material that accumulates in the sediments. Consequently, we observe a decline with distance offshore in both the Fe content of the sediments and proportion of terrestrial material in the sedimentary organic matter pool. Mössbauer spectroscopy and sequential extractions suggest that large amounts of Fe in sediments of the upper estuarine zone are associated with organic matter as unsulfidized Fe (II) complexes, or present in the form of ferrihydrite, implying a direct transfer of flocculated material to the sediments. Accordingly, the contribution of these components to the total sedimentary Fe declines with distance offshore while other Fe phases become proportionally more important. Sediment core records show that the observed lateral distribution of Fe minerals has remained similar over recent decades, despite variable Fe inputs from anthropogenic sources and eutrophication of the coastal zone. Pore water data suggest that the vertical zonation of diagenetic processes in the sediments is influenced by both the availability of Fe and by bottom water salinity, which controls the availability of sulfate (SO42 -). [ABSTRACT FROM AUTHOR]