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A study to measure the denitrification rates in six different estuaries of the Northern Baltic Sea is conducted. The results demonstrate that the nitrogen load on the Baltic Sea cannot be satisfactorily reduced by the sediments of the fast-flowing rivers and the estuary areas with short residence times.

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]

Determining accurate rates of benthic nitrogen (N) removal and retention pathways from diverse environments is critical to our understanding of process distribution and constructing reliable N budgets and models. The whole‐core 15N isotope pairing technique (IPT) is one of the most widely used methods to determine rates of benthic nitrate‐reducing processes and has provided valuable information on processes and factors controlling N removal and retention in aquatic systems. While the whole core IPT has been employed in a range of environments, a number of methodological and environmental factors may lead to the generation of inaccurate data and are important to acknowledge for those applying the method. In this review, we summarize the current state of the whole core IPT and highlight some of the important steps and considerations when employing the technique. We discuss environmental parameters which can pose issues to the application of the IPT and may lead to experimental artifacts, several of which are of particular importance in environments heavily impacted by eutrophication. Finally, we highlight the advances in the use of the whole‐core IPT in combination with other methods, discuss new potential areas of consideration and encourage careful and considered use of the whole‐core IPT. With the recognition of potential issues and proper use, the whole‐core IPT will undoubtedly continue to develop, improve our understanding of benthic N cycling and allow more reliable budgets and predictions to be made. [ABSTRACT FROM AUTHOR]

The largest pool of fixed nitrogen on Earth is dissolved organic nitrogen in the oceans, but its dynamics and transport between ocean zones are largely unknown. Writing in Global Biogeochemical [...]

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]

Low levels of oxygen (O2) in the hypolimnion layer of lakes are harmful to benthic animals and fish; they may also adversely affect nutrient cycles. Artificial aeration is often used in lake management to counteract these problems, but the effects of aeration on nitrogen (N) cycling are not known. We studied the effects of hypolimnetic aeration on N dynamics and temperature in a eutrophic lake by comparing continuous and pulsed aeration with a nonaerated station. Aeration decreased the accumulation of NH4 +-N deep in the lake (20-33 m) by supplying O2 for nitrification, which in turn provided substrate for denitrification and promoted N removal. Aeration also increased the temperature in the hypolimnion. Denitrification rate was highest in the nonaerated deep areas (average, 7.62 mg N m-2 d-1) due to very high rates during spring turnover of the water column, demonstrating that natural turnover provides O2 for nitrification. During stratification, denitrification was highest at the continuously aerated station (4.06 mg N m-2 d-1) and lowest at the nonaerated station (3.02 mg N m-2 d-1). At the periodically aerated station, aeration pauses did not restrict the increase in temperature but resulted in accumulation of NH4 +-N and decreased the contribution of denitrification as a nitrate reduction process. Our findings demonstrate that hypolimnetic aeration can substantially affect N cycling in lakes and that the effect depends on the aeration strategy. Because N is one of the main nutrients controlling eutrophication, the effects of aeration methods on N removal should be considered as part of strategies to manage water quality in lakes. [ABSTRACT FROM AUTHOR]

The effects of hypolimnetic aeration on oxygen penetration depth and oxygen flux into the sediment (DOU) were studied during two successive years. The study was conducted by comparing data from the aerated Enonselkä basin with the non-aerated Kajaanselkä basin of Lake Vesijärvi (southern Finland). Aeration increased the average O2 concentration in near-bottom layers. This was mainly due to shortened stratification period in the aerated basin, which was again attributed to the positive effect of aeration on hypolimnetic water temperature. Aeration did not prevent hypoxia during summer stratification and oxygen penetration depth in the sediment and DOU did not increase. During summer stratification DOU was even lower at the aerated than at the non-aerated basin. The weak effect of aeration on DOU and oxygen penetration was mostly due to the minor effect on hypolimnetic oxygen concentrations. The positive effect of aeration on hypolimnetic O2 concentration was negated by the positive effects of aeration on hypolimnetic temperature and turbulence that increase oxygen consumption in the water column. Due to the generally low effect on DOU, the present aeration effort in Enonselkä does not have positive effects on sediment quality. [ABSTRACT FROM AUTHOR]

Chemolithoautotrophic denitrification is an important mechanism of nitrogen loss in the water column of euxinic basins, but its isotope fractionation factor is not known. Sulfurimonas gotlandica GD1T, a recently isolated bacterial key player in Baltic Sea pelagic redoxcline processes, was used to determine the isotope fractionation of nitrogen and oxygen in nitrate during denitrification. Under anoxic conditions, nitrate reduction was accompanied by nitrogen and oxygen isotope fractionation of 23.8 ± 2.5° and 11.7 ± 1.1°, respectively. The isotope effect for nitrogen was in the range determined for heterotrophic denitrification, with only the absence of stirring resulting in a significant decrease of the fractionation factor. The relative increase in δ18ONO3 to δ15NNO3 did not follow the 1:1 relationship characteristic of heterotrophic, marine denitrification. Instead, δ18ONO3 increased slower than δ15NNO3, with a conserved ratio of 0.5:1. This result suggests that the periplasmic nitrate reductase (Nap) of S. gotlandica strain GD1T fractionates the N and O in nitrate differently than the membrane-bound nitrate reductase (Nar), which is generally prevalent among heterotrophic denitrifiers and is considered as the dominant driver for the observed isotope fractionation. Hence in the Baltic Sea redoxcline, other, as yet-unidentified factors likely explain the low apparent fractionation. [ABSTRACT FROM AUTHOR]

Nitrification is a crucial process in sediment nitrogen cycling. We compared two 15N tracer-based nitrification measurement techniques (isotope pairing technique (IPT) combined with 15N nitrate pool dilution and 15N ammonium oxidation) and three different 15N analyses from bottom water nitrate (ammonia diffusion, denitrifier and SPINMAS) in a sediment mesocosm. The 15N nitrate pool dilution technique combined with IPT can be used to quantify the in situ nitrification, but the minimum detection limit for the total nitrification is higher than that in the 15N ammonium oxidation technique. The 15N ammonium oxidation technique, however, is not applicable for sediments that have high ammonium content. If nitrate concentration and the amount of 15N label in the sample are low, the 15N nitrate analysis should be done with the denitrifier method. In higher 15N concentrations, the less sensitive SPINMAS method can also be applied. The ammonia diffusion method is not suitable for bottom water 15N nitrate analyses. [ABSTRACT FROM AUTHOR]

Abstract: The effects of the polychaetes Marenzelleria sp. (Polychaeta, Spionidae), nonindigenous, rapidly increasing species in the Baltic Sea, on benthic nutrient fluxes, denitrification and sediment pore water nutrient concentration were studied in laboratory experiments using a flow-through setup with muddy sediment from coastal regions of the Gulf of Finland. In addition, different forms of sediment phosphorus (P), separated by chemical fractionation, were studied in three sediment layers. At a population density corresponding to about half the highest measured in the northern Baltic Sea, Marenzelleria sp. increased the fluxes of P and ammonium to the water column. No effect could be recorded for denitrification. Since the previously dominant species of the area, Monoporeia affinis, can enhance denitrification and lower the amount of dissolved P in the pore water, the replacement of M. affinis with Marenzelleria spp. may lead to increased P flux to the water column and decreased denitrification, further increasing the ammonium flux to the water column. However, sediment reworking by Marenzelleria spp. also oxidizes the surface sediment in the long run, improving its ability to retain P and support nitrification. Therefore, the impact of Marenzelleria spp. on sediment nutrient release may not be as drastic as the initial reactions seen in our experiments suggest. [Copyright &y& Elsevier]

Benthic processes were measured at a coastal deposition area in the northern Baltic Sea, covering all seasons. The N2 production rates, 90–400 μmol N m−2 d−1, were highest in autumn-early winter and lowest in spring. Heterotrophic bacterial production peaked unexpectedly late in the year, indicating that in addition to the temperature, the availability of carbon compounds suitable for the heterotrophic bacteria also plays a major role in regulating the denitrification rate. Anaerobic ammonium oxidation (anammox) was measured in spring and autumn and contributed 10% and 15%, respectively, to the total N2 production. The low percentage did, however, result in a significant error in the total N2 production rate estimate, calculated using the isotope pairing technique. Anammox must be taken into account in the Gulf of Finland in future sediment nitrogen cycling research. [ABSTRACT FROM AUTHOR]

Estuaries have been suggested to have an important role in reducing the nitrogen load transported to the sea. We measured denitrification rates in six estuaries of the northern Baltic Sea. Four of them were river mouths in the Bothnian Bay (northern Gulf of Bothnia), and two were estuary bays, one in the Archipelago Sea (southern Gulf of Bothnia) and the other in the Gulf of Finland. Denitrification rates in the four river mouths varied between 330 and 905 µmol N m-2 d-1. The estuary bays at the Archipelago Sea and the Gulf of Bothnia had denitrification rates from 90 µmol N m-2 d-1 to 910 µmol N m-2 d-1 and from 230 µmol N m-2 d-1 to 320 µmol N m-2 d-1, respectively. Denitrification removed 3.6-9.0% of the total nitrogen loading in the river mouths and in the estuary bay in the Gulf of Finland, where the residence times were short. In the estuary bay with a long residence time, in the Archipelago Sea, up to 4.5% of nitrate loading and 19% of nitrogen loading were removed before entering the sea. According to our results, the sediments of the fast-flowing rivers and the estuary areas with short residence times have a limited capacity to reduce the nitrogen load to the Baltic Sea. [ABSTRACT FROM AUTHOR]

Coastal environments are nitrogen (N) removal hot spots, which regulate the amount of land-derived N reaching the open sea. However, mixing between freshwater and seawater creates gradients of inorganic N and bioavailable organic matter, which affect N cycling. In this study, we compare nitrate reduction processes between estuary and offshore archipelago environments in the coastal Baltic Sea. Denitrification rates were similar in both environments, despite lower nitrate and carbon concentrations in the offshore archipelago. However, DNRA (dissimilatory nitrate reduction to ammonium) rates were higher at the offshore archipelago stations, with a higher proportion of autochthonous carbon. The production rate and concentrations of the greenhouse gas nitrous oxide (N 2 O) were higher in the estuary, where nitrate concentrations and allochthonous carbon inputs are higher. These results indicate that the ratio between nitrate and autochthonous organic carbon governs the balance between N-removing denitrification and N-recycling DNRA, as well as the end-product of denitrification. As a result, a significant amount of the N removed in the estuary is released as N 2 O, while the offshore archipelago areas are characterized by efficient internal recycling of N. Our results challenge the current understanding of the role of these regions as filters of land-to-sea transfer of N. • The availability of bioavailable carbon defines nitrate reduction end-product. • Estuaries with low bioavailable organic carbon can release high amounts of N2O. • Nitrogen is recycled through DNRA in the archipelago areas. [ABSTRACT FROM AUTHOR]

Nitrification is a crucial process in sediment nitrogen cycling. We compared two (15)N tracer-based nitrification measurement techniques (isotope pairing technique (IPT) combined with (15)N nitrate pool dilution and (15)N ammonium oxidation) and three different (15)N analyses from bottom water nitrate (ammonia diffusion, denitrifier and SPINMAS) in a sediment mesocosm. The (15)N nitrate pool dilution technique combined with IPT can be used to quantify the in situ nitrification, but the minimum detection limit for the total nitrification is higher than that in the (15)N ammonium oxidation technique. The (15)N ammonium oxidation technique, however, is not applicable for sediments that have high ammonium content. If nitrate concentration and the amount of (15)N label in the sample are low, the (15)N nitrate analysis should be done with the denitrifier method. In higher (15)N concentrations, the less sensitive SPINMAS method can also be applied. The ammonia diffusion method is not suitable for bottom water (15)N nitrate analyses.