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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]

The diversity and dynamics of ammonia-oxidizing bacteria (AOB) and archaea (AOA) nitrifying communities in the sediments of the eutrophic Gulf of Finland (GoF) were investigated. Using clone libraries of ammonia monooxygenase ( amoA ) gene fragments and terminal restriction fragment length polymorphism (TRFLP), we found a low richness of both AOB and AOA. The AOB amoA phylogeny matched that of AOB 16S ribosomal genes from the same samples. AOA communities were characterized by strong spatial variation while AOB communities showed notable temporal patterns. At open sea sites, where transient anoxic conditions prevail, richness of both AOA and AOB was lowest and communities were dominated by organisms with gene signatures unique to the GoF. Given the importance of nitrification as a link between the fixation of nitrogen and its removal from aquatic environments, the low diversity of ammonia-oxidizing microbes across the GoF could be of relevance for ecosystem resilience in the face of rapid global environmental changes. [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]

Coastal areas are critical in mitigating the impact of nutrient runoffs and downstream eutrophication of aquatic ecosystems. In the Gulf of Finland, the easternmost sub-basin of the Baltic Sea, seasonal and long-term oxygen depletion at the surface of the sediment feeds back the eutrophication loop by promoting the release of nutrients locked in the sediment matrix. In order to understand how the bacterial community responds to the seasonal variations, we sequenced ribosomal gene fragments from the top sediment layer at two coastal sites in southern Finland in spring, summer and late autumn during two consecutive years. Analysis of the samples collected at a shallow (11 m) and deep site (33 m) revealed that the overall community composition was rather constant over time with an extensive collection of shared operational taxonomic units (OTU) between sites. The dominant taxa were related to organoheterotrophs and sulfate reducers and the variation in community structure was linked to the availability of organic matter in the surface sediment. Proteobacteria formed the most abundant and diverse group. The taxa characteristic of spring samples belonged primarily to Actinobacteria , possibly of fresh water origin and linked to humic carbon. Summer communities were characterized by an increase in the number of reads associated with heterotrophic bacteria such as Bacteroidetes which feed on labile organic matter from spring bloom. Taxa typical of autumn samples were linked to Cyanobacteria and other bloom-forming bacteria from the overlying water and to bacteria feeding on organic matter drifting from the phytal zone. [ABSTRACT FROM AUTHOR]