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.

The anthropogenically forced expansion of coastal hypoxia is a major environmental problem affecting coastal ecosystems and biogeochemical cycles throughout the world. The Baltic Sea is a semi-enclosed shelf sea whose central deep basins have been highly prone to deoxygenation during its Holocene history, as shown previously by numerous paleoenvironmental studies. However, long-term data on past fluctuations in the intensity of hypoxia in the coastal zone of the Baltic Sea are largely lacking, despite the significant role of these areas in retaining nutrients derived from the catchment. Here we present a 1500-year multiproxy record of near-bottom water redox changes from the coastal zone of the northern Baltic Sea, encompassing the climatic phases of the Medieval Climate Anomaly (MCA), the Little Ice Age (LIA), and the Modern Warm Period (MoWP). Our reconstruction shows that although multicentennial climate variability has modulated the depositional conditions and delivery of organic matter (OM) to the basin the modern aggravation of coastal hypoxia is unprecedented and, in addition to gradual changes in the basin configuration, it must have been forced by excess human-induced nutrient loading. Alongside the anthropogenic nutrient input, the progressive deoxygenation since the beginning of the 1900s was fueled by the combined effects of gradual shoaling of the basin and warming climate, which amplified sediment focusing and increased the vulnerability to hypoxia. Importantly, the eutrophication of coastal waters in our study area began decades earlier than previously thought, leading to a marked aggravation of hypoxia in the 1950s. We find no evidence of similar anthropogenic forcing during the MCA. These results have implications for the assessment of reference conditions for coastal water quality. Furthermore, this study highlights the need for combined use of sedimentological, ichnological, and geochemical proxies in order to robustly reconstruct subtle redox shifts especially in dynamic, non-euxinic coastal settings with strong seasonal contrasts in the bottom water quality.

Submarine groundwater discharge (SGD) has been implicated as a significant source of nutrients and potentially harmful substances to the coastal sea. Although the number of reported SGD sites has increased recently, their stratigraphical architecture and aquifer geometry are rarely investigated in detail. This study analyses a multifaceted dataset of offshore seismic sub-bottom profiles, multibeam and side-scan sonar images of the seafloor, radon measurements of seawater and groundwater, and onshore ground-penetrating radar and refraction seismic profiles in order to establish the detailed stratigraphical architecture of a high-latitude SGD site, which is connected to the Late-Pleistocene First Salpausselkä ice-marginal formation on the Hanko Peninsula in Finland. The studied location is characterized by a sandy beach, a sandy shore platform that extends 100–250 m seaward sloping gently to ca. 4 m water depth, and a steep slope to ca. 17 m water depth within ca. 50 m distance. The onshore radar and offshore seismic profiles are correlated based on unconformities, following the allostratigraphical approach. The aquifer is hosted in the distal sand-dominated part of a subaqueous ice-contact fan. It is interpreted that coarse sand interbeds and lenses in the distal fan deposits, and, potentially, sandy couplet layers in the overlying glaciolacustrine rhythmite, provide conduits for localized groundwater flow. The SGD takes place predominantly through pockmarks on the seafloor, which are documented on the shore platform slope by multibeam and side-scan sonar images. Elevated radon-222 activity concentrations measured 1 m above seafloor confirm SGD from two pockmarks in fine sand sediments, whereas there was no discharge from a third pockmark that was covered with a thin organic-rich mud layer. The thorough understanding of the local stratigraphy and the geometry and composition of the aquifer that have been acquired in this study are crucial for successful hydrogeological modelling and flux studies at the SGD site.