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 poor access to data on the marine environment is a handicap to government decision-making, a barrier to scientific understanding and an obstacle to economic growth. In this light, the European Commission initiated the European Marine Observation and Data Network (EMODnet) in 2009 to assemble and disseminate hitherto dispersed marine data. In the ten years since then, EMODnet has become a key producer of publicly available, harmonised datasets covering broad areas. This paper describes the methodologies applied in EMODnet Geology project to produce fully populated GIS layers of seabed substrate distribution for the European marine areas. We describe steps involved in translating national seabed substrate data, conforming to various standards, into a uniform EMODnet substrate classification scheme (i.e., the Folk sediment classification). Rock and boulders form an additional substrate class. Seabed substrate data products at scales of 1:250,000 and 1:1 million, compiled using descriptions and analyses of seabed samples as well as interpreted acoustic images, cover about 20% and 65% of the European maritime areas, respectively. A simple confidence assessment, based on sample and acoustic coverage, is helpful in identifying data gaps. The harmonised seabed substrate maps are particularly useful in supraregional, transnational and pan-European marine spatial planning.
We present 54Fe and 56Fe data on pyrite from burrow-like and irregularly shaped pyrite concretions from Holocene postglacial lacustrine clays in the northern Baltic Sea collected using a secondary ion mass spectrometry (SIMS) microanalysis technique. The burrow-like concretions were formed in reducing, mucus-coated worm burrows in oxic surface sediments. Framboidal pyrite in the cores of the burrow-like concretions shows extensively fractionated δ56Fe values down to −3.1‰. The framboids are cemented by poorly crystalline FeS2 with δ56Fe values between −2.1‰ and +1.4‰. The irregularly shaped concretions with microcrystalline textures were formed in organic-poor sediment pore spaces, and display a wide spread of δ56Fe values up to +4.1‰. The measured δ56Fe values reflect the preferential capture of 54Fe to pyrite in the diagenetic sequence and the 56Fe enrichment of remaining pore water. The diagenetic sequence of the pyrite materials is supported by previous petrographical study and 34S/32S microanalysis of the same samples. Our results demonstrate substantial early-diagenetic δ56Fe and δ34S heterogeneity within individual pyrite grains, underlining the necessity of high spatial resolution measurements in studying biological and abiological isotopic signatures.
Integrated sediment multiproxy studies and modeling were used to reconstruct past changes in the Baltic Sea ecosystem. Results of natural changes over the past 6000 years in the Baltic Sea ecosystem suggest that forecasted climate warming might enhance environmental problems of the Baltic Sea. Integrated modeling and sediment proxy studies reveal increased sea surface temperatures and expanded seafloor anoxia (in deep basins) during earlier natural warm climate phases, such as the Medieval Climate Anomaly. Under future IPCC scenarios of global warming, there is likely no improvement of bottom water conditions in the Baltic Sea. Thus, the measures already designed to produce a healthier Baltic Sea are insufficient in the long term. The interactions between climate change and anthropogenic impacts on the Baltic Sea should be considered in management, implementation of policy strategies in the Baltic Sea environmental issues, and adaptation to future climate change.
Anthropogenic radionuclides are among those human impacts, which can be seen widely in the marine and terrestrial ecosystems. Fallout from the 1986 Chernobyl nuclear power plant accident has rendered the Baltic Sea as the most polluted marine body in the world with respect to 137Cs. This research investigated sediment cores from 56 sites around the Gulf of Bothnia, Baltic Sea. Radioactivity from 137Cs in sediments has generally declined due to natural/radioactive decay of 137Cs over the last decades. However, 137Cs contents in subsurface sediments remain at elevated levels compared to pre-Chernobyl levels. The highest 137Cs activity contents in subsurface sediments (>4000 Bg kg-1) occur in coastal areas including estuaries. These areas often experience severe anthropogenic pressure. The southern Bothnian Sea, Kvarken archipelago, and southern Bothnian Bay all show elevated 137Cs values in subsurface sediments. Sedimentary 137Cs can also help constrain recent rates of sedimentation. Post-Chernobyl sedimentation rates in the Gulf of Bothnia varied from 0.1 to 4.8 cm/year with an average sedimentation rate of 0.54 cm/year.
Rivers draining the acid sulfate soils of western Finland are known to deliver large amounts of trace metals with detrimental environmental consequences to the recipient estuaries in the eastern Gulf of Bothnia, northern Baltic Sea. However, the distribution of these metals in the coastal sea area and the relevant metal transport mechanisms have been less studied. This study investigates the spatial and temporal distribution of metals in sediments at nine sites in the Kvarken Archipelago, which is the recipient system of Laihianjoki and Sulvanjoki rivers that are impacted by acid sulfate soils. The contents of Cd, Co, Cu, La, Mn, Ni, and Zn increased in the cores during the 1960s and 1970s as a consequence of intensive artificial drainage of the acid sulfate soil landscape. Metal deposition has remained at high levels since the 1980s. The metal enrichment in sea floor sediments is currently visible at least 25 km seaward from the river mouths. Comparison with sediment quality guidelines shows that the metal contents are very likely to cause detrimental effects on marine biota more than 12 km out from the river mouths. The dynamic sedimentary environment of the shallow archipelago makes these sediments potential future sources of metals to the ecosystem. Finally, the strong association of metals and nutrients in the same sediment grain size class of 2–6 µm suggests that the transformation of dissolved organic matter and metals to metal–organic aggregates at the river mouths is the key mechanism of seaward trace metal transport, in addition to co-precipitation with Mn oxyhydroxides identified in previous studies. The large share of terrestrial organic carbon in the total organic C in these sediments (interquartile range – 39 %–48 %) highlights the importance of riverine organic matter supply. These findings are important for the estimation of environmental risks and the management of biologically sensitive coastal sea ecosystems.