Iron-Phosphorus Feedbacks Drive Multidecadal Oscillations in Baltic Sea Hypoxia.

Hypoxia has occurred intermittently in the Baltic Sea since the establishment of brackish-water conditions at ∼8,000 years B.P., principally as recurrent hypoxic events during the Holocene Thermal Maximum (HTM) and the Medieval Climate Anomaly (MCA). Sedimentary phosphorus release has been implicated as a key driver of these events, but previous paleoenvironmental reconstructions have lacked the sampling resolution to investigate feedbacks in past iron-phosphorus cycling on short timescales. Here we employ Laser Ablation (LA)-ICP-MS scanning of sediment cores to generate ultra-high resolution geochemical records of past hypoxic events. We show that in-phase multidecadal oscillations in hypoxia intensity and iron-phosphorus cycling occurred throughout these events. Using a box model, we demonstrate that such oscillations were likely driven by instabilities in the dynamics of iron-phosphorus cycling under preindustrial phosphorus loads, and modulated by external climate forcing. Oscillatory behavior could complicate the recovery from hypoxia during future trajectories of external loading reductions.

Metaschoepite Dissolution in Sediment Column Systems-Implications for Uranium Speciation and Transport.

Metaschoepite is commonly found in U-contaminated environments and metaschoepite-bearing wastes may be managed via shallow or deep disposal. Understanding metaschoepite dissolution and tracking the fate of any liberated U is thus important. Here, discrete horizons of metaschoepite (UO3·nH2O) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield Ltd. site. The column systems either remained oxic or became anoxic due to electron donor additions, and the columns were sacrificed after 6- and 12-months for analysis. Solution chemistry, extractions, and bulk and micro/nano-focus X-ray spectroscopies were used to track changes in U distribution and behavior. In the oxic columns, U migration was extensive, with UO22+ identified in effluents after 6-months of reaction using fluorescence spectroscopy. Unusually, in the electron-donor amended columns, during microbially mediated sulfate reduction, significant amounts of UO2-like colloids (>60% of the added U) were found in the effluents using TEM. XAS analysis of the U remaining associated with the reduced sediments confirmed the presence of trace U(VI), noncrystalline U(IV), and biogenic UO2, with UO2 becoming more dominant with time. This study highlights the potential for U(IV) colloid production from U(VI) solids under reducing conditions and the complexity of U biogeochemistry in dynamic systems.

Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Hypoxia sustains cyanobacteria blooms in the Baltic sea.

Nutrient over-enrichment is one of the classic triggering mechanisms for the occurrence of cyanobacteria blooms in aquatic ecosystems. In the Baltic Sea, cyanobacteria regularly occur in the late summer months and form nuisance accumulations in surface waters and their abundance has intensified significantly in the past 50 years attributed to human-induced eutrophication. However, the natural occurrence of cyanobacteria during the Holocene is debated. In this study, we present records of cyanobacteria pigments, water column redox proxies, and nitrogen isotopic signatures for the past ca. 8000 years from Baltic Sea sediment cores. Our results demonstrate that cyanobacteria abundance and nitrogen fixation are correlated with hypoxia occurring during three main intervals: (1) ca. 7000-4000 B.P. during the Littorina transgression, (2) ca. 1400-700 B.P. during the Medieval Climate Anomaly, and (3) from ca. 1950 A.D. to the present. Issues of preservation were investigated, and we show that organic matter and pigment profiles are not simply an artifact of preservation. These results suggest that cyanobacteria abundance is sustained during periods of hypoxia, most likely because of enhanced recycling of phosphorus in low oxygen conditions.

Hypoxia in the Baltic Sea: biogeochemical cycles, benthic fauna, and management.

Hypoxia has occurred intermittently over the Holocene in the Baltic Sea, but the recent expansion from less than 10 000 km(2) before 1950 to >60 000 km(2) since 2000 is mainly caused by enhanced nutrient inputs from land and atmosphere. With worsening hypoxia, the role of sediments changes from nitrogen removal to nitrogen release as ammonium. At present, denitrification in the water column and sediments is equally important. Phosphorus is currently buried in sediments mainly in organic form, with an additional contribution of reduced Fe-phosphate minerals in the deep anoxic basins. Upon the transition to oxic conditions, a significant proportion of the organic phosphorus will be remineralized, with the phosphorus then being bound to iron oxides. This iron-oxide bound phosphorus is readily released to the water column upon the onset of hypoxia again. Important ecosystems services carried out by the benthic fauna, including biogeochemical feedback-loops and biomass production, are also lost with hypoxia. The results provide quantitative knowledge of nutrient release and recycling processes under various environmental conditions in support of decision support tools underlying the Baltic Sea Action Plan.

Linking sediment geochemistry with catchment processes, internal phosphorus loading and lake water quality.

Research in the field of sediment geochemistry suggests potential linkages between catchment processes (land use), internal phosphorus (P) loading and lake water quality, but evidence is still poorly quantified due to a limited amount of data. Here we address the issues based on a comprehensive data set from 27 lakes in southern Finland. Specifically, we aimed at: 1) elucidating factors behind spatial variations in sediment geochemistry; 2) assessing the impact of diagenetic transformation on sediment P regeneration across lakes based on the changes in the vertical distribution of sediment components; 3) exploring the role of the sediment P forms in internal P loading (IL), and 4) determining the impact of IL on lake water quality. The relationship between sediment P concentration and field area percentage (FA%) was statistically significant in (mainly eutrophic) lakes with catchments that included more than 10 % of fields. We found that sediment iron-bound P (Fe-P) increased with increasing FA%, which agrees with the high expected losses from the cultivated areas. Additionally, populated areas increased the pool of sediment Fe-P. Internal P loading was significantly positively related to both sediment Fe-P and sediment organic P (Org-P). However, Org-P was not significant (as the third predictor) in models that had a trophic state variable as the first predictor and Fe-P as the second predictor. Further, the vertical profiles of sediment components indicated a role of diagenetic transformations in the long-term sediment P release, especially in lakes with deeper maximum depth and longer water residence time. Finally, IL was significantly positively correlated to water quality variables including phytoplankton biomass, its proportion of cyanobacteria, chlorophyll a concentration and trophic state index. Our findings suggest that reduction of P losses from the field and populated areas will decrease internal P loads and increase water quality through a reduced pool of Fe-P.

Trace metals in coastal marine sediments: Natural and anthropogenic sources, correlation matrices, and proxy potentials.

Rapidly spreading industrialization since the 19th century has led to a drastic increase in trace metal deposition in coastal sediments. Provided that these trace metals have remained relatively immobile after deposition, their sedimentary enrichments can serve as records of local-regional pollution histories. Factors controlling this proxy potential include trace metal geochemistry (carrier-, and host phase affinity), and depositional environmental factors (redox variability, particulate shuttling, organic matter loading, bathymetry). Yet, the relative importance and interactions between these controls are still poorly understood, hampering the reliable use of trace metal-based environmental proxies. By summarizing nine site-specific correlation matrices of 16 metal (loid) s (Pb, Cd, Cu, Zn, Sb, Sn, Ni, As, Tl, V, Mo, U, Re, Fe, Mn, Al), total organic C, and S contents in short sediment cores into a single meta-matrix, we test a novel approach for quickly detecting common and contrasting trace metal enrichment patterns across different study locations. Our meta-matrix shows two trace metal groups, within which positive correlations of e.g., Pb, Cd, Zn, Cu, Sb suggest a primary "anthropogenically sourced" (group I) control, whereas known "redox-sensitive" (group II) trace metals (Mo, U, Re) are characterized by fewer positive correlations. However, some group I metals (Cd, Zn, Cu, Sb) also covary with group II metals, inferring that redox variability may obscure primary anthropogenic signals; Sb even shows advantages over Mo and U under oxic conditions. As a more robust pollution indicator we identified Pb; yet for reconstructing historical Pb atmospheric pollution signals (1970s Pb peak), it is crucial to consider the distance from shore. In near-shore environments, local (fluvial) pollution signals may overprint large-scale (atmospheric) signals. Our findings demonstrate that combining site-specific sedimentary correlation and distribution patterns with a meta-matrix considerably aids the understanding of trace metal sequestration in different coastal sedimentary environments, which thereby improves trace metal proxy reliability.

Biotic interactions between benthic infauna and aerobic methanotrophs mediate methane fluxes from coastal sediments.

Coastal ecosystems dominate oceanic methane (CH4) emissions. However, there is limited knowledge about how biotic interactions between infauna and aerobic methanotrophs (i.e. CH4 oxidizing bacteria) drive the spatial-temporal dynamics of these emissions. Here, we investigated the role of meio- and macrofauna in mediating CH4 sediment-water fluxes and aerobic methanotrophic activity that can oxidize significant portions of CH4. We show that macrofauna increases CH4 fluxes by enhancing vertical solute transport through bioturbation, but this effect is somewhat offset by high meiofauna abundance. The increase in CH4 flux reduces CH4 pore-water availability, resulting in lower abundance and activity of aerobic methanotrophs, an effect that counterbalances the potential stimulation of these bacteria by higher oxygen flux to the sediment via bioturbation. These findings indicate that a larger than previously thought portion of CH4 emissions from coastal ecosystems is due to faunal activity and multiple complex interactions with methanotrophs.

Ebullition dominates methane emissions in stratified coastal waters.

Coastal areas are an important source of methane (CH4). However, the exact origins of CH4 in the surface waters of coastal regions, which in turn drive sea-air emissions, remain uncertain. To gain a comprehensive understanding of the current and future climate change feedbacks, it is crucial to identify these CH4 sources and processes that regulate its formation and oxidation. This study investigated coastal CH4 dynamics by comparing water column data from six stations located in the brackish Tvärminne Archipelago, Baltic Sea. The sediment biogeochemistry and microbiology were further investigated at two stations (i.e., nearshore and offshore). These stations differed in terms of stratification, bottom water redox conditions, and organic matter loading. At the nearshore station, CH4 diffusion from the sediment into the water column was negligible, because nearly all CH4 was oxidized within the upper sediment column before reaching the sediment surface. On the other hand, at the offshore station, there was significant benthic diffusion of CH4, albeit the majority underwent oxidation before reaching the sediment-water interface, due to shoaling of the sulfate methane transition zone (SMTZ). The potential contribution of CH4 production in the water column was evaluated and was found to be negligible. After examining the isotopic signatures of δ13C-CH4 across the sediment and water column, it became apparent that the surface water δ13C-CH4 values observed in areas with thermal stratification could not be explained by diffusion, advective fluxes, nor production in the water column. In fact, these values bore a remarkable resemblance to those detected below the SMTZ. This supports the hypothesis that the source of CH4 in surface waters is more likely to originate from ebullition than diffusion in stratified brackish coastal systems.

Organic matter lability modifies the vertical structure of methane-related microbial communities in lake sediments.

Eutrophication increases the input of labile, algae-derived, organic matter (OM) into lake sediments. This potentially increases methane (CH4) emissions from sediment to water through increased methane production rates and decreased methane oxidation efficiency in sediments. However, the effect of OM lability on the structure of methane oxidizing (methanotrophic) and methane producing (methanogenic) microbial communities in lake sediments is still understudied. We studied the vertical profiles of the sediment and porewater geochemistry and the microbial communities (16S rRNA gene amplicon sequencing) at five profundal stations of an oligo-mesotrophic, boreal lake (Lake Pääjärvi, Finland), varying in surface sediment OM sources (assessed via sediment C:N ratio). Porewater profiles of methane, dissolved inorganic carbon (DIC), acetate, iron, and sulfur suggested that sites with more autochthonous OM showed higher overall OM lability, which increased remineralization rates, leading to increased electron acceptor (EA) consumption and methane emissions from sediment to water. When OM lability increased, the abundance of anaerobic nitrite-reducing methanotrophs (Candidatus Methylomirabilis) relative to aerobic methanotrophs (Methylococcales) in the methane oxidation layer of sediment surface decreased, suggesting that Methylococcales were more competitive than Ca. Methylomirabilis under decreasing redox conditions and increasing methane availability due to their more diverse metabolism (fermentation and anaerobic respiration) and lower affinity for methane. Furthermore, when OM lability increased, the abundance of methanotrophic community in the sediment surface layer, especially Ca. Methylomirabilis, relative to the methanogenic community decreased. We conclude that increasing input of labile OM, subsequently affecting the redox zonation of sediments, significantly modifies the methane producing and consuming microbial community of lake sediments. IMPORTANCE Lakes are important natural emitters of the greenhouse gas methane (CH4). It has been shown that eutrophication, via increasing the input of labile organic matter (OM) into lake sediments and subsequently affecting the redox conditions, increases methane emissions from lake sediments through increased sediment methane production rates and decreased methane oxidation efficiency. However, the effect of organic matter lability on the structure of the methane-related microbial communities of lake sediments is not known. In this study, we show that, besides the activity, also the structure of lake sediment methane producing and consuming microbial community is significantly affected by changes in the sediment organic matter lability.

A biogeochemical approach to evaluate the optimization and effectiveness of hypolimnetic withdrawal.

Hypolimnetic withdrawal (HW) is a lake restoration method that is based on the removal of phosphorus (P) along with near-bottom water. While it has often proven to be effective, the method also sets challenges: it is about balancing between effective P removal and maintenance of the thermal stratification of the lake. The success of different HW projects has been reviewed in some studies retrospectively, but scientific literature still lacks studies that use detailed data on the lake biogeochemistry to scale and optimize the method in advance, and to predict the outcomes of the restoration measure. In the current study, we investigated the seasonal biogeochemistry, P stocks and thermal stratification of a eutrophic lake (Lake Kymijärvi/Myllypohja basin, southern Finland) to determine an optimal withdrawal rate, to assess its effects on stratification, and to evaluate the expected success of HW. We found that by adjusting HW with P diffusive fluxes from the sediment (diffusion-adjusted HW), it is possible to remove a notable part of the cycling P without causing major disturbances to the thermal stratification even in a relatively shallow lake. Our results show that HW can have great potential in lake restoration: diffusion-adjusted HW in our study lake could increase the annual P output by 35-46%, shifting the P budget of the lake to negative. We thus propose a novel approach to optimize HW on the basis of the diffusive flux of P from the sediment, with the goal of extracting P continuously at an equivalent rate to the diffusive flux. We finally discuss how this can be achieved more effectively with HW based on a closed-circuit system.

Terrestrial organic matter input drives sedimentary trace metal sequestration in a human-impacted boreal estuary.

Coastal sediments play a fundamental role in processing anthropogenic trace metal inputs. Previous studies have shown that terrestrial organic matter (OM) is a significant vector for trace metal transport across the land-to-sea continuum, but little is known about the fate of land-derived metal-OM complexes in coastal sediments. Here, we use a comprehensive set of sediment pore water and solid-phase analyses to investigate how variations in terrestrial OM delivery since the 1950s have influenced trace metal accumulation and diagenesis in a human-impacted boreal estuary in the northern Baltic Sea. A key feature of our dataset is a strong correlation between terrestrial OM deposition and accumulation of metal-OM complexes in the sediments. Based on this strong coupling, we infer that the riverine input of terrestrial metal-OM complexes from the hinterland, followed by flocculation-induced settling in the estuary, effectively modulates sedimentary trace metal sequestration. While part of the trace metal pool associated with these complexes is efficiently recycled in the surface sediments during diagenesis, a substantial fraction is permanently buried as refractory metal-OM complexes or through incorporation into insoluble sulfides, thereby escaping further biological processing. These findings suggest that terrestrial OM input could play a more pivotal role in trace metal processing in coastal environments than hitherto acknowledged.

Sedimentation Pulse in the NE Gulf of Mexico following the 2010 DWH Blowout.

The objective of this study was to investigate the impacts of the Deepwater Horizon (DWH) oil discharge at the seafloor as recorded in bottom sediments of the DeSoto Canyon region in the northeastern Gulf of Mexico. Through a close coupling of sedimentological, geochemical, and biological approaches, multiple independent lines of evidence from 11 sites sampled in November/December 2010 revealed that the upper ~1 cm depth interval is distinct from underlying sediments and results indicate that particles originated at the sea surface. Consistent dissimilarities in grain size over the surficial ~1 cm of sediments correspond to excess (234)Th depths, which indicates a lack of vertical mixing (bioturbation), suggesting the entire layer was deposited within a 4-5 month period. Further, a time series from four deep-sea sites sampled up to three additional times over the following two years revealed that excess (234)Th depths, accumulation rates, and (234)Th inventories decreased rapidly, within a few to several months after initial coring. The interpretation of a rapid sedimentation pulse is corroborated by stratification in solid phase Mn, which is linked to diagenesis and redox change, and the dramatic decrease in benthic formanifera density that was recorded in surficial sediments. Results are consistent with a brief depositional pulse that was also reported in previous studies of sediments, and marine snow formation in surface waters closer to the wellhead during the summer and fall of 2010. Although sediment input from the Mississippi River and advective transport may influence sedimentation on the seafloor in the DeSoto Canyon region, we conclude based on multidisciplinary evidence that the sedimentation pulse in late 2010 is the product of marine snow formation and is likely linked to the DWH discharge.

Coupled dynamics of iron and phosphorus in sediments of an oligotrophic coastal basin and the impact of anaerobic oxidation of methane.

Studies of phosphorus (P) dynamics in surface sediments of lakes and coastal seas typically emphasize the role of coupled iron (Fe), sulfur (S) and P cycling for sediment P burial and release. Here, we show that anaerobic oxidation of methane (AOM) also may impact sediment P cycling in such systems. Using porewater and sediment profiles for sites in an oligotrophic coastal basin (Bothnian Sea), we provide evidence for the formation of Fe-bound P (possibly vivianite; Fe3(PO4)2(·)8H2O) below the zone of AOM with sulfate. Here, dissolved Fe(2+) released from oxides is no longer scavenged by sulfide and high concentrations of both dissolved Fe(2+) (>1 mM) and PO4 in the porewater allow supersaturation with respect to vivianite to be reached. Besides formation of Fe(II)-P, preservation of Fe-oxide bound P likely also contributes to permanent burial of P in Bothnian Sea sediments. Preliminary budget calculations suggest that the burial of Fe-bound P allows these sediments to act as a major sink for P from the adjacent eutrophic Baltic Proper.