Human activities, especially increased nutrient loads that set in motion a cascading chain of events related to eutrophication, accelerate development of hypoxia (lower oxygen concentration) in many ...areas of the world's coastal ocean. Climate changes and extreme weather events may modify hypoxia. Organismal and fisheries effects are at the heart of the coastal hypoxia issue, but more subtle regime shifts and trophic interactions are also cause for concern. The chemical milieu associated with declining dissolved oxygen concentrations affects the biogeochemical cycling of oxygen, carbon, nitrogen, phosphorus, silica, trace metals, and sulfide as observed in water column processes, shifts in sediment biogeochemistry, and increases in carbon, nitrogen, and sulfur, as well as shifts in their stable isotopes, in recently accumulated sediments.
Microanalysis of epoxy resin-embedded sediments is used to demonstrate the presence of authigenic iron (Fe) (II) phosphates and manganese (Mn)-calcium (Ca)-carbonate-phosphates in the deep euxinic ...basins of the Baltic Sea. These minerals constitute major burial phases of phosphorus (P) in this area, elevating the total P burial rate above that expected for a euxinic depositional environment. Particle shuttles of Fe and Mn oxides into the deep euxinic basins act as drivers for P-bearing mineral authigenesis. While Fe(II) phosphates are formed continuously in the upper sediments following the sulfidization of Fe-oxyhydroxides and release of associated P, Mn-Ca-carbonate-phosphates are formed intermittently following inflow events of oxygenated North Sea water into the deep basins. The mechanism of Fe(II) phosphate formation differs from previously reported occurrences of vivianite formation in marine sediments, by occurring within, rather than below, the sulfate-methane transition zone. The spatial distribution of both authigenic phases in Baltic sediments varies in accordance with the periodic expansion of anoxia on centennial to millennial timescales. The results highlight the potential importance of authigenic P-bearing minerals other than carbonate fluorapatite for total P burial in euxinic basins.
Studies of authigenic phosphorus (P) minerals in marine sediments typically focus on authigenic carbonate fluorapatite, which is considered to be the major sink for P in marine sediments and can ...easily be semi-quantitatively extracted with the SEDEX sequential extraction method. The role of other potentially important authigenic P phases, such as the reduced iron (Fe) phosphate mineral vivianite (Fe(II)3(PO4)*8H2O) has so far largely been ignored in marine systems. This is, in part, likely due to the fact that the SEDEX method does not distinguish between vivianite and P associated with Fe-oxides. Here, we show that vivianite can be quantified in marine sediments by combining the SEDEX method with microscopic and spectroscopic techniques such as micro X-ray fluorescence (μXRF) elemental mapping of resin-embedded sediments, as well as scanning electron microscope–energy dispersive spectroscopy (SEM–EDS) and powder X-ray diffraction (XRD). We further demonstrate that resin embedding of vertically intact sediment sub-cores enables the use of synchrotron-based microanalysis (X-ray absorption near-edge structure (XANES) spectroscopy) to differentiate between different P burial phases in aquatic sediments. Our results reveal that vivianite represents a major burial sink for P below a shallow sulfate/methane transition zone in Bothnian Sea sediments, accounting for 40–50% of total P burial. We further show that anaerobic oxidation of methane (AOM) drives a sink-switching from Fe-oxide bound P to vivianite by driving the release of both phosphate (AOM with sulfate and Fe-oxides) and ferrous Fe (AOM with Fe-oxides) to the pore water allowing supersaturation with respect to vivianite to be reached. The vivianite in the sediment contains significant amounts of manganese (∼4–8wt.%), similar to vivianite obtained from freshwater sediments. Our results indicate that methane dynamics play a key role in providing conditions that allow for vivianite authigenesis in coastal surface sediments. We suggest that vivianite may act as an important burial sink for P in brackish coastal environments worldwide.
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.
Phosphorus (P) is an essential nutrient for marine organisms. Its burial in hypoxic and anoxic marine basins is still incompletely understood. Recent studies suggest that P can be sequestered in ...sediments of such basins as reduced iron (Fe)-P but the exact phase and the underlying mechanisms that lead to its formation are unknown. In this study, we investigated sediments from the deepest basin in the Baltic Sea, the Landsort Deep (site M0063), that were retrieved during the Integrated Ocean Drilling Project (IODP) Baltic Sea Paleoenvironment Expedition 347. The record comprises the whole brackish/marine Littorina Sea stage including past intervals of extensive hypoxia in the Baltic Sea that occurred during the Holocene Thermal Maximum (HTMHI) and the Medieval Climate Anomaly (MCA1HI and MCA2HI). Various redox proxies (e.g. the presence of laminations and high Mo contents) suggest almost permanent bottom water hypoxia during the Littorina Sea stage in the Landsort Deep. The bottom waters were likely even seasonally anoxic or sulfidic during the MCA1HI and MCA2HI, and permanently sulfidic during the HTMHI. With the use of micro-analysis of sieved minerals (SEM-EDS, XRD and synchrotron-based XAS), we show that Mn- and Mg-rich vivianite crystals are present at various depths in the Littorina Sea sediments. We also have indications for vivianite in the MCA1HI, MCA2HI and HTMHI deposits. The formation of vivianite thus likely explains the high Fe-bound P fraction throughout the whole Littorina Sea stage. Shuttling of Fe and Mn from the shelves into the basin and high inputs of P in settling organic matter are likely key drivers for vivianite formation. Our study shows that vivianite can likely form in near-surface sediments under a broad range of bottom water redox conditions, varying from hypoxic and anoxic to sulfidic.
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•We combine solid-phase geochemistry and micro-analysis to study P burial phases.•Brackish/marine sediments from the Landsort Deep contain Mn- and Mg-rich vivianite.•Vivianite may be formed in sediments below hypoxic, anoxic and likely sulfidic waters.•Shelf-to-basin shuttling of Fe and Mn is a key driver for vivianite formation.
Nutrient input through submarine groundwater discharge (SGD) rivals river inputs in certain regions and may play a significant role in nutrient cycling and primary productivity in the coastal ocean. ...In this paper, we review the key factors determining the fluxes of nitrogen (N) and phosphorus (P) associated with SGD and present a compilation of measured rates. We show that, in particular, the water residence time and the redox conditions in coastal aquifers and sediments determine fluxes and ratios of N and P in SGD. In many coastal groundwater systems, and especially in contaminated aquifers, N/P ratios exceed those in river water and are higher than the Redfield ratio. Thus, anthropogenically driven increases in SGD of nutrients have the potential to drive the N-limited coastal primary production to P-limitation. River input of N and P to the coastal ocean has doubled over the past 50 yr. Results of a dynamic biogeochemical model for the C, N and P cycles of the global proximal coastal ocean (which includes large bays, the open water part of estuaries, deltas, inland seas and salt marshes), suggest that this has led to a factor 2 increase in primary production and biomass and a decline in water column N/P ratios, i.e. the system has become more N-limiting. With the same model, we show that an increase of SGD-N fluxes to ∼0.7–1.1
Tmol
yr
−1 (with a SGD N/P ratio of 100; equal to ∼45–70% of pre-human riverine N-inputs) is required to drive the coastal ocean to P-limitation within the next 50 yr.
The chemical forms of phosphorus (P) in sediments are routinely measured in studies of P in modern and ancient marine environments. However, samples for such analyses are often exposed to atmospheric ...oxygen during storage and handling. Recent work suggests that long-term exposure of pyrite-bearing sediments can lead to a decline in apatite P and an increase in ferric Fe-bound P. Here, we report on alterations in P speciation in reducing modern Baltic Sea sediments that we deliberately exposed to atmospheric oxygen for a period of either one week or one year. During oxidation of the sediment, extensive changes occurred in all measured P reservoirs. Exchangeable P all but disappeared during the first week of exposure, likely reflecting adsorption of porewater PO4 by Fe(III) (oxyhydr)oxides (i.e. ferric Fe-bound P formation). Detrital and organic P were also rapidly affected: decreases in both reservoirs were already observed after the first week of exposure to atmospheric oxygen. This was likely because of acidic dissolution of detrital apatite and oxidation of organic matter, respectively. These processes produced dissolved PO4 that was then scavenged by Fe(III) (oxyhydr)oxides. Interestingly, P in authigenic calcium phosphates (i.e. apatite: authigenic Ca-P) remained unaffected after the first week of exposure, which we attributed to the shielding effect of microfossils in which authigenic Ca-P occurs in Baltic Sea sediments. This effect was transient; a marked decrease in the authigenic Ca-P pool was observed in the sediments after one year of exposure to oxygen. In summary, we show that handling and storage of wet sediments under oxic conditions can lead to rapid and extensive alteration of the original sediment P speciation.
Methane (CH4) is produced in many natural systems that are vulnerable to change under a warming climate, yet current CH4 budgets, as well as future shifts in CH4 emissions, have high uncertainties. ...Climate change has the potential to increase CH4 emissions from critical systems such as wetlands, marine and freshwater systems, permafrost, and methane hydrates, through shifts in temperature, hydrology, vegetation, landscape disturbance, and sea level rise. Increased CH4 emissions from these systems would in turn induce further climate change, resulting in a positive climate feedback. Here we synthesize biological, geochemical, and physically focused CH4 climate feedback literature, bringing together the key findings of these disciplines. We discuss environment‐specific feedback processes, including the microbial, physical, and geochemical interlinkages and the timescales on which they operate, and present the current state of knowledge of CH4 climate feedbacks in the immediate and distant future. The important linkages between microbial activity and climate warming are discussed with the aim to better constrain the sensitivity of the CH4 cycle to future climate predictions. We determine that wetlands will form the majority of the CH4 climate feedback up to 2100. Beyond this timescale, CH4 emissions from marine and freshwater systems and permafrost environments could become more important. Significant CH4 emissions to the atmosphere from the dissociation of methane hydrates are not expected in the near future. Our key findings highlight the importance of quantifying whether CH4 consumption can counterbalance CH4 production under future climate scenarios.
Plain Language Summary
Methane is a powerful greenhouse gas, second only to carbon dioxide in its importance to climate change. Methane production in natural environments is controlled by factors that are themselves influenced by climate. Increased methane production can warm the Earth, which can in turn cause methane to be produced at a faster rate ‐ this is called a positive climate feedback. Here we describe the most important natural environments for methane production that have the potential to produce a positive climate feedback. We discuss how these feedbacks may develop in the coming centuries under predicted climate warming using a cross‐disciplinary approach. We emphasize the importance of considering methane dynamics at all scales, especially its production and consumption and the role microorganisms play in both these processes, to our understanding of current and future global methane emissions. Marrying large‐scale geophysical studies with site‐scale biogeochemical and microbial studies will be key to this.
Key Points
The key drivers of methane production and consumption are assessed for wetlands, marine and freshwaters, permafrost regions, and methane hydrates
The balance of microbial controlled methane production and consumption are critical to methane climate feedbacks in all environments
Wetlands and freshwater systems are likely to drive the methane climate feedback from natural settings in the coming century
Large amounts of methane, a potent greenhouse gas, are produced in anoxic sediments by methanogenic archaea. Nonetheless, over 90% of the produced methane is oxidized via sulfate-dependent anaerobic ...oxidation of methane (S-AOM) in the sulfate-methane transition zone (SMTZ) by consortia of anaerobic methane-oxidizing archaea (ANME) and sulfate-reducing bacteria (SRB). Coastal systems account for the majority of total marine methane emissions and typically have lower sulfate concentrations, hence S-AOM is less significant. However, alternative electron acceptors such as metal oxides or nitrate could be used for AOM instead of sulfate. The availability of electron acceptors is determined by the redox zonation in the sediment, which may vary due to changes in oxygen availability and the type and rate of organic matter inputs. Additionally, eutrophication and climate change can affect the microbiome, biogeochemical zonation, and methane cycling in coastal sediments. This review summarizes the current knowledge on the processes and microorganisms involved in methane cycling in coastal sediments and the factors influencing methane emissions from these systems. In eutrophic coastal areas, organic matter inputs are a key driver of bottom water hypoxia. Global warming can reduce the solubility of oxygen in surface waters, enhancing water column stratification, increasing primary production, and favoring methanogenesis. ANME are notoriously slow growers and may not be able to effectively oxidize methane upon rapid sedimentation and shoaling of the SMTZ. In such settings, ANME-2d (
) and ANME-2a may couple iron- and/or manganese reduction to AOM, while ANME-2d and NC10 bacteria (
) could couple AOM to nitrate or nitrite reduction. Ultimately, methane may be oxidized by aerobic methanotrophs in the upper millimeters of the sediment or in the water column. The role of these processes in mitigating methane emissions from eutrophic coastal sediments, including the exact pathways and microorganisms involved, are still underexplored, and factors controlling these processes are unclear. Further studies are needed in order to understand the factors driving methane-cycling pathways and to identify the responsible microorganisms. Integration of the knowledge on microbial pathways and geochemical processes is expected to lead to more accurate predictions of methane emissions from coastal zones in the future.
Phosphorus (P) is a key nutrient for marine organisms. The only long-term removal pathway for P in the marine realm is burial in sediments. Iron (Fe) bound P accounts for a significant proportion of ...this burial at the global scale. In sediments underlying anoxic bottom waters, burial of Fe-bound P is generally assumed to be negligible because of reductive dissolution of Fe(III) (oxyhydr)oxides and release of the associated P. However, recent work suggests that Fe-bound P is an important burial phase in euxinic (i.e. anoxic and sulfidic) basin sediments in the Baltic Sea. In this study, we investigate the role of Fe-bound P as a potential sink for P in Black Sea sediments overlain by oxic and euxinic bottom waters. Sequential P extractions performed on sediments from six multicores along two shelf-to-basin transects provide evidence for the burial of Fe-bound P at all sites, including those in the euxinic deep basin. In the latter sediments, Fe-bound P accounts for more than 20% of the total sedimentary P pool. We suggest that this P is present in the form of reduced Fe-P minerals. We hypothesize that these minerals may be formed as inclusions in sulfur-disproportionating Deltaproteobacteria. Further research is required to elucidate the exact mineral form and formation mechanism of this P burial phase, as well as its role as a sink for P in sulfide-rich marine sediments.
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