Sediment Redox Conditions Research Articles

Influence of environmental settings, including vegetation, on speciation of the redox-sensitive elements in the sediments of monomictic Lake Kinneret

AbstractThe redox conditions in the littoral limnic sediments may be affected by the penetration of plant roots which provide channels for oxygen transport into the sediment while decomposition of the dead roots results in consumption of oxygen. The goal of this work was to study the impact of environmental parameters including penetration of roots of Cyperus articulatus L. into the sediments on cycling of the redox-sensitive elements in Lake Kinneret. We measured roots content, porosity, and chemical parameters including pH, sulfur, iron and manganese speciation in the sediments from the shore, littoral and sublittoral zones with and without vegetation. Our results show that at ≥ 12 m water depth, the upper 10 cm of the sediments are affected by the active sulfur cycling with concentrations of hydrogen sulfide > 70 μM near the sediment–water interface. Speciation of sulfur, iron, and manganese in the upper 10 cm of littoral sediments, which are covered by < 20 cm of water, are affected by their permeability and, to a lesser extent, by roots penetration. In the case when sediments are not covered by water, oxygen penetration to the sediments by desiccation is an additional important control of the redox zonation in the surface sediments. In the shore sediments, despite relatively high concentrations of sulfate in the pore-waters, sulfur cycling may be described as “cryptic” as expressed by very low concentrations of hydrogen sulfide in the pore-waters. This is most likely a result of its fast reoxidation by the abundant highly reactive Fe(III) and Mn(IV) phases.

Heavy sulfur isotopes recorded in contrasted redox conditions in Holocene sediments from the Yangtze River Delta

Sulfur isotopic signatures of pyrite (δ34Spy) sensitively react to local environmental change. Here we elucidate mechanism of δ34Spy variation in the Holocene sedimentary strata of the Yangtze River Delta, through the analyses of multiple geochemical and physical indicators including total organic carbon, total nitrogen, stable isotopes of organic carbon, different iron solid phases, Sr/Ba ratios, and changes in sedimentation rates. Two heavy δ34Spy (∼30‰) layers that formed under contrasting redox conditions are preserved in the early Holocene transgressive tidal flat and late Holocene regressive mouth bar facies, respectively. Two hypotheses are proposed to explain these heavy δ34Spy layers: 1) in the transgression process, the heavy δ34Spy layers formed under stronger reducing conditions due to methane leakage; 2) in the regression process, the heavy δ34Spy layers formed under relatively weaker reducing conditions due to rapid deposition and low salinity. This study emphasizes the importance of physicochemical condition characterization in sediments, including redox conditions, in distinguishing the mechanisms that act to produce heavy δ34Spy signals.

Heterogeneity in Permeability and Particulate Organic Carbon Content Controls the Redox Condition of Riverbed Sediments at Different Timescales

AbstractThe hydrological and biogeochemical properties of the hyporheic zone in stream and riverine ecosystems have been extensively studied over the past two decades. Although it is widely acknowledged that sediment heterogeneity can influence biogeochemical reactions, little effort has been made to understand the role of heterogeneity on the spatiotemporal variability of riverbed redox conditions under changing flow dynamics at different timescales. Here we integrate a mechanistic model and field data to demonstrate that heterogeneity in permeability plays a vital role in modulating sediment redox conditions at both seasonal (annual) and event (daily‐to‐weekly) timescales, whereas heterogeneity in particulate organic carbon (POC) content only has a comparable influence on redox conditions at the seasonal timescale. These findings underscore the importance of accurately characterizing sediment heterogeneity, in terms of permeability and POC content, in quantifying biogeochemical dynamics in the riverbed and hyporheic zones of riverine ecosystems.

Long‐Term Variability in Pliocene North Pacific Ocean Export Production and Its Implications for Ocean Circulation in a Warmer World

AbstractUnlike in the high‐latitude North Atlantic, no deep water is formed in the modern subarctic North Pacific. It has previously been suggested that during climate states different from today, this dichotomy did not endure, and the formation of North Pacific Deepwater (NPDW) occurred in the subarctic North Pacific, which supported an active Pacific meridional overturning circulation (PMOC). Here we provide new records of productivity and sedimentary redox conditions from the central subarctic North Pacific spanning the late Miocene to early Pleistocene. These reconstructions indicate greater‐than‐modern and temporally varying North Pacific export production across the interval of ∼2.7–6 Ma. Our time series, combined with previously published data sets and model output for Pliocene North Pacific Ocean dynamics, support the presence of an active PMOC during the Pliocene, and suggest that the characteristics of NPDW formation varied during this warmer interval of Earth's history. This finding of elevated export production at a time of deep water formation presents a conundrum when considering Quaternary North Pacific Ocean dynamics, where subarctic North Pacific productivity declines during intervals when enhanced overturning is posited to occur. We evaluate our data considering the caveats of both (i.e., Pliocene and Quaternary North Pacific circulation) hypotheses, as well as additional mechanisms unrelated to ocean circulation. Because the Pliocene is a possible analogue for near‐future climate, our results and analyses have important ramifications for our understanding of regional and global climate in the coming decades as the planet continues to warm.

The Impact of Sea Ice Cover on Microbial Communities in Antarctic Shelf Sediments.

The area around the Antarctic Peninsula (AP) is facing rapid climatic and environmental changes, with so far unknown impacts on the benthic microbial communities of the continental shelves. In this study, we investigated the impact of contrasting sea ice cover on microbial community compositions in surface sediments from five stations along the eastern shelf of the AP using 16S ribosomal RNA (rRNA) gene sequencing. Redox conditions in sediments with long ice-free periods are characterized by a prevailing ferruginous zone, whereas a comparatively broad upper oxic zone is present at the heavily ice-covered station. Low ice cover stations were highly dominated by microbial communities of Desulfobacterota (mostly Sva1033, Desulfobacteria, and Desulfobulbia), Myxococcota, and Sva0485, whereas Gammaproteobacteria, Alphaproteobacteria, Bacteroidota, and NB1-j prevail at the heavy ice cover station. In the ferruginous zone, Sva1033 was the dominant member of Desulfuromonadales for all stations and, along with eleven other taxa, showed significant positive correlations with dissolved Fe concentrations, suggesting a significant role in iron reduction or an ecological relationship with iron reducers. Our results indicate that sea ice cover and its effect on organic carbon fluxes are the major drivers for changes in benthic microbial communities, favoring potential iron reducers at stations with increased organic matter fluxes.

Trace element, rare earth element and trace carbon compounds in Subglacial Lake Whillans, West Antarctica

Whillans Subglacial Lake (SLW) lies beneath 801 m of ice in the lower portion of the Whillans Ice Stream (WIS) in West Antarctica and is part of an extensive and active subglacial drainage network. Here, the geochemical characterization of SLW rare earth elements (REE), trace elements (TE), free amino acids (FAA), and phenolic compounds (PC) measured in lakewater and sediment porewater are reported. The results show, on average, higher values of REEs in the lakewater than in the porewater, and clear changes in all REE concentrations and select redox sensitive trace element concentrations in porewaters at a depth of ~15 cm in the 38 cm lake sediment core. This is consistent with prior results on the lake sediment redox conditions based on gas chemistry and microbiological data. Low concentrations of vanillyl phenols were measured in the SLW water column with higher concentrations in porewater samples and their concentration profiles in the sediments may also reflect changing redox conditions in the sediments. Vanillin concentrations increased with depth in the sediments as oxygenation decreases, while the concentrations of vanillic acid, the more oxidized component, were higher in the more oxygenated surface sediments. Collectively these results indicate redox changes occurring with the upper 38 cm of sediment in SLW and provide support for the existence of a seawater source, already hypothesized, in the sediments below the lowest measured depth, and of a complex and dynamic geochemical system beneath the West Antarctic Ice Sheet.Our results are the first to detail geochemical properties from an Antarctic subglacial environment using direct sampling technology. Due to their isolation from the wider environment, subglacial lakes represent one of our planets last pristine environments that provide habitats for microbial life and natural biogeochemical cycles but also impact the basal hydrology and can cause ice flow variations.

Relationships between Abyssal Redox Conditions and Rock Magnetic Properties of Surficial Sediments in the Western Pacific

Reconstructing changes in deep/bottom-water redox conditions are critical for understanding the role of the deep ocean in global carbon and metals cycling; nevertheless, the quantitative relationships between redox proxies and abyssal dissolved oxygen are poorly investigated. In this work, we studied the rock magnetic properties of surficial sediments in the western Pacific to investigate their relationship with regional redox conditions. Our results reveal a consistent sedimentary magnetic mineral assemblage in the western Pacific, dominated by pseudo-single-domain magnetite (Fe3O4), while the ratio of detrital and biogenic magnetite particles in different sites varies substantially. Detailed analyses identified two major magnetic-coercivity components, with modal coercivity values of 13.1 ± 1.6 mT and 54.7 ± 5.3 mT, respectively. All the magnetic parameters we measured, including both concentration-dependent and grainsize-dependent parameters, and the magnetic coercivities, are generally correlated to sedimentary redox conditions; however, the coercivities obtained by mathematical unmixing exhibit a stronger linkage, explaining about a quarter of variance of redox changes. Our findings confirm the potential of magnetic properties for tracing abyssal redox changes in the western Pacific, while the observed magnetic-redox relationships are complex and need further investigation.

Shallow Sediment as a Phosphorus Reservoir in an Oligotrophic Lake

AbstractLake sediment is an important reservoir for storage of phosphorus (P). Skaneateles Lake, a pristine oligotrophic, midsize lake in New York State, USA, is the primary unfiltered water source for the city of Syracuse and nearby communities. We conducted a lake‐wide survey of shallow sediments in Skaneateles Lake to inform understanding of the potential role of sediment in P storage and release into the water column. A total of 103 shallow samples of surface sediments were collected along 17 transects around the lake margin and analyzed for sediment and pore water elemental concentration, grain size, total organic carbon, nitrogen, carbonate content, stable isotopes of carbon, and mineral content. Reduction‐oxidation (redox) processes of Fe‐bound and Mn‐bound P appear to be a primary control of P storage and release. Sediment P concentrations are positively correlated with water depth and negatively correlated with Ca. Grain size and sediment P distributions around the lake are heterogeneous and patchy. Pore water concentrations reveal strong but variable partitioning of P, apparently controlled by sediment redox conditions. Pore water P concentrations (mean 90 μg L−1) are elevated compared with the oligotrophic water column (∼5 μg L−1) and may be an important source of nutrients to the water column of the lake.

Critical assessment of U, Ba and Ni as redox and productivity proxies in organic-rich sediments underneath dynamic, highly productive waters

Sediments of the continental shelf anoxic zones of the Benguela upwelling system (BUS) and the Peruvian upwelling system are present-day hotspots of trace element accumulation. However, contribution of the lithogenic trace element fraction and early diagenetic transformation processes are poorly constrained. The identification of source and accumulation mechanisms is necessary for the validation of trace elements as proxies for productivity and redox cycling, notably in highly dynamic upwelling systems such as the BUS. Here, we analyzed redox- and biosensitive elements (U, Ba, Ni), lithogenic tracers (Al, Ti, Zr), total organic carbon (TOC) and P in eleven short sediment cores from the Namibian shelf (ca. 22–25°S) as well as grain size fractionated hinterland samples from the Tsauchab Valley at Sossusvlei (∼25°S). These samples help to constrain the lithogenic trace element contributions, a prerequisite for a realistic interpretation of marine authigenic trace element data. Our findings corroborate previous findings that Zr is a sensitive tracer of the coarse fraction in marine sediment for dust input and/or sediment reworking. Hence, the combined analysis of the coarse fraction (Zr), organic matter, and P enrichments (TOC/P) differentiates between a calm, organic matter-rich central shelf environment and a more energetic phosphorite-rich southern shelf environment. A significant correlation of U with P in cores from the southern shelf corroborates previous findings of U incorporation into apatite, the initial formation of which requires oscillating oxic to sulfidic redox conditions. Non-apatite associated U dominates in the cores from the central shelf, where it is only enriched in the buried, anoxic parts of the sediment. This also supports oscillating oxic to sulfidic redox conditions in surface sediment, where U may be recycled. Hence, U accumulates either (i) in apatite under oscillating oxic to sulfidic conditions or (ii) in buried anoxic sediment sections. This strongly questions the use of U as indicator of suboxic conditions but rather anoxic conditions. While lithogenic fractions of U were negligible, the lithogenic fractions of Ba and Ni were found to be elevated. The calculation of authigenic Ba when accounting for lithogenic Ba from the Sossusvlei fine fractions gives more realistic authigenic Ba values. The high Ba enrichment in the BUS is interpreted as uptake of Ba by diatoms and/or nucleation of barite in P-rich diatom remains, as suggested previously. Given the shallow water depth of the cores, barite formation must already take place in subsurface waters (<50 m water depth) as opposed to previous suggesting greater water depths. The lithogenic background of Ni strongly varies from 23°S to 25°S based on Sossusvlei data and the literature. When authigenic Ni contents are calculated accordingly and plotted versus TOC, more systematic trends are seen (compared to total Ni versus TOC). Essentially all cores show an increase in the authigenic Ni/TOC ratio with sediment depth suggesting better preservation and retention of Ni as compared to TOC consistent with previous observations in sediments from the Peruvian upwelling system. This trend corroborates the use of Ni as a productivity indicator for upwelling sediments.

Geochemical conditions regulating chromium preservation in marine sediments

In the marine sediment record, concentrations and isotope ratios of chromium (Cr) can be used to reconstruct ocean biogeochemical conditions. These reconstructions rely on a detailed understanding of the chemical pathways that Cr undergoes as it is transferred from the water column to the sediment record. We examined Cr concentrations in marine pore fluids and sediments from six continental margin sites, which can be grouped into two basic environments: (1) sites where sediments are oxygenated and rich in solid phase Mn (herein termed oxic), and (2) sites where sediments are organic C (Corg)-rich and oxygen is depleted (anoxic). We found Cr concentrations to be lower (maximum of 12 nM in pore fluids and 124 ppm sediment solid phase) at oxic sites compared with anoxic sites (maximum of 77 nM and 184 ppm). Our findings confirm previously published interpretations of dissolved Cr in pore fluids (Brumsack and Gieskes, 1983; Shaw et al., 1990). In oxic surface sediments, particulate Cr(III) can be oxidised by Mn oxides, which leads to elevated concentrations of dissolved Cr co-occurring at the same depth as elevated Mn concentrations in the sediment. Under these oxidising conditions, down-core sediments contain relatively low solid-phase Cr concentrations. In oxic sediments, Cr speciation reveals that most of the pore fluid Cr is in the Cr(VI) state. At the site where Mn oxide-rich sediments rest below an oxic water column, oxidative loss of Cr from the sediment to the bottom water leads to the lowest estimated Cr burial efficiency of the sites examined here. Under anoxic Corg-rich conditions, both pore fluids and sediment solid phases contain high Cr concentrations, with 40–80% of dissolved pore fluid Cr present as Cr(III). This enrichment of Cr appears to be tightly linked to the presence of high total organic carbon (TOC) content and scavenging of Cr by (organic) particles in the water column. Combined, these data highlight the strong dependence of Cr on both sedimentary redox conditions as well as biological productivity. Based on the data from modern continental margin sediments, we propose that Cr concentrations and isotope compositions of the authigenic sediment fraction may record a combination of redox conditions and biological productivity in the water column. If confirmed by Cr isotope analyses, these findings will add support for the notion that Cr may serve as a proxy for ocean biological and chemical sedimentological conditions. Thus, careful assessment of the impact of organic matter on Cr is required for reconstructions of redox conditions with sedimentary records.

Unique benthic foraminiferal communities (stained) in diverse environments of sub-Antarctic fjords, South Georgia

Abstract. Sub-Antarctic fjords are among the environments most affected by the recent climate change. In our dynamically changing world, it is essential to monitor changes in these vulnerable settings. Here, we present a baseline study of “living” (rose-bengal-stained) benthic foraminifera from fjords of South Georgia, including fjords with and without tidewater glaciers. Their distribution is analyzed in the light of new fjord water and sediment property data, including grain size and sorting, total organic carbon, total sulfur, and δ13C of bulk organic matter. Four well-defined foraminiferal assemblages are recognized. Miliammina earlandi dominates in the most restricted, near-shore and glacier-proximal habitats, Cassidulinoides aff. parkerianus in mid-fjord areas, and Globocassidulina aff. rossensis and an assemblage dominated by Ammobaculites rostratus, Reophax subfusiformis, and Astrononion echolsi are in the outer parts of the fjords. Miliammina earlandi can tolerate strong glacial influence, including high sedimentation rates in fjord heads and sediment anoxia, as inferred from sediment color and total organic carbon / sulfur ratios. This versatile species thrives both in the food-poor inner reaches of fjords that receive mainly refractory petrogenic organic matter from glacial meltwater and in shallow-water coves, where it benefits from an abundant supply of fresh, terrestrial, and marine organic matter. A smooth-walled variant of C. aff. parkerianus, apparently endemic to South Georgia, is the calcareous rotaliid best adapted to inner-fjord conditions characterized by moderate glacial influence and sedimentation rates and showing no preference for particular sedimentary redox conditions. The outer parts of fjords with clear, well-oxygenated bottom water are inhabited by G. aff. rossensis. Ammobaculites rostratus, R. subfusiformis, and A. echolsi dominate in the deepest-water settings, with water salinities ≥ 33.9 PSU and temperatures 0.2–1.4 ∘C, characteristic of winter water and Upper Circumpolar Deep Water. The inner- and mid-fjord foraminiferal assemblages seem specific to South Georgia, although with continued warming and deglaciation, they may become more widespread in the Southern Ocean.

Anaerobic carbon oxidation in sediment of two Brazilian mangrove forests: the influence of tree roots and crab burrows

This study evaluated the effects of biogenic structures (tree roots and crab burrows) on sediment carbon (C), sulfur (S), and iron (Fe) biogeochemistry during the wet season in the Olaria mangrove forests near the city of Cananéia, São Paulo state, Brazil and the Nobrega mangrove forest approximately 2 km from the city. Anaerobic C oxidation pathways were assessed from sediment profiles and anaerobic incubations and related to the abundance of biogenic structures in the form of pneumatophores and crab burrows. Porewater depth profiles of dissolved inorganic carbon (DIC) and SO42- were less steep in the presence than absence of biogenic structures. While Fe(II) appeared unaffected by biogenic structures, Fe(III) levels were significantly higher in the upper 4 cm of the sediment in the presence than absence of vegetation and bioturbation. Surprisingly, the concentration of Fe(III) in this layer was 2-6 times higher in the Nobrega forest (6-13 µmol cm-3) than in the Olaria forest (1.5-6.5 µmol cm-3). Accordingly, depth integrated sulfate reduction (SR) tended to be highest at Olaria, while iron reduction (FeR) was highest at Nobrega. SR accounted for 54-83% of DIC production, with no diference between forested sites, while FeR accounted for 8-24% of DIC production, with a 2-3 times higher contribution in the Nobrega versus the Olaria forest. The results suggest that mangrove roots and crab burrows in mangrove sediments only promote FeR at the expense of SR in the Nobrega forest. It appears that anthropogenic discharge from Cananéia city may have overridden the impact of biogenic structures on sediment redox conditions at Olaria, thereby diminishing the role of FeR without strong stimulation of overall C oxidation rates.

The first data on methane concentrations in degassing griffins of Lake Baskunchak

For the first time, the distribution of methane in the brine and bottom sediments of the Ulan-Blag stream (tributary of Lake Baskunchak), fed by underground degassing springs, as well as directly in Baskunchak Lake at a distance from underground sources. The composition of the main ions in brine, acid-base and redox conditions in bottom sediments have been established. The brine mineralization in Baskunchak Lake is 312 g/dm3, which is 2.1 times higher than the mineralization of the Ulan-Blag stream. The chemical composition of the brine of both stations is classified as chloride type, sodium cationic composition. The concentration of methane in the brine of the studied underground degassing sources in the ravine stream of the Ulan-Blag reaches high values (up to 215 µl/dm3), exceeding by 1–2 orders of magnitude its concentration in the brine of Lake Baskunchak. The low concentrations of methane in the brine of the lake are probably due to its insignificant flow from the bottom sediments into the water due to the presence of a salt crust that prevents gas emission, as well as due to its small concentrations in the upper layers of sediments.

Experimental investigation of short-term warming on arsenic flux from contaminated sediments of two well-oxygenated subarctic lakes.

Legacy arsenic (As) contamination from past mining operations remains an environmental concern in lakes of the Yellowknife area (Northwest Territories, Canada) due to its post-depositional mobility in sediment and potential for continued remobilization to surface waters. Warmer temperatures associated with climate change in this subarctic region may impact As internal loading from lake sediments either by a direct effect on sediment porewater diffusion rate or indirect effects on microbial metabolism and sediment redox conditions. This study assessed the influence of warmer temperatures on As diffusion from contaminated sediment of two lakes with contrasting sediment characteristics using an experimental incubation approach. Sediments from Yellowknife Bay (on Great Slave Lake) contained predominately clay and silt with low organic matter (10%) and high As content (1675 μg/g) while sediments of Lower Martin Lake had high organic matter content (~70%) and approximately half the As (822 μg/g). Duplicate sediment batches from each lake were incubated in a temperature-controlled chamber, and overlying water was kept well-oxygenated while As flux from sediment was measured during four weekly temperature treatments (7°C to 21°C, at ~5°C intervals). During the experiment, As diffused from sediment to overlying water in all cores and temperature treatments, with As fluxes ranging from 48-956 μg/m2/day. Arsenic fluxes were greater from Yellowknife Bay sediments, which had higher solid-phase As concentrations, compared to those of Lower Martin Lake. Short-term warming did not stimulate As flux from duplicate cores of either sediment type, in contrast with reported temperature enhancement in other published studies. We conclude that warmer temperatures were insufficient to strongly enhance sediment As diffusion into overlying oxic waters. These observations are relevant for evaluating climate-warming effects on sediment As mobility in subarctic lakes with little or no thermal stratification and a well-oxygenated water column.

Pyrites in a salt marsh-ria system: Quantification, morphology, and mobilization

Galician Rias are among the most productive ecosystems in the world. Consequently, the soils of their salt marshes and sediments of the intertidal flats show high organic matter contents, reactive Fe, and sulfate, which promote pyrite synthesis and accumulation, using sulfate for organic matter decomposition. This work studies the morphological variability and concentration of pyrites (individual crystals and framboids) in different geochemical environments found in the Ria de Ortigueira (salt marsh soils and bottom sediments in the inner, middle, and outer section), addressing their dynamics in the marsh-ria system in relation to the hydrodynamic characteristics defined by tides and river discharges. Framboidal pyrites were the dominant morphology in marsh soils and sediments in the middle and inner sections of the Ria, while isolated crystals dominated its outer section. The results showed that lower marsh soils (colonized by Spartina) are the most favorable environment for pyrite synthesis, showing high pyritic Fe concentrations and high degrees of pyritization, largely exceeding the values observed in sediments from Galician Rias and from most sedimentary environments worldwide. However, the amount of framboidal pyrites present in the lower marsh (SPE: 4–5 × 104 framboids) was clearly lower than in bottom sediments of the inner and middle part of the Ria de Ortigueira (∼2–7 × 106 framboids), mainly due to the fact that pyrites were found to form large framboids in lower salt marsh soils. Thus, the amount of framboidal pyrites does not seem to be a good indicator of redox conditions in modern marine sediments. Pyrite crystals found in the sediments of the Ria showed poorly defined vertices and facets, indicating their degradation and suggesting that a significant amount of the pyrites found in the middle and inner sections derive from marsh collapse. Finally, the output of framboidal pyrites towards the outer Ria de Ortigueira reflects the low intensity of residual flows in this Ria. Therefore, the pyrites observed in the outer section consisted only of isolated crystals, presumably formed in situ under low sulfate-reducing activity conditions.

Isoetid mediated radial oxygen loss prevents iron reduction and the related mobilisation of ammonium and methane: an experimental approach

Isoetids are slow growing ecosystem-engineers that maintain an oligotrophic environment through high radial oxygen losses (ROL) from their roots. This ROL could potentially reduce methane (CH4) emission by maintaining sediment redox conditions unfavourable for methanogenesis. Isoetids have declined in many European countries as an effect of eutrophication and inorganic carbon enrichment. To assess the effect of sudden disappearance of isoetids on biogeochemical carbon and nutrient cycling in organic rich sediments, we set up a greenhouse experiment. Intact vegetated sediment patches with Lobelia dortmanna and Littorella uniflora were collected from ten boreal Norwegian softwater lakes. From half of the patches, isoetids were manually removed. We determined the effect of removal on sediment redox potential, pore water chemistry and CH4 emission. In addition, germination success of L. dortmanna seeds was tested on the sediments where isoetids were removed. The absence of ROL after isoetid removal led to a drop in sediment redox potential, resulting in anaerobic breakdown of organic matter using alternative electron acceptors, especially iron(hydr)oxides. Consequently, increased porewater concentrations of ammonium, iron, inorganic carbon and CH4 were observed in sediments where isoetids had been removed compared to the isoetid vegetated sediments. Moreover, over 20 times higher emission of CH4 was observed from the sediments where isoetids had been removed. On the highly reduced sediments, the germination of L. dortmanna was hampered. When isoetids are unable to recolonise after disturbance events, it is expected that the absence of ROL eventually results in a long-term increase in lake productivity and CH4 emission.

The role of physico-chemical interactions in the seasonality of toxic dinoflagellate cyst assemblages: The case of the NW Patagonian fjords system

Harmful algal blooms (HABs) are recurrent in the NW Patagonia fjords system and their frequency has increased over the last few decades. Outbreaks of HAB species such as Alexandrium catenella, a causal agent of paralytic shellfish poisoning, and Protoceratium reticulatum, a yessotoxins producer, have raised considerable concern due to their adverse socioeconomic consequences. Monitoring programs have mainly focused on their planktonic stages, but since these species produce benthic resting cysts, the factors influencing cyst distributions are increasingly gaining recognition as potentially important to HAB recurrence in some regions. Still, a holistic understanding of the physico-chemical conditions influencing cyst distribution in this region is lacking, especially as it relates to seasonal changes in drivers of cyst distributions, as the characteristics that favor cyst preservation in the sediment may change through the seasons. In this study, we analyzed the physico–chemical properties of the sediment (temperature, pH, redox potential) and measured the bottom dissolved oxygen levels in a “hotspot” area of southern Chile, sampling during the spring and summer as well as the fall and winter, to determine the role these factors may play as modulators of dinoflagellate cyst distribution, and specifically for the cysts of A. catenella and P. reticulatum. A permutational analysis of variance (PERMANOVA) showed the significant effect of sediment redox conditions in explaining the differences in the cyst assemblages between spring-summer and fall-winter periods (seasonality). In a generalized linear model (GLM), sediment redox potential and pH were associated with the highest abundances of A. catenella resting cysts in the spring-summer, however it was sediment temperature that most explained the distribution of A. catenella in the fall-winter. For P. reticulatum, only spring-summer sediment redox potential and temperature explained the variation in cyst abundances. The implications of environmental (physico-chemical) seasonality for the resting cysts dynamics of both species are discussed.

A Depth‐Transect of Ocean Deoxygenation During the Paleocene‐Eocene Thermal Maximum: Magnetofossils in Sediment Cores From the Southeast Atlantic

AbstractThe Paleocene‐Eocene Thermal Maximum (PETM, ∼56 Ma) presents a past analog for future global warming. Previous studies provided evidence for major loss of dissolved oxygen during the PETM, although understanding the degree and distribution of oxygen loss poses challenges. Magnetofossils produced by magnetotactic bacteria are sensitive to redox conditions in sediments and water columns, and have been used to reconstruct paleoredox conditions over a range of geological settings. Here, we present records of well‐preserved magnetofossils from cores along Walvis Ridge in the Southeast Atlantic that span the PETM across a depth transect (∼1,500–3,600 m paleodepth). Hysteresis, isothermal remanent magnetization curves, first‐order reversal curve diagrams, and low‐temperature magnetic measurements document large variations in magnetic properties of magnetofossils, which relate to time and water depth. Abundant magnetofossil grains are present within the studied sediments, and their morphologies change with paleodepth, as shown by transmission electron microscope observations. Magnetofossils from samples within the PETM onset at the deeper sites (∼2,600–3,600 m paleodepth) have lower coercivity values, a higher oxidation degree, and smaller grain sizes than those from shallower sites (∼1,500–1,800 m paleodepth), likely reflecting changes in paleoredox conditions at different paleodepths. We use the magnetofossil records to reconstruct relative changes in dissolved oxygen content at different water depths through the PETM, and suggest that ocean deoxygenation likely expanded downwards in the early stages of the PETM. We thus demonstrate the value of magnetofossil records for paleoenvironmental reconstructions over time and space, particularly for sediments that lack carbonate fossils.

Taphonomic bias on calcareous micro and nannofossils and paleoenvironmental evolution across the Messinian Salinity Crisis onset: Insights from the Sorbas Basin (SE Spain)

During the Messinian Salinity Crisis (MSC, 5.97–5.33 Ma) the synergy between tectonic and climatic processes promoted the deposition of evaporites throughout the Mediterranean Basin. The disappearance of calcareous nannofossils and foraminifers at the MSC onset has been traditionally interpreted as the result of the establishment of hypersaline conditions in the water column, which were lethal for most marine eukaryotes. Here, we investigate the calcareous micro and nannofossil assemblages from the Sorbas Basin (SE Spain) spanning the onset and the first phase of the MSC (~ 5.9–5.7 Ma) in order to test whether their disappearance was related to adverse environmental conditions and/or to preferential dissolution of biogenic calcite. Micropaleontological analyses and petrographic observations suggest that the disappearance of calcareous fossils was the result of a taphonomic bias related to paleoceanographic changes that favoured the oxidation of both pyrite and organic matter at the sea floor. A poorly preserved benthic and planktic assemblage and aragonitic laminated sediment characterize the deposits of the first phase of the MSC from 5.93 Ma onward; aragonite deposition was likely bio-mediated in response to enhanced photosynthesis, as suggested by its δ13C signature. The fossil assemblage preserved in these deposits indicates a shallowing upward trend of the basin with respect to the pre-evaporitic phase, and the establishment of a lagoon-like environment characterized by episodic improvement of the connections with the open sea. We conclude that the temporary disappearance of calcareous fossils approximately at the MSC onset was related to ongoing basin restriction, which increased the sensitivity of the basin to fresh-water input and temperature changes, promoting marked fluctuations of the redox conditions in bottom sediments. This finding challenges the view of a marine biotic crisis related to hypersaline conditions at the MSC onset and opens new perspectives on the paleoenvironmental conditions that characterized this time interval.

Dynamic Responses of Trace Metal Bioaccessibility to Fluctuating Redox Conditions in Wetland Soils and Stream Sediments

Dynamic Responses of Trace Metal Bioaccessibility to Fluctuating Redox Conditions in Wetland Soils and Stream Sediments