Depth and intensity of the sulfate-methane transition zone control sedimentary molybdenum and uranium sequestration in a eutrophic low-salinity setting

Molybdenum (Mo) and uranium (U) contents in sedimentary archives are often used to reconstruct past changes in seafloor oxygenation. However, their sequestration processes are as yet poorly constrained in low-salinity coastal waters, which often suffer from anthropogenic eutrophication but only mild oxygen depletion. Due to the consequent lack of robust long-term paleo-redox reconstructions in such settings often characterized by a shallow front of dissolved sulfide accumulation within the sediment pore waters, inadequate understanding of the long-term drivers behind oxygen loss impedes cost-effective mitigation of this environmental problem. Here, we investigate the mechanisms of Mo and U sequestration in an oxic, low-salinity coastal setting in the northern Baltic Sea where anthropogenic eutrophication over the 20th century has resulted in formation of a shallow sulfate-methane transition zone (SMTZ) in the sediment column of this brackish-water basin. Our results demonstrate remarkably similar patterns for authigenic Mo and U sequestration, whereby the depth and intensity of the SMTZ exerts a first-order control on their solid-phase uptake. Sequential extraction analysis suggests that a large part of the authigenic Mo pool is hosted by refractory Fe-S phases such as pyrite and nanoscale FeMoS4, implying that the Fe-sulfide pathway is the dominating process of authigenic Mo scavenging. However, we also observe a pool of extremely labile Mo deep within the SMTZ, which might record an intermediate phase in authigenic Mo sequestration and/or partial switch to the organic matter (OM) pathway at low dissolved Fe levels. Authigenic U resides in acid-extractable and refractory phases, likely reflecting uptake into poorly crystalline monomeric U(IV) and crystalline uraninite, respectively. Similarly to Mo, authigenic U uptake is active at two fronts within the SMTZ, paralleled by increases in dissolved sulfide levels, suggesting coupling between sulfide production and U reduction. Our results imply that both Mo and U could provide viable proxies for mild bottom water deoxygenation in these settings, through the indirect link between seafloor oxygen conditions and the depth of SMTZ. Of these, Mo appears to more robustly capture variations in seafloor oxygen levels due to the significantly higher share of the authigenic pool. However, temporal resolution of these proxies is limited by the vertical offset between seafloor and the zone of authigenic uptake, and the superimposed character of the signal at a given depth due to vertical migrations of the SMTZ. These results have important implications for the use of Mo and U as paleo-redox proxies in other low-salinity coastal settings exposed to eutrophication.Peer reviewe

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. (c) 2020 The Authors. Published by Elsevier B.V.Peer reviewe

Water and Blood Repellent Flexible Tubes

A top-down scalable method to produce flexible water and blood repellent tubes is introduced. The method is based on replication of overhanging nanostructures from an aluminum tube template to polydimethylsiloxane (PDMS) via atomic layer deposition (ALD) assisted sacrificial etching. The nanostructured PDMS/titania tubes are superhydrophobic with water contact angles 163 +/- 1 degrees (advancing) and 157 +/- 1 degrees (receding) without any further coating. Droplets are able to slide through a 4 mm (inner diameter) tube with low sliding angles of less than 10 degrees for a 35 mu L droplet. The superhydrophobic tube shows up to 5,000 times increase in acceleration of a sliding droplet compared to a control tube depending on the inclination angle. Compared to a free falling droplet, the superhydrophobic tube reduced the acceleration by only 38.55%, as compared to a 99.99% reduction for a control tube. The superhydrophobic tubes are blood repellent. Blood droplets (35 mu L) roll through the tubes at 15 degrees sliding angles without leaving a bloodstain. The tube surface is resistant to adhesion of activated platelets unlike planar control titania and smooth PDMS surfaces.Peer reviewe

Supergravity origin of the MSSM inflation

We consider the supergravity origin of the recently proposed MSSM inflationary model, which relies on the existence of a saddle point along a dimension six flat direction. We derive the conditions that the Kahler potential has to satisfy for the saddle point to exist irrespective of the hidden sector vevs. We show that these conditions are satisfied by a simple class of Kahler potentials, which we find to have a similar form as in various string theory compactifications. For these potentials, slow roll MSSM inflation requires no fine tuning of the soft supersymmetry breaking parameters.Comment: v3: 10 pages, no figures; version accepted for publication. Typos correcte

Depth and intensity of the sulfate-methane transition zone control sedimentary molybdenum and uranium sequestration in a eutrophic low-salinity setting

Molybdenum (Mo) and uranium (U) contents in sedimentary archives are often used to reconstruct past changes in seafloor oxygenation. However, their sequestration processes are as yet poorly constrained in low-salinity coastal waters, which often suffer from anthropogenic eutrophication but only mild oxygen depletion. Due to the consequent lack of robust long-term paleo-redox reconstructions in such settings often characterized by a shallow front of dissolved sulfide accumulation within the sediment pore waters, inadequate understanding of the long-term drivers behind oxygen loss impedes cost-effective mitigation of this environmental problem. Here, we investigate the mechanisms of Mo and U sequestration in an oxic, low-salinity coastal setting in the northern Baltic Sea where anthropogenic eutrophication over the 20th century has resulted in formation of a shallow sulfate-methane transition zone (SMTZ) in the sediment column of this brackish-water basin. Our results demonstrate remarkably similar patterns for authigenic Mo and U sequestration, whereby the depth and intensity of the SMTZ exerts a first-order control on their solid-phase uptake. Sequential extraction analysis suggests that a large part of the authigenic Mo pool is hosted by refractory Fe–S phases such as pyrite and nanoscale FeMoS4, implying that the Fe-sulfide pathway is the dominating process of authigenic Mo scavenging. However, we also observe a pool of extremely labile Mo deep within the SMTZ, which might record an intermediate phase in authigenic Mo sequestration and/or partial switch to the organic matter (OM) pathway at low dissolved Fe levels. Authigenic U resides in acid-extractable and refractory phases, likely reflecting uptake into poorly crystalline monomeric U(IV) and crystalline uraninite, respectively. Similarly to Mo, authigenic U uptake is active at two fronts within the SMTZ, paralleled by increases in dissolved sulfide levels, suggesting coupling between sulfide production and U reduction. Our results imply that both Mo and U could provide viable proxies for mild bottom water deoxygenation in these settings, through the indirect link between seafloor oxygen conditions and the depth of SMTZ. Of these, Mo appears to more robustly capture variations in seafloor oxygen levels due to the significantly higher share of the authigenic pool. However, temporal resolution of these proxies is limited by the vertical offset between seafloor and the zone of authigenic uptake, and the superimposed character of the signal at a given depth due to vertical migrations of the SMTZ. These results have important implications for the use of Mo and U as paleo-redox proxies in other low-salinity coastal settings exposed to eutrophication.</p

Kahler potentials for the MSSM inflation and the spectral index

Recently it has been argued that some of the fine-tuning problems of the MSSM inflation associated with the existence of a saddle point along a flat direction may be solved naturally in a class of supergravity models. Here we extend the analysis and show that the constraints on the Kahler potentials in these models are considerably relaxed when the location of the saddle point is treated as a free variable. We also examine the effect of supergravity corrections on inflationary predictions and find that they can slightly alter the value of the spectral index. As an example, for flat direction field values $|\bar{\phi}_0|=1\times10^{-4}M_P$ we find $n\sim0.92 ... 0.94$ while the prediction of the MSSM inflation without any corrections is $n\sim0.92$.Comment: 13 pages, one figure. Typos corrected and a reference adde

A microfluidic oxygen sink to create a targeted cellular hypoxic microenvironment under ambient atmospheric conditions

Physiological oxygen levels within the tissue microenvironment are usually lower than 14%, in stem cell niches these levels can be as low as 0-1%. In cell cultures, such low oxygen levels are usually mimicked by altering the global culture environment either by O-2 removal (vacuum or oxygen absorption) or by N-2 supplementation for O-2 replacement. To generate a targeted cellular hypoxic microenvironment under ambient atmospheric conditions, we characterised the ability of the dissolved oxygen-depleting sodium sulfite to generate an in-liquid oxygen sink. We utilised a microfluidic design to place the cultured cells in the vertical oxygen gradient and to physically separate the cells from the liquid. We demonstrate generation of a chemical in-liquid oxygen sink that modifies the surrounding O-2 concentrations. O-2 level control in the sink-generated hypoxia gradient is achievable by varying the thickness of the polydimethylsiloxane membrane. We show that intracellular hypoxia and hypoxia response element-dependent signalling is instigated in cells exposed to the microfluidic in-liquid O-2 sink-generated hypoxia gradient. Moreover, we show that microfluidic flow controls site-specific microenvironmental kinetics of the chemical O-2 sink reaction, which enables generation of intermittent hypoxia/re-oxygenation cycles. The microfluidic O-2 sink chip targets hypoxia to the cell culture microenvironment exposed to the microfluidic channel architecture solely by depleting O-2 while other sites in the same culture well remain unaffected. Thus, responses of both hypoxic and bystander cells can be characterised. Moreover, control of microfluidic flow enables generation of intermittent hypoxia or hypoxia/re-oxygenation cycles. (C) 2018 Published by Elsevier Ltd on behalf of Acta Materialia Inc.Peer reviewe

Sedimentary molybdenum and uranium : Improving proxies for deoxygenation in coastal depositional environments

Sedimentary molybdenum (Mo) and uranium (U) enrichments are widely used to reconstruct changes in bottom water oxygen conditions in aquatic environments. Until now, most studies using Mo and U have focused on restricted suboxic-euxinic basins and continental margin oxygen minimum zones (OMZs), leaving mildly reducing and oxic (but eutrophic) coastal depositional environments vastly understudied. Currently, it is un-known: (1) to what extent Mo and U enrichment factors (Mo-and U-EFs) can accurately reconstruct oxygen conditions in coastal sites experiencing mild deoxygenation, and (2) to what degree secondary (depositional environmental) factors impact Mo-and U-EFs. Here we investigate 18 coastal sites with varying bottom water redox conditions, which we define by means of five "redox bins", ranging from persistently oxic to persistently euxinic, from a variety of depositional environments. Our results demonstrate that Mo-and U-EF-based redox proxies and sedimentary Mo and U contents can be used to differentiate bottom water oxygen concentration among a range of modern coastal depositional environments. This is underpinned by the contrasting EFs of Mo and U along the redox gradient, which shows a substantial difference of Mo-EFs between redox bins 3-5 (ir/ regularly suboxic - ir/regularly dysoxic - persistently oxic) and of U-EFs between redox bins 1-2 (persistently euxinic - ir/regularly euxinic). Surprisingly, we observe comparatively low redox proxy potential for U in en-vironments of mild deoxygenation (redox bins 3-5). Further, we found that secondary factors can bias Mo-and U-EFs to such an extent that EFs do not reliably reflect bottom water redox conditions. We investigate the impact of limited Mo sedimentary sequestration in sulfidic depositional environments (i.e., the "basin reservoir effect", equilibrium with FeMoS4), Fe/Mn-(oxy)(hydr)oxide "shuttling", oxidative dissolution, the sulfate methane transition zone in the sediment, sedimentation rate, and the local Al background on Mo-and U-EFs.Peer reviewe

Curvaton Dynamics in Brane-worlds

We study the curvaton dynamics in brane-world cosmologies. Assuming that the inflaton field survives without decay after the end of inflation, we apply the curvaton reheating mechanism to Randall-Sundrum and to its curvature corrections: Gauss-Bonnet, induced gravity and combined Gauss-Bonnet and induced gravity cosmological models. In the case of chaotic inflation and requiring suppression of possible short-wavelength generated gravitational waves, we constraint the parameters of a successful curvaton brane-world cosmological model. If density perturbations are also generated by the curvaton field then, the fundamental five-dimensional mass could be much lower than the Planck massComment: 47 pages, 1 figure, references added, to be published in JCA

Sedimentary molybdenum and uranium: Improving proxies for deoxygenation in coastal depositional environments

Sedimentary molybdenum (Mo) and uranium (U) enrichments are widely used to reconstruct changes in bottom water oxygen conditions in aquatic environments. Until now, most studies using Mo and U have focused on restricted suboxic-euxinic basins and continental margin oxygen minimum zones (OMZs), leaving mildly reducing and oxic (but eutrophic) coastal depositional environments vastly understudied. Currently, it is unknown: (1) to what extent Mo and U enrichment factors (Mo- and U-EFs) can accurately reconstruct oxygen conditions in coastal sites experiencing mild deoxygenation, and (2) to what degree secondary (depositional environmental) factors impact Mo- and U-EFs. Here we investigate 18 coastal sites with varying bottom water redox conditions, which we define by means of five “redox bins”, ranging from persistently oxic to persistently euxinic, from a variety of depositional environments. Our results demonstrate that Mo- and U-EF-based redox proxies and sedimentary Mo and U contents can be used to differentiate bottom water oxygen concentration among a range of modern coastal depositional environments. This is underpinned by the contrasting EFs of Mo and U along the redox gradient, which shows a substantial difference of Mo-EFs between redox bins 3–5 (ir/regularly suboxic – ir/regularly dysoxic – persistently oxic) and of U-EFs between redox bins 1–2 (persistently euxinic – ir/regularly euxinic). Surprisingly, we observe comparatively low redox proxy potential for U in environments of mild deoxygenation (redox bins 3–5). Further, we found that secondary factors can bias Mo-and U-EFs to such an extent that EFs do not reliably reflect bottom water redox conditions. We investigate the impact of limited Mo sedimentary sequestration in sulfidic depositional environments (i.e., the “basin reservoir effect”, equilibrium with FeMoS4), Fe/Mn-(oxy)(hydr)oxide “shuttling”, oxidative dissolution, the sulfate methane transition zone in the sediment, sedimentation rate, and the local Al background on Mo- and U-EFs