Benthic fluxes of oxygen and inorganic nutrients in the archipelago of Gulf of Finland, Baltic Sea – Effects of sediment resuspension measured in situ

Abstract Benthic fluxes of oxygen and dissolved inorganic nutrients; phosphate (DIP), ammonium (NH4), nitrate + nitrite (NOx), and silicate (DSi); and the effects of resuspension on these were studied in situ with the Göteborg benthic landers in the Gulf of Finland archipelago, Baltic Sea. The benthic fluxes were examined at two shallow stations at depths of 7 m and 20 m in May and August 2014. Resuspension altered benthic fluxes of oxygen and nutrients in most of the experiments in August, but not in May, which was mainly due to weaker resuspension treatments in spring. Additionally, the benthic nutrient regeneration rates were higher and redox conditions lower in August when the water was warmer. In August, resuspension increased the benthic oxygen uptake by 33–35%, which was, in addition to stronger resuspension treatment, attributed to higher amounts of dissolved reduced substances in the sediment pore water in comparison to conditions in May. Adsorption onto newly formed iron oxyhydroxides could explain the uptake of DIP by the sediment at the 20 m station and the lowering of the DSi efflux by 31% at the 7 m station during resuspension in August. In addition, resuspension promoted nitrification, as indicated by increased NOx fluxes at both stations (by 30% and 27% at the 7 m and 20 m station, respectively) and a lowered NH4 flux (by 48%) at the 7 m station. Predicted increases in the magnitude and frequency of resuspension will thus markedly affect the transport of phosphorus and silicon and the cycling of nitrogen in the shallow areas of the Gulf of Finland.Peer reviewe

Sulfide oxidation in deep Baltic Sea sediments upon oxygenation and colonization by macrofauna

Coastal and shelf sediments affected by transient or long-term bottom water anoxia and sulfidic conditions undergo drastic changes in macrofauna communities and abundances. This study investigates how early colonization by two macrofaunal functional traits (epifauna vs. infauna) affects oxygen, sulfide, and pH dynamics in anoxic sediment upon recent bottom water oxygenation. Large mesocosms (area 900 cm 2) with 150-m-deep Baltic Sea soft sediments were exposed to three treatments: (1) no animals; (2) addition of 170 polychaetes (Marenzelleria arctia); (3) addition of 181 amphipods (Monoporeia affinis). Porewater chemistry was investigated repeatedly by microsensor profiling over a period of 65 days. Colonization by macrofauna did not significantly deepen penetration of oxygen compared to the animal-free sediment. Bioturbation by M. affinis increased the volume of the oxidized, sulfide-free sediment by 66% compared to the animal-free control already after 13 days of incubation. By the end of the experiment M. affinis and M. arctia increased the oxidized sediment volume by 87 and 35%, respectively. Higher efficiency of epifaunal amphipods in removing hydrogen sulfide than deep-burrowing polychaetes is likely due to more substantial re-oxidation of manganese and/or nitrogen compounds associated with amphipod mixing activity. Our results thus indicate that early colonization of different functional groups might have important implications for the later colonization by benthic macrofauna, meiofauna and microbial communities that benefit from oxidized and sulfide-free sediments

Benthic fluxes of biogenic elements in the Baltic Sea : Influence of oxygen and macrofauna

This thesis investigates how benthic fluxes of phosphorus (P), nitrogen (N), and silicon (Si) change upon oxygenation of anoxic soft bottoms in the brackish, eutrophicated Baltic Sea. Direct measurements in situ by benthic landers demonstrated that fluxes of dissolved inorganic P (DIP) from anoxic bottom sediments in the Eastern Gotland Basin are higher than previously thought (Paper I). It is argued that the benthic DIP flux has a much larger influence on the DIP inventory in the Baltic proper than the external sources. Similarly, benthic fluxes of DIP and dissolved inorganic N (DIN) from anoxic sediment in the coastal Kanholmsfjärden Basin, Stockholm archipelago, were sufficiently high to renew the pools of these nutrients below the upper mixed layer in roughly one year (Paper II). A natural inflow of oxygen rich water into the deep, and previously long-term anoxic part of Kanholmsfjärden Basin, increased the P content in the sediment by 65% and lowered DIP and dissolved silica (DSi) concentrations in the pore water. These changes, as well as the large increases in benthic effluxes of these solutes following de-oxygenation of the bottom water, suggest that they are influenced similarly by changing oxygen conditions. Experimental results in papers III and IV show that common benthic macrofauna species in the Baltic Sea can stimulate benthic release of DIN and DSi, as well as dissolved organic and particulate bound nutrients. Thus, if benthic oxygen conditions would improve in the Baltic, initial effects on benthic–pelagic nutrient coupling will change due to animal colonisation of currently azoic soft bottoms. A new box corer was designed (Paper V) which can be used to obtain highly needed virtually undisturbed samples from soft bottom sediments – if lowered slowly and straight into the bottom strata – as demonstrated by in situ videography and turbidimetry. The commonly used USNEL box corer caused severe biasing during sediment collection.At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 4: Manuscript. Paper 5: Manuscript.Baltic oxygenation projec

Benthic fluxes of biogenic elements in the Baltic Sea : Influence of oxygen and macrofauna

This thesis investigates how benthic fluxes of phosphorus (P), nitrogen (N), and silicon (Si) change upon oxygenation of anoxic soft bottoms in the brackish, eutrophicated Baltic Sea. Direct measurements in situ by benthic landers demonstrated that fluxes of dissolved inorganic P (DIP) from anoxic bottom sediments in the Eastern Gotland Basin are higher than previously thought (Paper I). It is argued that the benthic DIP flux has a much larger influence on the DIP inventory in the Baltic proper than the external sources. Similarly, benthic fluxes of DIP and dissolved inorganic N (DIN) from anoxic sediment in the coastal Kanholmsfjärden Basin, Stockholm archipelago, were sufficiently high to renew the pools of these nutrients below the upper mixed layer in roughly one year (Paper II). A natural inflow of oxygen rich water into the deep, and previously long-term anoxic part of Kanholmsfjärden Basin, increased the P content in the sediment by 65% and lowered DIP and dissolved silica (DSi) concentrations in the pore water. These changes, as well as the large increases in benthic effluxes of these solutes following de-oxygenation of the bottom water, suggest that they are influenced similarly by changing oxygen conditions. Experimental results in papers III and IV show that common benthic macrofauna species in the Baltic Sea can stimulate benthic release of DIN and DSi, as well as dissolved organic and particulate bound nutrients. Thus, if benthic oxygen conditions would improve in the Baltic, initial effects on benthic–pelagic nutrient coupling will change due to animal colonisation of currently azoic soft bottoms. A new box corer was designed (Paper V) which can be used to obtain highly needed virtually undisturbed samples from soft bottom sediments – if lowered slowly and straight into the bottom strata – as demonstrated by in situ videography and turbidimetry. The commonly used USNEL box corer caused severe biasing during sediment collection.At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 4: Manuscript. Paper 5: Manuscript.Baltic oxygenation projec

On benthic fluxes of phosphorus in the Baltic Sea proper – drivers and estimates

This Thesis focuses on the exchange of phosphorus (P) across the sediment–water interface in the Baltic Sea proper, with particular attention to the influence of bioturbating macrofauna and benthic redox conditions. Benthic P fluxes have major influence on P availability in the water column, which in turn regulates growth conditions for dinitrogen fixating cyanobacteria in the Baltic proper. Presently, a very large area of bottom sediment is overlain by oxygen depleted bottom water and is therefore devoid of aerobic organisms. In paper I, anoxic sediment from the Western Gotland Basin was oxygenated and exposed to bioturbation by three macrofauna species in a laboratory experiment. The experimental design allowed for detailed studies of how bioturbating animals influence the P fluxes on a species-specific level. All species (Monoporeia affinis, Mysis mixta, and Macoma balthica) mobilised dissolved organic P from the bottom sediment to the supernatant water. Also, particulate P was released by the two former species. None of these P fractions showed any mobility in control sections of the aquarium system. These animal-dependent P fluxes are a previously largely overlooked but potentially significant source of bioavailable P in coastal marine areas, such as the Baltic Sea. In paper II, we estimate a contemporary reflux of 146 kton dissolved inorganic P (DIP) from bottom sediments in the Baltic proper. This estimate is based on data from a large number of in situ benthic flux measurements using benthic chamber landers along a depth gradient in the Eastern Gotland Basin. DIP effluxes increased with increasing water depth, and decreasing bottom water oxygen concentrations. Bottom water anoxia was identified as a major driver for the mobilisation of DIP from bottom sediments. During such conditions, the DIP efflux was well correlated to carbon oxidation rate, while on oxic bottoms DIP fluxes were low irrespectively of the carbon oxidation rate. Our data support the hypothesis of a positive feedback loop of self-amplifying eutrophication in the Baltic Sea. Thus, both nutrient emission cuts and active mitigation actions to strengthen sedimentary P sinks are warranted for effective remediation of eutrophication in the Baltic Sea

Effects of oxygen on recycling of biogenic elements from sediments of a stratified coastal Baltic Sea basin

Benthic nutrient dynamics in the coastal basin Kanholmsfj\ue4rden, NW Baltic proper, were studied by in situflux measurements and sediment samplings in 2010–2013. The benthic release of NH4 and DIP from anoxicsediments in Kanholmsfj\ue4rden were calculated to renew the standing stock inventories of DIN and DIP in theoverlying water in roughly 1 year.Starting in summer 2012, mixing of oxygen-rich water into the deep part of the basin temporarily improved theoxygen conditions in the deepwater. During the 1 year oxygenated period, the total phosphorus inventory in thesurficial sediment increased by 0.4 g Pm−2 or 65%. Thiswasmost likely due to stimulated bacterial P assimilationunder oxygenated conditions.By July 2013, the bottomwater had again turned anoxic, and DIP and DSi fluxes were even higher than earlier inthe study period. These high fluxes are attributed to degradation of sedimentary pools of P and Si that had accumulatedduring the bottom water oxygenation in 2012. The strong correlation between DIP and DSi fluxes andthe similar dynamics of DIP and DSi in the sediment pore water and near bottom water, suggest a similarredox dependency of benthic–pelagic exchange for these nutrients.\ua9 2015 The Authors. Published by Elsevier B.V. This is an ope

Phosphorus recycling in sediments of the central Baltic Sea

Benthic fluxes of phosphorus (P) were measured in situ in the Eastern Gotland Basin (EGB), central Baltic Sea, using benthic landers. A total of 40 flux measurements of dissolved inorganic P (DIP) on 13 stations at water depthsranging 30–210 m and under different oxygen regimes were carried out on three cruises during three consecutive years (2008–2010) in August–September. Our study is the first toreport in situ DIP fluxes in the Baltic proper, and it provides the most comprehensive dataset of benthic fluxes of DIP and dissolved organic P (DOP) in the Baltic proper existing to date. DIP fluxes increased with increasing waterdepth and with decreasing bottom water oxygen concentration. Average DIP fluxes were calculated for oxic bottomwater conditions (−0.003\ub10.040 mmol m−2 d−1), hypoxic conditions (0.027\ub10.067 mmol m−2 d−1) and anoxic conditions (0.376\ub10.214 mmol m−2 d−1). The mean DIP flux at anoxic bottoms was higher than previous estimates based on ex situ measurements of pore water gradients. The DIP flux was positively correlated with the organic carbon inventoryof sediment, and the benthic flux of dissolved inorganic carbon (DIC) at anoxic stations, but these variables were uncorrelated at oxic stations. The positive correlation between DIP and DIC fluxes suggests that the benthic DIP efflux from anoxic bottoms in the Baltic Proper is mainly controlled by rates of deposition and degradation of organic matter. The flux from anoxic sediment was very P rich in relation to both C and nitrogen (N). The average C : P ratio in fluxes at anoxic accumulation bottoms was 69\ub115, which is well below theRedfield C : P ratio of 106 : 1. At oxic stations, however, the C : P flux ratio was much higher than the Redfield ratio, consistent with well-known P retention mechanisms associated with iron and bacteria in oxidised sediment. Using a benthic mass balance approach, a burial efficiency estimate of 0.2–12% was calculated for the anoxic part of the EGB,which suggests that anoxic Baltic sediments are very efficient in recycling deposited P. Based on the measured fluxes and the average areal extent of anoxic bottoms during years1999–2006, an internal DIP load of 152 kton yr−1 was calculated. This is almost 9 times higher than the average externaltotal phosphorus (TP) supply to the Baltic proper during the same period. This comparison clearly highlights the dominance of internally regenerated P as a DIP source in the Baltic Sea

Catalytic Nanotruss Structures Realized by Magnetic Self-Assembly in Pulsed Plasma

Tunable nanostructures that feature a high surface area are firmly attached to a conducting substrate and can be fabricated efficiently over significant areas, which are of interest for a wide variety of applications in, for instance, energy storage and catalysis. We present a novel approach to fabricate Fe nanoparticles using a pulsed-plasma process and their subsequent guidance and self-organization into well-defined nanostructures on a substrate of choice by the use of an external magnetic field. A systematic analysis and study of the growth procedure demonstrate that nondesired nanoparticle agglomeration in the plasma phase is hindered by electrostatic repulsion, that a polydisperse nanoparticle distribution is a consequence of the magnetic collection, and that the formation of highly networked nanotruss structures is a direct result of the polydisperse nanoparticle distribution. The nanoparticles in the nanotruss are strongly connected, and their outer surfaces are covered with a 2 nm layer of iron oxide. A 10 mu m thick nanotruss structure was grown on a lightweight, flexible and conducting carbon-paper substrate, which enabled the efficient production of H-2 gas from water splitting at a low overpotential of 210 mV and at a current density of 10 mA/cm(2)

Catalytic Nanotruss Structures Realized by Magnetic Self-Assembly in Pulsed Plasma

Tunable nanostructures that feature a high surface area are firmly attached to a conducting substrate and can be fabricated efficiently over significant areas, which are of interest for a wide variety of applications in, for instance, energy storage and catalysis. We present a novel approach to fabricate Fe nanoparticles using a pulsed-plasma process and their subsequent guidance and self-organization into well-defined nanostructures on a substrate of choice by the use of an external magnetic field. A systematic analysis and study of the growth procedure demonstrate that nondesired nanoparticle agglomeration in the plasma phase is hindered by electrostatic repulsion, that a polydisperse nanoparticle distribution is a consequence of the magnetic collection, and that the formation of highly networked nanotruss structures is a direct result of the polydisperse nanoparticle distribution. The nanoparticles in the nanotruss are strongly connected, and their outer surfaces are covered with a 2 nm layer of iron oxide. A 10 mu m thick nanotruss structure was grown on a lightweight, flexible and conducting carbon-paper substrate, which enabled the efficient production of H-2 gas from water splitting at a low overpotential of 210 mV and at a current density of 10 mA/cm(2)

Magnetically Collected Platinum/Nickel Alloy Nanoparticles as Catalysts for Hydrogen Evolution

The hydrogen evolution reaction (HER) is a key process in electrochemical water splitting. To lower the cost and environmental impact of this process, it is highly motivated to develop electrocatalysts with low or no content of noble metals. Here, we report on an ingenious synthesis of hybrid PtxNi1-x electrocatalysts in the form of a nanoparticle-nanonetwork structure with very low noble metal content. The structure possesses important features such as good electrical conductivity, high surface area, strong interlinking, and substrate adhesion, which render an excellent HER activity. Specifically, the best performing Pt0.05Ni0.95 sample demonstrates a Tafel slope of 30 mV dec-1 in 0.5 M H2SO4 and an overpotential of 20 mV at a current density of 10 mA cm-2 with high stability. The impressive catalytic performance is further rationalized in a theoretical study, which provides insight into the mechanism on how such small platinum content can allow for close-to-optimal adsorption energies for hydrogen.Funding Agencies|Vetenskapsraodet [2017-04862, 2017-04380]; Energimyndigheten [45419-1, 50779-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO Mat LiU) [2009 00971]</p