Maija Heller

Superoxide decay kinetics in the southern ocean.

Measurements of superoxide (O(2)(-)) reaction kinetics were made during a transect with the research icebreaker Polarstern (ANT24-3) in the Antarctic through the Drake Passage in austral autumn 2008. Our sampling strategy was designed to investigate the sinks of superoxide in Polar waters; principally through reactions with dissolved organic matter (DOM) or metals (copper and iron). We modified an existing chemiluminescence flow injection system using methyl Cypridina luciferin analog (MCLA) for the detection of O(2)(-) and added O(2)(-) using KO(2) as the source. Our results indicate that O(2)(-) in ambient seawater had a half-life ranging from 9.3 to 194 s. DTPA additions to seawater, to remove the effects of reactions with metals, revealed O(2)(-) decay rates consistent with a second order reaction, indicating that the dismutation reaction dominated and that reactions with DOM were not significant. Titrations of seawater by the addition of nanomolar amounts of iron or copper revealed the importance of organic chelation of Fe and/or Cu in controlling the reactivity with O(2)(-). Throughout the water column reactions with Cu appeared to be the major sink for superoxide in the Southern Ocean. This new strategy suggests an alternative approach for speciation measurements of Fe and Cu in seawater.

Application of a superoxide (O2−) thermal source (SOTS-1) for the determination and calibration of O2− fluxes in seawater

Superoxide (O(2)(-)) is an important short lived transient reactive oxygen species (ROS) in seawater. The main source of O(2)(-) in the ocean is believed to be through photochemical reactions though biological processes may also be important. Sink terms for O(2)(-) include redox reactions with bioactive trace metals, including Cu and Fe, and to a lesser extent dissolved organic matter (DOM). Information on the source fluxes, sinks and concentration of superoxide in the open ocean are crucial to improving our understanding of the biogeochemical cycling of redox active species. As O(2)(-) is a highly reactive transient species present at low concentrations it is not a trivial task to make accurate and precise measurements in seawater. In this study we developed the appropriate numerical analysis tools and investigated a number of superoxide sources and methods for the purposes of calibrating O(2)(-) concentrations and/or fluxes specifically in seawater. We found the superoxide thermal source bis(4-carboxybenzyl)hyponitrite (SOTS)-1 easy to employ as a reliable source of O(2)(-) which could be successfully applied in seawater. The thermal decomposition of SOTS-1 in seawater was evaluated over a range of seawater temperatures using both a flux based detection scheme developed using two spectrophotometric methods: (i) 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) and (ii) ferricytochrome c (FC), or a concentration based detection scheme using a chemiluminescence flow injection method based on the Cypridina luciferin analog 2-methyl-6-(p-methoxyphenyl)3-7-dihydroimidazol[1,2-alpha]pyrazin-3-one (MCLA) as reagent. Our results suggest SOTS-1 is the best available O(2)(-) source for determining concentrations and fluxes, all detection systems tested have their pros and cons and the choice of which to use depends more on the duration and type of experiment that is required.

The Importance of Kinetics and Redox in the Biogeochemical Cycling of Iron in the Surface Ocean

It is now well established that Iron (Fe) is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model and/or its successor the biotic ligand model. Similarly most field work on iron biogeochemistry generally consists of a single profile which is in essence a “snap-shot” in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, dry and wet, are also important perturbations to iron cycling as they bring in new iron to the system and alter the equilibrium between iron species and phases. Here we utilize new field data collected in the open ocean on the complexation kinetics of iron in the surface ocean to identify the important role of weak iron binding ligands (i.e., those that cannot maintain iron in solution indefinitely at seawater pH: αFeL < αFe′) in allowing transient increases in iron solubility in response to iron deposition events. Experiments with the thermal O2- source SOTS-1 also indicate the short term impact of this species on iron solubility also with relevance to the euphotic zone. This data highlights the roles of kinetics, redox, and weaker iron binding ligands in the biogeochemical cycling of iron in the ocean.

Pathways of superoxide (O2(-)) decay in the Eastern Tropical North Atlantic.

Superoxide (O2(-): IUPAC name dioxide (•1-)) is an important transient reactive oxygen species (ROS) in the ocean formed as an intermediate in the redox transformation of oxygen (O2) into hydrogen peroxide (H2O2) and vice versa. This highly reactive and very short-lived radical anion can be produced both via photochemical and biological processes in the ocean. In this paper we examine the decomposition rate of O2(-) throughout the water column, using new data collected in the Eastern Tropical North Atlantic (ETNA) Ocean. For this approach we applied a semi factorial experimental design to identify and quantify the pathways of the major identified sinks in the ocean. In this work we occupied six stations, two on the West African continental shelf and four open ocean stations, including the CVOO time series site adjacent to Cape Verde. Our results indicate that, in the surface ocean impacted by Saharan aerosols and coastal sediment resuspension, the main decay pathways for superoxide are via reactions with Mn(II) and organic matter.

Basin scale survey of marine humic fluorescence in the Atlantic: Relationship to iron solubility and H2O2

Iron (Fe) is a limiting nutrient for phytoplankton productivity in many different oceanic regions. A critical aspect underlying iron limitation is its low solubility in seawater as this controls the distribution and transport of iron through the ocean. Processes which enhance the solubility of iron in seawater, either through redox reactions or organic complexation, are central to understanding the biogeochemical cycling of iron. In this work we combined iron solubility measurements with parallel factor (PARAFAC) data analysis of CDOM fluorescence along a meridional transect through the Atlantic (PS ANT XXVI-4) to examine the hypothesis that marine humic fluorescence is a potential proxy for iron solubility in the surface ocean. PARAFAC analysis revealed 4 components, two humic like substances and two protein-like. Overall none of the 4 components were significantly correlated with iron solubility, though humic-like components were weakly correlated with iron solubility in iron replete waters. Our analysis suggests that the ligands responsible for maintaining iron in solution in the euphotic zone are sourced from both remineralisation processes and specific ligands produced in response to iron stress and are not easily related to bulk CDOM properties. The humic fluorescence signal was sharply attenuated in surface waters presumably most likely due to photo bleaching, though there was only a weak correlation with the transient photo product H2O2, suggesting longer lifetimes in the photic zone for the fluorescent components identified here. Key Points: - humic-like components correlated with Fe solubility in iron repleted water - ligands are sourced from remineralisation processes produced to Fe stress - humic flu sharply attenuated in surface waters, but only weak corr. with H2O2

Reactivity of inorganic Mn and Mn Desferrioxamine B with O2, O2-and H2O2in seawater

Manganese (Mn) is a required element for oceanic phytoplankton as it plays a critical role in photosynthesis, through its unique redox chemistry, as the active site in photosystem II, and in enzymes that act as defenses against reactive oxygen species (ROS), most notably for protection against superoxide (O2(-)), through the action of superoxide dismutase (SOD), and against hydrogen peroxide (H2O2) via peroxidases and catalases. The distribution and redox speciation of Mn in the ocean is also apparently controlled by reactions with ROS. Here we examine the connections between ROS and dissolved Mn species in the upper ocean using field and laboratory experimental data. Our results suggest it is unlikely that significant concentrations of Mn(III) are produced in the euphotic zone, as in the absence of evidence for the existence of strong Mn(III) ligands, Mn(II) reacts with O2(-) to form the short-lived transient manganous superoxide, MnO2(+), which may react rapidly with other redox species in a manner similar to O2(-). Experiments with the strong Mn(III) chelator, desferrioxamine B (DFB), in seawater indicated that the Mn(III) species are unlikely to form, as formation of the precursor Mn(II) complex is hindered due to the stability of the Ca complex with DFB.

Identifying the sources and sinks of CDOM/FDOM across the Mauritanian Shelf and their potential role in the decomposition of superoxide (O2- )

Superoxide (O2-) is a short lived reactive oxygen species (ROS) formed in seawater by photochemical or biological sources, it is important in the redox cycling of trace elements and organic matter in the ocean. The photoproduction of O2- is now thought to involve reactions between O2 and reactive reducing (radical) intermediates formed from dissolved organic matter (DOM) via intramolecular reactions between excited singlet state donors and ground-state acceptors (Zhang et al., 2012). In seawater the main pathways identified for the decomposition of O2- into H2O2 and O2, involve reactions with Cu, Mn and DOM. In productive regions of the ocean, the reaction between DOM and O2- can be a significant sink for O2-. Thus DOM is a key component of both the formation and decomposition of O2- and formation of H2O2. In the present work we examined the relationships between O2- decay rates and parameters associated with chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) by using the thermal O2- source SOTS-1. Filtered samples (0.2 µm) were run both in the presence, and absence, of the metal chelator diethylenetriaminepentaacetic acid (DTPA) to determine the contribution from DOM. Samples were collected along a transect across the continental shelf of the Mauritanian continental shelf during a period of upwelling. In this region we found that reactions with DOM, are a significant sink for O2- in the Mauritanian Upwelling, constituting on average 58 ± 13 % of the O2- loss rates. Superoxide reactivity with organic matter showed no clear correlation with bulk CDOM or FDOM properties (as assessed by PARAFAC analysis) suggesting that future work should concentrate at the functional group level to clearly elucidate which molecular species are involved as bulk properties represent a wide spread of chemical moieties with different O2- reactivities. Analysis of FDOM parameters indicates that many of the markers used previously for terrestrial sources of DOM and FDOM are called into question as marine sources exist. In particular recent work (Rico et al., 2013) indicates that algal species may also produce syringic, vanillic and cinnamic acids, which had previously been ascribed solely to terrestrial vegetation.

Utilizing Radioisotopes for Trace Metal Speciation Measurements in Seawater

The chemical speciation of trace metals in seawater is of critical importance to studies in marine biogeochemistry; as such information is essential for interpreting and understanding the chemical reactivity of trace metals in the environment.