Description: Superoxide (O−2) 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 O−2 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 O−2 into H2O2 and O2, involve reactions with Cu, Mn, and DOM. In productive regions of the ocean, the reaction between DOM and O−2 can be a significant sink for O−2. Thus, DOM is a key component of both the formation and decomposition of O−2 and formation of H2O2. In the present work we examined the relationships between O−2 decay rates and parameters associated with chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) by using the thermal O−2 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 O−2 in the Mauritanian Upwelling, constituting on average 58 ± 13% of the O−2 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 O−2 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.

Description: 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 yes 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.

Description: The oceans are by far the largest global reservoir of carbon that is available on climate relevant timescales (〈 1000 yrs). A fraction of this oceanic carbon pool, comparable in magnitude with the CO2 inventory of today’s atmosphere, is transformed via biological assimilation of inorganic carbon into dissolved or particulate organic material within the sun-lit surface ocean. Subsequently this material can be respired, returning to the ocean as CO2, or it can sink to the sediments and this forms the basis of the ‘biological pump’. The efficiency of this pump is limited by the availability of nutrients, which are essential prerequisites for the growth of phytoplankton. We now know that vast areas of the surface ocean have extremely low nutrient concentrations limiting productivity. For instance, in the subtropical oceanic gyres, which comprise more than 40% of the Earth’s surface, the macronutrients nitrate, nitrite, ammonia and phosphate are depleted to trace levels which limit phytoplankton abundance so strongly such that the term “oceanic desert” was coined for these regions.