Seasonal cycle of copper speciation in Gullmar Fjord, Sweden

The chemical speciation of dissolved Cu was investigated by voltammetric methods in Gullmar Fjord, Sweden, over the course of a year from September 1996 until August 1997. Sampling was carried out on a roughly monthly basis, with an intensive survey carried out in May 1997. Surface water temperatures ranged from 21 to 22°C, whereas bottom waters in the fjord were approximately 6°C throughout. Macronutrient concentrations in the fjord during the period of the survey were investigated independently by the Göteborgs och Bohus läns Vattenvårdsförbund (Water Quality Association of Göteborg and Bohus). Surface phosphate concentrations were highest in early spring with low levels ( 12.5) were not detected during the winter or early spring and could be related to the temperature-related seasonal appearance of the cyanobacterium Synechoccocus in these waters. The appearance of the strong Cu ligands led to a decrease in the concentration of free copper, resulting in a seasonal cycle for free copper in the fjord. This is the first study to examine Cu speciation over an annual cycle in a coastal environmen

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

Application of cross-flow filtration for determining the solubility of iron species in open ocean seawater

Measurements of soluble iron species (organic and inorganic) are important for understanding the transport of iron within the ocean and its bioavailability. Recent developments in ultrafiltration equipment and analytical detection techniques for low level Fe determination has turned the spotlight on obtaining data on soluble iron species. However there have, until now, been few studies that have characterized the performance of an ultrafiltration system with respect to well described soluble iron complexes. In the present work, we describe a methodological study characterizing the behavior of soluble and colloidal iron species in seawater by combining a crossflow ultrafiltration system (Vivaflow 50TM) with a radioisotope (55Fe). During this study, we were able to maintain excellent mass balances by including all components: not only the solution phases (retentate and permeate) but wall-adsorbed and filter-adsorbed iron, which were recovered by an acid-rinsing step. Wall and filter adsorption were unavoidable when solutions were saturated with respect to Fe'. However in undersaturated solutions, such as with an excess of desferrioxamine B, wall and filter adsorption were minimized, indicating that these effects should be slight for natural samples where iron-binding ligands are in excess. Our results have important implications for the use of ultrafiltration membranes for open ocean iron biogeochemical studies

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