Iron organic speciation determination in rainwater using cathodic stripping voltammetry

A sensitive method using Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) has been developed to determine for the first time iron (Fe) organic speciation in rainwater over the typical natural range of pH. We have adapted techniques previously developed in other natural waters to rainwater samples, using the competing ligand 1-nitroso-2-naphthol (NN). The blank was equal to 0.17 ± 0.05 nM (n = 14) and the detection limit (DL) for labile Fe was 0.15 nM which is 10–70 times lower than that of previously published methods. The conditional stability constant for NN under rainwater conditions was calibrated over the pH range 5.52–6.20 through competition with ethylenediaminetetraacetic acid (EDTA). The calculated value of the logarithm of β′Fe3+3(NN)β′Fe3+(NN)3 increased linearly with increasing pH according to log β′Fe3+3(NN)=2.4±0.6×pH+11.9±3.5log β′Fe3+(NN)3=2.4±0.6×pH+11.9±3.5 (salinity = 2.9, T = 20 °C). The validation of the method was carried out using desferrioxamine mesylate B (DFOB) as a natural model ligand for Fe. Adequate detection windows were defined to detect this class of ligands in rainwater with 40 μM of NN from pH 5.52 to 6.20. The concentration of Fe-complexing natural ligands was determined for the first time in three unfiltered and one filtered rainwater samples. Organic Fe-complexing ligand concentrations varied from 104.2 ± 4.1 nM equivalent of Fe(III) to 336.2 ± 19.0 nM equivalent of Fe(III) and the logarithm of the conditional stability constants, with respect to Fe3+, varied from 21.1 ± 0.2 to 22.8 ± 0.3. This method will provide important data for improving our understanding of the role of wet deposition in the biogeochemical cycling of iron.

Mercury presence and speciation in the South Atlantic Ocean along the 40°S transect

Mercury (Hg) natural biogeochemical cycle is complex and a significant portion of biological and chemical transformation occurs in the marine environment. To better understand the presence and abundance of Hg species in the remote ocean regions, waters of South Atlantic Ocean along 40°S parallel were investigated during UK-GEOTRACES cruise GA10. Total mercury (THg), methylated mercury (MeHg), and dissolved gaseous mercury (DGM) concentrations were determined. The concentrations were very low in the range of pg/L (femtomolar). All Hg species had higher concentration in western than in eastern basin. THg did not appear to be a useful geotracer. Elevated methylated Hg species were commonly associated with low-oxygen water masses and occasionally with peaks of chlorophyll a, both involved with carbon (re)cycling. The overall highest MeHg concentrations were observed in themixed layer (500m) and in the vicinity of the Gough Island. Conversely, DGM concentrations showed distinct layering and differed between the water masses in a nutrient-like manner. DGM was lowest at surface, indicating degassing to the atmosphere, and was highest in the Upper Circumpolar Deep Water, where the oxygen concentration was lowest. DGM increased also in Antarctic Bottom Water. At one station, dimethylmercury was determined and showed increase in region with lowest oxygen saturation. Altogether, our data indicate that the South Atlantic Ocean could be a source of Hg to the atmosphere and that its biogeochemical transformations depend primarily upon carbon cycling and are thereby additionally prone to global ocean change.

Reactivity of Inorganic Mn and Mn Desferrioxamine B with O2, O2–, and H2O2 in 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.

Evaluating The Ribosomal Internal Transcribed Spacer (ITS) as a Candidate Dinoflagellate Barcode Marker

DNA barcoding offers an efficient way to determine species identification and to measure biodiversity. For dinoflagellates, an ancient alveolate group of about 2000 described extant species, DNA barcoding studies have revealed large amounts of unrecognized species diversity, most of which is not represented in culture collections. To date, two mitochondrial gene markers, Cytochrome Oxidase I (COI) and Cytochrome b oxidase (COB), have been used to assess DNA barcoding in dinoflagellates, and both failed to amplify all taxa and suffered from low resolution. Nevertheless, both genes yielded many examples of morphospecies showing cryptic speciation and morphologically distinct named species being genetically similar, highlighting the need for a common marker. For example, a large number of cultured Symbiodinium strains have neither taxonomic identification, nor a common measure of diversity that can be used to compare this genus to other dinoflagellates.

Modelling large-scale CO2 leakages in the North Sea

A three dimensional hydrodynamic model with a coupled carbonate speciation sub-model is used to simulate large additions of CO2into the North Sea, representing leakages at potential carbon sequestration sites. A range of leakage scenarios are conducted at two distinct release sites, allowing an analysis of the seasonal, inter-annual and spatial variability of impacts to the marine ecosystem. Seasonally stratified regions are shown to be more vulnerable to CO2release during the summer as the added CO2remains trapped beneath the thermocline, preventing outgasing to the atmosphere. On average, CO2 injected into the northern North Sea is shown to reside within the water column twice as long as an equivalent addition in the southern North Sea before reaching the atmosphere. Short-term leakages of 5000 tonnes CO2over a single day result in substantial acidification at the release sites (up to -1.92 pH units), with significant perturbations (greater than 0.1 pH units) generally confined to a 10 km radius. Long-term CO2leakages sustained for a year may result in extensive plumes of acidified seawater, carried by major advective pathways. Whilst such scenarios could be harmful to marine biota over confined spatial scales, continued unmitigated CO2emissions from fossil fuels are predicted to result in greater and more long-lived perturbations to the carbonate system over the next few decades.