Quantification of Iron in Seawater at the Low Picomolar Range Based on Optimization of Bromate/Ammonia/Dihydroxynaphtalene System by Catalytic Adsorptive Cathodic Stripping Voltammetry

A new analytical protocol for the challenging analysis of total dissolved iron at the low picomolar level in oceanic waters suitable for onboard analysis is presented. The method is based on the revision of the adsorptive properties of the iron/2,3-dihydroxynaphthalene (Fe/DHN) complexes on the hanging mercury drop electrode with catalytic enhancement by bromate ions. Although it was based on a previously proposed reagent combination, we show here that the addition of an acidification/alkalinization step is essential in order to cancel any organic complexation, and that an extra increment of the pH to 8.6-8.8 leads to the definition of a preconcentration-free procedure with the lowest detection limit described up to now. For total dissolved iron analysis, samples were acidified to pH 2.0 in the presence of 30 \u3bcM DHN and left to equilibrate overnight. A 10 mL sample was subsequently buffered to a pH of 3c8.7 in the presence of 20 mM bromate: a 60 s deposition at 0 V led to a sensitivity of 34 nA nM-1 min-1, a 4-fold improvement over previous methods, that translated in a limit of detection of 5 pM (2-20 fold improvement). Several tests proved that a nonreversible reaction in the time scale of the analysis, triggered by the acidification/alkalinization step, was behind the signal magnification. The new method was validated onboard via the analysis of reference material and via intercalibration against flow injection analysis-chemiluminescence on Southern Ocean surface samples

Controls of primary production in two phytoplankton blooms in the Antarctic Circumpolar Current

The Antarctic Circumpolar Current has a high potential for primary production and carbon sequestration through the biological pump. In the current study, two large-scale blooms observed in 2012 during a cruise with R.V. Polarstern were investigated with respect to phytoplankton standing stocks, primary productivity and nutrient budgets. While net primary productivity was similar in both blooms, chlorophyll a –specific photosynthesis was more efficient in the bloom closer to the island of South Georgia (39 °W, 50 °S) compared to the open ocean bloom further east (12 °W, 51 °S). We did not find evidence for light being the driver of bloom dynamics as chlorophyll standing stocks up to 165 mg m-2 developed despite mixed layers as deep as 90 m. Since the two bloom regions differ in their distance to shelf areas, potential sources of iron vary. Nutrient (nitrate, phosphate, silicate) deficits were similar in both areas despite different bloom ages, but their ratios indicated more pronounced iron limitation at 12 °W compared to 39 °W. While primarily the supply of iron and not the availability of light seemed to control onset and duration of the blooms, higher grazing pressure could have exerted a stronger control toward the declining phase of the blooms

Copper complexation by thiol compounds in estuarine waters

The stability of copper complexes with thiol substances in estuarine waters was determined for the first time using a new procedure based on cathodic stripping voltammetry (CSV). The free thiol concentration was monitored during titrations with copper in the presence of a competing ligand salicylaldoxime (SA); concentrations of copper-complexing ligands and conditional stability constants were determined simultaneously but independently. The decrease in the free thiol concentration with increasing copper concentration was used as an independent measure of the thiol-complex stability. The conditional stability constant of the thiol complexes (log KCuThiol') was between 12.3 and 14.1, and decreased with increasing salinity. The copper complexing titrations were found to fit to two complexing ligands: L1 with concentrations between 10 and 33 nM, and L2 between 14 and 300 nM. The complex stability of most of the thiols was similar to that of CuL2. Titrations at different detection windows showed a shift in the thiol complex stability suggesting that a second thiol species was present. It is therefore possible that L1 is also a thiol species. The estimated thiol concentrations can account for up to half of the total ligand concentration at low to intermediate salinities and for all of the ligands at high salinities

Towards a zero-blank, preconcentration-free voltammetric method for iron analysis at picomolar concentrations in unbuffered seawater

[eng] A method with negligible blank values for the determination of total iron at the ultratrace level in seawater has been optimized and validated exploring for the first time the performance and limitations of Adsorptive Cathodic Stripping Voltammetry (AdCSV) in non-buffered solutions. The method is based on the CSV determination of the Fe-dihydroxynaphthalene (DHN) complex using atmospheric oxygen to catalytically enhance the signal via hydrogen peroxide formation at the electrode/solution interface. The accumulation of hydroxyl ions, the by-product of the hydrogen peroxide formation, increased the pH in the diffusion layer in the absence of buffer bringing it to 9, the optimum for the analytical performance of the method. Voltammograms in UV digested seawater showed no stability or reproducibility drawbacks. The negligible, lower than 5 pM, blank level, is due to the simplicity of the procedure requiring no sample manipulation and a maximum of three reagents only, necessarily the ligand DHN and a base only for those samples previously acidified to raise the pH to circumneutral values (here HCl and NH3 according to common trace metals protocols). These reagents do not require cleaning before use, further simplifying the overall procedure. Analysis of seawater previously acidified at pH ~1.5 with HCl and neutralized with ammonia showed interferences due to the buffering properties of the NH3/NH4Cl couple and the transient formation of a volatile electroactive interference that can be easily removed by simply allowing a set time before analysis. In general, the proposed method features several advantages, including high sample throughput, an excellent limit of detection at 12 pM, minimum sample handling (no preconcentration or change of matrix is required), cost effectiveness and mainly a negligible blank. The method was successfully validated using open ocean consensus samples (SAFe D2 and S)

Cadmium determination in natural water samples with an automatic multisyringe flow injection system coupled to a flow-through screen printed electrod

Heavy metals, as cadmium, attract a rising attention in environmental studies due to their increasing release by human activities and acute toxicity. In situ analytical methods are needed to minimize current uncertainties caused by the transport and conservation of samples. Here, we present the completely automatic determination of Cd in natural waters using a newly developed screen printed electrode sensor (SPE), inserted in a homemade purpose-built flow cell coupled to a Multi-Syringe Flow Injection Analysis system (MSFIA). The working electrode of SPEs was constituted by a carbon film modified with Nafion. Cd was plated on an in situ bismuth film and determined using Square Wave Anodic Stripping Voltammetry. Different chemical conditions of deposition and stripping were studied. A sample/acetic buffer mixture was found to be a well suited medium to form the Bi film and perform the analysis. Cd was quantified via calibration by on line standard additions. The limit of detection was found to be 0.79 g L−1, well below the limit stipulated by the European directive (5 g L−1). Good sample throughput (14 h−1) and low consumption of reagent and sample (1.3 mL) were also obtained in line with previous works in Cd flow analysis

From the origin of Feces - The impact of krill and salp fecal pellets on iron chemistry and iron bioavailability to Southern Ocean phytoplankton

The Southern Ocean is considered to be a major player in the climate system of our planet while being extremely sensitive to climate change itself. The pelagic Southern Ocean is limited by the bioavailability of iron. Zooplankton has a large impact on the remineralization of iron in the water column and thereby an important influence on primary production. Indications exist that due to increasing water temperatures in the course of climate change, vast areas of the Southern Ocean might shift from a krill to a salp-dominated community. Since the degree of iron remineralization is dependent on the taxonomic group of zooplankton, we investigated the different impacts that salp and krill fecal pellets have on iron chemistry and its bioavailability to Southern Ocean phytoplankton, during a Polarstern cruise in spring 2018. We incubated salp and krill fecal pellet material in Antarctic low-iron water without phytoplankton. In a second step, a concentrated natural phytoplankton community was added into the thusly preconditioned water and for the first time ever the iron uptake into the living cells, in respect to the fecal pellet type that acted as an iron source, was determined. Our results indicate that iron released from salp fecal pellets into the seawater was significantly more bioavailable to phytoplankton than iron from krill fecal pellets, since phytoplankton picked up 0.28 nM Fe d-1 from water treated with salp fecal pellets and 0.16 nM Fe d-1 from water treated with krill fecal pellets. These results demonstrate that salps might actually play a role in stimulating phytoplankton growth in the Southern Ocean, thusly influencing the biological carbon pump

Interpretation of complexometric titration data: an intercomparison of methods for estimating models of trace metal complexation by natural organic ligands

With the common goal of more accurately and consistently quantifying ambient concentrations of free metal ions and natural organic ligands in aquatic ecosystems, researchers from 15 laboratories that routinely analyze trace metal speciation participated in an intercomparison of statistical methods used to model their most common type of experimental dataset, the complexometric titration. All were asked to apply statistical techniques that they were familiar with to model synthetic titration data that are typical of those obtained by applying state-of-the-art electrochemical methods – anodic stripping voltammetry (ASV) and competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE-ACSV) – to the analysis of natural waters. Herein, we compare their estimates for parameters describing the natural ligands, examine the accuracy of inferred ambient free metal ion concentrations ([Mf]), and evaluate the influence of the various methods and assumptions used on these results.The ASV-type titrations were designed to test each participant's ability to correctly describe the natural ligands present in a sample when provided with data free of measurement error, i.e., random noise. For the three virtual samples containing just one natural ligand, all participants were able to correctly identify the number of ligand classes present and accurately estimate their parameters. For the four samples containing two or three ligand classes, a few participants detected too few or too many classes and consequently reported inaccurate ‘measurements’ of ambient [Mf]. Since the problematic results arose from human error rather than any specific method of analyzing the data, we recommend that analysts should make a practice of using one's parameter estimates to generate simulated (back-calculated) titration curves for comparison to the original data. The root–mean–squared relative error between the fitted observations and the simulated curves should be comparable to the expected precision of the analytical method and upon visual inspection the distribution of residuals should not be skewed.Modeling the synthetic, CLE-ACSV-type titration dataset, which comprises 5 titration curves generated at different analytical windows or levels of competing ligand added to the virtual sample, proved to be more challenging due to the random measurement error that was incorporated. Comparison of the submitted results was complicated by the participants' differing interpretations of their task. Most adopted the provided ‘true’ instrumental sensitivity in modeling the CLE-ACSV curves, but several estimated sensitivities using internal calibration, exactly as is required for actual samples. Since most fitted sensitivities were biased low, systematic error in inferred ambient [Mf] and in estimated weak ligand (L2) concentrations resulted.The main distinction between the mathematical approaches taken by participants lies in the functional form of the speciation model equations, with their implicit definition of independent and dependent or manipulated variables. In ‘direct modeling’, the dependent variable is the measured [Mf] (or Ip) and the total metal concentration ([M]T) is considered independent. In other, much more widely used methods of analyzing titration data – classical linearization, best known as van den Berg/Ruži?, and isotherm fitting by nonlinear regression, best known as the Langmuir or Gerringa methods – [Mf] is defined as independent and the dependent variable calculated from both [M]T and [Mf]. Close inspection of the biases and variability in the estimates of ligand parameters and in predictions of ambient [Mf] revealed that the best results were obtained by the direct approach. Linear regression of transformed data yielded the largest bias and greatest variability, while non-linear isotherm fitting generated results with mean bias comparable to direct modeling, but also with greater variability.Participants that performed a unified analysis of ACSV titration curves at multiple detection windows for a sample improved their results regardless of the basic mathematical approach taken. Overall, the three most accurate sets of results were obtained using direct modeling of the unified multiwindow dataset, while the single most accurate set of results also included simultaneous calibration. We therefore recommend that where sample volume and time permit, titration experiments for all natural water samples be designed to include two or more detection windows, especially for coastal and estuarine waters. It is vital that more practical experimental designs for multi-window titrations be developed.Finally, while all mathematical approaches proved to be adequate for some datasets, matrix-based equilibrium models proved to be most naturally suited for the most challenging cases encountered in this work, i.e., experiments where the added ligand in ACSV became titrated. The ProMCC program (Omanovi? et al., this issue) as well as the Excel Add-in based KINETEQL Multiwindow Solver spreadsheet (Hudson, 2014) have this capability and have been made available for public use as a result of this intercomparison exercise