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\u27s 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\u27s 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\u27 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/Ružić, 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 (Omanović 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

Improved voltammetric methodology for chromium redox speciation in estuarine waters

Chromium is a toxic element naturally present in natural waters whose chemical speciation regulates its cycling, mobility and bioavailability. We present here: 1- an improved analytical method for chromium speciation (Cr(VI) vs Cr(III)) in estuarine samples by catalytic adsorptive cathodic stripping voltammetric (cat-AdCSV) and 2- a study highlighting a significant change of redox speciation during summer and winter. Initial measurements first revealed that surface-active substances (SAS) present in estuarine samples strongly influenced the analytical determination of Cr by partially masking the Cr peak through an increase of the background current. We found that the application of a low negative accumulation potential (−1.65 V) resulted in much better voltammograms compared to those obtained using the usual accumulation potential of −1.0 V. Using humic acid (HA) as a model SAS of natural origin, we show that this negative potential clearly prevents adsorption of SAS on the Hg-electrode surface, which in turns benefits the adsorption of the in-situ formed Cr(III)-DTPA complex and the resulting signal. The optimised method was applied to determine chromium redox speciation and distribution along the 23 km long salinity gradient, well oxygenated, Krka River estuary (Croatia). Cr(VI) was found to be the dominant redox species in both summer and winter, with Cr(III) contribution being lower in summer (up to ∼30%, average of ∼5%) than in winter (up to ∼50%, average of ∼30%). In summer, lower concentrations of Cr(VI) were found in the freshwater end-member (2.5 nM) than in the seawater end-member (4–5 nM), while the opposite trend was found in winter. Hexavalent chromium exhibited a non-conservative behaviour along the salinity gradient for both seasons. Chromium predominantly exists in dissolved phase, and contribution of particles reactive Cr(III) was minor

Identification of dissolved organic matter size components in freshwater and marine environments

Dissolved organic matter (DOM) in the transition zone from freshwater to marine systems was analyzed with a new approach for parameterizing the size distribution of organic compounds. We used size-exclusion chromatography for molecular size analysis and quantified colored DOM (CDOM) on samples from two coastal environments in the Baltic Sea (Roskilde Fjord, Denmark and Gulf of Gdansk, Poland). We applied a Gaussian decomposition method to identify peaks from the chromatograms, providing information beyond bulk size properties. This approach complements methods where DOM is separated into size classes with pre-defined filtering cutoffs, or methods where chromatograms are used only to infer average molecular weight. With this decomposition method, we extracted between three and five peaks from each chromatogram and clustered these into three size groups. To test the applicability of our method, we linked our decomposed peaks with salinity, a major environmental driver in the freshwater-marine continuum. Our results show that when moving from freshwater to low-salinity coastal waters, the observed steep decrease of apparent molecular weight is mostly due to loss of the high-molecular-weight fraction (HMW; >2 kDa) of CDOM. Furthermore, most of the CDOM absorbance in freshwater originates from HMW DOM, whereas the absorbing moieties are more equally distributed along the smaller size range (<2 kDa) in marine samples.Peer reviewe

Electrochemical detection of commercial silver nanoparticles: identification, sizing and detection in environmental media.

The electrochemistry of silver nanoparticles contained in a consumer product has been studied. The redox properties of silver particles in a commercially available disinfectant cleaning spray were investigated via cyclic voltammetry before particle-impact voltammetry was used to detect single particles in both a typical aqueous electrolyte and authentic seawater media. We show that particle-impact voltammetry is a promising method for the detection of nanoparticles that have leached into the environment from consumer products, which is an important development for the determination of risks associated with the incorporation of nanotechnology into everyday products

Nanoparticle impacts show high-ionic-strength citrate avoids aggregation of silver nanoparticles.

Quantitative analytical detection and sizing of silver nanoparticles is achieved by applying the new electrochemical method nanoparticle coulometry. For the first time, tri-sodium citrate is used as both an electrolyte and a nanoparticle stabilizing agent, allowing the individual particles to be addressed

Distribution and chemical speciation of arsenic and heavy metals in highly contaminated waters used for health care purposes (Srebrenica, Bosnia and Herzegovina)

International audienceDetermination of distribution and chemical speciation of arsenic and heavy metals in five acidic springs and in the receiving river near Srebrenica (Bosnia and Herzegovina) was carried out. These waters were used for centuries, and continue to be used, for health-care purposes. The composition and properties of all springs and the river water (after all inputs) resembled that of an acid mine drainage. Very low pH ( 7. Geochemical speciation modelling (PHREEQC and WHAM-VI) revealed that As was mainly present as As(V), and Fe as Fe(III). Complexation of dissolved metals by organic matter was predicted to be significant only for the two river sites with neutral pH

Flood inputs in a Mediterranean coastal zone impacted by a large urban area: Dynamic and fate of trace metals

Trace elements and organic carbon inputs to the Mediterranean sea from an urbanized area (Marseille city) were studied and characterized during flood events. Inputs were brought to the sea by two small coastal rivers whose waters were mixed together and also with treated wastewaters (TWW) just before discharge. The monitoring of the rivers during flood events showed the high temporal dynamics of water flow, suspended particulate matter (SPM), organic carbon and trace metals concentrations, typical of small coastal Mediterranean rivers and requiring an appropriate sampling strategy. Dissolved/particulate partition coefficient (log Kd) in rivers during floods remained quasi-constant for a given trace element, but differed from one element to another according to their affinity toward particles. Because of high SPM concentrations, trace elements were mainly brought to the sea during floods as particles, despite a weaker affinity for particles when compared to baseflow conditions for all studied elements but Pb. If the contribution of TWW dominated the elements baseflow discharge to the coastal zone, rivers outweighed during floods. When discharged to the sea, most trace elements underwent partial desorption in the salinity gradient, especially at highest salinity. Laboratory desorption experiments results were consistent with field data and showed slower desorption kinetics than in baseflow conditions, suggesting that trace elements desorption rates from particles are slower than sedimentation rates. With regard to heavy particles, it results in a potential impact of the sediment on benthic organisms and a possible further desorption after sediment resuspension events. With regard to light particles, it results possible additional desorption during offshore transport

Get more out of your data: a new approach to agglomeration and aggregation studies using nanoparticle impact experiments.

Anodic particle coloumetry is used to size silver nanoparticles impacting a carbon microelectrode in a potassium chloride/citrate solution. Besides their size, their agglomeration state in solution is also investigated solely by electrochemical means and subsequent data analysis. Validation of this new approach to nanoparticle agglomeration studies is performed by comparison with the results of a commercially available nanoparticle tracking analysis system, which shows excellent agreement. Moreover, it is demonstrated that the electrochemical technique has the advantage of directly yielding the number of atoms per impacting nanoparticle irrespective of its shape. This is not true for the optical nanoparticle tracking system, which requires a correction for the nonspherical shape of agglomerated nanoparticles to derive reasonable information on the agglomeration state

Cd transfers during marine sediment resuspension over short and long-term period: Associated risk for coastal water quality

International audienceCadmium (Cd) is a highly toxic metal, regularly monitored uniformly for water quality across 21 Europe, but scarcely for sediments. This study was designed to compare the kinetics of Cd 22 remobilization and the amplitude of its transfers with different marine sediments. The results 23 showed a highly reproducible transfer kinetics. Dissolved Cd was strongly and quickly 24 removed from the dissolved phase (from 5 minutes up to 7 hours). Then, the dissolved Cd 25 concentration increased progressively to reach a maximal value after two weeks of mixing. 26 The influence of the resuspension intensity representing light wind-induced resuspension up 27 to dredging operations was observed after 2 weeks. The intensity of the sediment resuspension 28 clearly impacted the amplitude of Cd remobilization, dissolved Cd ranging from a few ngL-1 29 to few hundreds of ngL-1 , exceeding the maximal dissolved Cd concentration accepted by the 30 European Union Water Framework Directive (WFD-2008/105 32 / EC)