A new windows-based, user friendly program (ProMCC) for (i) the determination of metal complexation parameters (ligand concentration (L) and conditional stability constants (K′)) and for (ii) ...theoretical simulation of metal complexometric titration, assuming discrete ligand model, is developed. Although primarily intended for treatment of experimental data obtained either by anodic stripping voltammetry (ASV) or competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-AdCSV), it could manage titration-type data of other techniques (e.g. ISE, sorption isotherm). Currently, the program is capable to process (fit and/or simulate) titration data up to three discrete ligand classes. Procedure for adjustment of “true” analytical sensitivity incorporated in ProMCC was found to provide reasonably good estimates of sensitivity either for one-ligand or two-ligand system. The particular feature of ProMCC is that it incorporates two complementary fitting methodologies: (1) a non-linear fitting of conventional linearized transformations (e.g. Ružić/Van Den Berg, Langmuir/Gerringa) and (2) a “complete complexation model” — a matrix based optimization of mass balance equations. Comparison test of different non-linear fitting modes and titration types revealed that a slight underestimation of ligand concentration and overestimation of conditional stability constant may occur if titration is performed in logarithmic mode, mainly due to unfavorable noise distribution. An advantage of implemented “complete complexation model” fitting mode is that it allows simultaneous analysis of titrations obtained at multiple detection windows as unified dataset (multi-detection window approach), providing complexation parameters for up to three ligand classes. A new alternative “RAL-approach” in analyzing complexometric titrations obtained at multiple detection windows for copper–salicylaldoxime (Cu–SA) system is suggested. It assumes that the analytical sensitivity is changing along the titration curve respecting the true speciation of Cu–SA in sample. An adapted empirical equation for calculation of relative intensity (RAL) is proposed. Flexibility in adjusting parameters, immediate graphical feedback and visualizations make ProMCC handy for treatment of large set of experimental data, and a tool for research in refinement of the methods of metal complexing capacity determination which is continuously improving.
•A new user-friendly tool for analysis of complexometric titration data is developed.•Non-linear and “complete complexation model” fitting modes were incorporated.•An efficient method for correction of true sensitivity was validated.•Simultaneous analysis of multiple analytical windows (CLE-AdCSV) as unified dataset.•An alternative “RAL-approach” for Cu–SA system is proposed.
Fluorescence excitation-emission matrices (EEMs) are a useful tool in aquatic sciences for monitoring and studying the biogeochemistry of organic matter in natural waters and engineered systems. Yet, ...the interpretation of the wealth of information available in EEMs requires the use of appropriate software. Existing software tools for the analysis of EEMs, offered by instrument producers, have limited treatment capabilities, while other freely available tools are based on the MATLAB or R programming languages, which require a certain level of programming skills and a pre-installation of MATLAB or R. Here, we present TreatEEM, the first non-commercial, stand-alone Windows-based software tool that provides comprehensive treatment of EEMs. Its greatest advantage is its user-friendly and interactive graphical user interface, providing a convivial and responsive graphical feedback on any action performed on either a single spectrum (recorded at one excitation wavelength) or EEM. The capabilities of TreatEEM, including (a) basic EEM treatment, such as simple inner filter correction, scatter removal, blank subtraction, Raman normalisation, smoothing, drift alignment etc., (b) extraction of useful parameters for DOM characterisation (Coble peaks and fluorescence indices) and (c) preparation of data for PARAFAC analysis plus presentation/manipulation of obtained PARAFAC components, are described in detail, along with a basic theoretical background on these most commonly used treatment steps of EEMs.
Copper (Cu) is a bio-essential trace element that is of concerns due to its potential toxicity at concentrations commonly encountered in coastal waters. Here, we revisit the applicability of Cu(II) ...ion selective electrode (Cu-ISE) based on a jalpaite membrane for the measurement of Cufree in seawater. At high total Cu concentration (>0.1 mM), (near)Nernstian slope was obtained and determination of Cufree down to fM levels was possible. However, this slope decreases with decreasing total Cu concentration (e.g. 7 mV/decade at 15 nM total Cu) making the use of a common single calibration approach unreliable. To solve this problem, we carried out several calibrations at different levels of total Cu (15 nM - 1 mM) and ethylenediamine (EN: 5 μM - 15 mM) and fitted the calibration parameters (slope and intercept) as a function of total Cu using the Gompertz function (a meta-calibration approach). The derived empirical equations allowed the determination of Cufree at any total Cu concentration above 20 nM (determination of Cufree at lower total Cu levels is prevented by the dissolution of the electrode). We successfully tested this meta-calibration approach in UV digested seawater in presence of a synthetic ligand (EN), isolated natural organic matter (humic acid, HA) and in a natural estuarine sample. In each case, our meta-calibration approach provided a good agreement with modeled speciation data (Visual MINTEQ), while standard single approach failed. We provide here a new method for the direct determination of the free Cu ion concentration in seawater at levels relevant for coastal waters.
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•Revised application of Cu-ISE for determination of Cufree in marine waters.•Electrode slope strongly depends on the total Cu concentration.•A meta-calibration approach should be used for reliable applications.•Method suitable for Cu speciation in marine waters above 20 nM of total Cu.•fM concentrations range easily reachable in ligand buffered solutions.
Humic substances (HS) in natural waters can be determined with a new, simple and sensitive method based on their influence on the background current in a differential pulse - adsorptive cathodic ...stripping voltammetry. The proposed method, termed PB-HS (pulsed background - humic substances) is discussed in detail, including its application in natural samples from the Krka River estuary. The method was additionally compared with absorbance measurements as well as with the typical electrochemical HS quantification in natural waters based on HS complexation with molybdenum (Mo). A good correlation between methods was observed, with PB-HS showing slightly better sensitivity to humic compounds than classical spectrophotometry. Higher HS concentrations measured with the Mo-method may be due to the enhanced hydrophobicity reached at pH 2 that is required by the method. Advantages of the proposed PB-HS method, compared to existing voltammetric methods for HS quantification, are that it does not require any reagent addition (except buffer) and that it can be used at the natural pH of water as well as in a wide salinity range, which is crucial for its application in estuarine waters.
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•Simple and sensitive method for determination of humic substances in natural waters.•Background current increases as a function of humic substances concentration.•Resolving the humic fraction from the mixed pool of surface-active substances.•The proposed method valid in a wide salinity and pH range.•Decreased abundance of humic substances with increased salinity in the Krka estuary.
Copper (Cu) has a narrow range between optimal concentrations as a micronutrient critical for phytoplankton growth and concentrations potentially toxic to living organisms. This sensitivity indicates ...an ecosystem vulnerability that threatens not only nature but also human health due to bioaccumulation. An important source of elevated Cu concentrations in coastal environments are biocides used as antifouling protection on ships. A pilot study conducted in the Marine Protected Area (MPA) of the Krka Estuary (Croatia) over a period of 16 months investigated the relationship between ship traffic and Cu concentrations. The aim was to contribute to more informed environmental management by assessing the associated risks. In the study presented here, Cu concentrations were monitored, analyzed, and correlated with vessel traffic. Observations revealed that the seasonal increase in maritime traffic caused by nautical tourism was associated with an increase in Cu concentrations of more than five times, posing a toxicity risk to the environment. In order to understand the distribution of copper emissions, a mapping of maritime traffic was carried out by counting transits, radar imagery, and drone photography. This approach has proven sufficient to identify the potential risks to the marine environment and human health, thus providing an effective assessment tool for marine stakeholders.
Recent advancements in electroanalytical methodologies for the analysis of trace metals in natural waters are summarized. The research and technological progress was centered on the development of ...new “green” sensors, as well as well-established electroanalytical methods, comprising improvements in sensitivity, robustness, versatility, disposability and reliability.
•Performance of electroanalytical techniques for trace metals analysis reviewed.•Recent improvements of methodologies for monitoring of trace metals summarized.•Current approaches for trace metal speciation in natural waters highlighted.
To study the processes that govern the post-depositional mobility of metals in the estuarine sediment, five sediment cores were sampled in the Krka River estuary (Croatia). The obtained concentration ...ranges in the pore water were 0.057–49.7 μM for Fe, 0.310–100 μM for Mn, 0.068–26.8 nM for Co, 0.126–153 nM for Cu, 11.5–2793 nM for Zn, 0.222–31.3 nM for Pb, 4.09–59.4 nM for U, 38.8–2228 nM for Mo, and 0.065–2.29 nM for As. The vertical distribution of metals in the dissolved and solid fraction of the sediment, coupled with other diagenetic tracers (e.g., dissolved sulphide), demonstrate the importance of early diagenetic reactions, in particular Fe and Mn oxyhydroxide and sulphate reduction, for the cycling of metals in the sediment. The redox zonation in the sediment was compressed, and the suboxic zone occurs immediately below the sediment–water interface. The estimated benthic fluxes in the estuary were 5220 kg y−1 for Fe, 27,100 kg y−1 for Mn, 6.00 kg y−1 for Co, 20.5 kg y−1 for Cu, 5.16 kg y−1 for Pb, 111 kg y−1 for Mo, and 87.3 kg y−1 for As. The riverine input was more important than the benthic flux, except in the case of Mn and Fe.
The determination of trace elements using stripping voltammetry may be seriously affected by the presence of intensive matrix background or interfering peaks, leading to poorer detection limits ...and/or inaccurate quantitative results. In this work, we have tested the use of signal transformation (e.g., second derivative) in the analysis of platinum in seawater and sediment digests by means of catalytic adsorptive stripping voltammetry. In natural waters, the limit of detection of Pt is affected by a broad background wave due to the formazone complex used in the sample matrix for its determination, while in sediment digests, the Pt peak may be interfered with due to the presence of elevated concentrations of Zn, affecting the accuracy of the determination. Results applying second derivative signal transformation revealed a significant improvement (2–3-fold) of the detection limit in water due to the minimization of background effects, therefore allowing shorter accumulation times and faster determinations. In the presence of interfering peaks, the inaccuracy resulting from erroneous baseline selection in the original signal is eliminated when the second derivative is used. Signal processing should be considered as a useful tool for other voltammetric methodologies where more accurate or faster determinations are needed.
The method of competitive ligand exchange followed by adsorptive cathodic stripping voltammetry (CLE-AdCSV) allows for the determination of dissolved iron (DFe) organic speciation parameters, i.e., ...ligand concentration (LFe) and conditional stability constant (log KFe′Lcond). Investigation of DFe organic speciation by CLE-AdCSV has been conducted in a wide range of marine systems, but aspects of its application pose challenges that have yet to be explicitly addressed. Here, we present a set of observations and recommendations to work toward establishing best practice for DFe organic speciation measurements using the added ligand salicylaldoxime (SA). We detail conditioning procedures to ensure a stable AdCSV signal and discuss the processes at play during conditioning. We also present step-by-step guidelines to simplify CLE-AdCSV data treatment and interpretation using the softwares ECDSoft and ProMCC and a custom spreadsheet. We validate our application and interpretation methodology with the model siderophore deferoxamine B (DFO-B) in a natural seawater sample. The reproducibility of our application and interpretation methodology was evaluated by running duplicate titrations on 19 samples, many of which had been refrozen prior to the duplicate analysis. Nevertheless, 50% of the duplicate analyses agreed within 10% of their relative standard deviation (RSD), and up to 80% within 25% RSD, for both LFe and log KFe′Lcond. Finally, we compared the sequential addition and equilibration of DFe and SA with overnight equilibration after simultaneous addition of DFe and SA on 24 samples. We found a rather good agreement between both procedures, with 60% of samples within 25% RSD for LFe (and 43% of samples for log KFe′Lcond), and it was not possible to predict differences in LFe or log KFe′Lcond based on the method applied, suggesting specific association/dissociation kinetics for different ligand assemblages. Further investigation of the equilibration kinetics against SA may be helpful as a potential way to distinguish natural ligand assemblages.
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