Competitive Ligand Exchange-adsorptive Stripping Voltammetry Research Articles

Speciation study of aluminium in beverages by Competitive Ligand Exchange–Adsorptive Stripping Voltammetry

Competitive Ligand Exchange-Adsorptive Stripping Voltammetry (CLE-AdSV) was used for determining the speciation of aluminium in commonly consumed beverages (water, tea, infusion, coffee, orange juice, tomato juice, beer and red wine). Aluminium determination involves the adsorption of Al-complexes with the ligand cupferron onto a hanging mercury drop electrode. All samples were studied at pH 6.5 with an accumulation step at -0.60 V (all potential values in the paper are given versus the Ag/AgCl, [KCl]=3 M reference electrode) during 60 s, and a final cupferron concentration of 4 × 10(-4)M. These conditions were used to establish (i) the concentration of electro-labile aluminium, (ii) the range of ligand concentrations and (iii) the conditional stability constants of beverage samples using titration procedures. The results based on Ruzic plots were compared to computer simulation with Visual MINTEQ. This comparison suggests that labile monomeric Al-forms and soluble organic complexes of low molecular weight can be quantified by the CLE-AdSV procedure. Overall the relative uncertainties on the determination of the electro-active Al fraction and the complexing parameters, i.e., concentration and conditional stability constant of natural ligands in the samples, are less than 15%. Thanks to these results, information on Al bioavailability in beverages was collected and discussed. This study also illustrates the value of computer simulations when complex, time-consuming voltammetric techniques are applied.

Speciation of Co(II) and Ni(II) in Anaerobic Bioreactors Measured by Competitive Ligand Exchange−Adsorptive Stripping Voltammetry

Competitive ligand exchange-adsorptive stripping voltammetry is applied to speciation analysis of dissolved Ni(II) and Co(II) in an anaerobic bioreactor and similar batch media. Co and Ni speciation in these media can be measured down to concentration levels of ca. 1 nM. Sulfide interference is avoided via removal as H2S. In methanogenic bioreactors, up to 95% of the dissolved Co and Ni is present in strongly bound forms, with complex stabilities > or =10(8)-10(9) and 10(7)-10(8) mol(-1) L, respectively. In effluent from sulfate-reducing bioreactors, Co is also found to be present in a strongly bound form, and up to micromolar levels of strongly complexing excess ligand was detected. The predominant presence of Co and Ni in strong complexes, with concomitant low free dissolved concentrations, is significant for limitation by these elements in anaerobic bioreactors.

Kinetic Limitations in Measuring Stabilities of Metal Complexes by Competitive Ligand Exchange-Adsorptive Stripping Voltammetry (CLE-AdSV)

The kinetic limitations of Competitive Ligand Exchange-Adsorptive Stripping Voltammetry, CLE-AdSV, for the determination of very stable metal complexes are explained in detail. For a given type of metal, from a certain lower limit of the complex stability constant, K, the usual simple equilibrium interpretation of CLE-AdSV measurements is not generally valid. By critical assessment of data for natural waters we show that in many cases the reported stability constants appearto derive from nonequilibrium conditions in the bulk sample and hence overestimate the real values. Fe(II) is a special case due to the particular kinetic features of hydroxide as a ligand. Our results call for validation of such data by analysis on the basis of the kinetics involved and/or by independent kinetic-free experimental approaches. Earlier speculations from CLE-AdSV results on very strong ligands and derived features such as the potential bioavailability of trace metals in natural waters require reconsideration.

Dynamic aspects of metal speciation by competitive ligand exchange–adsorptive stripping voltammetry (CLE–AdSV)

Competitive ligand exchange–adsorptive stripping voltammetry (CLE–AdSV) measures speciation of a metal M via a bulk exchange reaction with an adsorptive ligand L ad followed by electrochemical detection of the adsorbed metal complex. Thermodynamic aspects of the detection window of the technique are well understood. Here, we analyse the kinetic aspects including those involved with the adsorptive accumulation step. The upper border of the kinetic detection window is defined by the requirement of equilibration before accumulation of the complex ML ad at the electrode surface. Analysis of the exchange step demonstrates that complexes with sample ligands that remain unaffected by the exchange step are generally nonlabile and do not contribute to the AdSV signal. Any residual free metal, however, does contribute to the accumulation process, but this contribution will be negligible in the usual situation of a sufficiently strong complex ML ad and an excess of L ad over M. The adsorption of the surface-active complex ML ad is of a transient nature in the initial stage of the accumulation period, before the diffusive adsorption process approaches a steady-state nature.

Measuring Marine Iron(III) Complexes by CLE-AdSV

Environmental Context. Iron is an essential element for life in the world's oceans, and in some regions its concentration limits the growth of phytoplankton. The amount of iron(iii) which is available to an organism depends on the exact chemical form in which it exists, for example as dissolved ions or associated with organic compounds. There are widespread reports that marine iron(iii) is predominantly bound in extremely strong complexes. We show that such claims might be the result of an artefact of the measurement technique, CLE-AdSV. Ensuing ideas about the iron biogeochemistry in marine systems might require reconsideration as well. Abstract. Iron(iii) speciation data, as determined by competitive ligand exchange?adsorptive stripping voltammetry (CLE-AdSV), is reconsidered in the light of the kinetic features of the measurement. The very large stability constants reported for iron(iii) in marine ecosystems are shown to be possibly due to an artefact of the technique, arising from the assumption that equilibrium is achieved between all iron(iii) species of relevance. Particular kinetic properties, related to the special nature of hydroxide as a metal complexant, have the consequence that CLE-AdSV measurements of iron(iii) in seawater generally correspond to the hydroxide complexes only. By the same token, dissolved hydroxide complexes are the key components of the bioavailable iron(iii) pool. The analysis presented herein opens opportunities to exploit CLE-AdSV for more rigorous investigation of the links between the speciation and the bioavailability of iron(iii).