Lability of a mixture of metal complexes under steady-state planar diffusion in a finite domain

The rigorous analytical solution for the fluxes from a mixture of 1:1 metal complexes toward an active surface under steady-state planar diffusion in a finite domain and excess ligand conditions allows for the computation of the global degree of lability of the system as well as particular degrees of lability of each complex in the mixture. This kind of system is found in a variety of fields ranging from electrochemical techniques (such as stripping chronopotentiometry at scanned deposition potential, SSCP) to analytical devices (such as diffusion gradients in thin-film gels, DGT). Among the specific effects arising from the presence of a mixture of ligands competing for the metal we highlight the following: (i) The degree of lability of a complex in the mixture differs from its degree of lability in an unmixed system with the same ligand concentration, and (ii) the degree of lability of one complex depends on (i.e., can be modified with) the concentrations of the ligands in the mixture. The impact of these characteristics on the metal flux crossing the active surface reaches the highest value when both complexes are partially labile. The complex contribution to the metal flux goes through a maximum when the thickness of the diffusion domain is varied. Thus, the thickness of the diffusion domain can be chosen to enhance the contribution of one particular complex. Lability criteria for each complex of the mixture within the reaction layer approximation are also reported. In particular, the reaction layer formulation for a complex is discussed in detail for two limiting cases: the rest of complexes are all nonlabile or the rest of complexes are all labile.     

Determination of Dynamic Metal Complexes and their Diffusion Coefficients in the Presence of Different Humic Substances by Combining Two Analytical Techniques

The combined use of a competing ligand exchange (CLE) method and a diffusive gradient in thin films (DGT) technique in a quasi-labile system provides a better understanding of dynamic metal (Cu and Ni) complexes in the presence of humic substances of different origins. The CLE and DGT techniques provide total labile (dynamic) metal complexes (Cu and Ni) and their dissociation rate constants in environmental systems. DGT was found to estimate lower concentrations of labile metal complexes than CLE. These discrepancies were caused by diffusion controlled metal flux (towards the binding resin gel) in the diffusive gel of DGT. The interactions of Cu and Ni with humic acids are stronger than their interactions with fulvic acid and natural organic matter. Changes in the lability of Ni and Cu complexes (complexed with humic substances of different origins) with the changing analytical detection window indicate that the complexes of these metals were formed with different binding sites with diverse binding energies in the humic substances. The combination of these two techniques was found to be very useful in determining diffusion coefficients of labile metal-humate complexes in quasi-labile systems. The values of diffusion coefficients of labile Ni and Cu complexes determined in this study are in good agreement with limited results from the literature. This finding is novel and can be very useful in further improving our understanding of the metal-humate interactions in natural environments.     

Ligand mixture effects in metal complex lability

The degree of lability of a given metal complex species is modified in the presence of a mixture of ligands. This modification is a consequence of the coupling of the association and dissociation processes of all of the complexes according to the competitive complexation reaction scheme. We show that, because of the mixture effect, the lability of a given complex usually increases when another more labile complex is added into the system, while it decreases upon addition of a less labile one. Typically, complexes tend to adapt to the global lability of the mixture. A quantitative evaluation of these effects for diffusion-limited conditions in a finite domain by rigorous numerical simulation in a system with two complexes indicates that the lability degree of a complex can change by more than 100% with respect to that in the single ligand system. The impact of the mixture effect on the metal flux depends at least on two main factors: the respective abundance of the metal species and the particular values of their lability degrees. Dominant complexes (i.e., those most abundant when these complexes have equal diffusion coefficients) undergo smaller changes in their own lability degree, but these changes have the greater impact on the overall metal flux. Partially labile complexes are more easily influenced by the mixture than labile or inert ones. Some mixture effects can be qualitatively predicted by an analytical expression for the lability index derived using the reaction layer approximation. For a mixture of many complexes, the change in the lability degree of a complex due to the mixture effect can be understood as a combination of the changes due to all of the complexes present.     

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile.     

Metal speciation measurement by diffusive gradients in thin films technique with different binding phases

Since its invention in the mid-1990s, the diffusive gradients in thin films (DGT) technique has rapidly become one of the most promising in situ sampling techniques for trace metal measurement in natural waters. We investigated here the possibility of using DGT devices with different binding phases to determine different DGT labile fractions of Cd and Cu in laboratory solutions and in natural waters. Several binding phases were studied, including conventional Chelex 100 resin imbedded polyacrylamide hydrogel (Chelex) and several recently developed binding phases, poly(acrylamide-co-acrylic acid) (PAM-PAA) gel, poly(acrylamidoglycolic acid-co-acrylamide) (PAAG-PAM) gel, Whatman P81 cellulose phosphate ion-exchange membrane (P81), and poly(4-styrenesulfonate) (PSS) aqueous solution. Laboratory testing in metal solutions spiked with EDTA or humic acid suggested that all the DGT devices measured only free metal ions and inorganic metal complexes. Upon field testing at both freshwater and seawater sites it was found that the DGT labile metal concentrations measured by different binding phases can be significantly different, suggesting that the DGT labile metal fractions were dependent on binding strength of the binding phase. By designing binding phases that can compete with different natural water complexing ligands to varying extents, it is possible to use these different DGT devices to measure metal speciation in natural waters.     

Lability criteria for successive metal complexes in steady-state planar diffusion

The lability of sequential metal complexes, ML, ML2, ML3, ... , up to a general 1:n metal/ligand stoichiometric ratio is considered for the case of metal ions (M) being accumulated at a surface (analytical sensor or organism). The analytical solution for the steady-state diffusion of M within a sequential complexation scheme allows quantification of the contribution from the dissociation of all of the complex species to the metal flux through the so-called lability degree, xi. A lability degree for each sequential complexation step is also defined which, due to the sequential character of the complexation scheme, depends not only on the proper kinetic constants of the given complexation step but also on the kinetics of the previous ones. When all contributions from the complexes are diffusion limited, the system is fully labile and xi=1. To provide simple lability criteria, the reaction layer approximation is extended to specifically deal with this sequential complexation scheme, so that a reaction layer thickness is defined when the existence of one particular rate-limiting step is assumed. Expressions for the classical lability parameter, L, are formulated using the reaction layer approximation. The change of the lability of the system as the diffusion layer thickness is modified is analyzed in detail. The contribution of the complex flux reflects the evolution of the system from labile to inert as the thickness of the sensor is appropriately decreased.     

Copper and nickel speciation in mine effluents by combination of two independent techniques

To control potentially toxic metals in water resources it is necessary to know metal speciation and changes in the metal speciation that occur after aqueous effluents containing metals are discharged into freshwaters. This work explores the speciation of nickel and copper in metal-mining aqueous effluents. Diffusive gradients in thin films (DGT) technique and competing ligand exchange (CLE) method have been applied to determine the speciation of nickel and copper. The results of this investigation demonstrate that combination of two analytical techniques having complementary analytical capabilities can provide a better physicochemical picture of metal speciation than either one of the analytical technique can do alone. The combined use of these techniques revealed that copper formed labile complexes having slow diffusion coefficient along with the presence of small labile copper complexes. Nickel-dissolved organic complexes (DOC) complexes in the aqueous effluent have been found to have fast diffusion coefficient. The results are likely to have environmental significance for providing a link between the metal species in mine aqueous effluent and their bioavailability by determining the characteristics of copper and nickel complexes in metal-mine aqueous effluents. This knowledge is expected to promote a better understanding of the lability of DOC complexes of copper and nickel in mining effluents.     

Mercury depth profiles in river and marine sediments measured by the diffusive gradients in thin films technique with two different specific resins

The diffusive gradients in thin films technique (DGT) was used to measure depth profiles of mercury in river and marine sediments in situ to a spatial resolution of 0.5 cm. Agarose gel was used as the diffusive gel in the DGT probes. Two different selective resins—Chelex 100 with iminodiacetic groups and Spheron-Thiol with thiol groups incorporated in the polyacrylamide resin gel—were tested. The different capture efficiencies of the two adsorbents enabled the fractions of mercury bound in different species in sediment pore water to be estimated. Mercury concentrations obtained by DGT with Spheron-Thiol resin were very similar to those obtained after centrifugation. This indicates that DGT with Sheron-Thiol resin reports on total dissolved mercury levels. The concentration of mercury measured by DGT with Chelex-100 resin was much lower (by a factor of 5–20) for the same sediment samples. Chelex-100 does not have such a high affinity to mercury as Spheron-Thiol, and so it only reports on the content of labile mercury species, such as inorganic ions and weak complexes. The content of labile mercury species in the river sediment was approximately 20% of the total dissolved mercury in pore water, whereas in marine sediment only 7% of the mercury was present as labile species.     

Influence of the settling of the resin beads on diffusion gradients in thin films measurements

Binding resin beads used in DGT (diffusion gradients in thin films) tend to settle to one side of the resin during casting. This phenomenon might be relevant for metal accumulation when partially labile complexes dominate the metal speciation, especially after recognizing the important role played by complex dissociation in the resin domain. The influence of the inhomogeneity of the binding agent distribution on metal accumulation is here assessed by numerical simulation of DGT devices with binding beads in only one half of the resin disc, as a reasonable model of the standard resin discs. Results indicate that a decrease in mass accumulation of less than 13% can arise in these inhomogeneous devices (as compared with an ideal disc with homogeneous dispersion of the resin beads) when complexes with stability constant K < 10² m³ mol⁻¹ (K < 10⁵ L mol⁻¹) dominate the metal speciation. The loss increases as K increases, but the percentage of mass loss always remains lower than the volume fraction of resin disc without beads. For very labile or inert complexes, the impact of the inhomogeneous distribution of binding resin beads is negligible. As kinetic dissociation constants of complexes can be estimated from the distribution of the metal accumulation in a DGT device with a stack of two resin discs, the influence of the inhomogeneity on the recovered kinetic constant is also assessed. For the cases studied, the recovered kinetic dissociation constant, k_d,recovered, retains the correct order of magnitude, being related to the true k_d by k_d ≈ f⁻¹ k_d,recovered, quite independently of K and k_d values, being f the fraction of volume of the resin disc where resin beads are dispersed.     

Application of diffusive gradient in thin films technique (DGT) to measurement of mercury in aquatic systems

The diffusive gradient in thin films (DGT) technique was investigated and used to measure mercury concentration in river water. Mercury ions are covalently bound to amide nitrogen groups of commonly used polyacrylamide, which makes this gel unsuitable as a diffusive medium. In contrast, agarose gel was found as the diffusive gel for mercury measurements. Basic performance tests of agarose DGT verified the applicability of Fick's first law for DGT measurements. Two selective resins, Chelex-100 with iminodiacetic groups and Spheron-Thiol with thiol groups were used. The measured diffusion coefficient in agarose gel was close to that in water. The concentration of mercury in Svitava river measured by DGT with Speron-Thiol resin gel was higher (0.0116 ± 0.0009 μg l⁻¹) than those obtained by Chelex-100 (0.0042 ± 0.0005 μg l⁻¹). Different capture efficiencies of two adsorbents enable to estimate fractions of mercury bonded in different complexes in the river water. The concentrations of mercury found by DGT both Chelex-100 and Speron-Thiol resin gels are much lower than that measured directly in the river water (0.088 ± 0.012 μg l⁻¹). This difference indicates that DGT concerns inorganic ions and labile species only, and that it is not able to include inert organic species and colloids.     

Trace metal speciation measurements in waters by the liquid binding phase DGT device

The speciation measurements of trace metals by the diffusive gradients in thin-films technique (DGT) using a poly(4-styrenesulfonate) (PSS) aqueous solution as a binding phase and a cellulose dialysis membrane (CDM) as a diffusive layer, CDM-PSS DGT, were investigated and showed good agreement with computer modelling calculations. The diffusion coefficients of ethylenediaminetetraacetic acid (EDTA) complexes with Cd²⁺ and Cu²⁺ were measured and compared with those of the inorganic metal ions. CDM-PSS DGT device was tested for speciation measurement in sample solutions containing EDTA, tannic acid (TA), glucose (GL), dodecylbenzenesulfonic acid (DBS) and humic acid (HA) as complexing ligands forming organic complexes with varying stability constants. Lower percentages of DGT labile copper concentrations over total filterable copper concentrations obtained from the deployments in freshwater sites indicated that copper complexes with organic matter were basically not measured by the devices.     

Determination of labile inorganic and organic species of Al and Cu in river waters using the diffusive gradients in thin films technique

The diffusive gradients in thin films (DGT) technique, using a diffusive gel or a restrictive gel, was evaluated for the determination of labile inorganic and organic species of Al and Cu in model synthetic solutions and river water samples. Experiments were performed both in situ and in the laboratory. In the solutions containing Al ions, the major labile fraction consisted of inorganic species. The organic complex fractions were mainly kinetically inert. For the model Cu solutions, the most labile fraction consisted of inorganic species; however, significant amounts of labile organic complexes of Cu were also present. A comparison was made between the results obtained using restrictive gel DGT and tangential flow ultrafiltration (TF-UF). The Cu fraction determined by restrictive gel DGT (corresponding to the "free" ions plus the labile fraction of small molecular size complexes) was larger than that determined by TF-UF (corresponding to all small molecular size ions), suggesting that the techniques exhibited different porosities for discrimination of inorganic species. For the river water samples analyzed in the laboratory, less than 45% of the analytes were present in labile forms, with most being organic species. For the in situ measurements, the labile inorganic and organic fractions were larger than those obtained in the laboratory analyses. These differences could have been due to errors incurred during sample collection and storage. All results were consistent with those found using two different methods, namely, solid-phase extraction and the DGT technique employing the apparent diffusion coefficient.     

Speciation of copper and zinc in natural freshwater: comparison of voltammetric measurements, diffusive gradients in thin films (DGT) and chemical equilibrium models

In situ measurements of copper and zinc using diffusive gradients in thin films (DGT) in two distinct natural water systems were compared to metal speciation assessed by competitive ligand exchange (CLE) and voltammetric measurements. In a dynamic river system, where dissolved metal concentrations vary significantly over short-time periods, DGT technique provided averaged values of the metal concentrations over time. In microcosms, at different total dissolved concentrations of copper and zinc, DGT technique measured a similar fraction as measurements of labile metal performed by voltammetry. The proportion of DGT and voltammetric-labile zinc to dissolved zinc was 61±4% and, respectively, 76±9%. DGT technique was measuring 81±8% of exchangeable copper (by exchange with catechol). These two fractions were similarly influenced by the addition of NTA. In the absence of NTA, copper measured by DGT represented 34±4% of dissolved copper whereas in the presence of NTA, this proportion raised to 57±2%. These measurements were compared to calculations performed with speciation programs using several models for the complexation by humic and fulvic substances, namely Model VI (WHAM), NICA-Donnan and SHM. The predicted speciation by these three models was similar. The prediction of free zinc ion and labile zinc concentrations were in agreement with experimental data. Calculated concentrations of free copper ion were overestimated because these models are not considering strong specific copper-binding ligands probably present in natural water.     

Diffusive gradients in thin films technique for uranium measurements in river water

The diffusive gradients in thin films technique (DGT) was used for uranium measurements in water. DGT devices with Dowex resin binding phase (Dow DGT) were tested in synthetic river water, which gave 84% response to total uranium concentration. The devices were also deployed in natural river water and compared to devices with other types of binding phases, Chelex 100 resin beads imbedded in polyacrylamide hydrogel (Chelex DGT) and DE 81 anion exchange membrane (DE DGT), deployed in the same location at the same time. The measurement by Dow DGT was the lowest among the different types of the DGT devices, 45% of total uranium, while measurement by DE DGT was the highest, 98% of total uranium. The results achieved by the three types of DGT devices were explained by three DGT working mechanisms, equilibrium between complexes of resin/uranyl carbonates and complexes of resin/competitive ligands in water, effective reduction of uranyl carbonate concentration by the binding phase and dissociation of UO₂(CO₃)₂²⁻ and UO₂(CO₃)₃⁴⁻ within the diffusive layer in a DGT device. It is hoped that by deploying the DGT devices with different binding phases in natural waters, additional information on uranium speciation could be obtained.     

New analytical procedure based on a cellulose bag and ionic exchanger with p-aminobenzoic acid groups for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed for the in situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory to evaluate the influence of complexation time, mass of exchanger, pH, metal ions (Cu, Cd, Fe, Mn, and Ni), and concentration of organic matter on the relative lability of metal species. It was found that the pH and kinetics strongly influence the process of metal complexation by the DM-Cell-PAB system. At all pH levels, Cd, Mn, and Ni showed lower complexation with Cell-PAB resin than Cu and Fe metals. Note that relative lability of metals complexed to aquatic humic substances (AHS) in the presence of Cell-PAB resin showed the following order: Cu≅Fe≫Ni>Mn=Cd. The results presented here also indicate that increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS–metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems.     

Determination of trace metal complexes by natural organic and inorganic ligands in coastal seawater.

It is well-documented that organic compounds form strong complexes with most metals in aquatic systems, and that seawater is a complex medium which contains a large variety of organic and inorganic ligands, including colloidal matter. We suggest that most trace metals are complexed in seawater and that some inorganic metals complexes are either labile or not stable. In contrast, metal-organic complexes are often stable and need various and specific treatments to be dissociated. In this paper we try to illustrate a good tendency of some trace metals to be complexed by organic ligands in seawater. A solid-phase extraction method was applied using a C18 column as a resin that is able to separate metals complexed by neutral organic ligands, and the chelamine resin to separate metal species that are present as labile inorganic complexes. The determination of total dissolved metal concentrations was achieved by formatting a metal-8-hydroxyquinoline complex, followed by adsorption on C18 columns and ICP-AES analysis.     

What should be impossible: resolution of the mononuclear gallium coordination complex, Tris(benzohydroxamato)gallium(III)

Complexes of Ga3+, a d10 metal ion which lacks ligand-field-stabilization energy, are considered labile. In fact, hexaaquagallium(III) has a ligand exchange rate of 403 s-1, 2.5 times that of the analagous Fe3+ complex (Hugi-Cleary, D.; Helm, L.; Merbach, A. E. J. Am. Chem. Soc. 1987, 109, 4444-4450). Given this lability, resolution of Ga3+ complexes should be impossible. Despite this, we report the resolution of the Lambda and Delta isomers of tris(benzohydroxamate)gallium (III) (1), the first resolution of a mononuclear gallium complex. Not only is resolution possible, but these resolved complexes show remarkable resistance to racemization in aprotic solvents. The unprecedented stability of Lambda- and Delta-1 is a surprise, and as such, alters our understanding of classical coordination chemistry.     

Effect of competitive cation binding on the measurement of Mn in marine waters and sediments by diffusive gradients in thin films

The possible adverse effect of competitive binding on DGT (diffusive gradients in thin films) measurements of metals in marine situations was investigated. Of the divalent transition metals, manganese binds most weakly to Chelex resin and is most likely to be affected by competition. In media resembling seawater, the Chelex within DGT devices becomes saturated with Ca and Mg within 2 h, and at pH 5–6 the sensitivity of the DGT measurement for Mn is substantially reduced, due to the appreciable concentration of Mn in contact with the resin. For media resembling freshwater DGT gives a near theoretical response for Mn. Iron was shown to be capable of displacing Mn and to a more limited extent Cd from the resin when its capacity for Fe is approached. Vertical profiles of Mn in a mesocosm sediment, obtained by deploying DGT for different times, could be explained by this displacement effect. The problem only occurs when Fe concentrations are exceptionally high and can be avoided by using short deployment times, typically less than 12 h. Whilst most trace metals can be simply measured by deploying DGT in marine systems, for Mn consideration should be given to possible effects associated with the capacity of the Chelex binding layer being approached by accumulation of the other cations present.     

Speciation of Charged Complexes by Donnan Dialysis

Abstract

The assignment of metal complexes to various regimes on the basis of their dissociation kinetics is one type of metal speciation study. The most common scheme, which involves column ion-exchange as a means of separating free metal ions and metals in the form of highly labile complexes from other forms of metals in the sample, is demonstrated to categorize incorrectly stable, charged complexes such as iron(II) and nickel(II) o-phenanthroline as labile. Donnan dialysis is an alternative ion-exchange method for metal speciation studies. Data are provided which demonstrate that the above complexes are correctly assigned by the Donnan dialysis method. The relative labilities of ethylenediamine and triethylenetetramine complexes of iron (II) and nickel (II) are also correctly determined by Donnan dialysis.     

薄膜梯度扩散技术结合相研究进展

薄膜梯度扩散(DGT)技术是一种新型原位被动采样技术,已被广泛应用于水体、土壤、沉积物中目标物的采集与测量。结合相是DGT技术的重要组成部分,决定了与目标物的结合能力、结合速度、结合容量以及目标物的形态选择性等。DGT结合相分为固态结合相和液态结合相。本文重点综述了树脂、氧化物、无机盐、活性炭、改性硅胶、分子印迹、共聚物、复合、液态等结合相在DGT技术中的应用,展望了DGT结合相的发展前景。