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Intrinsic fluorescence quenching of humic substances (HS) and the sensitization of Ln(3+) luminescence (Ln3+ Tb3+, Eu3+) in HS complexes were investigated. Both measurements yielded complementary information on the complexation of metals by HS. Large differences between fulvic acids(FA)and humic acids (HA) were found. From time-resolved luminescence measurements it is concluded that a combination of energy transfer and energy back transfer between HS and Ln(3+) is responsible for the observed luminescence decay characteristics. In the case of Eu3+, an additional participation of charge-transfer states is suggested. A new concept for the evaluation of the sensitized luminescence decays of Ln(3+) was adapted
The fluorescence properties and the fluorescence quenching by Tb3+ of substituted benzoic acid were investigated in solution at different pH. The substituted benzoic acids were used as simple model compounds for chromophores present in humic substances (HS). It is shown that the fluorescence properties of the model compounds resemble fluorescence of HS quite well. A major factor determining the fluorescence of model compounds are proton transfer reactions in the electronically excited state. It is intriguing that the fluorescence of the model compounds was almost not quenched by Tb3+ while the HS fluorescence was decreased very effectively. From our results we concluded that proton transfer reactions as well as conformational reorientation processes play an important role in the fluorescence of HS. The luminescence of bound Tb3+ was sensitized by an energy transfer step upon excitation of the model compounds and of HS, respectively. For HS the observed sensitization was dependent on its origin indicating differences 1) in the connection between chromophores and binding sites and 2) in the energy levels of the chromophore triplet states. Hence, the observed sensitization of the Tb3+ luminescence could be useful to characterize structural differences of HS in solution. Interlanthanide energy transfer between Tb3+ and Nd3+ was used to determine the average distance R between both ions using the well-known formalism of luminescence resonance energy transfer. R was dependent on the origin of the HS reflecting the difference in structure. The value of Rmin seemed to be a unique feature of the HS. It was further found that upon variation of the pH R also changed. This demonstrates that the measurement of interlanthanide energy transfer can be used as a direct method to monitor conformational changes in HS.
In an area that contains high concentrations of natural organic matter, it is expected that it plays an important role on the behavior of rare earth elements (REE), like europium, and of trivalent actinides. Competitive interactions with H+, inorganic species, major cations, e.g. Ca(II) or Mg(II), could influence these metals transport and bioavailability. Competitive experiments between cations, which can bind differently to humic substances and Eu3+,will bring an improved understanding of the competitive mechanisms. The aim of this study is to acquire data for Eu(III)/Cu(II) and Eu(III)/Ca(II) competitive binding to a sedimentary originated humic acid (Gorleben, Germany). The NICA-Donnan parameters for Ca2+, Cu2+, and Eu3+ obtained from competitive binding experiments using Ca2+ or Cu2+ ion selective electrodes were used to model time-resolved laser fluorescence spectroscopy (TRLFS) measurements. Eu3+ and Cu2+ are in direct competition for the same type of sites,whereas Ca2+ has an indirect influence through electrostatic binding.
Characterization of competitive binding of Eu(III)/Cu(II) and Eu(III)/Ca(II) to Gorleben humic acid
(2009)
The competition between REE, alkaline earth and d-transition metals for organic matter binding sites is still an open field of research; particularly, the mechanisms governing these phenomena need to be characterized in more detail. In this study, we examine spectroscopically the mechanisms of competitive binding of Eu(III)/Cu(II) and Eu(III)/ Ca(II) pair to Gorleben humic acid (HA), as previously proposed in the framework of the NICA-Donnan model. The evolution of time-resolved laser induced luminescence spectra of humic-complexed Eu(Ill) showed two strikingly different environments for a comparable bound proportion for Cu(II) and Ca(II). Cu(II) seems to compete more effectively with Eu(III) inducing its release into the Donnan phase, and into the bulk solution as free Eu3+. This is evidenced both by the shapes of the spectra and by the decrease in the luminescence decay times. In contrast with that, Ca(II) induces a modification of the HA structure, which enhances the luminescence of humic-bound Eu(III), and causes a minor modification of the chemical environment of the complexed rare earth ion.
Intramolecular deactivation processes in complexes of salicylic acid or glycolic acid with Eu(III)
(2010)
The complexation of Eu(III) by 2-hydroxy benzoic acid (2HB) or glycolic acid (GL) was investigated using steady- state and time-resolved laser spectroscopy. Experiments were carried out in H2O as well as in D2O in the temperature range of View the MathML source. The Eu(III) luminescence spectra and luminescence decay times were evaluated with respect to the temperature dependence of (i) the luminescence decay time ;, (ii) the energy of the View the MathML source transition, (iii) the width of the View the MathML source transition, and (iv) the asymmetry ratio calculated from the luminescence intensities of the View the MathML source and View the MathML source transition, respectively. The differences in ligand-related luminescence quenching are discussed. Based on the temperature dependence of the luminescence decay times an activation energy for the ligand-specific non-radiative deactivation in Eu(III)-2HB or Eu(III)-GL complexes was determined. It is stressed that ligand-specific quenching processes (other than OH quenching induced by water molecules) need to be determined and considered in detail, in order to extract speciation- relevant information from luminescence data (e.g., estimation of the number of water molecules nH2O in the first coordination sphere of Eu(III)). In case of 2HB, conclusions drawn from the evaluation of the Eu(III) luminescence are compared with results of a X-ray structure analysis.
This article gives an overview of the current status of knowledge concerning the role of nanoparticles (inorganic and organic) in deep geological host rocks and the potential influence of these nanoparticles on radionuclide migration in far-field systems. The manuscript is not intended to be a full review paper or overview paper concerning nanoparticles, here the intention is to refer to recent publications but to highlight the progress made in the 6th framework project IP FUNMIG (Fundamental processes of radionuclide migration) and the open literature over the past 5 a concerning the process understanding of nanoparticle related issues in the three host rock formations investigated, namely: claystones, crystalline rocks and salt rock overburden. The results show inter alia that the inorganic nanoparticle concentration in deep groundwaters of advection dominated systems rarely exceeds 1 mg L (1) and is expected to be in the ng L (1) range in diffusion controlled systems. For organic nanoparticles DOC concentrations up to tens of milligrams in diffusion-controlled indurated clays with molecular sizes mostly <500 Da have been found. Fulvic acid type organics have been identified in crystalline environments and plastic Clay formations (Boom Clay) with molecular sizes <= 300 kDa. Additional sources of inorganic nanoparticles from the repository near-field (compacted bentonite) were identified and the initial erosion rates were determined. The results indicate under stagnant conditions similar to 38 mg cm (2) a (1) for bi-distilled water, similar to 20 mg cm (2) a (1) for glacial melt water (Grimsel groundwater) and very low rates similar to 0.02 mg cm (2) a (1) for 5 mM CaCl2 contact water. The low critical coagulation concentration (CCC) indicative for purely diffusion controlled coagulation of 1 mM L (1) Ca2+ found in bentonite nanoparticle stability analysis matches the low nanoparticle mobilization from compacted bentonite found in these systems.
The applicability of equilibrium models for humic-bound transport of toxic or radioactive metals is affected by kinetic processes leading to an increasing inertness of metal-humic complexes. The chemical background is not yet understood. It is widely believed that bound metals undergo an in-diffusion process within the humic colloids, changing from weaker to stronger binding sites. This work is focussed on the competition effect of Al(III) on complexation of Tb(III) or Eu(III) as analogues of trivalent actinides. By using ion exchange and spectroscopic methods, their bound fractions were determined for solutions of Al and humic acid that had been pre-equilibrated for different periods of time. Whilst the amount of bound Al remained unchanged, its blocking effect was found to increase over a time frame of 2 days, which corresponds to the kinetics of the increase in complex inertness reported in most pertinent studies. Thus, the derived "diffusion theory'' turned out to be inapplicable, since it cannot explain an increase in competition for the "initial'' sites. A delayed degradation of polynuclear species (as found for Fe) does not occur. Consequently, the temporal changes must be based on structural rearrangements in the vicinity of bound Al, complicating the exchange or access. Time-dependent studies by laser fluorescence spectroscopy (steady-state and time-resolved) yielded evidence of substantial alterations, which were, however, immediately induced and did not show any significant trend on the time scale of interest, suggesting that the stabilisation process is based on comparatively moderate changes.