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Environmental contextThe concentration, types and distribution of antibiotics in soils can have environmental effects and can be modelled using laboratory systems. Adsorption of ofloxacin (OFL) and levofloxacin (LEV) enantiomers to goethite can probe this behaviour and each binds differently to the solid phase. The different behaviour of LEV and OFL in relation to solid-solution partitioning will affect their environmental fate. AbstractThe adsorption of ofloxacin enantiomers, namely levofloxacin (LEV) and ofloxacin (OFL), to goethite was investigated using batch experiments. Structural information of aqueous and adsorbed LEV or OFL was obtained with ultraviolet–visible (UV-Vis), three-dimensional excitation–emission matrix (EEM) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopic methods. The results indicated that LEV molecules formed a bridging bidentate complex (≡(FeO)2–LEV) with the surface of goethite, and OFL formed a monodentate complex (≡FeO–OFL). The adsorption of OFL to goethite was stronger than that of LEV, owing to differences in their physicochemical properties and bonding modes. The adsorption of LEV and OFL to goethite in single systems was well simulated using the charge distribution multi-site complexation (CD-MUSIC) model, but their adsorption in the LEV–OFL–goethite systems was overestimated at pH ~5.2 and high concentrations of LEV–OFL mixture (19.59μM), in which the predicted amounts of adsorbed LEV and OFL were higher (20.0, 30.8%) than the experimental results. Compared with the unprotonated LEV or OFL, the protonated (>99.9%) ones were mainly adsorbed to the surface of goethite, and the single species may be used during their following modelling.

Environmental contextThe environmental behaviour of trace metals in soils and waters largely depends on the chemical form (speciation) of the metals. Speciation software programs combining models for the binding of metals to soil and sediment constituents are powerful tools in environmental risk assessment. This paper describes a new combination of speciation software with a fitting program to optimise geochemical model parameters that describes proton and metal binding to humic substances. AbstractHere we describe the coupling of the chemical speciation software ORCHESTRA with the parameter estimation software PEST. This combination enables the computation of optimised model parameters from experimental data for the ion binding models implemented in ORCHESTRA. For testing this flexible tool, the NICA-Donnan model parameters for proton-, Cd- and Zn-binding to Laurentian fulvic acid were optimised. The extensive description of the method implementation and the examples provided facilitate the use of this tool by students and researchers. Three procedures were compared which derive the proton binding parameters, differing in the way they constrain the model parameters and in the implementation of the electrostatic Donnan model. Although the different procedures resulted in significantly different sets of model parameters, the experimental data fit obtained was of similar quality. The choice of the relation between the Donnan volume and the ionic strength appears to have a strong influence on the derived set of optimal model parameters, especially on the values of the protonation constants, as well as on the Donnan potential and Donnan volume. Optimised results are discussed in terms of their physico-chemical plausibility. Coherent sets of NICA-Donnan parameters were derived for Cd and Zn binding to Laurentian fulvic acid.

Environmental context Free ion concentrations determine the effects of nutrients and pollutants on organisms in the environment. The Donnan membrane technique provides a measure of free ion concentrations. This paper presents clear guidelines on the application of the Donnan membrane technique for determining free ion concentrations in both synthetic and natural samples. Abstract The Donnan membrane technique (DMT) can be applied to measure free ion concentrations both in laboratory and in situ in the field. In designing DMT experiments, different strategies can be taken, depending on whether accumulation is needed. (1) When the free ion concentration is above the detection limit of the analytical technique (e.g. ICP-MS), no accumulation is needed and no ligand is added to the acceptor. Measurement can be based on the Donnan membrane equilibrium. (2) When an accumulation of less than 500 times is needed, an appropriate amount of ligand can be added to the acceptor and measurement can be based on the Donnan membrane equilibrium. (3) When an accumulation factor of larger than 500 times is needed, a relatively large amount of ligand is added to the acceptor and measurement can be based on the transport kinetics. In this paper, several issues in designing the DMT experiments are discussed: choice of DMT cell, measurement strategies and ligands and possible implication of slow dissociation of metal complexes in the sample solution (lability issue). The objective of this paper is to give better guidance in the application of DMT for measuring free ion concentrations in both synthetic and natural samples.