Understanding the bioavailability and sequestration of different metal cations in the presence of a biodegradable chelant MGDA in biological fluids and natural waters

Abstract

Thermodynamic information about the metal-ligand interaction between Fe3+, Zn2+, Cu2+ and Sn2+, and a biodegradable ligand as MGDA is reported. The speciation scheme was obtained by means of potentiometric measurements and isothermal titration calorimetry (to determine enthalpy changes) in NaCl medium. The formation of the ML and MLOH species was evidenced for all the metal cations, and for Fe3+ also the ML2 and ML(OH)2 were found. The relative stability, for the ML species, follows the order: Sn2+ > Fe3+ > Cu2+ > Zn2+. Stability constants and enthalpy changes were obtained at different ionic strengths, and data were modeled using the Debye-Hückel and SIT approaches to obtain data in a standard state. At infinite dilution, the enthalpy changes are largely negative for Cu2+ (−34.1 kJ mol−1) and Sn2+ (−16.6 kJ mol−1), slightly negative for Fe3+ (−3.3 kJ mol−1) and positive for Zn2+ (8.7 kJ mol−1). In all cases, the entropic contribution to the stability is predominant. The sequestering ability of MGDA was evaluated determining the pL0.5 values in different conditions. Comparing the data reported in this work and literature ones, some empirical relationships were obtained with predictive purpose. For example, using 11 data in the test set we have:log K (M/MGDA) ± 0.1 = 1.13 + 0.84·log K (M/NTA)Case studies were built up in the conditions of seawater, fresh water and urine to study the possible use of MGDA towards the metal cations here studied. Some considerations were also done in the light of the ocean acidification.