Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange—an on-site approach

Abstract

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators (diethylenetetraaminepentaacetic acid (DTPA), ethylendiaminetetraacetic acid (EDTA)) and metal exchange with strongly competitive cations (Cu(II)) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake (Venner Moor, Münsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC (dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES (inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species (Fe, Mn, Zn) could be characterized. Conditional exchange constants K_ex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn >> Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu(II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.