A potentiometric and 113Cd NMR study of cadmium complexation by natural organic matter at two different magnetic field strengths.
The binding of cadmium to Suwannee River natural organic matter (NOM) has been investigated across a broad range of Cd/C ratios (0.00056-0.0056) and pH values (3.5-11) by (113)Cd NMR spectroscopy at two magnetic field strengths (B(0) = 9.4 and 11.7 T). Caused by the very peculiar and highly complex nature of the Cd-NOM exchanging system, these (113)Cd NMR spectra are characterized by a pH- and concentration-dependent superposition of slow, intermediate, and fast chemical exchange. The complex interplay of solution chemistry and chemical exchange requires a thorough mapping of this Cd-NOM chemically exchanging system through NMR acquisition at two magnetic field strengths and a systematic variation of Cd/C ratios and pH values. The interpretation of (113)Cd NMR spectra is greatly facilitated and constrained by simultaneous measurements of pH and pCd, which allows a model-independent calculation of organically bound Cd(2+) under all experimental conditions. Within the range of chemical conditions applied in this study, (113)Cd NMR spectrometric evidence is consistent with coordination of cadmium by oxygen, nitrogen, and sulfur ligands in NOM. Under all experimental conditions, cadmium is primarily coordinated to oxygen; however, several lines of evidence point to the participation of nitrogen ligands, even in acidic solutions where nitrogen ligands are primarily bound to protons. Under alkaline conditions, up to one-third of cadmium may be coordinated to nitrogen, and a small, but unquantifiable, percentage of cadmium is coordinated to sulfur ligands, as evidenced by far-low-field (113)Cd NMR resonances.
Hertkorn
N
N
Institut für Okologische Chemie, GSF-Forschungszentrum für Umwelt und Gesundheit, 85758 Neuherberg, Germany. hertkorn@gsf.de
Perdue
E M
EM
Kettrup
A
A