Relating Cd2 + binding by humic acids to molecular weight: A modeling and spectroscopic study

Molecular weight(Mw) is a fundamental property of humic acids(HAs), which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid(HA) extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna(NICA-Donnan) models combined with fluorescence excitation-emission matrix(EEM) quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd~(2+) to Mw fractions of HA followed the order UF1( 5 kDa) UF2(5–10 kDa) UF4( 30 kDa) UF3(10–30 kDa). Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd~(2+) among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd~(2+) to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.     

Effect of natural organic matter on thallium and silver speciation

Natural organic matter (NOM) is known to play an important role in the transport and binding of trace metal elements in aquatic and soil systems. Thallium is a pollutant for which the extent of the role played by NOM is poorly known. Consequently, this study investigates thallium(I) and its complexation to a purified humic substance as proxy for NOM. Experiments were performed with the Donnan Membrane Technique to separate, for the first time, the free Tl⁺ ion from its complexed form in the bulk solution. Various pH and concentrations were investigated at constant ionic strength and constant NOM proxy concentrations in solution. Experimental results were described with NICA-Donnan model. Thallium complexation was compared to silver complexation using literature data and using the same NICA-Donnan formalism. Parameters for these two cations (Tl⁺ and Ag⁺) are reported in this article, for the first time. Results display low thallium complexation to the NOM proxy while silver competes with divalent cations for the NOM binding sites. Calculated speciation for dissolved thallium highlights the dominance of free thallium (Tl⁺) in solution whereas Tl-NOM complexes contribute roughly 15% to total Tl(I) species in river and lake type waters. Similar results are obtained for soil solutions, Tl-bound to NOM < 30% of total, from UK soils with different land use and geochemistry.