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Cation binding by acid‐washed peat, interpreted with Humic Ion‐Binding Model VI‐FD

A sample of ombrotrophic peat from Moor House in northern England was extensively extracted with dilute nitric acid (pH 1) to free it of bound cations. Suspensions of the acid‐washed peat (5–30 g l−1), prepared with different concentrations of background electrolyte (NaCl and KCl), were used to conduct batch acid–base titrations. A strong dependence of proton release on ionic strength (I) was observed, the apparent acid dissociation constant (pKapp) being found to decrease by approximately 1.0 for each tenfold increase in I. This behaviour could not be explained satisfactorily with Humic Ion‐Binding Model VI, a discrete‐site/electrostatic model of cation binding by humic substances, parameterized with data from laboratory studies on isolated samples. More success was obtained by abandoning the impermeable‐sphere electrostatic submodel used in Model VI, and instead assuming the peat to consist of aggregates with fixed internal volume, and with counterion accumulation described by the Donnan model, as proposed by Marinsky and colleagues. The fixed‐volume Donnan model (Model VI‐FD) could also approximately explain other reported results from acid–base titrations of peat, including the effects on the titrations of complexing cations (Al, Ca, Cu). Copper titrations of the Moor House sample were performed using an ion‐selective electrode, with peat suspensions in the acid pH range, at two ionic strengths, and in the presence of Al and Ca. The measured concentrations of Cu2+ were in the range 10−13−10−5 m. Model VI‐FD provided reasonable fits of the experimental data, after optimization of the intrinsic binding constant for Cu, the optimized value being close to the default value derived previously from data referring to isolated humic substances. The optimized constants for Al and Ca, derived from their competition effects, were also close to their default values. Additional experiments were performed in which the centrifugation‐depletion method was used to measure the binding of a cocktail of metals (Al, Ni, Cu, Zn, Cd, Eu, Pb) at a single pH. The model correctly predicted strong binding of Al, Cu, Eu and Pb, and weaker binding of Ni, Zn and Cd. For the strongly binding metals, the dissolved forms were calculated to be mainly due to complexes with dissolved humic matter, whereas the free ions (Ni2+, Zn2+, Cd2+) dominated for the weakly binding metals. Acid‐washed soil appears to provide a valuable intermediate between isolated humic substances and untreated soil for the investigation of cation binding by natural organic matter in the natural environment.