Adsorption of Pb and Cd onto metal oxides and organic material in natural surface coatings as determined by selective extractions: new evidence for the importance of Mn and Fe oxides

Abstract

Surface coatings (biofilms and associated minerals) were collected on glass slides in the oxic surface waters of Cayuga Lake (New York State, U.S.A.) and were used to evaluate the relative contributions of Fe, Mn and Al oxides and organic material to total observed Pb and Cd adsorption by the surface coating materials. Several alternative selective extraction techniques were evaluated with respect to both selectivity and alteration of the residual unextracted material. Pb and Cd adsorption was measured under controlled laboratory conditions (mineral salts solution with defined metal speciation, ionic strength 0.05 M, 25°C and pH 6.0) before and after extractions to determine by difference the adsorptive properties of the extracted component(s). Hydroxylamine hydrochloride (0.01 M NH2OH·HCl+0.01 M HNO3) was used to selectively remove Mn oxides, sodium dithionite (0.3 M Na2S2O4) was used to remove Mn and Fe oxides, and 10% oxalic acid was used to remove metal oxides and organic materials. Several other extractants were evaluated, but preliminary experiments indicated that they were not suitable for these experiments because of undesirable alterations of the residual, unextracted material. The selected extraction methods removed target components with efficiencies between 71 and 83%, but significant amounts of metal oxides and organic materials other than the target components were also removed by the extractants (up to 39%). Nonlinear regression analysis of the observed Pb and Cd adsorption based on the assumption of additive Langmuir adsorption isotherms was used to estimate the relative contributions of each surface coating constituent to total Pb and Cd binding of the biofilms. Adsorption of Cd to the lake biofilms was dominated by Fe oxides, with lesser roles attributed to adsorption by Mn and Al oxides and organic material. Adsorption of Pb was dominated by Mn oxides, with lesser roles indicated for adsorption to Fe oxides and organic material, and the estimated contribution of Al oxides to Pb adsorption was insignificant. The fitted Pb adsorption isotherm for Fe oxides was in excellent agreement with those obtained through direct experiments and reported in independent investigations. The estimated Pb distribution between surface coating components also agreed well with that previously predicted by an additive adsorption model based on Pb adsorption isotherms for laboratory surrogates for Mn, Fe and Al oxides and defined biological components.