Correlation of the partitioning of dissolved organic matter fractions with the desorption of Cd, Cu, Ni, Pb and Zn from 18 Dutch soils

Abstract

Eighteen Dutch soils were extracted in aqueous solutions at varying pH. Extracts were analyzed for Cd, Cu, Ni, Pb and Zn by ICP-AES. Extract dissolved organic carbon (DOC) was also concentrated onto a macroreticular resin and fractionation into three operationally defined fractions: hydrophilic acids (Hyd), humic acids (HA) and fulvic acids (FA). In this manner, change in absolute solution concentration and relative percentage for each fraction could be calculated as a function of extraction equilibrium pH. The soils were also analyzed for solid phase total organic carbon and total recoverable metals (EPA Method 3051). Partitioning coefficients were calculated for the metals and organic carbon (OC) based on solid phase concentrations (less the metal or OC removed by the extraction) divided by solution concentrations. Cu and Pb concentrations in solution as a function of extract equilibrium pH are greatest at low and high pH resulting in parabolic desorption/dissolution curves. While processes such as proton competition and proton promoted dissolution can account for high solution metal concentrations at low pH, these processes cannot account for higher Cu and Pb concentrations at high pH. DOC increases with increasing pH, concurrently with the increase in Cu and Pb solution concentrations. While the absolute concentrations of FA and HA generally increase with increasing pH, the relative proportional increase is greatest for HA . Variation in HA concentrations spans three orders of magnitude while FA concentrations vary an order of magnitude over the pH range examined. Correlation analysis strongly suggests that HA plays a major role in increasing the concentration of solution Cu and Pb with increasing pH in the 18 soils studied. The percentage of the OC that was due to FA was nearly constant over a wide pH range although the FA concentration increased with increasing pH and its concentration was greater than that of the HA fraction at lower pH values (pH = 3-5). Thus, in more acidic environments, FA may play a larger role than HA in governing organo-metallic interactions. For Cd, Ni, and Zn, the desorption/dissolution pattern shows high metal solution concentrations at low pH with slight increases in solution concentrations at extremely high pH values (pH>10). The results presented here suggest that the effects of dissolved organic carbon on the mobilization of Cd, Ni, and Zn may only occur in systems governed by very high pH. At high pH, it is difficult to distinguish in this study whether the slightly increased solution-phase concentrations of these cations is due to DOC or hydrolysis reactions. These high pH environments would rarely occur in natural settings.