Complexation of Aqueous Elements by DOC in a Clay Aquitard

Abstract

The extent of partitioning of several elements (Cu, Mn, Mo, Ni, Sr, U, and Zn) on dissolved organic carbon (DOC) was investigated in pore water samples collected from a clay-rich aquitard. High DOC concentrations in the aquitard, ranging from 21 to 143 mg C/L, and natural aqueous metal concentrations higher than in most ground water environments facilitated complexation studies at this site. Analyses were conducted using on-line coupling of asymmetrical flow field-flow fractionation with ultraviolet, total organic carbon, and inductively coupled plasma-mass spectrometry detectors. Of the elements investigated, only U and Zn were complexed with all DOC samples, ranging from 2.2 to 60 microg U/g DOC (0.4% to 3% of the total U in the pore water) and 0.04 to 0.5 microg Zn/g DOC (0.1% to 0.9% of the total Zn in the pore water), respectively. Laboratory experiments conducted over a range in pH (1.3 to 9.7) and geochemical modeling supported the measured complexation of U and Zn on the DOC. The in situ association constant, K(d), for U decreased with depth from 76 mL/g C for pore water samples at 2.2 m below ground (BG) to 24 mL/g C at 9.7 m BG. The decrease was attributed to a decrease in aromaticity of the DOC with depth. Zn K(d)constants ranged from 2 to 12 mL/g C and exhibited no trend with depth. Results of the current study suggest minor masses of U and Zn (less than or equal to 4% of total) complex with this DOC under in situ pH conditions. Our data suggest that competitive complexation by other ligands may limit the importance of DOC-facilitated transport of the elements studied in water of similar chemical composition.