Sorption Selectivity in Natural Organic Matter Probed with Fully Deuterium-Exchanged and Carbonyl-13C-Labeled Benzophenone and 1H–13C NMR Spectroscopy

Xiaoyan Cao , C. Lattao , J. -J. Pignatello , Jingdong Mao # and Klaus Schmidt-Rohr #
Environ. Sci. Technol.


Specific functional-group or domain interactions of fully deuterium-exchanged, carbonyl-13C-labeled benzophenone and different types of natural organic matter (NOM) were investigated through two-dimensional 1H–13C heteronuclear correlation NMR spectroscopy. The sorbents included Beulah-Zap lignite, type II kerogen (IL-6), Pahokee peat, Amherst humic acid, and a polystyrene-poly(vinylmethyl ether) (PS-PVME) blend. PS-PVME consists of PS and PVME chains that are mixed on a scale of <5 nm. The NOM sorbents all consist predominantly of a mixed aromatic–alkyl or aromatic–O-alkyl matrix that is homogeneous on the 3 nm scale, as evidenced by fast equilibration of aromatic and alkyl 1H magnetization. In addition, Beulah lignite and IL-6 kerogen exhibit small fractions of distinct polymethylene (CH2)n domains, and Pahokee peat contains significant fractions of polar and nonpolar alkyl domains. Benzophenone-(13C═O)-d10 shows proximity to both aromatic rings and alkyl segments in all samples but preferentially interacts with aromatic rings in PS-PVME and Beulah lignite, possibly due to π–π electron donor–acceptor interactions. The data for IL-6 kerogen are also compatible with preferential location of benzophenone near the alkyl-substituted edges of aromatic rings, while in Pahokee peat, clear signatures of benzophenone affinity to both aromatic-rich and nonpolar alkyl domains have been detected. Amherst humic acid shows evidence of some affinity to polar alkyl segments but which is weaker than that to aromatic rings. Our results indicate that specific interactions of the sorbate and the presence of domains in the sorbent influence the magnitude and selectivity of sorption.