We present a new stable isotope mass balance method for measuring the enhanced aqueous solubility of specific organic compounds in the presence of natural dissolved organic matter (DOM). It involves interfacing a standard dissolved organic carbon (DOC) analyzer with a stable isotope ratio monitoring system, is applicable to a wide range of model organic compounds and can be tuned to provide maximum precision for a given range of compound solubility and initial natural DOC concentration. Using 13C-labeled styrene as a model compound, we applied the method to investigate the reactivity of Dismal Swamp DOM as a function of season, nominal molecular size and chemical composition as determined using Fourier Transform Infrared Spectroscopy (FTIR). The solubility enhancement of styrene ranged from 23% to 118% relative to deionized water, while DOC-normalized enhancements varied from about 0.04 to 0.35 μM styrene/μM DOC as a function of season and nominal molecular weight. Statistical analysis of FTIR spectra reveals a strong positive correlation between the styrene concentration and the carboxyl content of the natural DOM. Reactivity differences between high molecular weight (HMW), low molecular weight (LMW) and total DOM samples are consistent with potential variations in their higher order structures.
Bibliographical noteFunding Information:
We thank to L. Mier (REU MUST Program) for help in setting up the DOC-IRMS system and two anonymous reviewers for constructive comments. The work was supported by the National Science Foundation (OCE 0453777 to R.F.D and E.C.M).