What Do We Know about DOM Chemical Composition Based on Its Optical Properties?

Dissolved organic matter (DOM) optical measurements (UV-Vis light absorbance and fluorescence) provide useful information related to DOM composition and reactivity, and can serve as proxies for DOM concentration and the concentrations of some metals, such as mercury. While these measurements are useful for a range of objectives, they only measure aromatic molecules that absorb UV-Vis light and a smaller subset of these molecules that fluoresce. They provide no information about the substantial fraction of DOM that is non-chromophoric. Based on chromatographic fractionation on XAD resins, DOM optical properties measured on whole water samples strongly correlate with both the concentration and composition of the hydrophobic acid (HPOA) fraction of the DOM. In this presentation the results of DOM optical measurements, DOM fractionation analyses, and ¹³C-nuclear magnetic resonance (NMR) and ultrahigh-resolution mass spectrometry (FTICR_MS) of HPOA fractions obtained from a wide range a natural waters will be presented to examine the relationships between DOM optical properties and DOM chemical composition. The HPOA fractions within and between rivers exhibit a wide range of optical behaviors reflective of sources and transformations compared to other DOM fractions. While, ¹³C-NMR and FTICR-MS analyses generally show greater relative concentrations of aromatic molecules for those samples with strong optical signals, they also indicate that the HPOA fractions are mostly composed of a large number of non-chromophoric molecules, such as carbohydrates carboxyl-rich alicyclic molecules (CRAM), and other aliphatic molecules, all of which have implications regarding DOM reactivity, biolability, sources, and age. The utility and short-comings of employing optical data for assessing sources and transformations of DOM in natural waters will be examined using case studies involving organic matter in the Yukon River Basin and riverine export of DOM to the Gulf of Maine.