Emerging investigator series: critical review of photophysical models for the optical and photochemical properties of dissolved organic matter.

Optical measurements (absorbance and fluorescence) are widely used to track dissolved organic matter (DOM) quantity and quality in natural and engineered systems. Despite many decades of research on the optical properties of DOM, there is a lack of understanding with regards to the underlying photophysical model that is the basis for these optical properties. This review both summarizes advances to date on the photophysical properties of DOM and seeks to critically evaluate the photophysical models for DOM optical properties. Recent studies have refined the quantitative understanding of DOM photophysical properties such as excited state lifetimes and energies, rates of different photophysical processes, and quantum yields. Considering fundamental models, more clarity is needed on whether DOM photophysical processes are due to a superposition of non-interacting components (superposition model), or whether a portion of optical signals can be ascribed to electronically interacting moieties, for example in the form of electron donor-acceptor complexes (charge transfer model). Multiple studies over more than two decades have provided evidence for the charge transfer model. Questions have been raised, however, about the broad applicability of the charge transfer model. The charge transfer and superposition model are critically reviewed in light of this current research. Recommendations are given for future studies to help clarify the accuracy of these competing photophysical models.