Meta-Analysis of Optical Surrogates for the Characterization of Dissolved Organic Matter.

Abstract

Optical surrogates, derived from absorbance and fluorescence spectra, are widely used to infer dissolved organic matter (DOM) composition (molecular weight, aromaticity) and genesis (autochthonous vs allochthonous). Despite the broad adoption of optical surrogates, several limitations exist, such as context- and sample-specific factors. These limitations create uncertainty about how compositional interpretations based on optical surrogates are generalized across contexts, specifically if there is duplicative or contradictory information in those interpretations. To explore these limitations, we performed a meta-analysis of optical surrogates for DOM from diverse sources, both from natural systems and after water treatment processes (n = 762). Prior to analysis, data were screened using a newly developed, standardized methodology that applies systematic quality control criteria before reporting surrogates. There was substantial overlap in surrogate values from natural and treated samples, suggesting that the gradients governing the surrogate variability can be generated in both contexts. This overlap provides justification for using optical surrogates originally developed in the context of natural systems to describe DOM changes in engineered systems, although the interpretations may change. Absorbance-based surrogates that describe the amount of spectral tailing (e.g., E2:E3 and S275-295) had a high frequency of strong correlations with one another but not to specific absorbance (SUVA254) or absorbance slope ratio (SR). The fluorescence index (FI) and biological index (β/α) were strongly correlated with one another and to the peak emission wavelength but not to the humification index (HIX). Although SUVA254 and FI have both been correlated to DOM aromaticity in prior research, there was a lack of reciprocity between these optical surrogates across this data set. Additionally, there were patterns of deviations in the wastewater subset, suggesting that effluent organic matter may not follow conventional interpretations, urging caution in the use of optical surrogates to track DOM in water reuse applications. Finally, the meta-analysis highlights that three aspects should be captured when optical spectra are used for DOM interpretation: specific absorbance, absorbance tailing, and the extent of red-shifted fluorescence. We recommend that SUVA254, E2:E3, and FI or β/α be prioritized in future DOM studies to capture these aspects, respectively.