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Abstract Dissolved organic matter (DOM) impacts the structure and function of aquatic ecosystems. DOM absorbs light in the UV and visible (UV–Vis) wavelengths, thus impacting light attenuation. Because absorption by DOM depends on its composition, UV–Vis absorbance is used to constrain DOM composition, source, and amount. Ferric iron, Fe(III), also absorbs in the UV–Vis; when Fe(III) is present, DOM-attributed absorbance is overestimated. Here, we explore how differing behavior of DOM and Fe(III) at the catchment scale impacts UV–Vis absorbance and evaluate how system-specific variability impacts the effectiveness of existing Fe(III) correction factors in a temperate watershed. We sampled five sites in the Connecticut River mainstem bi-weekly for ~ 1.5 years, and seven sites in the Connecticut River watershed once during the summer 2019. We utilized size fractionation to isolate the impact of DOM and Fe(III) on absorbance and show that variable contributions of Fe(III) to absorbance at 254 nm (a 254 ) and 412 nm (a 412 ) by size fraction complicates correction for Fe(III). We demonstrate that the overestimation of DOM-attributed absorbance by Fe(III) is correlated to the Fe(III):dissolved organic carbon concentration ratio; thus, overestimation can be high even when Fe(III) is low. a 254 overestimation is highly variable even within a single system, but can be as high as 53%. Finally, we illustrate that UV-Vis overestimation might impart bias to seasonal, discharge, and land-use trends in DOM quality. Together, these findings argue that Fe(III) should be measured in tandem with UV–Vis absorbance for estimates of CDOM composition or amount.
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This content will become publicly available on June 1, 2026
Optical transformation of riverine colored dissolved organic matter during salt-induced flocculation
Abstract Flocculation of riverine dissolved organic matter (DOM) in estuaries is crucial for transforming and removing terrestrial carbon inputs across the land-to-ocean aquatic continuum. We measured variations in chromophoric DOM (CDOM) absorption and fluorescence of riverine DOM through mixing experiments conducted across various seasons and environments, identifying patterns in salt-induced flocculation. Our observations show a systematic reduction in CDOM absorption in the 250–450 nm range at salinity 2, with a sharper decrease at higher wavelengths. Flocculation led to decreased relative fluorescence intensity below emission wavelength of 360 nm and an increased intensity at higher emission wavelengths across the excitation spectrum measured (250–450 nm). We introduce a new metric,red shift ratio, a fluorescence-based metric calculated as the ratio of emission intensity at 300–350 nm to that at 360–500 nm, at excitation wavelengths between 250 and 300 nm, for detecting flocculation-induced changes in CDOM across estuarine systems. The observed sensitivity of CDOM to flocculation in low salinities challenges its use as a conservative tracer in coastal gradients, suggesting that recalibrations are required for remote sensing algorithms and carbon flux estimations across land-sea continuum, particularly in systems with similar characteristics.
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- Award ID(s):
- 2049388
- PAR ID:
- 10617981
- Publisher / Repository:
- Springer
- Date Published:
- Journal Name:
- Biogeochemistry
- Volume:
- 168
- Issue:
- 3
- ISSN:
- 1573-515X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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