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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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Time series of in situ Uv-Vis absorbance spectra and high-frequency predictions of total and soluble Fe and Mn concentrations measured at multiple depths in Falling Creek Reservoir (Vinton, VA, USA) in 2020 and 2021
High-frequency measurements of light absorbance were collected at multiple depths in Falling Creek Reservoir (FCR; Vinton, VA, USA) using a s::can Spectrolyser UV-Visible spectrophotometer coupled with a multiplexor pumping system. The system pumps water samples from individual depths into a flow-through cuvette where the UV-vis absorbance spectra of the sample are measured by the spectrophotometer. The system used in our study collected measurements of light absorbance every 2.5 nm wavelengths from 200 nm to 732.5 nm (optical path length of 10 mm) approximately at an hourly time step for seven monitoring depths in the reservoir. Data was collected during two periods; the first deployment (16 October to 9 November 2020) was to observe changes in Fe and Mn concentrations before, during, and after reservoir fall turnover and the second deployment (26 May to 21 June 2021) was to observe the effects of engineered hypolimnetic oxygenation on Fe and Mn concentrations. Partial least squares regression models were developed to generate predictions of total and soluble Fe and Mn concentrations based on the correlation between absorbance spectra and sampling data.
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- PAR ID:
- 10478778
- Publisher / Repository:
- Environmental Data Initiative
- Date Published:
- Edition / Version:
- 1
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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