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Streams in the southeastern United States Coastal Plains serve as an essential source of energy and nutrients for important estuarine ecosystems, and dissolved organic matter (DOM) exported from these streams can have profound impacts on the biogeochemical and ecological functions of fluvial networks. Here, we examined hydrological and temperature controls of DOM during low-flow periods from a forested stream located within the Coastal Plain physiographic region of Alabama, USA. We analyzed DOM via combining dissolved organic carbon (DOC) analysis, fluorescence excitation–emission matrix combined with parallel factor analysis (EEM-PARAFAC), and microbial degradation experiments. Four fluorescence components were identified: terrestrial humic-like DOM, microbial humic-like DOM, tyrosine-like DOM, and tryptophan-like DOM. Humic-like DOM accounted for ~70% of total fluorescence, and biodegradation experiments showed that it was less bioreactive than protein-like DOM that accounted for ~30% of total fluorescence. This observation indicates fluorescent DOM (FDOM) was controlled primarily by soil inputs and not substantially influenced by instream production and processing, suggesting that the bulk of FDOM in these streams is transported to downstream environments with limited in situ modification. Linear regression and redundancy analysis models identified that the seasonal variations in DOM were dictated primarily by hydrology and temperature. Overall, high discharge and shallow flow paths led to the enrichment of less-degraded DOM with higher percentages of microbial humic-like and tyrosine-like compounds, whereas high temperatures favored the accumulation of high-aromaticity, high-molecular-weight, terrestrial, humic-like compounds in stream water. The flux of DOC and four fluorescence components was driven primarily by water discharge. Thus, the instantaneous exports of both refractory humic-like DOM and reactive protein-like DOM were higher in wetter seasons (winter and spring). As high temperatures and severe precipitation are projected to become more prominent in the southeastern U.S. due to climate change, our findings have important implications for future changes in the amount, source, and composition of DOM in Coastal Plain streams and the associated impacts on downstream carbon and nutrient supplies and water quality.
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DOM Molecular Weight Fractionation and Fluorescence Quantum Yield Assessment Using a Coupled In-Line SEC Optical Property System
Size exclusion chromatography (SEC) in combination with optical measurements has become a popular form of analysis to characterize dissolved organic matter (DOM) as a function of molecular size. Here, SEC coupled with in-line absorbance scans and fluorescence emission scans was utilized to derive apparent fluorescence quantum yield (Φf) as a function of molecular weight (MW) for DOM. Individual instrument-specific SEC-fluorescence detector correction factors were developed by comparison of an SEC-based excitation emission matrix (EEM) to an EEM generated by a calibrated benchtop fluorometer. The method was then applied to several sample sets to demonstrate how to measure the Φf of unknown DOM samples and to observe changes to Φf following a processing mechanism (ozonation). The Φf of riverine water samples and DOM fulvic acid isolates from Suwannee River and Pony Lake increased from < 0.5% to a maximum of ∼2.5–3% across the medium- to low-MW range. Following ozonation of PLFA, Φf increased most notably in the large-MW fractions (elution volumes < 40 mL). Overall, this method provides a means by which highly fluorescent size fractions of DOM can be identified for more detailed analyses of chemical composition and its changes through different processing mechanisms.
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- PAR ID:
- 10382794
- Date Published:
- Journal Name:
- ACS ES&T Water
- ISSN:
- 2690-0637
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acsestwater.2c00318
