Controls of Land Use and the River Continuum Concept on Dissolved Organic Matter Composition in an Anthropogenically Disturbed Subtropical Watershed.

About 250 Tg of dissolved organic carbon are annually transported from inland waters to coastal systems making rivers a critical link between terrestrial and ocean carbon pools. During transport through fluvial systems, various biogeochemical processes selectively remove or transform labile material, effectively altering the composition of dissolved organic matter (DOM) exported to the ocean. The river continuum concept (RCC) has been historically used as a model to predict the fate and quality of organic matter along a river continuum. However, the conversion of natural landscapes for urban and agricultural practices can also alter the sources and quality of DOM exported from fluvial systems, and the RCC may be significantly limited in predicting DOM quality in anthropogenically impacted watersheds. Here, we studied DOM dynamics in the Altamaha River watershed in Georgia, USA, a fluvial system where headwater streams are highly impacted by anthropogenic activities. The primary goal of this study was to quantitatively assess the importance of both the RCC and land use as environmental drivers controlling DOM composition. Land use was a stronger predictor of spatial variation (∼50%) in DOM composition defined by both excitation-emission matrix-parallel factor analysis (EEM-PARAFAC) and ultrahigh-resolution mass spectrometry. This is compared to an 8% explained variability that can be attributed to the RCC. This study highlights the importance of incorporating land use among other controls into the RCC to better predict the fate and quality of DOM exported from terrestrial to coastal systems.

Biogeochemistry of upland to wetland soils, sediments, and surface waters across Mid-Atlantic and Great Lakes coastal interfaces.

Transferable and mechanistic understanding of cross-scale interactions is necessary to predict how coastal systems respond to global change. Cohesive datasets across geographically distributed sites can be used to examine how transferable a mechanistic understanding of coastal ecosystem control points is. To address the above research objectives, data were collected by the EXploration of Coastal Hydrobiogeochemistry Across a Network of Gradients and Experiments (EXCHANGE) Consortium - a regionally distributed network of researchers that collaborated on experimental design, methodology, collection, analysis, and publication. The EXCHANGE Consortium collected samples from 52 coastal terrestrial-aquatic interfaces (TAIs) during Fall of 2021. At each TAI, samples collected include soils from across a transverse elevation gradient (i.e., coastal upland forest, transitional forest, and wetland soils), surface waters, and nearshore sediments across research sites in the Great Lakes and Mid-Atlantic regions (Chesapeake and Delaware Bays) of the continental USA. The first campaign measures surface water quality parameters, bulk geochemical parameters on water, soil, and sediment samples, and physicochemical parameters of sediment and soil.

Agricultural land use changes stream dissolved organic matter via altering soil inputs to streams.

Agricultural land use leads to significant changes in both the quality (e.g., sources and compositions) and quantity of dissolved organic matter (DOM) exported from terrestrial to aquatic ecosystems. However, the effect of agricultural activities often interacts with those of hydroclimatic drivers, making it difficult to delineate agriculture-induced changes and identify associated mechanisms. Using partial least square path modeling (PLS-PM), we examined the relative importance of agricultural land use, stream order, precipitation, and temperature in mediating allochthonous versus autochthonous sources and pathways that influenced stream DOM quality and quantity. We analyzed stream water DOM from 15 small streams draining watersheds across a gradient of agricultural land use in Southeast USA for about one year. For DOM quantity, agricultural land use increased the export of DOC and various DOM pools (terrestrial humic, microbial humic, and protein-like DOM) from land to streams, and for DOM quality, agricultural streams showed greater proportions of microbial humic compounds than forested streams. The PLS-PM model for DOM quantity accounted for 75.5% of total variance and identified that agricultural land use increased stream water DOM quantity primarily through increasing allochthonous inputs, which can be attributed to shallower flow paths in agricultural watersheds that enabled the export of organic materials from the upper, organic-rich soil horizon. PLS-PM models for DOM quality only explained ~13% of the total variance, highlighting the complex dynamics between environmental drivers and stream water DOM. Relative to commonly used multivariate statistic modeling (e.g., redundancy analysis (RDA)), PLS-PM models offer the advantages of identifying the primary pathway by which agricultural lands alter freshwater DOM and quantifying the relative importance of interactive effects of agriculture and hydroclimatic drivers. Therefore, structural equation modeling is a powerful tool that should be more widely adopted to distinguish among multiple drivers and mechanisms regulating freshwater biogeochemistry.

Surface waters as a sink and source of atmospheric gas phase ethanol.

This study reports the first ethanol concentrations in fresh and estuarine waters and greatly expands the current data set for coastal ocean waters. Concentrations for 153 individual measurements of 11 freshwater sites ranged from 5 to 598 nM. Concentrations obtained for one estuarine transect ranged from 56 to 77 nM and levels in five coastal ocean depth profiles ranged from 81 to 334 nM. Variability in ethanol concentrations was high and appears to be driven primarily by photochemical and biological processes. 47 gas phase concentrations of ethanol were also obtained during this study to determine the surface water degree of saturation with respect to the atmosphere. Generally fresh and estuarine waters were undersaturated indicating they are not a source and may be a net sink for atmospheric ethanol in this region. Aqueous phase ethanol is likely converted rapidly to acetaldehyde in these aquatic ecosystems creating the undersaturated conditions resulting in this previously unrecognized sink for atmospheric ethanol. Coastal ocean waters may act as either a sink or source of atmospheric ethanol depending on the partial pressure of ethanol in the overlying air mass. Results from this study are significant because they suggest that surface waters may act as an important vector for the uptake of ethanol emitted into the atmosphere including ethanol from biofuel production and usage.