Seasonal Changes in Estuarine Dissolved Organic Matter Due to Variations in Discharge, Flushing Times and Wind-driven Mixing Events

Estuaries are highly productive habitats that transport and transform organic matter (OM), experience large changes in ionic composition and act as a transition zone between terrestrial and marine environments (Paerl et al. 1998; Markager et al. 2011; Osburn et al. 2012). OM source and matrix effects (such as salinity and pH) influence the chemical structure of DOM in estuaries and therefore affect its bioavailability, photo-reactivity, and its overall fate in these systems (Jaffe et al. 2004; Boyd et al. 2010; Pace et al. 2012; Osburn et al. 2012; Cawley et al. 2013). Within estuaries, dissolved organic matter (DOM) is a heterogeneous mixture of aromatic and aliphatic compounds, and its composition in aquatic systems varies spatially and temporally with source (Bauer and Bianchi 2011). However, the main source of DOM in estuaries, rivers and other aquatic systems, originates from vascular plant detritus, soil humus, older fossil (i.e., petrogenic) organic carbon, black carbon, marine OM and in situ production (Hedges 2002; Houghton 2007; Bauer and Bianchi 2011).;Chromophoric dissolved organic matter (CDOM), the light absorbing fraction of DOM, can be characterized using optical methods such as absorption and fluorescence spectroscopy (e.g. Coble, 1996; Stedmon and Markager, 2003). By analyzing the spatial and temporal variability of DOM and CDOM within estuaries, information pertaining to OM source and fate across the freshwater-marine continuum can be obtained. These methods offer an inexpensive, non-destructive means for obtaining sensitive measurements of a diverse group of organic compounds. By using this technology to analyze the spatial and temporal variability of CDOM within estuaries, information pertaining to OM source and fate across the freshwater-marine continuum can be obtained (Fellman et al. 2011; Osburn et al. 2012; Murphy et al. 2014).;Chemical biomarkers are also routinely used to identify DOM sources in coastal waters. Examples are carbon stable isotopes (Bauer, 2002) and lignin (e.g., Benner and Opsahl, 2001; Harvey and Mannino, 2001). Marine DOM derived from phytoplankton typically has carbon stable isotope (delta13C) values that range from --20 to --22‰, while terrestrial DOM derived from C3 land plants typically have delta13C values that range from --26 to --28‰ (Bauer, 2002). Lignin is an important component of vascular plants, thus making it a unique geochemical biomarker, which can be used to trace the fate of terrestrial DOM in coastal seawater (e.g., Hernes and Benner, 2003; Walker et al. 2009; Osburn and Stedmon, 2011). Further, the ratios of the different phenolic compounds derived from the oxidation of lignin can be used to distinguish between plant sources (e.g. angiosperm vs. gymnosperm, or woody vs. non-woody tissue) and the extent of exposure to degradation (Hedges et al. 1988).;The highly productive, eutrophic waters of the Neuse River Estuary (NRE), in eastern North Carolina, USA, serve as a transition zone for terrigenous DOM between the head of the Neuse River and Pamlico Sound. Previous studies have determined that the NRE is dominated by inputs from riverine discharge, yet very clear shifts in DOM quality are apparent as discharge varied (Paerl et al. 1998; Osburn et al. 2012). Furthermore, flushing times within the NRE will aid in determining whether DOM is primarily autochthonous or allochthonous and if it is processed internally or transported downstream to the Pamlico Sound (Paerl et al. 1998; Mari et al. 2007, Peierls et al. 2012). Therefore, the main sources of DOM and its composition can change throughout an estuary depending on the hydrodynamic conditions. For example, increases in flushing time may allow for the accumulation of autochthonous DOM because of (1) planktonic communities within the water column having more time to utilize nutrients within the system, resulting in phytoplankton blooms and (2) lower inputs of allochthonous OM from the NRE's watershed (Dixon et al. accepted). Therefore, the main sources of DOM and its composition can change throughout an estuary depending on the hydrodynamic conditions.