Seasonal and spatial variation in the chemical character of dissolved organic matter within a small boreal forest watershed

Dissolved organic matter (DOM) is a significant carbon reservoir and component of the terrestrial-to-aquatic flux (Qualls et al., 1991). The terrestrial-to-aquatic carbon flux, a relatively new addition to global carbon models, is currently estimated to transfer a total of 1.7 petagrams (Pg) carbon (C) yr⁻¹ globally (IPCC, 2013). Terrestrially derived DOM has been identified as a significant pool of organic matter in the aquatic environment. However, the quantity and chemical composition of DOM transferred, as well as the mechanisms driving its transfer, are less understood. This thesis focuses on expanding our knowledge of the processing DOM undergoes as it is transferred from terrestrial-to-aquatic environments by: 1) developing a standardized extraction methodology that can yield representative eluates when applied to sourced samples from throughout the terrestrial-to-aquatic interface and 2) applying the designed methodology to conduct a year long study of DOM quantity and composition in the terrestrial-to-aquatic interface in a boreal forest watershed. Experimental results suggest that although solid phase extraction with a divinyl benzene sorbent (SPE-PPL) yields high extraction efficiencies when applied to DOM, it is subject to selectivity. Extractions performed at high loading volumes were found to select against O-alkyl DOM hydrogen constituents, additionally all SPE-PPL experiments were found to select against nitrogenous DOM components. However, by considering proper extraction parameters, SPE-PPL can produce bulk representative eluates for nuclear magnetic resonance (NMR) analysis from land positions spanning the terrestrial-to-aquatic interface. Results from the field study revealed that DOM transferred from terrestrial-to-aquatic land positions in a boreal forest watershed is both temporally and regionally variable, however, proximity immediately downstream of ponds appeared to be a major hydrologic control, while seasonal variation in hydrologic flow paths may represent another control in boreal forest watersheds. Dissolved organic matter chemical composition and quantity in traditional boreal forest streams related to shifts in the hydraulic flow path of the watershed, indicated by changes in riverine DOM chemical composition that correlated to seasonal wet and dry periods. Increases in both dissolved organic carbon (DOC) concentration and the presence of O-alkyl DOM hydrogen functionalities in the stream indicated a shift from groundwater sources during the dry period to soil water sources during the wet period. Conversely streams downslope of ponds seemed to be buffered against shifts in DOM chemical composition associated with changes in hydrologic flow paths. Dissolved organic matter chemical composition of streams downslope of ponds were relatively constant throughout the year resembling the characterization of pond outflows, even during periods of high hydraulic conductivity, via additions of autochthonous DOM produced in the pond. These additions of autochthonous DOM are negligible in streams not downslope of ponds. Further application of this approach during key periods of DOM export, such as spring snowmelt and fall rain periods may prove help to reveal the processes controlling the terrestrial-to-aquatic carbon flux in boreal forest landscapes