Groundwater travel times predict DOC in streams and riparian soils across a heterogeneous boreal landscape.

Dissolved organic carbon (DOC) in surface waters is an important component of the boreal landscape carbon budget and a critical variable in water quality. A dominant terrestrial DOC source in the boreal landscape is the riparian zone. These near stream areas play a key role in regulating DOC transport between land and aquatic ecosystems. The groundwater dynamics at this interface have been considered a major controlling variable for DOC export to streams. This study focuses on the regulating role of groundwater levels and mean travel times (MTT) on riparian DOC concentrations and, subsequently, stream DOC. This is done by comparing them as explanatory variables to capture the spatial and intra-annual variability of the stream and riparian groundwater DOC. We used a physically based 3D hydrological model, Mike SHE, to simulate DOC concentrations of the riparian zones for 14 sub-catchments within the Krycklan catchment (Sweden). The model concept assumes that DOC concentrations will be higher in groundwater moving through shallow flow paths. In the model, this can be linked to the position of the groundwater table at a point of observation or the travel time, which will generally be shorter for water that has travelled through shallow and more conductive soil layers. We compared the results with both observed stream and groundwater concentrations. The analysis revealed that the correlation between modelled and observed annual averages of stream DOC increased from r = 0.08 to r = 0.87 by using MTT instead of groundwater level. MTT also better captured the observed spatial variability in riparian DOC concentrations and more successfully represented seasonal variability of stream DOC. We, therefore, suggest that MTT is a better predictor than groundwater level for riparian DOC concentration because it can capture a greater variety of catchment heterogeneities, such as variation in soil properties, catchment size, and input from deep groundwater sources.

Hydrological control of water quality - Modelling base cation weathering and dynamics across heterogeneous boreal catchments.

Linking biogeochemical processes to water flow paths and solute travel times is important for understanding internal catchment functioning and control of water quality. Base cation weathering is a process closely linked to key factors affecting catchment functioning, including water pathways, soil contact time, and catchment characteristics, particularly in silicate-dominated areas. However, common process-based weathering models are often calibrated and applied for individual soil profiles, which can cause problems when trying to extrapolate results to catchment scale and assess consequences for stream water and groundwater quality. Therefore, in this work, base cation export was instead modelled using a fully calibrated 3D hydrological model (Mike SHE) of a boreal catchment, which was expanded by adding a relatively simple but still reasonably flexible and versatile weathering module including the base cations Na, K, Mg, and Ca. The results were evaluated using a comprehensive dataset of water chemistry from groundwater and stream water in 14 nested sub-catchments, representing different catchment sizes and catchment characteristics. The strongest correlations with annual and seasonal observations were found for Ca (r = 0.89-0.93, p < 0.05), Mg (r = 0.90-0.95, p < 0.05), and Na (r = 0.80-0.89, p < 0.05). These strong correlations suggest that catchment hydrology and landscape properties primarily control weathering rates and stream dynamics of these solutes. Furthermore, catchment export of Mg, Ca, and K was strongly connected to travel times of discharging stream water (r = 0.78-0.83). Conversely, increasing Na export was linked to a reduced areal proportion of mires (r = -0.79). The results suggest that a significant part (~45%) of the catchment stream export came from deep-soil weathering sources (>2.5 m). These results have implications for terrestrial and aquatic water quality assessments. If deep soils are present, focusing mainly on the shallow soil could lead to misrepresentation of base cation availability and the acidification sensitivity of groundwater and water recipients such as streams and lakes.

Metal transport in the boreal landscape-the role of wetlands and the affinity for organic matter.

Stream water concentrations of 13 major and trace elements (Al, Ba, Ca, Cr, Cu, La, Mg, Na, Ni, Si, Sr, U, Y) were used to estimate fluxes from 15 boreal catchments. All elements displayed a significant negative correlation to the wetland coverage, but the influence of wetlands was stronger for organophilic metals; 73% of the spatial differences in the normalized element fluxes could be explained based only on the wetland coverage and the affinity for organic matter, which was quantified using thermodynamic modeling. When the analysis was restrained to the smaller streams (<10 km(2)) the explanatory power increased to 88%. The results suggest that wetlands may decrease the fluxes of metals from boreal forests to downstream recipients by up to 40% at otherwise similar runoff. We suggest that the decrease in element fluxes is caused by a combination of low weathering in peat soils and accumulation of organophilic metals in peat. The model could not explain the spatial patterns for some metals with low affinity for organic matter, some redox-sensitive metals, and some metals with exceptionally high atmospheric deposition, but the results still demonstrate that wetlands play an important role for the biogeochemical cycling of many metals in the boreal landscape.

Distribution and transport of radionuclides in a boreal mire--assessing past, present and future accumulation of uranium, thorium and radium.

The spatial distribution of (238)U, (226)Ra, (40)K and the daughters of (232)Th, (228)Ra and (228)Th, were measured in a small mire in northern Sweden. High activity concentrations of (238)U and (232)Th (up to 41 Bq (238)U kg(-1)) were observed in parts of the mire with a historical or current inflow of groundwater from the surrounding till soils, but the activities declined rapidly further out in the mire. Near the outlet and in the central parts of the mire the activity concentrations were low, indicating that uranium and thorium are immobilized rapidly upon their entering the peat. The (226)Ra was found to be more mobile with high activity concentrations further out into the mire (up to 24 Bq kg(-1)), although the central parts and the area near the outlet of the mire still had low activity concentrations. Based on the fluxes to and from the mire, it was estimated that approximately 60-70% of the uranium and thorium entering the mire currently is retained within it. The current accumulation rates were found to be consistent with the historical accumulation, but possibly lower. Since much of the accumulation still is concentrated to the edges of the mire and the activities are low compared to other measurements of these radionuclides in peat, there are no indications that the mire will be saturated with respect to radionuclides like uranium, thorium and radium in the foreseen future. On the contrary, normal peat growth rates for the region suggest that the average activity concentrations of the peat currently may be decreasing, since peat growth may be faster than the accumulation of radionuclides. In order to assess the total potential for accumulation of radionuclides more thoroughly it would, however, be necessary to also investigate the behaviour of other organophilic elements like aluminium, which are likely to compete for binding sites on the organic material. Measurements of the redox potential and other redox indicators demonstrate that uranium possibly could be reduced in parts of the mire. The results of the study suggest that this mire currently is, and historically has been, an important sink for radionuclides and that it most likely will continue to be so for a long time to come.

Selenium dynamics in boreal streams: the role of wetlands and changing groundwater tables.

The concentrations of selenium in 10 catchments of a stream network in northern Sweden were monitored over two years, yielding almost 350 observations of selenium concentrations in streamwater. The export of selenium was found to be systematically greater from forests than from mires. Accounting for atmospheric deposition, which was monitored over four years, there was a net accumulation of selenium in mires, while the export from forest soils was approximately equal to the atmospheric deposition. In forest dominated catchments the concentrations of selenium oscillated rapidly back and forth from high to low levels during spring floods. High selenium concentrations coincided with rising groundwater tables in the riparian forest soils, while low selenium concentrations were associated with receding groundwater. Thermodynamic modeling indicated that precipitation of elemental selenium would occur under reducing conditions in the riparian soils. Since changes in the redox conditions are likely to occur near the transition from the unsaturated to the saturated zone, it is hypothesized that the transport of selenium from forest soils to streams is controlled by redox reactions in riparian soils.