José L. J. Ledesma

Long-term dynamics of dissolved organic carbon: Implications for drinking water supply

Surface waters are the main source of drinking water in many regions. Increasing organic carbon concentrations are a cause for concern in Nordic countries since both dissolved and particulate organic carbon can transport contaminants and adversely affect drinking water treatment processes. We present a long-term study of dynamics of total (particulate and dissolved) organic carbon (TOC) concentrations in the River Fyris. This river supplies drinking water to approximately 200000 people in Uppsala, Sweden. The River Fyris is a main tributary to Lake Mälaren, which supplies drinking water to approximately 2 million people in the greater Stockholm area. Utilities responsible for drinking water supply in both Uppsala and Stockholm have expressed concerns about possible increases in TOC. We evaluate organic carbon dynamics within the Fyris catchment by calculating areal mass exports using observed TOC concentrations and modeled flows and by modeling dissolved organic carbon (as a proxy for TOC) using the dynamic, process based INCA-C model. Exports of TOC from the catchment ranged from 0.8 to 5.8 g m(-2) year(-1) in the period 1995-2010. The variation in annual exports was related to climatic variability which influenced seasonality and amount of runoff. Exports and discharge uncoupled at the end of 2008. A dramatic increase in TOC concentrations was observed in 2009, which gradually declined in 2010-2011. INCA-C successfully reproduced the intra- and inter-annual variation in concentrations during 1996-2008 and 2010-2011 but failed to capture the anomalous increase in 2009. We evaluated a number of hypotheses to explain the anomaly in 2009 TOC values, ultimately none proved satisfactory. We draw two main conclusions: there is at least one unknown or unmeasured process controlling or influencing surface water TOC and INCA-C can be used as part of the decision-making process for current and future use of rivers for drinking water supply.

Boreal forest riparian zones regulate stream sulfate and dissolved organic carbon.

In boreal forest catchments, solute transfer to streams is controlled by hydrological and biogeochemical processes occurring in the riparian zone (RZ). However, RZs are spatially heterogeneous and information about solute chemistry is typically limited. This is problematic when making inferences about stream chemistry. Hypothetically, the strength of links between riparian and stream chemistry is time-scale dependent. Using a ten-year (2003-2012) dataset from a northern Swedish catchment, we evaluated the suitability of RZ data to infer stream dynamics at different time scales. We focus on the role of the RZ versus upslope soils in controlling sulfate (SO4(2)(-)) and dissolved organic carbon (DOC). A priori, declines in acid deposition and redox-mediated SO4(2)(-) pulses control sulfur (S) fluxes and pool dynamics, which in turn affect dissolved organic carbon (DOC). We found that the catchment is currently a net source of S, presumably due to release of the S pool accumulated during the acidification period. In both, RZ and stream, SO4(2-) concentrations are declining over time, whereas DOC is increasing. No temporal trends in SO4(2-) and DOC were observed in upslope mineral soils. SO4(2-) explained the variation of DOC in stream and RZ, but not in upslope mineral soil. Moreover, as SO4(2-) decreased with time, temporal variability of DOC increased. These observations indicate that: (1) SO4(2-) is still an important driver of DOC trends in boreal catchments and (2) RZ processes control stream SO4(2-) and subsequently DOC independently of upslope soils. These phenomena are likely occurring in many regions recovering from acidification. Because water flows through a heterogeneous mosaic of RZs before entering the stream, upscaling information from limited RZ data to the catchment level is problematic at short-time scales. However, for long-term trends and annual dynamics, the same data can provide reasonable representations of riparian processes and support meaningful inferences about stream chemistry.

Local‐ and landscape‐scale impacts of clear‐cuts and climate change on surface water dissolved organic carbon in boreal forests

Forest harvesting and climate change may significantly increase concentrations and fluxes of dissolved organic carbon (DOC) in boreal surface waters. However, the likely magnitude of any effect will vary depending on the landscape-element type and spatial scale. We used a chain of hydrological, empirical and process-based biogeochemical models coupled to an ensemble of downscaled Regional Climate Model (RCM) experiments to develop scenario storylines for local and landscape-scale effects of forest harvesting and climate change on surface water DOC concentrations and fluxes. Local-scale runoff, soil temperature and DOC dynamics were simulated for a range of forest and wetland landscape-element types and at the larger landscape scale. The results indicated that climate change will likely lead to greater winter flows and earlier, smaller spring peaks. Both forest harvesting and climate change scenarios resulted in large increases in summer and autumn runoff and higher DOC fluxes. Forest harvesting effects were clearly apparent at local scales. While at the landscape scale, approximately 1 mg L−1 (or 10%) of the DOC in surface waters can be attributed to clear-cuts, both climate change and intensified forestry can each increase DOC concentrations by another 1 mg L−1 in the future, which is less than that seen in many waterbodies recovering from acidification. These effects of forestry and climate change on surface water DOC concentrations are additive at a landscape scale but not at the local scale, where a range of landscape-element specific responses were observed.

Towards an Improved Conceptualization of Riparian Zones in Boreal Forest Headwaters

The boreal ecoregion supports about one-third of the world’s forest. Over 90% of boreal forest streams are found in headwaters, where terrestrial–aquatic interfaces are dominated by organic matter (OM)-rich riparian zones (RZs). Because these transition zones are key features controlling catchment biogeochemistry, appropriate RZ conceptualizations are needed to sustainably manage surface water quality in the face of a changing climate and increased demands for forest biomass. Here we present a simple, yet comprehensive, conceptualization of RZ function based on hydrological connectivity, biogeochemical processes, and spatial heterogeneity. We consider four dimensions of hydrological connectivity: (1) laterally along hillslopes, (2) longitudinally along the stream, (3) vertically down the riparian profile, and (4) temporally through event-based and seasonal changes in hydrology. Of particular importance is the vertical dimension, characterized by a ‘Dominant Source Layer’ that has the highest contribution to solute and water fluxes to streams. In addition to serving as the primary source of OM to boreal streams, RZs shape water chemistry through two sets of OM-dependent biogeochemical processes: (1) transport and retention of OM-associated material and (2) redox-mediated transformations controlled by RZ water residence time and availability of labile OM. These processes can lead to both retention and release of pollutants. Variations in width, hydrological connectivity, and OM storage drive spatial heterogeneity in RZ biogeochemical function. This conceptualization provides a useful theoretical framework for environmental scientists and ecologically sustainable and economically effective forest management in the boreal region and elsewhere, where forest headwaters are dominated by low-gradient, OM-rich RZs.

Evaluating hillslope and riparian contributions to dissolved nitrogen (N) export from a boreal forest catchment

Catchment science has long held that the chemistry of small streams reflects the landscapes they drain. However, understanding the contribution of different landscape units to stream chemistry remains a challenge which frequently limits our understanding of export dynamics. For limiting nutrients such as nitrogen (N), an implicit assumption is that the most spatially extensive landscape units (e.g., uplands) act as the primary sources to surface waters, while near-stream zones function more often as sinks. These assumptions, based largely on studies in high-gradient systems or in regions with elevated inputs of anthropogenic N, may not apply to low-gradient, nutrient-poor, and peat-rich catchments characteristic of many northern ecosystems. We quantified patterns of N mobilization along a hillslope transect in a northern boreal catchment to assess the extent to which organic matter-rich riparian soils regulate the flux of N to streams. Contrary to the prevailing view of riparian functioning, we found that near-stream, organic soils supported concentrations and fluxes of ammonium (NH4+) and dissolved organic nitrogen that were much higher than the contributing upslope forest soils. These results suggest that stream N chemistry is connected to N mobilization and mineralization within the riparian zone rather than the wider landscape. Results further suggest that water table fluctuation in near-surface riparian soils may promote elevated rates of net N mineralization in these landscapes.

The interplay between total mercury, methylmercury and dissolved organic matter in fluvial systems: A latitudinal study across Europe

Large-scale studies are needed to identify the drivers of total mercury (THg) and monomethyl-mercury (MeHg) concentrations in aquatic ecosystems. Studies attempting to link dissolved organic matter (DOM) to levels of THg or MeHg are few and geographically constrained. Additionally, stream and river systems have been understudied as compared to lakes. Hence, the aim of this study was to examine the influence of DOM concentration and composition, morphological descriptors, land uses and water chemistry on THg and MeHg concentrations and the percentage of THg as MeHg (%MeHg) in 29 streams across Europe spanning from 41°N to 64 °N. THg concentrations (0.06-2.78 ng L-1) were highest in streams characterized by DOM with a high terrestrial soil signature and low nutrient content. MeHg concentrations (7.8-159 pg L-1) varied non-systematically across systems. Relationships between DOM bulk characteristics and THg and MeHg suggest that while soil derived DOM inputs control THg concentrations, autochthonous DOM (aquatically produced) and the availability of electron acceptors for Hg methylating microorganisms (e.g. sulfate) drive %MeHg and potentially MeHg concentration. Overall, these results highlight the large spatial variability in THg and MeHg concentrations at the European scale, and underscore the importance of DOM composition on mercury cycling in fluvial systems.

Long-Term Climatic and Anthropogenic Impacts on Streamwater Salinity in New York State: INCA Simulations Offer Cautious Optimism

The long-term application of road salts has led to a rise in surface water chloride (Cl-) concentrations. While models have been used to assess the potential future impacts of continued deicing practices, prior approaches have not incorporated changes in climate that are projected to impact hydrogeology in the 21st century. We use an INtegrated CAtchment (INCA) model to simulate Cl- concentrations in the Tioughnioga River watershed. The model was run over a baseline period (1961-1990) and climate simulations from a range of GCMs run over three 30-year intervals (2010-2039; 2040-2069; 2070-2099). Model projections suggest that Cl- concentrations in the two river branches will continue to rise for several decades, before beginning to decline around 2040-2069, with all GCM scenarios indicating reductions in snowfall and associated salt applications over the 21st century. The delay in stream response is most likely attributed to climate change and continued contribution of Cl- from aquifers. By 2100, surface water Cl- concentrations will decrease to below 1960s values. Catchments dominated by urban lands will experience a decrease in average surface water Cl-, although moderate compared to more rural catchments.

An evaluation of high frequency turbidity as a proxy for riverine total phosphorus concentrations

Surface water eutrophication resulting from excessive phosphorus (P) inputs is one of todays most challenging environmental issues. Riverine total phosphorus (TP) concentrations have high temporal variability, which complicates flux estimation. We evaluated the usefulness of high frequency in-situ turbidity measurements as a proxy for TP in Sävjaån, a river draining a mixed land use catchment (722 km2) in central Sweden. Turbidity was monitored every 10th-15th minute during 6 consecutive years (2012-2017). Linear regression showed a good relationship between high frequency turbidity and TP (r2 = 0.64) and could hence be used for comparison of flux estimation methods. Predictive power of the turbidity-TP relationship was not improved by adding seasons, hydrograph rising/falling limb or high/low stream discharge to the model which argues for a single transfer function relating turbidity and TP. Both TP and turbidity were log-normally distributed. However, flux estimates were sensitive to data transformation; predicted TP concentrations and fluxes based on log-transformed data were biased towards lower concentrations and fluxes compared to non-transformed data. In five of six years grab sample and high frequency estimated TP fluxes were similar (grab sample estimates -10% to +13% P transport compared to high frequency flux estimates). The exception was in 2013, when a 50-year spring flood occurred, and the grab sample estimated flux was 56% larger than that estimated from high frequency data. Thus, the flux comparisons were mostly affected by stream discharge, which underlines the importance of capturing high discharge episodes with, e.g. in situ sensors. While uncertainties regarding the use of turbidity as a proxy for TP remain, it is clear that credible water chemistry data can be obtained with current high frequency sensors. We conclude that high frequency data can be used to better understand catchment response to external pressures and gain insights into water quality that will be missed with grab sampling.

Stream Dissolved Organic Matter Composition Reflects the Riparian Zone, Not Upslope Soils in Boreal Forest Headwaters

Despite the strong quantitative evidence that riparian zones (RZs) are the dominant source of dissolved organic carbon (DOC) to boreal streams, there is still a debate about the potential contribution of upslope areas to fluvial carbon export. To shed new light into this debate, we investigated the molecular composition of dissolved organic matter (DOM) in four upslope-riparian-stream transects in a Northern Swedish forest catchment using absorbance (A254/A365 and SUVA254) and fluorescence (fluorescence and freshness indices) metrics. Based on these metrics, our results indicate that stream water DOM molecular composition resembles that of RZs and significantly differs from that of upslope areas. The resemblance between stream and riparian DOM was most apparent for the ‘‘Dominant Source Layer’’ (DSL), a narrow RZ stratum that, theoretically, contributes the most to solute and water fluxes to streams. Spectroscopic characterization based on traditional interpretations of the metrics suggested that mineral upslope (podzol) DOM is less aromatic, more microbially derived, and more recently produced than organic riparian (histosol) and stream DOM. We conclude that RZs, and specifically DSLs, are the main sources of DOC to boreal headwater streams and potentially to other streams located in low-gradient, organic matter-rich catchments. Plain Language Summary Understanding carbon cycling in natural ecosystems is critical because ongoing climate change can promote the release of previously stored carbon in forest soils to streams and rivers, with the potential to form carbon dioxide, the main greenhouse gas. This is particularly important in boreal ecosystems, which are the largest stores of terrestrial carbon in the world. In this study, we identify the near-stream area, the so-called riparian zone, as the main source of carbon from boreal forest soils to streams. We provide qualitative data to support this, which together with previous quantitative analyses, make up enough evidence to support that the riparian zone is the main source of carbon to streams. As there is still a debate about the potential contribution of other areas in the ecosystem to the fluvial carbon export, our study importantly highlights that the riparian zone should be the focus of scientific assessments and management strategies in relation to carbon exports in surface waters.

Minimal climate change impacts on natural organic matter forecasted for a potable water supply in Ireland

Natural organic matter poses an increasing challenge to water managers because of its potential adverse impacts on water treatment and distribution, and subsequently human health. Projections were made of impacts of climate change on dissolved organic carbon (DOC) in the primarily agricultural Boyne catchment which is used as a potable water supply in Ireland. The results indicated that excluding a potential rise in extreme precipitation, future projected loads are not dissimilar to those observed under current conditions. This is because projected increases in DOC concentrations are offset by corresponding decreases in precipitation and hence river flow. However, the results presented assume no changes in land use and highlight the predicted increase in DOC loads from abstracted waters at water treatment plants.