Effects of bedrock groundwater discharge on spatial variability of dissolved carbon,nitrogen, and phosphorous concentrations in stream water within a forest headwater catchment

The quantitative evaluation of the effects of bedrock groundwater discharge on spatial variability of stream dissolved organic carbon (DOC), dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorous (DIP) concentrations has still been insufficient. We examined the relationships between stream DOC, DIN and DIP concentrations and bedrock groundwater contribution to stream water in forest headwater catchments in warm-humid climate zones. We sampled stream water and bedrock springs at multiple points in September and December 2013 in a 5 km² forest headwater catchment in Japan and sampled groundwater in soil layer in small hillslopes. We assumed that stream water consisted of four end members, groundwater in soil layer and three types of bedrock groundwater, and calculated the contributions of each end member to stream water from mineral-derived solute concentrations. DOC, DIN and DIP concentrations in stream water were compared with the calculated bedrock groundwater contribution. The bedrock groundwater contribution had significant negative linear correlation with stream DOC concentration, no significant correlation with stream DIN concentration, and significant positive linear correlation with stream DIP concentration. These results highlighted the importance of bedrock groundwater discharge in establishing stream DOC and DIP concentrations. In addition, stream DOC and DIP concentrations were higher and lower, respectively, than those expected from end member mixing of groundwater in soil layer and bedrock springs. Spatial heterogeneity of DOC and DIP concentrations in groundwater and/or in-stream DOC production and DIP uptake were the probable reasons for these discrepancies. Our results indicate that the relationships between spatial variability of stream DOC, DIN and DIP concentrations and bedrock groundwater contribution are useful for comparing the processes that affect stream DOC, DIN and DIP concentrations among catchments beyond the spatial heterogeneity of hydrological and biogeochemical processes within a catchment.     

Mobilisation and transport of dissolved organic carbon and iron in peat catchments—Insights from the Lehstenbach stream in Germany using generalised additive models

During the last decades, increasing exports of both dissolved organic carbon (DOC) and iron were observed from peat catchments in North America and Europe with potential consequences for water quality of streamwater and carbon storages of soils. As mobilisation and transport processes of DOC and iron in peat catchments are only partly understood, the purpose of this study was to elucidate these processes in an intensively monitored and studied system. Specifically, it was hypothesised that dissimilatory iron reduction in riparian peatland soils mobilises DOC initially adsorbed to iron minerals. During stormflow conditions, both DOC and iron will be transported into the stream network. Ferrous iron may be reoxidised at redox interfaces on its way to the stream, and subsequently, ferric iron could be transported together with DOC as complexes. To test these hypotheses, generalised additive models (GAMs) were applied to 14 years of weekly time series of discharge and concentrations of selected solutes measured in a German headwater stream called Lehstenbach. This stream drains a 4.19‐km² forested mountain catchment; one third of which is covered by riparian peatland soils. We interpreted results of different types of GAM in the way that (a) iron reduction drove the mobilisation of DOC from peatland soils and that (b) both iron and DOC were transported as complexes after their joint mobilisation to and within the steam. It was speculated that low nitrate availability in the uppermost wetland soil layer, particularly during the growing season, promoted iron reduction and thus the mobilisation of DOC. However, the influence of nitrate on the DOC mobilisation remains relatively uncertain. This influence could be further investigated using methods similar to the GAM analysis conducted here for other catchments with long‐term data as well as detailed measurements of the relevant species in riparian wetland soils and the adjacent stream network.     

Hydrochemical behaviour of dissolved nitrogen and carbon in a headwater stream of the Canadian Shield: relevance of antecedent soil moisture conditions

This paper examines the impact of contrasting antecedent soil moisture conditions on the hydrochemical response, here the changes in dissolved nitrogen (NO₃^?, NH₄⁺ and dissolved organic nitrogen (DON)) and dissolved organic carbon (DOC) concentrations, of a first‐order stream during hydrological events. The study was performed in the Hermine, a 5 ha forested watershed of the Canadian Shield. It focused on a series of eight precipitation events (spring, summer and fall) sampled every 2 or 3 h and showing contrasted antecedent moisture conditions. The partition of the eight events between two groups (dry or wet) of antecedent moisture conditions was conducted using a principal component analysis (PCA). The partition was controlled (first axis explained 86% of the variability) by the antecedent streamflow, the streamflow to precipitation ratio Q/P and by the antecedent groundwater depth. The mean H⁺, NO₃^?, NH₄⁺, total dissolved nitrogen and DOC concentrations and electrical conductivity values in the stream were significantly higher following dry antecedent conditions than after wetter conditions had prevailed in the Hermine, although the temporal variability was high (17 to 138%). At the event scale, a significantly higher proportion of the changes in DON, NO₃^?, and DOC concentrations in the stream was explained by temporal variations in discharge compared with the seasonal and annual scales. Two of the key hydrochemical features of the dry events were the synchronous changes in DOC and flow and the frequent negative relationships between discharge and NO₃^?. The DON concentrations were much less responsive than DOC to changes in discharge, whereas NH was not in phase with streamflow. During wet events, the synchronicity between streamflow and DON or NO₃^? was higher than during dry events and discharge and NO₃^? were generally positively linked. Based on these observations, the hydrological behaviour of the Hermine is conceptually compatible with a two‐component model of shallow (DON and DOC rich; variable NO₃^?) and deep (DON and DOC poor; variable NO₃^?) subsurface flow. The high NO₃^? and DOC levels measured at the early stages of dry events reflected the contribution from NO₃^?‐rich groundwaters. The contribution of rapid surface flow on water‐repellent soil materials located close to the stream channel is hypothesized to explain the DOC levels. An understanding of the complex interactions between antecedent soil moisture conditions, the presence of soil nutrients available for leaching and the dynamics of soil water flow paths during storms is essential to explain the fluxes of dissolved nitrogen and carbon in streams of forested watersheds. Copyright © 2007 John Wiley & Sons, Ltd.     

Fluvial transport of suspended sediment and organic carbon during flood events in a large agricultural catchment in southwest France

Water draining from a large agricultural catchment of 1 110 km² in southwest France was sampled over an 18‐month period to determine the temporal variability in suspended sediment (SS) and dissolved (DOC) and particulate organic carbon (POC) transport during flood events, with quantification of fluxes and controlling factors, and to analyze the relationships between discharge and SS, DOC and POC. A total of 15 flood events were analyzed, providing extensive data on SS, POC and DOC during floods. There was high variability in SS, POC and DOC transport during different seasonal floods, with SS varying by event from 513 to 41 750 t; POC from 12 to 748 t and DOC from 9 to 218 t. Overall, 76 and 62% of total fluxes of POC and DOC occurred within 22% of the study period. POC and DOC export from the Save catchment amounted to 3090 t and 1240 t, equivalent to 1·8 t km^?2 y^?1 and 0·7 t km^?2 y^?1, respectively. Statistical analyses showed that total precipitation, flood discharge and total water yield were the major factors controlling SS, POC and DOC transport from the catchment. The relationships between SS, POC and DOC and discharge over temporal flood events resulted in different hysteresis patterns, which were used to deduce dissolved and particulate origins. In both clockwise and anticlockwise hysteresis, POC mainly followed the same patterns as discharge and SS. The DOC‐discharge relationship was mainly characterized by alternating clockwise and anticlockwise hysteresis due to dilution effects of water originating from different sources in the whole catchment. Copyright © 2011 John Wiley & Sons, Ltd.     

Seasonal and storm flow dynamics of dissolved organic carbon in a Mediterranean mountain catchment (Vallcebre,eastern Pyrenees)

To improve understanding of DOC dynamics in seasonal Mediterranean environments, rainfall, soil water, groundwater and stream water samples were taken during a 27-month period in the Can Vila catchment (northeast Spain). Using these data, we characterized DOC dynamics in the different hydrological compartments and analysed the factors affecting them. We also analysed DOC dynamics during storm events and the factors that control DOC delivery to the stream. The results show some seasonality in rainwater and soil water DOC concentrations, while no clear seasonality was observed in stream water and groundwater, where DOC dynamics were strongly related to discharge and water table variations. For storm events with several discharge peaks, the slope of the discharge–DOC concentration relationship was higher for the first peak. The rather similar dynamics of stream water DOC concentration in all floods contrast with the observed diversity of hydrological processes. This raises the question of the origin of the observed rapid DOC increase.

EDITOR M.C. Acreman

ASSOCIATE EDITOR K. Heal     

Groundwater flushing of solutes at wetland and hillslope positions during storm events in a small glaciated catchment in western New York,USA

While the role of groundwater in flushing of solutes has long been recognized, few studies have explicitly studied the within‐event changes in groundwater chemistry. We compared the changes in groundwater chemistry during storm events for a wetland and hillslope position in a small (1·5 ha) glaciated, forested catchment in western New York. Flushing responses for dissolved organic carbon (DOC) and nitrogen (DON), nitrate (NO₃) and sulfate (SO₄) in wetland and hillslope groundwaters were also compared against the corresponding responses in stream water. Eight storm events with varying intensity, amount, and antecedent moisture conditions were evaluated. Solute flushing patterns for wetland and hillslope groundwaters differed dramatically. While DOC concentrations in wetland groundwater followed a dilution trend, corresponding values for hillslope groundwater showed a slight increase. Concentrations for NO₃ in wetland groundwater were below detection limits, but hillslope groundwaters displayed high NO₃ concentrations with a pronounced increase during storm events. Flushing responses at all positions were also influenced by the size of the event and the time between events. We attributed the differences in flushing to the differences in hydrologic flow paths and biogeochemical conditions. Flushing of the wetland did appear to influence storm‐event stream chemistry but the same could not be said for hillslope groundwaters. This suggests that while a variety of flushing responses may be observed in a catchment, only a subset of these responses affect the discharge chemistry at the catchment outlet. Copyright © 2009 John Wiley & Sons, Ltd.     

Drivers of interannual and intra‐annual variability of dissolved organic carbon concentration in the River Thames between 1884 and 2013

The world's longest record of river water quality (River Thames—130 years) provides a unique opportunity to understand fluvial dissolved organic carbon (DOC) concentrations dynamics. Understanding riverine DOC variability through long‐term studies is crucial to capture patterns and drivers influencing sources of DOC at scales relevant for decision making. The Thames basin (United Kingdom) has undergone massive land‐use change, as well as increased urbanisation and population during the period considered. We aimed to investigate the drivers of intra‐annual to interannual DOC variability, assess the variability due to natural and anthropogenic factors, and understand the causes for the increased DOC variability over the period. Two approaches were used to achieve these aims. The first method was singular spectrum analysis, which was used to reconstruct the major oscillatory modes of DOC, hydroclimatic variables, and atmospheric circulation patterns and to visualise the interaction between these variables. The second approach used was generalised additive modelling, which was used to investigate other non‐natural drivers of DOC variability. Our study shows that DOC variability increased by 80% over the data period, with the greatest increase occurring from the beginning of World War II onwards. The primary driver of the increase in DOC variability was the increase in the average value of fluvial DOC over the period of record, which was itself linked to the increase in basin population and diffuse DOC sources to the river due to land‐use and land‐management changes. Seasonal DOC variability was linked to streamflow and temperature. Our study allows to identify drivers of fluvial intra‐annual and interannual DOC variability and therefore empowers actions to reduce high DOC concentrations.     

Relationship of topography to surface water chemistry with particular focus on nitrogen and organic carbon solutes within a forested watershed in Hokkaido,Japan

We studied the relationships between streamwater chemistry and the topography of subcatchments in the Dorokawa watershed in Hokkaido Island, northern Japan, to examine the use of topography as a predictor of streamwater chemistry in a watershed with relatively moderate terrain compared with other regions of Japan. Topographic characteristics of the Dorokawa watershed and its subcatchments were expressed as topographic index (TI) values, which ranged from 4·5 to 20·4 for individual grid cells (50 × 50 m²), but averaged from 6·4 to 7·4 for the 20 subcatchments. Streamwater samples for chemical analyses were collected four times between June and October 2002 from 20 locations in the watershed. The pH of water that passed through the watershed increased from ～5·0 to 7·0, with major increases in Na⁺ and Ca²⁺ and marked decreases in NO₃^? and SO . Distinctive spatial patterns were observed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and NO₃^? concentrations of streamwater across the watershed. Statistical analyses indicated significant linear relationships between the average TI values of subcatchments and DOC, DON, and NO₃^? concentrations. Furthermore, the proportion of DOC in streamwaters in the wet season increased with TI values relative to other nitrogen species, whereas NO₃^? concentrations decreased with TI. The gradients of soil wetness and the presence of wetlands explained many of the observed spatial and temporal patterns of DOC, DON, and NO₃^? concentrations in the surface waters of the Dorokawa watershed. Our results suggest that the TI is especially useful for predicting the spatial distribution of DOC, DON and NO₃^? in the surface waters of Hokkaido, where topographical relief is moderate and wetlands more common than in other regions of Japan. Copyright © 2006 John Wiley & Sons, Ltd.     

Variability of particulate (SS,POC) and dissolved (DOC,NO3) matter during storm events in the Alegria agricultural watershed

The temporal variability of suspended sediment, nitrates (NO₃) and dissolved (DOC) and particulate organic carbon concentrations was analysed in the Alegria agricultural watershed over a 2‐year period. Nine storm events were studied, including an exhaustive analysis of hydrometeorological conditions, quantification of fluxes, and concentration‐discharge hysteresis loop characterization. The overall aim was to study the variability in these components during storm events and determine the mechanisms (flow paths) affecting the trajectories, from the source to the stream. The forms, rotational patterns and trends of hysteretic loops were investigated, and relationships between hysteresis features and hydrological parameters were studied. The results revealed clear differences between particulate (suspended sediment, particulate organic carbon) and dissolved (DOC, NO₃) matter transport responses. Movement of the particulate matter was attributed to surface water, as reflected in clockwise hysteresis loops, whereas dissolved matter showed, in general, counterclockwise hysteresis loops, indicating a time delay in the arrival of solutes to the stream. This could be related to subsurface flow paths for DOC and a groundwater source for NO₃. Copyright © 2013 John Wiley & Sons, Ltd.