Seasonal and interannual variations of nitrate and chloride in stream waters related to spatial and temporal patterns of groundwater concentrations in agricultural catchments

Nitrate concentrations in streamwater of agricultural catchments often exhibit interannual variations, which are supposed to result from land‐use changes, as well as seasonal variations mainly explained by the effect of hydrological and biogeochemical cycles. In catchments on impervious bedrock, seasonal variations of nitrate concentrations in streamwater are usually characterized by higher nitrate concentrations in winter than in summer. However, intermediate or inverse cycles with higher concentrations in summer are sometimes observed. An experimental study was carried out to assess the mechanisms that determine the seasonal cycles of streamwater nitrate concentrations in intensive agricultural catchments. Temporal and spatial patterns of groundwater concentrations were investigated in two adjacent catchments located in south‐western Brittany (France), characterized by different seasonal variations of streamwater nitrate concentrations. Wells were drilled across the hillslope at depths ranging from 1·5 to 20 m. Dynamics of the water table were monitored and the groundwater nitrate and chloride concentrations were measured weekly over 2 years. Results highlighted that groundwater was partitioned into downslope domains, where denitrification induced lower nitrate concentrations than into mid‐slope and upslope domains. For one catchment, high subsurface flow with high nitrate concentrations during high water periods and active denitrification during low water periods explained the higher streamwater nitrate concentrations in winter than in summer. For the other catchment, the high contribution of groundwater with high nitrate concentrations smoothed or inverted this trend. Increasing bromide/chloride ratio and nitrate concentrations with depth argued for an effect of past agricultural pressure on this catchment. The relative contribution of flows in time and correlatively the spatial origin of waters, function of the depth and the location on the hillslope, and their chemical characteristics control seasonal cycles of streamwater nitrate concentrations and can influence their interannual trends. Copyright © 2004 John Wiley & Sons, Ltd.     

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.     

Acidification recovery in a changing climate: Observations from thirty-five years of stream chemistry monitoring in forested headwater catchments at the Turkey Lakes watershed,Ontario

Long-term ecosystem studies are valuable for understanding integrated ecosystem response to global changes in atmospheric deposition and climate. We examined trends for a 35-year period (1982/83–2017/18) in concentrations of a range of solutes in precipitation and stream water from nine headwater catchments spanning elevation and surficial geology gradients at the Turkey Lakes watershed (TLW) in northeastern Ontario, Canada. Average annual water year (WY, October to September) concentrations in precipitation significantly declined over the period for sulphate (SO₄²⁻), nitrate (NO₃⁻) and chloride (Cl⁻), while calcium (Ca²⁺) and potassium (K⁺) concentrations increased, resulting in a significant pH increase from 4.2 to 5.7. Trends in stream chemistry through time are generally consistent with expectations associated with acidification recovery. Concentration of many stream water solutes (SO₄²⁻, Cl⁻, calcium [Ca²⁺], magnesium [Mg²⁺] and NH₄⁺ generally decreased, while others (silica [SiO₂] and dissolved organic carbon [DOC]) generally increased. Increases were also observed for alkalinity (six of nine catchments), acid neutralizing capacity ([ANC]; six of nine catchments) and pH (eight of nine catchments), while conductivity declined (six of nine catchments). Variability in trends among catchments are associated with differences in surficial geology and wetland cover. While absolute solute concentrations were generally lower at bedrock dominated high-elevation catchments compared to till dominated lower elevation catchments, the rate of change of concentration was often greater for high elevation catchments. This study confirms continued, but non-linear stream chemistry recovery from acidification, particularly at the less buffered high and moderate elevation sites. The heterogeneity of responses among catchments highlights our incomplete understanding of the relative importance of different mechanisms influencing stream chemistry and the consequences for downstream ecosystems.     

Evaluating spatiotemporal variation in water chemistry of the upper Colorado River using longitudinal profiling

Stream water chemistry is traditionally measured as variation over time at fixed sites, with sparse sites providing a crude understanding of spatial heterogeneity. An alternative Lagrangian reference frame measures changes with respect to both space and time as water travels through a network. Here, we collected sensor-based measurements of water chemistry at high spatial resolution along nearly 500 km of the Upper Colorado River. Our objective was to understand sources of spatiotemporal heterogeneity across different solutes and determine whether longitudinal change manifests as smooth gradients as suggested by the River Continuum Concept (RCC) or as abrupt changes as suggested by the Serial Discontinuity Concept (SDC). Our results demonstrate that Lagrangian sampling integrates spatiotemporal variation, and profiles reflect processes that vary in both space and time and over different scales. Over each day of sampling, water temperature (T) and dissolved oxygen (DO) varied strongly in response to diel solar cycles, with most of the variation driven by sampling time rather than sampling location. Equilibration of T and DO with the atmosphere limited small scale spatial heterogeneity, with variation at the entire profile scale driven by regional climate gradients. As such, T and DO profiles more closely approximated the smooth gradients of the RCC (though including temporal sampling artefacts). Conversely, variation in specific conductance and nitrate (NO₃-N) was largely driven by spatial patterns of lateral inflows such as tributaries and groundwater. This resulted in discrete shifts in the profiles at or downstream of discontinuities, appearing as the profiles expected with the SDC. The concatenation of spatiotemporal variation that produces observed Lagrangian profiles presents interpretive challenges but also augments our understanding of where, how, and critically why water chemistry changes in time and space as it moves through river networks.     

The controls on boreal peatland surface water chemistry in Northern Alberta,Canada

Spatial and temporal variability in surface water chemistry, organic soil chemistry and hydrologic indicators were investigated at three poor‐fen complexes in two boreal catchments in Northern Alberta to provide insight into the dominant controls on surface water chemistry. Improved understanding of these controls is required to enable prediction of runoff chemistry in the region under changing atmospheric deposition conditions. Surface water chemistry exhibited considerable variability; within each fen conductivity, dissolved organic carbon (DOC), and Cl⁻ tended to decrease and pH tended to increase with increasing distance from the lake edge. Variations in evaporative isotopic enrichment in ²H and ¹⁸O, expressed as deuterium excess, were used to distinguish between throughflow waters and those that were more evaporatively enriched. Throughflow surface waters were more acidic primarily due to higher concentrations of DOC and NO₃⁻. Exchangeable base saturation and pH of organic soils were strongly related to surface water chemistry at two of the fen complexes, demonstrating the capacity for cation exchange to influence surface water chemistry. Fen surface water concentrations of most elements and DOC increased during the summer period (between June and August), while pH of water decreased. Evaporative concentration of the surface waters was a dominant driver, with surface water temperature increasing at both catchments. Localized groundwater discharge was an important contributor of base cations to the fens, while the organic soils are sinks for atmospherically deposited SO₄²⁻, N and Cl⁻. Copyright © 2010 John Wiley & Sons, Ltd.     

Total waterborne carbon export and DOC composition from ten nested subarctic peatland catchments—importance of peatland cover,groundwater influence,and inter‐annual variability of precipitation patterns

Waterborne carbon (C) export from terrestrial ecosystems is a potentially important flux for the net catchment C balance and links the biogeochemical C cycling of terrestrial ecosystems to their downstream aquatic ecosystems. We have monitored hydrology and stream chemistry over 3 years in ten nested catchments (0.6–15.1 km²) with variable peatland cover (0%–22%) and groundwater influence in subarctic Sweden. Total waterborne C export, including dissolved and particulate organic carbon (DOC and POC) and dissolved inorganic carbon (DIC), ranged between 2.8 and 7.3 g m^–2 year^–1, representing ~10%–30% of catchment net ecosystem exchange of CO₂. Several characteristics of catchment waterborne C export were affected by interacting effects of peatland cover and groundwater influence, including magnitude and timing, partitioning into DOC, POC, and DIC and chemical composition of the exported DOC. Waterborne C export was greater during the wetter years, equivalent to an average change in export of ~2 g m^–2 year^–1 per 100 mm of precipitation. Wetter years led to a greater relative increase in DIC export than DOC export due to an inferred relative shift in dominance from shallow organic flow pathways to groundwater sources. Indices of DOC composition (SUVA₂₅₄ and a₂₅₀/a₃₆₅) indicated that DOC aromaticity and average molecular weight increased with catchment peatland cover and decreased with increased groundwater influence. Our results provide examples on how waterborne C export and DOC composition might be affected by climate change. Copyright © 2012 John Wiley & Sons, Ltd.     

Adjacent catchments with similar patterns of land use and climate have markedly different dissolved organic carbon concentration and runoff dynamics

Temporal patterns in specific runoff, dissolved organic carbon concentrations [DOC] and fluxes were examined during two periods: 1994–1997 (period 1) and 2007–2009 (period 2) in five adjacent tributary catchments of Lake Simcoe, the largest lake in southern Ontario, Canada. The catchments displayed similar patterns of land use change with increases in urbanization (5–16%) and forest cover (0.2–4%) and declines in agriculture (4–8%) between 1994 and 2008. Climate in the catchments was similar; temperature increased slightly, but no significant change in precipitation was observed. Despite similar pattern of climate and land use, runoff responses and tributary [DOC] were different across the catchments. Following a very dry year (i.e. 1999), runoff increased steadily until the end of record. We observed increased variability in tributary [DOC] and higher DOC exports in period 2. This led to ~10% increase in [DOC] and a 13% increase in flux between the two study periods. Between the two periods, [DOC] increased by 15% in spring and 25% in summer, whereas flux increased by 17% in spring and 48% in summer. [DOC] was consistently higher in the growing (summer + autumn) than the dormant (winter + spring, minus spring melt months) seasons, but no unique pattern or simple linear flow/concentrations relationships existed. This suggests complex spatial and temporal pattern to runoff controls on DOC and flow dynamics in adjacent catchments. We therefore caution against extrapolating from monitored to unmonitored catchments. Copyright © 2012 John Wiley & Sons, Ltd.     

Long-term annual groundwater storage trends in Australian catchments

The period of direct groundwater storage measurements is often too short to allow reliable inferences of groundwater storage trends at catchment scales. However, as groundwater storage sustains low flows in catchments during dry periods, groundwater storage can also be estimated indirectly from daily streamflow based on hydraulic groundwater theory; this idea was applied herein to 17 selected Australian catchments to examine their long-term (half a century or longer) groundwater storage trends. On average, over past 45 years, groundwater storage exhibited negative trends in all the selected catchments, except in the Katherine River catchment located in the Northern Territory. These negative trends persisted over longer periods, close to 100 years in some catchments and the strongest decreasing trend of 0.241 mm per year was observed in the Barron River catchment in New South Wales. However, groundwater storage exhibited different trends over the different shorter periods. Thus, while during the period of 1997–2007, 15 out of the 17 catchments showed negative trends in groundwater storage, during the period of 1980–2000, 12 out of the 17 catchments exhibited positive trends in groundwater storage; this underscores the fact that record lengths of one or even two decades are inadequate to derive meaningful trends. Strong consistencies in the trends exist across most catchments, indicating that groundwater storage is affected by large-scale climate factors.     

The relationship between dissolved organic carbon in stream water and soil organic carbon pools at different spatial scales

The relationship between stream water DOC concentrations and soil organic C pools was investigated at a range of spatial scales in subcatchments of the River Dee system in north‐east Scotland. Catchment percentage peat cover and soil C pools, calculated using local, national and international soils databases, were related to mean DOC concentrations in streams draining small‐ (<5 km²), medium‐ (12–38 km²) and large‐scale (56–150 km²) catchments. The results show that, whilst soil C pool is a good predictor of stream water DOC concentration at all three scales, the strongest relationships were found in the small‐scale catchments. In addition, in both the small‐ and large‐scale catchments, percentage peat cover was as a good predictor of stream water DOC concentration as catchment soil C pool. The data also showed that, for a given soil C pool, streams draining lowland (<700 m) catchments had higher DOC concentrations than those draining upland (>700 m) catchments, suggesting that disturbance and land use may have a small effect on DOC concentration. Our results therefore suggest that the relationship between stream water DOC concentration and catchment soil C pools exists at a range of spatial scales and this relationship appears to be sufficiently robust to be used to predict the effects of changes in catchment soil C storage on stream water DOC concentration. Copyright © 1999 John Wiley & Sons, Ltd.     

Synoptic sampling reveals spatial stability in flow and chemistry patterns despite large seasonal variability in a subarctic mountain catchment

Seasonality plays a critical role in cold mountain regions as variation in air temperature, ground thermal status, and precipitation phase alter the rate, timing and magnitude of hydrological and chemical transport. Additionally, cold mountain catchments can have highly variable topography, geology, permafrost, and landcover, which intrinsically add to this irregularity. Understanding how external and internal variability act to control mass fluxes requires sampling at a high spatial resolution over time, which rarely occurs in cold remote regions. In this work, we conduct five snapshot sampling surveys across 34 subcatchments during the ice-free period in Wolf Creek Research Basin (a mesoscale montane subarctic catchment) and two additional winter surveys across a subset of sites to assess the drivers of variability in stream chemistry and discharge. We sampled for specific conductance (SpC), major ions, and dissolved organic carbon (DOC) and used statistical metrics and Bayesian mixing analysis to quantify patterns of flow and chemistry across space and time. Our results indicate patterns in both flow and chemistry remain largely consistent across seasons for all solutes. However, there was weaker correlation of chemistry between sites, suggesting asynchronous behaviour within the catchment. There was evidence of increasing production of ions and DOC along the stream network during high spring flows but not during low flows. Although concentrations and flows exhibit high seasonality in subarctic mountains, this seasonal variability does not alter spatial patterns that arise from highly variable catchment characteristics.     

Sources of variability in springwater chemistry in Fool Creek,a high-elevation catchment of the Rocky Mountains,Colorado, USA

Springs are the point of origin for most headwater streams and are important regulators of their chemical composition. We analysed solute concentrations of water emerging from 57 springs within the 3 km² Fool Creek catchment at the Fraser Experimental Forest and considered sources of spatial variation among them and their influence on the chemical composition of downstream water. On average, calcium and acid neutralizing capacity (bicarbonate-ANC) comprised 50 and 90% of the cation and anion charge respectively, in both spring and stream water. Variation in inorganic chemical composition among springs reflected distinct groundwater sources and catchment geology. Springs emerging through glacial deposits in the upper portion of the catchment were the most dilute and similar to snowmelt, whereas lower elevation springs were more concentrated in cations and ANC. Water emerging from a handful of springs in a geologically faulted portion of the catchment were more concentrated than all others and had a predominant effect on downstream ion concentrations. Chemical similarity indicated that these springs were linked along surface and subsurface flowpaths. This survey shows that springwater chemistry is influenced at nested spatial scales including broad geologic conditions, elevational and spatial attributes and isolated local features. Our results highlight the role of overlapping factors on solute export from headwater catchments.     

Dynamic stream network intermittence explains emergent dissolved organic carbon chemostasis in headwaters

Dissolved organic carbon (DOC) concentrations vary among headwaters, with variation typically decreasing with watershed area. We hypothesized that streamflow intermittence could be an important source of variation in DOC concentrations across a small watershed, through (a) temporal legacies of drying on organic matter accumulation and biotic communities and (b) spatial patterns of connectivity with DOC sources. To test these hypotheses, we conducted three synoptic water chemistry sampling campaigns across a 25.5‐km² watershed in south‐eastern Idaho during early spring, late summer, and late fall. Using changepoint analysis, we found that DOC variability collapsed at a consistent location (watershed areas ~1.3 to ~1.8 km²) across seasons, which coincided with the watershed area where variability in streamflow intermittence collapsed (~1.5 km²). To test hypothesized mechanisms through which intermittence may affect DOC, we developed temporal, spatial, and spatio‐temporal metrics of streamflow intermittence and related these to DOC concentrations. Streamflow intermittence was a strong predictor of DOC across seasons, but different metrics predicted DOC depending on season. Seasonal changes in the effects of intermittence on DOC reflected seasonal changes from instream to flowpath controls. A metric that captured spatial connectivity to sources significantly predicted DOC during high flows, when DOC is typically controlled by transport. In contrast, a reach‐scale temporal metric of intermittence predicted DOC during the late growing season, when DOC is typically controlled by instream processes and when legacy effects of drying (e.g., diminished biological communities) would likely affect DOC. The effects of intermittence on DOC extend beyond temporal legacies at a point. Our results suggest that legacy effects of intermittence do not propagate downstream in this system. Instead, snapshots of spatial patterns of intermittence upstream of a reach are critical for understanding spatial patterns of DOC through connectivity to DOC sources, and these processes drive patterns of DOC even in perennial reaches.     

A univariate model of river water nitrate time series

Four time series were taken from three catchments in the North and South of England. The sites chosen included two in predominantly agricultural catchments, one at the tidal limit and one downstream of a sewage treatment works. A time series model was constructed for each of these series as a means of decomposing the elements controlling river water nitrate concentrations and to assess whether this approach could provide a simple management tool for protecting water abstractions. Autoregressive (AR) modelling of the detrended and deseasoned time series showed a “memory effect”. This memory effect expressed itself as an increase in the winter–summer difference in nitrate levels that was dependent upon the nitrate concentration 12 or 6 months previously. Autoregressive moving average (ARMA) modelling showed that one of the series contained seasonal, non-stationary elements that appeared as an increasing trend in the winter–summer difference. The ARMA model was used to predict nitrate levels and predictions were tested against data held back from the model construction process – predictions gave average percentage errors of less than 10%. Empirical modelling can therefore provide a simple, efficient method for constructing management models for downstream water abstraction.     

Potential mechanistic causes of increased baseflow across northern Eurasia catchments underlain by permafrost

Warming in the Arctic is occurring at twice the rate of the global average, resulting in permafrost thaw and a restructuring of the Arctic hydrologic cycle as indicated by increased stream discharge during low-flow periods. In these cold regions, permafrost thaw is postulated to increase low-flow discharge, or baseflow, through either: (a) localized increases in groundwater storage and discharge to streams due to increased aquifer transmissivity from thickening of the freeze–thaw layer above permafrost known as the active layer or (b) long-term increases in regional groundwater circulation via enhancement of groundwater–surface water interactions due to extensive permafrost loss over decades. While increasing baseflow has been observed throughout northern Eurasia, the precise mechanistic causes remain elusive. In this study, we differentiate between where these two subsurface physical mechanisms of baseflow increase are occurring by performing a baseflow recession analysis using daily streamflow records from 1913 to 2003 for 139 stations in northern Eurasia underlain by varying permafrost areal extents. Results indicate that from 1913 to 2003, the majority of catchments underlain by continuous permafrost have an increasing trend in their recession flow intercepts, a proxy for increasing active layer thickness. Alternatively, the majority of catchments underlain by permafrost types that are less spatially extensive (e.g., discontinuous, sporadic, isolated, or no permafrost) have decreasing trends in their recession flow intercepts, indicating that a potential increase in active layer thickness is not the driving factor of baseflow variations in these catchments. This may indicate that in catchments underlain by continuous permafrost, active layer thickening correlates with increases in baseflow, whereas, in other catchments with less extensive permafrost, increases in baseflow may be caused by wholesale permafrost loss and vertical talik expansion that enhances regional groundwater circulation. The results of this work may inform our understanding of the subsurface mechanisms responsible for the changing Arctic hydrologic cycle.     

Spatial Variability of Nitrate and Ammonium in Pleistocene Aquifer of Central Yangtze River Basin

It becomes increasingly important and challenging for nitrogen pollution prevention to identify key controls for spatial variability of nitrogen in groundwater that could be affected by multiple factors, including anthropogenic input, groundwater flow, and local geochemistry. This study characterized spatial variability of both nitrate and ammonium in the Pleistocene aquifer of central Yangtze River Basin and assessed the effect of various factors in controlling nitrate and ammonium levels based on multiple statistical approaches (correlation, geostatistics, multiple liner regression). The results indicate that nitrate is mostly influenced by Cl⁻ that represents anthropogenic input, while Eh representing local redox state is a secondary variable influencing nitrate concentrations. The groundwater with elevated nitrate concentrations are estimated to occur mainly in areas with higher-permeability near-surface sediments which can facilitate more anthropogenic nitrate transport and less nitrate removal owing to more oxidized state. Ammonium is mostly correlated to Eh, followed by dissolved organic carbon (DOC), but only DOC improves significantly the accuracy of co-kriging prediction model. The groundwater with elevated ammonium concentrations are estimated to occur mainly in areas with more organic-rich sediments within or around the aquifer which can facilitate more ammonium release owing to natural organic matter consumption accompanying strong reducing conditions. The regional groundwater flow is not a factor significantly controlling nitrate or ammonium levels owing to flat topography and sluggish lateral flow.     

The role of wetland coverage within the near‐stream zone in predicting of seasonal stream export chemistry from forested headwater catchments

Stream chemistry is often used to infer catchment‐scale biogeochemical processes. However, biogeochemical cycling in the near‐stream zone or hydrologically connected areas may exert a stronger influence on stream chemistry compared with cycling processes occurring in more distal parts of the catchment, particularly in dry seasons and in dry years. In this study, we tested the hypotheses that near‐stream wetland proportion is a better predictor of seasonal (winter, spring, summer, and fall) stream chemistry compared with whole‐catchment averages and that these relationships are stronger in dryer periods with lower hydrologic connectivity. We evaluated relationships between catchment wetland proportion and 16‐year average seasonal flow‐weighted concentrations of both biogeochemically active nutrients, dissolved organic carbon (DOC), nitrate (NO₃‐N), total phosphorus (TP), as well as weathering products, calcium (Ca), magnesium (Mg), at ten headwater (<200 ha) forested catchments in south‐central Ontario, Canada. Wetland proportion across the entire catchment was the best predictor of DOC and TP in all seasons and years, whereas predictions of NO₃‐N concentrations improved when only the proportion of wetland within the near‐stream zone was considered. This was particularly the case during dry years and dry seasons such as summer. In contrast, Ca and Mg showed no relationship with catchment wetland proportion at any scale or in any season. In forested headwater catchments, variable hydrologic connectivity of source areas to streams alters the role of the near‐stream zone environment, particularly during dry periods. The results also suggest that extent of riparian zone control may vary under changing patterns of hydrological connectivity. Predictions of biogeochemically active nutrients, particularly NO₃‐N, can be improved by including near‐stream zone catchment morphology in landscape models.     

Spatial variation of wetlands and flux of dissolved organic carbon in boreal headwater streams

In order to investigate the relation between water chemistry and functional landscape elements, spatial data sets of characteristics for 68 small (0·2–1·5 km²) boreal forest catchments in western central Sweden were analysed in a geographical information system (GIS). The geographic data used were extracted from official topographic maps. Water sampled four times at different flow situations was analysed chemically. This paper focuses on one phenomenon that has an important influence on headwater quality in boreal, coniferous forest streams: generation and export of dissolved organic carbon (DOC). It is known that wetland cover (bogs and fens) in the catchment is a major source of DOC. In this study, a comparison was made between a large number of headwater catchments with varying spatial locations and areas of wetlands. How this variation, together with a number of other spatial variables, influences the DOC flux in the streamwater was analysed by statistical methods. There were significant, but not strong, correlations between the total percentages of wetland area and DOC flux measured at a medium flow situation, but not at high flow. Neither were there any significant correlations between the percentage of wetland area connected to streams, nor the percentage of wetland area within a zone 50 m from the stream and the DOC flux. There were, however, correlations between catchment mean slope and the DOC flux in all but one flow situations. This study showed that, considering geographical data retrieved from official sources, the topography of a catchment better explains the variation in DOC flux than the percentage and locations of distinct wetland areas. This emphasizes the need for high‐resolution elevation models accurate enough to reveal the sources of DOC found in headwater streams. Copyright © 2007 John Wiley & Sons, Ltd.     

Spatial and temporal patterns of dissolved organic matter quantity and quality in the Mississippi River Basin, 1997–2013

Recent studies have found insignificant or decreasing trends in time‐series dissolved organic carbon (DOC) datasets, questioning the assumption that long‐term DOC concentrations in surface waters are increasing in response to anthropogenic forcing, including climate change, land use, and atmospheric acid deposition. We used the weighted regressions on time, discharge, and season (WRTDS) model to estimate annual flow‐normalized concentrations and fluxes to determine if changes in DOC quantity and quality signal anthropogenic forcing at 10 locations in the Mississippi River Basin. Despite increases in agriculture and urban development throughout the basin, net increases in DOC concentration and flux were significant at only 3 of 10 sites from 1997 to 2013 and ranged between ?3.5% to +18% and ?0.1 to 19%, respectively. Positive shifts in DOC quality, characterized by increasing specific ultraviolet absorbance at 254 nm, ranged between +8% and +45%, but only occurred at one of the sites with significant DOC quantity increases. Basinwide reductions in atmospheric sulfate deposition did not result in large increases in DOC either, likely because of the high buffering capacity of the soil. Hydroclimatic factors including annual discharge, precipitation, and temperature did not significantly change during the 17‐year timespan of this study, which contrasts with results from previous studies showing significant increases in precipitation and discharge over a century time scale. Our study also contrasts with those from smaller catchments, which have shown stronger DOC responses to climate, land use, and acidic deposition. This temporal and spatial analysis indicated that there was a potential change in DOC sources in the Mississippi River Basin between 1997 and 2013. However, the overall magnitude of DOC trends was not large, and the pattern in quantity and quality increases for the 10 study sites was not consistent throughout the basin.     

Seasonal controls on DOC dynamics in nested upland catchments in NE Scotland

Spatial and temporal variability of hydrological responses affecting surface water dissolved organic carbon (DOC) concentrations are important for determining upscaling patterns of DOC export within larger catchments. Annual and intra‐annual variations in DOC concentrations and fluxes were assessed over 2 years at 12 sites (3·40–1837 km²) within the River Dee basin in NE Scotland. Mean annual DOC fluxes, primarily correlated with catchment soil coverage, ranged from 3·41 to 9·48 g m^?2 yr^?1. Periods of seasonal (summer–autumn and winter–spring) DOC concentrations (production) were delineated and related to discharge. Although antecedent temperature mainly determined the timing of switchover between periods of high DOC in the summer‐autumn and low DOC in winter‐spring, inter‐annual variability of export within the same season was largely dependent on its associated water flux. DOC fluxes ranged from 1·39 to 4·80 g m^?2 season^?1 during summer–autumn and 1·43 to 4·15 g m^?2 season^?1 in winter–spring.Relationships between DOC areal fluxes and catchment scale indicated that mainstem fluxes reflect the averaging of highly heterogeneous inputs from contrasting headwater catchments, leading to convergent DOC fluxes at catchment sizes of ca 100 km². However, during summer–autumn periods, in contrast to winter–spring, longitudinal mainstem DOC fluxes continue to decrease, most likely because of increasing biological processes. This highlights the importance of considering seasonal as well as annual changes in DOC fluxes with catchment scale. This study increases our understanding of the temporal variability of DOC upscaling patterns reflecting cumulative changes across different catchment scales and aids modelling of carbon budgets at different stages of riverine systems. Copyright © 2010 John Wiley & Sons, Ltd.     

Fine scale variations of surface water chemistry in an ephemeral to perennial drainage network

Although temporal variation in headwater stream chemistry has long been used to document baseline conditions and response to environmental drivers, less attention is paid to fine scale spatial variations that could yield clues to processes controlling stream water sources. We documented spatial and temporal variation in water composition in a headwater catchment (41 ha) at the Hubbard Brook Experimental Forest, NH, USA. We sampled every 50 m along an ephemeral to perennial stream network as well as groundwater from seeps and 35 shallow wells across varying flow conditions. Groundwater influences on surface water in this region have not been considered to be important in past studies as relatively coarse soils were assumed to be well drained in steep catchments with flashy runoff response. However, seeps displayed perennial discharge, upslope accumulated areas (UAA) smaller than those for channel initiation sites and higher pH, Ca and Si concentrations than streams, suggesting relatively long groundwater residence time or long subsurface flow paths not bound by topographic divides. Coupled with a large range in groundwater chemistry seen in wells, these results suggest stream chemistry variation reflects the range of connectivity with, and quality of, groundwater controlled by hillslope hydropedological processes. The magnitude of variations of solute concentrations seen in the first order catchment was as broad as that seen at the fifth order Hubbard Brook Valley (3519 ha). Reduction in variation in solute concentrations with increasing UAA suggested a representative elementary area (REA) value of less than 3 ha in the first order catchment, compared with 100 ha for the fifth order basin. Thus, the REA is not necessarily an elementary catchment property. Rather, the partitioning of variation between highly variable upstream sources and relatively homogenous downstream characteristics may have different physical significance depending on the scale and complexity of the catchment under examination. Copyright © 2012 John Wiley & Sons, Ltd.