Effect of NAPL exposure on the wettability and two‐phase flow in a single rock fracture

Surface‐wetting properties are an important cause of changing the groundwater and two‐phase fluid flows. Various factors affecting the surface wettability were investigated in a parallel‐walled glass fracture with non‐aqueous phase liquid (NAPL) (gasoline, diesel, trichloroethylene, and creosote) wetted surfaces. First, the effect of the duration of NAPL exposure on wettability change was considered at pre‐wet fracture surfaces using the various NAPL species, and the result showed that the surface became hydrophobic after the exposure time of NAPL exceeded 2000 min. Second, the initial wetting state of the surface affected the timing when the wettability change begins as well as the extent of the wettability change in an NAPL‐wetted rock fractures. Under the dry condition, the wettability change was completed within a very short time of exposure to NAPL (~5 min), and then it finally reached the intermediate and weakly NAPL wetting (contact angle of 118°). Under the pre‐wet condition, a relatively long time of exposure (~5000 min) was needed to observe the obvious change of the surface wettability, which was changed up to strongly NAPL wetting (contact angle of 142°). Third, the wettability changed by NAPL exposure was stable and maintained for a long time, regardless of water flushing rate and temperature. Finally, the wettability change by the exposure of NAPL on parallel fracture surfaces was evaluated at various groundwater flow velocities. Result showed that groundwater flow velocity has an important impact upon measured contact angle. Although fracture surfaces were exposed to NAPL at the low groundwater flow velocity, the wettability was not changed from hydrophilic to hydrophobic when the contact time between NAPL and mineral surfaces was not sufficient owing to the pulse‐type movement of NAPL. This implies that the variation of exposure pattern due to groundwater flow on the wettability change can be an important factor affecting the wettability change of fracture surface and migration behaviour at natural fractured rock aquifers in case of NAPL spill. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of the geometry of two‐dimensional fractures on their hydraulic aperture and on the validity of the local cubic law

Flow through rough fractures is investigated numerically in order to assess the validity of the local cubic law for different fracture geometries. Two‐dimensional channels with sinusoidal walls having different geometrical properties defined by the aperture, the amplitude, and the wavelength of the walls' corrugations, the corrugations asymmetry, and the phase shift between the two walls are considered to represent different fracture geometries. First, it is analytically shown that the hydraulic aperture clearly deviates from the mean aperture when the walls' roughness, the phase shift, and/or the asymmetry between the fracture walls are relatively high. The continuity and the Navier–Stokes equations are then solved by means of the finite element method and the numerical solutions compared to the theoretical predictions of the local cubic law. Reynolds numbers ranging from 0.066 to 66.66 are investigated so as to focus more particularly on the effect of flow inertial effects on the validity of the local cubic law. For low Reynolds number, typically less than 15, the local cubic law properly describes the fracture flow, especially when the fracture walls have small corrugation amplitudes. For Reynolds numbers higher than 15, the local cubic law is valid under the conditions that the fracture presents a low aspect ratio, small corrugation amplitudes, and a moderate phase lag between its walls.     

Roughness scale dependence of the relationship between tracer longitudinal dispersion and Peclet number in variable‐aperture fractures

The relationship between the longitudinal dispersion (D_L) and Peclet number (Pe) is crucial for predicting and simulating tracer through the variable‐aperture fracture. In this study, the roughness of the self‐affine fracture wall was decomposed into primary roughness (relatively large‐scale waviness) and secondary roughness (relatively small‐scale waviness) by a multiscaled wavelet analysis technique. Based on the complete dispersion mechanism (diffusion, macrodispersion, and Taylor dispersion) in the variable‐aperture fracture, three relationships (second‐order, power‐law, and linear relationships) between the D_L and Pe were investigated at large and small scales, respectively. Our results showed that the primary roughness mostly controlled the Taylor dispersion mechanism, whereas the secondary roughness was a dominant factor for the macrodispersion mechanism. Increasing the Hurst exponent and removing the secondary roughness led to the decreasing range of Pe where macrodispersion mechanism dominated the solute transport. It was found that estimating the D_L from the power‐law relationship based on Taylor dispersion theory resulted in considerable errors, even in the range of Pe where the Taylor dispersion mechanism dominated. The exponent of the power‐law relationship increased as the secondary roughness was removed. Analysing the linear relationship between the D_L and Pe revealed that the longitudinal dispersivity α_L increased linearly. However, this linear increase became weak as the Taylor dispersion mechanism dominated. In the range of Pe where the macrodispersion mechanism dominated, increasing the Hurst exponent caused the increase of α_L and the secondary roughness played a significant role in enhancing the α_L. As the Taylor dispersion mechanism dominated, the α_L was insensitive to the influence of multiscale roughness in variable‐aperture fractures.     

Effect of non‐uniformity of flow on velocity and turbulence intensities over a cobble‐bed

Non‐uniform flows encompassing both accelerating and decelerating flows over a cobble‐bed flume have been experimentally investigated in a flume at a scale of intermediate relative submergence. Measurements of mean longitudinal flow velocity u, and determinations of turbulence intensities u′, v′, w′, and Reynolds shear stress ?u_fw_f have been made. The longitudinal velocity distribution was divided into the inner zone close to the bed and the outer zone far from the bed. In the inner zone of the boundary layer (near the bed) the velocity profile closely followed the ‘Log Law’; however, in the outer zone the velocity distribution deviated from the Log Law consistently for both accelerating and decelerating flows and the changes in bed slopes ranging from ?2% to + 2% had no considerable effect on the outer zone. For a constant bed slope (S = ±0·015), the larger the flow rate, the smaller the turbulence intensities. However, no detectable pattern has been observed for u′, v′ and w′ distributions near the bed. Likewise, for a constant flow rate (Q = 0·040 m³/s), with variation in bed slope the longitudinal turbulent intensity profile in the longitudinal direction remained concave for both accelerating and decelerating flows; whereas vertical turbulent intensity (w′) profile presented no specific form. The results reveal that the positions of maximum values of turbulence intensities and the Reynolds shear stress depend not only on the flow structure (accelerating or decelerating) but also on the intermediate relative submergence scale. Copyright © 2009 John Wiley & Sons, Ltd.     

Anisotropy and depth‐related heterogeneity of hydraulic conductivity in a bog peat. II: modelling the effects on groundwater flow

Anisotropy and heterogeneity of hydraulic conductivity (K) are seldom considered in models of mire hydrology. We investigated the effect of anisotropy and heterogeneity on groundwater flow in bog peat using a steady‐state groundwater model. In five model simulations, four sets of K data were used. The first set comprised measured K values from an anisotropic and heterogeneous bog peat. These data were aggregated to produce the following simplified data sets: an isotropic and heterogeneous distribution of K; an isotropic and homogeneous distribution; and an anisotropic and homogeneous distribution. We demonstrate that, where anisotropy and heterogeneity exist, groundwater flow in bog peat is complex. Fine‐scale variations in K have the potential to influence patterns and rates of groundwater flow. However, for our data at least, it is heterogeneity and not anisotropy that has the greater influence on producing complex patterns of groundwater flow. We also demonstrate that patterns and rates of groundwater flow are simplified and reduced when measured K values are aggregated to create a more uniform distribution of K. For example, when measured K values are aggregated to produce isotropy and homogeneity, the rate of modelled seepage is reduced by 28%. We also show that when measured K values are used, the presence of a drainage ditch can increase seepage through a modelled cross‐section. Our work has implications for the accurate interpretation of hydraulic head data obtained from peat soils, and also the understanding of the effect of drainage ditches on patterns and rates of groundwater flow. Copyright © 2002 John Wiley & Sons, Ltd.     

The effect of low‐permeability fault zones on groundwater flow in a compartmentalized system. Experimental evidence from a carbonate aquifer (Southern Italy)

The hydrogeological behaviour of fault zones in carbonate aquifers is often neglected in conceptual and numerical models. Furthermore, no information is available regarding the relationships between piezometric levels when significant compartmentalization occurs due to the occurrence of low‐flow fault zones. The aim of this study was to refine the conceptualization of subsurface flow in faulted carbonate aquifers and to analyse relationships between sub‐basins within a compartmentalized aquifer system in Southern Italy. The interactions between compartments that straddle low‐flow faults were investigated over four hydrologic years using a statistical approach to compare (i) the hydraulic heads within two wells located up‐ and down‐gradient of tectonic discontinuities as well as (ii) the rainfall and piezometric levels. The results of this study suggest that a set of barriers exists between the wells, and, therefore, the total head loss observed between the wells (approximately 80 m) should be distributed across several aquitards, with one aquitard exhibiting a relatively high permeability or low degree of integrity. Due to slight differences in permeability, transient conditions in aquitards can occur over relatively short periods, which is in agreement with the results of the statistical data analysis. Consequently, rather than being caused by pure aquitards, aquifer system compartmentalization likely results from slight differences in the permeability between lower‐permeability fault zones and adjacent higher‐permeability protoliths. Copyright © 2014 John Wiley & Sons, Ltd.     

Predictability of river flow and suspended sediment transport in the Mississippi River basin: a non‐linear deterministic approach

As the Mississippi River plays a major role in fulfilling various water demands in North America, accurate prediction of river flow and sediment transport in the basin is crucial for undertaking both short‐term emergency measures and long‐term management efforts. To this effect, the present study investigates the predictability of river flow and suspended sediment transport in the basin. As most of the existing approaches that link water discharge, suspended sediment concentration and suspended sediment load possess certain limitations (absence of consensus on linkages), this study employs an approach that presents predictions of a variable based on history of the variable alone. The approach, based on non‐linear determinism, involves: (1) reconstruction of single‐dimensional series in multi‐dimensional phase‐space for representing the underlying dynamics; and (2) use of the local approximation technique for prediction. For implementation, river flow and suspended sediment transport variables observed at the St. Louis (Missouri) station are studied. Specifically, daily water discharge, suspended sediment concentration and suspended sediment load data are analysed for their predictability and range, by making predictions from one day to ten days ahead. The results lead to the following conclusions: (1) extremely good one‐day ahead predictions are possible for all the series; (2) prediction accuracy decreases with increasing lead time for all the series, but the decrease is much more significant for suspended sediment concentration and suspended sediment load; and (3) the number of mechanisms dominantly governing the dynamics is three for each of the series. Copyright © 2005 John Wiley & Sons, Ltd.     

Influence of water pressure dynamics and fluid flow on the streaming‐potential response for unsaturated conditions

Streaming‐potentials are produced by electrokinetic effects in relation to fluid flow and are used for geophysical prospecting. The aim of this study is to model streaming potential measurements for unsaturated conditions using an empirical approach. A conceptual model is applied to streaming potential measurements obtained from two drainage experiments in sand. The streaming potential data presented here show a non‐monotonous behaviour with increasing water saturation, following a pattern that cannot be predicted by existing models. A model involving quasi‐static and dynamic components is proposed to reproduce the streaming potential measurements. The dynamic component is based on the first time derivative of the driving pore pressure. The influence of this component is investigated with respect to fluid velocity, which is very different between the two experiments. The results demonstrate that the dynamic component is predominant at the onset of drainage in experiments with the slowest water flow. On the other hand, its influence appears to vanish with increasing drainage velocity. Our results suggest that fluid flow and water distribution at the pore scale have an important influence on the streaming potential response for unsaturated conditions. We propose to explain this specific streaming potential response in terms of the behaviour of both rock/water interface and water/air interfaces created during desaturation processes. The water/air interfaces are negatively charged, as also observed in the case of water/rock interfaces. Both the surface area and the flow velocity across these interfaces are thought to contribute to the non‐monotonous behaviour of the streaming potential coefficient as well as the variations in its amplitude. The non‐monotonous behaviour of air/water interfaces created during the flow was highlighted as it was measured and modelled by studies published in the literature. The streaming potential coefficient can increase to about 10 to 40 when water saturation decreases. Such an increase is possible if the amount of water/air interfaces is increased in sufficient amount, which can be the case.     

Multiple‐indicator study of groundwater flow and chemistry and the impacts of river and paddy water on groundwater in the alluvial fan of the Tedori River,Japan

To investigate the source, flow paths, and chemistry of rich resources of high‐quality, shallow groundwater in the alluvial fan between the Tedori and Sai rivers in central Japan, we analysed stable isotope ratios of H, O, and Sr and concentrations of major dissolved ions and trace elements in groundwater, river water, and paddy water. The ⁸⁷Sr/⁸⁶Sr ratios of the groundwater are related to near‐surface geology: groundwater in sediment from the Tedori River has high ⁸⁷Sr/⁸⁶Sr ratios (>0.711), whereas that from the Sai River in the north of the fan has low ⁸⁷Sr/⁸⁶Sr ratios (<0.711). δ²H and δ¹⁸O values and ⁸⁷Sr/⁸⁶Sr ratios indicate that groundwater in the central and southern fans is recharged by the Tedori River, whereas recharge in the north is from the Sai River. Mg²⁺, Ca²⁺, Sr²⁺, HCO₃^?, and SO₄^2? concentrations and δ²H and δ¹⁸O values in the groundwater are high in the central fan and, except for the northern area, tend to increase with distance from the Tedori River. There are linear relationships between ⁸⁷Sr/⁸⁶Sr ratio and the reciprocal concentrations of Sr²⁺, Mg²⁺, and Ca²⁺. These geochemical characteristics suggest that as groundwater recharged from the Tedori River flows towards the central fan, it mixes with waters derived from precipitation and paddy water that have become enriched in these components during downward infiltration. These results are consistent with our hydrological analysis and numerical simulation of groundwater flow, thus verifying the validity of the model we used in our simulation of groundwater flow. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of permafrost thaw on the dynamics of lakes recharged by ice‐jam floods: case study of Yukon Flats,Alaska

Large river floods are a key water source for many lakes in fluvial periglacial settings. Where permeable sediments occur, the distribution of permafrost may play an important role in the routing of floodwaters across a floodplain. This relationship is explored for lakes in the discontinuous permafrost of Yukon Flats, interior Alaska, using an analysis that integrates satellite‐derived gradients in water surface elevation, knowledge of hydrogeology, and hydrologic modelling. We observed gradients in water surface elevation between neighbouring lakes ranging from 0.001 to 0.004. These high gradients, despite a ubiquitous layer of continuous shallow gravel across the flats, are consistent with limited groundwater flow across lake basins resulting from the presence of permafrost. Permafrost impedes the propagation of floodwaters in the shallow subsurface and constrains transmission to ‘fill‐and‐spill’ over topographic depressions (surface sills), as we observed for the Twelvemile‐Buddy Lake pair following a May 2013 ice‐jam flood on the Yukon River. Model results indicate that permafrost table deepening of 1–11 m in gravel, depending on watershed geometry and subsurface properties, could shift important routing of floodwater to lakes from overland flow (fill‐and‐spill) to shallow groundwater flow (‘fill‐and‐seep’). Such a shift is possible in the next several hundred years of ground surface warming and may bring about more synchronous water level changes between neighbouring lakes following large flood events. This relationship offers a potentially useful tool, well suited to remote sensing, for identifying long‐term changes in shallow groundwater flow resulting from thawing of permafrost. Copyright © 2015 John Wiley & Sons, Ltd.     

Variations in thickness of fault‐controlled dikes and its implications: A case study of Gosung area,South‐East Korea

Dikes are natural records that can be used to understand the way magma flows in the crust. Coastal platform outcrops in Gosung, South Korea, show clear evidences that their intrusion took place along pre‐existing fractures. We analyzed outcropping dikes, measuring variations in dike thickness as well as fracture density (cumulative number of fractures along strike) and geometry around the dikes. The geometry and thickness variations of dikes intruded along pre‐existing fractures can be interpreted to understand the effect of pre‐existing fractures to evolution on magma flow, especially related with fault damage zones. This helps us to gain a better understanding of magma and fluid flow along pre‐existing fractures. Magma flow is greater along planes that strike perpendicular to the direction of least compressive horizontal stress, and along well connected fractures that show a high degree of connectivity. At the fault tip and linkage damage zone, there is a concentration of extensional fractures; in these areas injected dikelets can form. As faults become linked, the fracture density increases, until they become fully linked and act as one through‐going fault plane. As faults evolve, the boundary conditions of the faults vary and this has an impact on dike characteristics. Fracture geometry around dikes that intruded pre‐existing faults can be used as a record of fault evolution and this can give insights into how the maturity of a fault system can affect to the related magma or fluid flow characteristics.     

Solute concentrations of overland flow water in a cultivated field: spatial variations,intra‐ and inter‐storm trends

Major solute concentrations in overland flow water (OFW) were measured in an agricultural field of Brittany (western France). Two storm events were monitored in detail to examine the short time‐scale processes. During one year, samples were taken at different positions on the slope after each storm event to describe the spatial and seasonal variations of OFW chemistry. Although the total dissolved load in OFW is not much higher than in rain water, distinctive features are observed. K⁺, Ca²⁺, NH₄ , Cl⁻ and SOare the major solutes. The main origin of the elements (sea salts, exchangeable soil complex or fertilizers) determined most of the variations observed. Spatial variations along the slope are mainly seen for exchangeable cations, while seasonal variations are predominant for sea salts. Rainfall intensity and suspended sediment load induce strong differences between the two storm events studied in detail. However, the within‐storm variations and the seasonal monitoring show that this relationship is complex. Within‐storm variations suggest that, in addition to desorption processes, mixing with pre‐event water may occur. The lack of a relationship between sediment load and dissolved load is attributed to the high rate of the exchange processes, which has been checked by a simple experiment in vitro. It is concluded that the conditions of the transit of water on the field (velocity, length, status of the surface, crusted or not) may well play a major role in the chemical changes between rain water and OFW. The results suggest that vegetated buffer strips designed to reduce the sediment load only, and not the amount of overland flow, will have little effect on the transfer of dissolved pollutants to the watercourses. Copyright © 1999 John Wiley & Sons, Ltd.     

The effect of terrace geology on ground‐water movement and on the interaction of ground water and surface water on a mountainside near Mirror Lake,New Hampshire,USA

The west watershed of Mirror Lake in the White Mountains of New Hampshire contains several terraces that are at different altitudes and have different geologic compositions. The lowest terrace (FSE) has 5 m of sand overlying 9 m of till. The two next successively higher terraces (FS2 and FS1) consist entirely of sand and have maximum thicknesses of about 7 m. A fourth, and highest, terrace (FS3) lies in the north‐west watershed directly adjacent to the west watershed. This highest terrace has 2 m of sand overlying 8 m of till. All terraces overlie fractured crystalline bedrock. Numerical models of hypothetical settings simulating ground‐water flow in a mountainside indicated that the presence of a terrace can cause local ground‐water flow cells to develop, and that the flow patterns differ based on the geologic composition of the terrace. For example, more ground water moves from the bedrock to the glacial deposits beneath terraces consisting completely of sand than beneath terraces that have sand underlain by till. Field data from Mirror Lake watersheds corroborate the numerical experiments. The geology of the terraces also affects how the stream draining the west watershed interacts with ground water. The stream turns part way down the mountainside and passes between the two sand terraces, essentially transecting the movement of ground water down the valley side. Transects of water‐table wells were installed across the stream's riparian zone above, between, and below the sand terraces. Head data from these wells indicated that the stream gains ground water on both sides above and below the sand terraces. However, where it flows between the sand terraces the stream gains ground water on its uphill side and loses water on its downhill side. Biogeochemical processes in the riparian zone of the flow‐through reach have resulted in anoxic ground water beneath the lower sand terrace. Results of this study indicate that it is useful to understand patterns of ground‐water flow in order to fully understand the flow and chemical characteristics of both ground water and surface water in mountainous terrain. Copyright © 2007 John Wiley & Sons, Ltd.     

On determining the geometric and kinematic characteristics of coherent flow structures over a gravel bed: a new approach using combined PLIF‐PIV

In gravel‐bed rivers, the microtopography of the bed is known to exert a significant influence on the generation of turbulent flow structures that owe their origin to fluid shear generated near the bed. Although field and laboratory measurements have indicated that flows over gravel beds contain a range of coherent flow structures, the kinematic and dynamic properties of these structures are still poorly understood. This paper describes a new experimental methodology to quantify simultaneously both the kinematic and dynamic characteristics of coherent flow structures based upon combined planar laser‐induced fluorescence and particle imaging velocimetry (PLIF‐PIV). The results confirm that the primary generative mechanism of coherent flow structures is at the bed, where merging hairpin vortices form around bed clasts and generate larger‐scale fluid motions that advect downstream. Copyright © 2010 John Wiley & Sons, Ltd.     

The influence of preferential flow on hillslope hydrology in a semi‐arid watershed (in the Spanish Dehesas)

Preferential flow is known to influence hillslope hydrology in many areas around the world. Most research on preferential flow has been performed in temperate regions. Preferential infiltration has also been found in semi‐arid regions, but its impact on the hydrology of these regions is poorly known. The aim of this study is to describe and quantify the influence of preferential flow on the hillslope hydrology from small scale (infiltration) to large scale (subsurface stormflow) in a semi‐arid Dehesa landscape. Precipitation, soil moisture content, piezometric water level and discharge data were used to analyse the hydrological functioning of a catchment in Spain. Variability of soil moisture content during the transition from dry to wet season (September to November) within horizontal soil layers leads to the conclusion that there is preferential infiltration into the soils. When the rainfall intensity is high, a water level rapidly builds up in the piezometer pipes in the area, sometimes even reaching soil surface. This water level also drops back to bedrock within a few hours (under dry catchment conditions) to days (under wet catchment conditions). As the soil matrix is not necessarily wet while this water layer is built up, it is thought to be a transient water table in large connected pores which drain partly to the matrix, partly fill up bedrock irregularities and partly drain through subsurface flow to the channels. When the soil matrix becomes wetter the loss of water from macropores to the matrix and bedrock decreases and subsurface stormflow increases. It may be concluded that the hillslope hydrological system consists of a fine matrix domain and a macropore domain, which have their own flow characteristics but which also interact, depending on the soil matrix and macropore moisture contents. The macropore flow can result in subsurface flow, ranging from 13% contribution to total discharge for a large event of high intensity rainfall or high discharge to 80% of total discharge for a small event with low intensity rainfall or low discharge. During large events the fraction of subsurface stormflow in the discharge is suppressed by the large amount of surface runoff. Copyright © 2008 John Wiley & Sons, Ltd.     

The importance of surface controls on overland flow connectivity in semi‐arid environments: results from a numerical experimental approach

In semi‐arid environments, the characteristics of the land surface determine how rainfall is transformed into surface runoff and influences how this runoff moves from the hillslopes into river channels. Whether or not water reaches the river channel is determined by the hydrological connectivity. This paper uses a numerical experiment‐based approach to systematically assess the effects of slope length, gradient, flow path convergence, infiltration rates and vegetation patterns on the generation and connectivity of runoff. The experiments were performed with the Connectivity of Runoff Model, 2D version distributed, physically based, hydrological model. The experiments presented are set within a semi‐arid environment, characteristic of south‐eastern Spain, which is subject to low frequency high rainfall intensity storm events. As a result, the dominant hydrological processes are infiltration excess runoff generation and surface flow dynamics. The results from the modelling experiments demonstrate that three surface factors are important in determining the form of the discharge hydrograph: the slope length, the slope gradient and the infiltration characteristics at the hillslope‐channel connection. These factors are all related to the time required for generated runoff to reach an efficient flow channel, because once in this channel, the transmission losses significantly decrease. Because these factors are distributed across the landscape, they have a fundamental role in controlling the landscape hydrological response to storm events. Copyright © 2013 John Wiley & Sons, Ltd.     

A long‐term study of stable isotopes as tracers of processes governing water flow and quality in a lowland river basin: the upper Thames,UK

A long‐term study of O, H and C stable isotopes has been undertaken on river waters across the 7000‐km² upper Thames lowland river basin in the southern UK. During the period, flow conditions ranged from drought to flood. A 10‐year monthly record (2003–2012) of the main River Thames showed a maximum variation of 3‰ (δ¹⁸O) and 20‰ (δ²H), although interannual average values varied little around a mean of –6.5‰ (δ¹⁸O) and –44‰ (δ²H). A δ²H/δ¹⁸O slope of 5.3 suggested a degree of evaporative enrichment, consistent with derivation from local rainfall with a weighted mean of –7.2‰ (δ¹⁸O) and –48‰ (δ²H) for the period. A tendency towards isotopic depletion of the river with increasing flow rate was noted, but at very high flows (>100 m³/s), a reversion to the mean was interpreted as the displacement of bank storage by rising groundwater levels (corroborated by measurements of specific electrical conductivity). A shorter quarterly study (October 2011–April 2013) of isotope variations in 15 tributaries with varying geology revealed different responses to evaporation, with a well‐correlated inverse relationship between Δ¹⁸O and baseflow index for most of the rivers. A comparison with aquifer waters in the basin showed that even at low flow, rivers rarely consist solely of isotopically unmodified groundwater. Long‐term monitoring (2003–2007) of carbon stable isotopes in dissolved inorganic carbon (DIC) in the Thames revealed a complex interplay between respiration, photosynthesis and evasion, but with a mean interannual δ¹³C‐DIC value of –14.8 ± 0.5‰, exchange with atmospheric carbon could be ruled out. Quarterly monitoring of the tributaries (October 2011–April 2013) indicated that in addition to the aforementioned factors, river flow variations and catchment characteristics were likely to affect δ¹³C‐DIC. Comparison with basin groundwaters of different alkalinity and δ¹³C‐DIC values showed that the origin of river baseflow is usually obscured. The findings show that long‐term monitoring of environmental tracers can help to improve the understanding of how lowland river catchments function. Copyright © NERC 2015. Hydrological Processes © 2015 John Wiley & Sons, Ltd.