A smoothed particle hydrodynamics model for droplet and film flow on smooth and rough fracture surfaces

Flow on fracture surfaces has been identified by many authors as an important flow process in unsaturated fractured rock formations. Given the complexity of flow dynamics on such small scales, robust numerical methods have to be employed in order to capture the highly dynamic interfaces and flow intermittency. In this work we use a three-dimensional multiphase Smoothed Particle Hydrodynamics (SPH) model to simulate surface tension dominated flow on smooth fracture surfaces. We model droplet and film flow over a wide range of contact angles and Reynolds numbers encountered in such flows on rock surfaces. We validate our model via comparison with existing empirical and semi-analytical solutions for droplet flow. We use the SPH model to investigate the occurrence of adsorbed trailing films left behind droplets under various flow conditions and its importance for the flow dynamics when films and droplets coexist. It is shown that flow velocities are higher on prewetted surfaces covered by a thin film which is qualitatively attributed to the enhanced dynamic wetting and dewetting at the trailing and advancing contact lines. Finally, we demonstrate that the SPH model can be used to study flow on rough surfaces.     

Automated contact angle estimation for three-dimensional X-ray microtomography data

Multiphase flow in capillary regimes is a fundamental process in a number of geoscience applications. The ability to accurately define wetting characteristics of porous media can have a large impact on numerical models. In this paper, a newly developed automated three-dimensional contact angle algorithm is described and applied to high-resolution X-ray microtomography data from multiphase bead pack experiments with varying wettability characteristics. The algorithm calculates the contact angle by finding the angle between planes fit to each solid/fluid and fluid/fluid interface in the region surrounding each solid/fluid/fluid contact point. Results show that the algorithm is able to reliably compute contact angles using the experimental data. The in situ contact angles are typically larger than flat surface laboratory measurements using the same material. Wetting characteristics in mixed-wet systems also change significantly after displacement cycles.     

A simulation of large‐scale groundwater flow and travel time in a fractured rock environment for waste disposal purposes

Two‐dimensional regional groundwater flow was simulated based on a conceptual model of low‐permeability crystalline rocks of the Whiteshell Research Area (WRA) in south‐eastern Manitoba. The conceptual model consists of fracture zones that strike in different directions and dip at various angles in the background rock mass. The thickness and hydraulic properties of the fracture zones in the conceptual model were varied as were the fluid properties and the boundary conditions of the groundwater flow system. The effects of these variations on the groundwater flow pattern and on the convective travel time along pathways from a hypothetical disposal vault at 500 m depth to discharge locations at the ground surface were evaluated. The vault was located in the regional discharge area of the groundwater system. A homogeneous conceptual model of the WRA, having only freshwater flow, formed a groundwater flow pattern with a regional flow system. Local flow systems developed increasingly with the introduction of fracture zones 20 m and 3 m thick, and depth‐dependent fluid density. This indicates a reduction in groundwater residence time by fracture zones and fluid density. Flow pathways were analysed using both a stream‐function and a particle‐tracking technique. The pathways and their lengths from the location of the vault to the surface varied spatially according to the flow patterns. The minimum travel time along these pathways was less than 150 000 and greater than 4 000 000 years in models with and without fracture zones, respectively, indicating that the presence of fracture zones was the major controlling factor. A precise knowledge and refinement of conceptual model parameters is necessary during site selection for waste disposal purposes. Copyright © 2004 John Wiley & Sons, Ltd.     

Dissolution of residual non-aqueous phase liquids in porous media: pore-scale mechanisms and mass transfer rates

Experiments designed to elucidate the pore-scale mechanisms of the dissolution of a residual non-aqueous phase liquid (NAPL), trapped in the form of ganglia within a porous medium, are discussed. These experiments were conducted using transparent glass micromodels with controlled pore geometry, so that the evolution of the size and shape of individual NAPL ganglia and, hence, the pore-scale mass transfer rates and mass transfer coefficients could be determined by image analysis. The micromodel design permitted reasonably accurate control of the pore water velocity, so that the mass transfer coefficients could be correlated in terms of a local (pore-scale) Peclet number. A simple mathematical model, incorporating convection and diffusion in a slit geometry was developed and used successfully to predict the observed mass transfer rates. For the case of non-wetting NAPL ganglia, water flow through the corners in the pore walls was seen to control the rate of NAPL dissolution, as recently postulated by Dillard and Blunt [Water Resour. Res. 36 (2000) 439–454]. Break-up of doublet non-wetting phase ganglia into singlet ganglia by snap-off in pore throats was also observed, confirming the interplay between capillarity and mass transfer. Additionally, the effect of wettability on dissolution mass transfer was demonstrated. Under conditions of preferential NAPL wettability, mass transfer from NAPL films covering the solid surfaces was seen to control the dissolution process. Supply of NAPL from the trapped ganglia to these films by capillary flow along pore corners was observed to result in a sequence of pore drainage events that increase the interfacial area for mass transfer. These observations provide new experimental evidence for the role of capillarity, wettability and corner flow on NAPL ganglia dissolution.     

Patterns of soil water repellency change with wetting and drying: the influence of cracks,roots and drainage conditions

Laboratory experiments were used to investigate the influence of simulated cracks and roots on soil water repellency (SWR) dynamics with and without basal drainage impedance in wetting–drying cycles. Observations and measurements were taken following water application equivalent to 9.2‐mm rainfall and then periodically during 80 h of drying. In total, 180 experiments were carried out using 60 samples of three homogeneous, reconstituted soils with different organic matter contents and textures, but of similar initial severity of SWR [18% molarity of an ethanol droplet (MED)]. Water flowing down the cracks and roots left the soil matrix largely dry and water repellent except for vertical zones adjacent to them and a shallow surface layer. A hydrophilic shallow basal layer was produced in experiments where basal drainage was impeded. During drying, changes in SWR were largely confined to the zones that had been wetted. Soil that had remained dry retained the initial severity of SWR, while wetted soil re‐established either the same or slightly lower severity of SWR. In organic‐rich soil, the scale of recovery to pre‐wetting MED levels was much higher, perhaps associated with temporarily raised levels (up to 36% MED) of SWR recorded during drying of these soils. With all three soils, the re‐establishment of the original SWR level was less widespread for surface than subsurface soil and with impeded than unimpeded basal drainage. Key findings are that as follows: (1) with unimpeded basal drainage, the soils remained at pre‐wetting repellency levels except for a wettable thin surface layer and zones close to roots and cracks, (2) basal drainage impedance produced hydrophilic basal and surface layers, (3) thorough wetting delayed a return to water‐repellent conditions on drying, and (4) temporarily enhanced SWR occurred in organic‐rich soils at intermediate moisture levels during drying. Hydrological implications are discussed, and the roles of cracks and roots are placed into context with other influences on preferential flow and SWR under field conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

A multiphase flow and multispecies reactive transport model for DNAPL-involved Compound Specific Isotope Analysis

This study presents a multiphase flow and multispecies reactive transport model for the simultaneous simulation of NAPL and groundwater flow, dissolution, and reactive transport with isotope fractionation, which can be used for better interpretation of NAPL-involved Compound Specific Isotope Analysis in 3D heterogeneous hydrogeologic systems. The model was verified for NAPL-aqueous phase equilibrium partitioning, aqueous phase multi-chain and multi-component reactive transport, and aqueous phase multi-component transport with isotope fractionation. Several illustrative examples are presented to investigate the effect of DNAPL spill rates, degradation rate constants, and enrichment factors on the temporal and spatial distribution of the isotope signatures of chlorinated aliphatic hydrocarbon groundwater plumes. The results clearly indicate that isotope signatures can be significantly different when considering multiphase flow within the source zone. A series of simulations indicate that degradation and isotope enrichment compete with dissolution to determine the isotope signatures in the source zone: isotope ratios remain the same as those of the source if dissolution dominates the reaction, while heavy isotopes are enriched in reactants along groundwater plume flow paths when degradation becomes dominant. It is also shown that NAPL composition can change from that of the injected source due to the partitioning of components between the aqueous and NAPL phases even when degradation is not allowed in NAPL phase. The three-dimensional simulation is presented to mechanistically illustrate the complexities in determining and interpreting the isotopic signatures with evolving DNAPL source architecture.     

Identifying and linking source areas of flow and P transport in dairy‐grazed headwater catchments,North Island,New Zealand

We examined the applicability of the critical‐source area (CSA) concept to the dairy‐grazed 192‐ha Upper Toenepi catchment and its 8·7‐ha Kiwitahi sub‐catchment, New Zealand. We evaluated if phosphorus (P) transport from land into stream is dominated by saturation‐excess (SE) and infiltration‐excess (IE) runoff during stormflow and by sub‐surface (<1·5 m depth) flows during baseflow. We measured stream flow and shallow groundwater levels, collected monthly stream, tile drain (TDA) and groundwater samples, and flow‐proportional stream samples from the Kiwitahi sub‐catchment, and determined their dissolved reactive phosphorus (DRP) and total phosphorus (TP) concentrations. In the Kiwitahi sub‐catchment, during storm events, IE contributions were significant. Contributions from SE appeared significant in the Upper Toenepi catchment. However, in both catchments, sub‐surface contributions dominated stormflow and baseflow periods. Absence of water table at the surface and the water table gradient towards the stream indicated that P transport during events was not limited to surface runoff. The dynamics of the groundwater table and the occurrence of SE areas were influenced by proximity to the stream and hillslope positions. Baseflow accounted for 42% of the annual flow in the Kiwitahi sub‐catchment, and contributed 37 and 52% to the DRP and TP loads, respectively. The P transport during baseflow appeared equally important as P losses from CSAs during stormflow. The close resemblance in P levels between groundwater and stream samples during baseflow demonstrates the importance of shallow groundwater for stream flow. In the Upper Toenepi catchment, contributions from effluent ponds (EFFs) dominated P loads. Management strategies should focus on controlling P release from EFFs, and on decreasing Olsen P concentrations in soil to minimize leaching of P via sub‐surface flow to streams. Research is needed to quantify the role of sub‐surface flow as well as to expand management strategies to minimize P transfers during stormflow and baseflow conditions. Copyright © 2010 John Wiley & Sons, Ltd.     

Nitrate fluctuations at the water table: implications for recharge processes and solute transport in the Chalk aquifer

This study investigates fluctuations in nitrate concentration at the water table to improve understanding of unsaturated zone processes in the Chalk aquifer. Sampling was conducted using a novel multi‐level sampler during periods of water table rise over 5 years at a vertical resolution of 0.05 m. Nitrate concentration increased as the water table seasonally recovered, with similar inter‐annual trends with depth. The rising water table activated horizontal fractures facilitating the delivery of water elevated by up to 10 mg/l of nitrate with respect to the adjacent groundwater below. These fractures are considered to activate via piston displacement of water from the adjoining matrix. Hydrograph analysis identified 16 events which significantly perturbed the water table within 24–48 h of rainfall. Consistent nitrate concentrations indicate recharge through persistent fracture flow from the surface was not generally the primary driver of the rapid water table response during these events. Instead, the response was attributed to the piston displacement of porewater immediately above the water table. However, a single event in November 2012 delivered relatively dilute recharge indicating rapid persistent fracture flow following rainfall was possible to a depth of 14–15 m. Decreases in porewater nitrate concentration around fracture horizons and the dilution of many groundwater samples with respect to porewaters indicate a fresher source of water at depth. This was considered most likely to be a result of near surface water bypassing the matrix because of widespread mineralization on fracture surfaces, which retard water and solute exchange. Therefore, persistent fracture flow maybe considered a frequent process, operating independently of the matrix, and is not necessarily event driven. Copyright © 2015 John Wiley & Sons, Ltd.     

Prediction of Groundwater Quality Trends Resulting from Anthropogenic Changes in Southeast Florida

The effects of surface water flow system changes caused by constructing water‐conservation areas and canals in southeast Florida on groundwater quality under the Atlantic Coastal Ridge was investigated with numerical modeling. Water quality data were used to delineate a zone of groundwater with low total dissolved solids (TDS) within the Biscayne aquifer under the ridge. The delineated zone has the following characteristics. Its location generally coincides with an area where the Biscayne aquifer has high transmissivities, corresponds to a high recharge area of the ridge, and underlies a part of the groundwater mound formed under the ridge prior to completion of the canals. This low TDS groundwater appears to be the result of pre‐development conditions rather than seepage from the canals constructed after the 1950s. Numerical simulation results indicate that the time for low TDS groundwater under the ridge to reach equilibrium with high TDS surface water in the water‐conservation areas and Everglades National Park are approximately 70 and 60 years, respectively. The high TDS groundwater would be restricted to the water‐conservation areas and the park due to its slow eastward movement caused by small hydraulic gradients in Rocky Glades and its mixing with the low TDS groundwater under the high‐recharge area of the ridge. The flow or physical boundary conditions such as high recharge rates or low hydraulic conductivity layers may affect how the spatial distribution of groundwater quality in an aquifer will change when a groundwater flow system reaches equilibrium with an associated surface water flow system.     

Parameters affecting maximum fluid transport in large aperture fractures

We present results of laboratory experiments to study the behavior of liquids moving in unsaturated wide-aperture fractures. A 5-mm-thick glass plate cut with a 1.7-mm aperture was used as a fractured rock analog to study behavior of film and capillary droplet flow modes. Flow rates ranged between 0.6 and 6.0 ml/min. Variability in the ambient barometric pressure, resulting from weather conditions, seemed to play a role in the natural selection of flow mode. For droplet mode, constant input conditions resulted in highly variable transport properties within the fracture. The advancing meniscus exhibited a dynamic contact angle that was a function of the droplet speed and much larger than the static contact angle. Flow rate was reduced due to the larger contact angle. Analytical expressions for droplet velocity and flow capacity are presented as a function of the dynamic rather than the static contact angle.     

Mixing of event and pre‐event water in a shallow Entisol in sloping farmland based on isotopic and hydrometric measurements,SW China

Water percolation and flow processes in subsurface geologic media play an important role in determining the water source for plants and the transport of contaminants or nutrients, which is essential for water resource management and the development of measures for pollution mitigation. During June 2013, the dynamics of the rainwater, soil water, subsurface flows and groundwater in a shallow Entisol on sloping farmland were monitored using a hydrometric and isotopic approach. The results showed that effective mixing of rainwater and soil water occurred in hours. The rebound phenomenon of δD profiles in soils showed that most isotope‐depleted rainwater largely bypassed the soil matrix when the water saturation in the soil was high. Preferential‐flow, which was the dominant water movement pattern in the vadose zone, occurred through the whole soil profile, and infrequent piston‐flow was mainly found at 20–40 cm in depth. The interflow in the soil layer, composed of 75.2% rainwater, was only generated when the soil profile had been saturated. Underflow in the fractured mudrock was the dominant flow type in this hillslope, and outflow was dominated by base flow (groundwater flow) with a mean contribution of 76.7%. The generation mechanism of underflow was groundwater ridging, which was superimposed upon preferential‐flow composed mainly of rainwater. The quick mixing process of rainwater and soil water and the rapid movement of the mixture through preferential channels in the study soil, which shows a typical bimodal pore size distribution, can explain the prompt release of pre‐event water in subsurface flow. Water sources of subsurface flows at peak discharge could be affected by the antecedent soil water content, rain characteristics and antecedent groundwater levels. Copyright © 2016 John Wiley & Sons, Ltd.     

Effects of fractional wettability on capillary pressure–saturation–relative permeability relations of two-fluid systems

Capillary pressure (P_c)–saturation (S)–relative permeability (k_r) relationships must be quantified to accurately predict non-aqueous phase liquid (NAPL) distribution in the subsurface. Several experimental techniques are presented here for two-fluid P_c–S–k_r relationships for various saturation paths to better define the effect of fractional wettability on these relationships. During the primary drainage path of the P_c–S curves, the air–water system showed no distinct trend as a function of the fraction of sand treated by organosilane (S) to render it non-water wetting. In a NAPL–water system, however, a consistent decrease of capillary pressure with increase of the fraction of non-water wetting sands was observed. The much lower contact angle for air–water (a–w) system may result in the observed insensitivity of the a–w P_c–S curves to fractional wettability, at least for the PD pathway. For the main imbibition path of NAPL–water system, capillary pressure decreased as the fraction of the S component increased, requiring forced imbibition (negative capillary pressures) for a certain range of saturations. Systems with an increasing percentage of the S component also exhibited a higher water k_r and lower NAPL or air k_r at a given saturation for the primary drainage and main imbibition paths in both air–water and NAPL–water systems. The increase of water k_r with increase of the fraction of the S component can be explained by the ability of water to occupy larger and highly conductive pores in such a system. Experimental k_r–S data for the primary drainage path of NAPL–water system presented here were used to test the Bradford et al. [Bradford SA, Abriola LM, Leij FJ. Wettability effects on two- and three-fluid relative permeabilities. J Contam Hydrol 1997;28:171–91] model and the modified Mualem model for estimating the k_r–S curves from measured P_c–S data as a function of fractional wettability. Both models predicted significantly less variation in the k_r–S curves than measured indicating that they did not adequately represent the system under investigation.     

Spatial delineation of groundwater–surface water interactions through intensive in‐stream profiling

The dominance of ‘old’ pre‐event water in headwater storm runoff has been recorded in numerous upland catchment studies; however, the mechanisms by which this pre‐event water enters the stream channel are poorly understood. Understanding these processes is fundamental to determining the controls on surface water quality and associated impacts on stream ecology. Previous studies in the upland forested catchment of the Afon Hafren (River Severn) at Plynlimon, mid‐Wales, identified an active bedrock groundwater system that was discharging into the stream channel during storm response. Detailed analysis showed that these discharges were small and could not account for the majority of pre‐event storm water response identified at this site; pre‐event storm runoff had to be sourced predominantly from further upstream. An intensive stream survey was used to determine the spatial nature of groundwater–surface water (GW–SW) interactions in the Hafren Catchment. Detailed physico‐chemical in‐stream profiling identified a marked change in water quality indicating a significant discrete point of bedrock groundwater discharge upstream of the Hafren Transect study site. The in‐stream profiling showed the importance of high spatial resolution sampling as a key to understanding processes of GW–SW interaction and how quick and cost‐effective measurements of specific electrical conductance of stream waters could be used to highlight in‐stream heterogeneity. This approach is recommended for use in headwater catchments for initial characterisation of the stream channel in order to better locate instrumentation and to determine more effective targeted sampling protocols in upland catchment research. Copyright © 2012 John Wiley & Sons, Ltd.     

Spatial and temporal variability of groundwater dynamics in a sub‐Mediterranean mountain catchment

The temporal and spatial dynamics of groundwater was investigated in a small catchment in the Spanish Pyrenees, which was extensively used for agriculture in the past. Analysis of the water table fluctuations at five locations over a 6‐year period demonstrated that the groundwater dynamics had a marked seasonal cycle involving a wetting‐up period that commenced with the first autumn rainfall events, a saturation period during winter and spring and a drying‐down period from the end of spring until the end of the summer. The length of the saturation period showed great interannual variability, which was mainly influenced by the rainfall and evapotranspiration characteristics. There was marked spatial variability in the water table, especially during the wetting‐up period, which could be related to differences in slope and drainage area, geomorphology, soil properties and local topography. Areas contributing to runoff generation were identified within the catchment by field mapping of moisture conditions. Areas contributing to infiltration excess runoff were correlated with former cultivated fields affected by severe sheetwash erosion. Areas contributing to saturation excess runoff were characterized by a marked spatial dynamics associated with catchment wetness conditions. The saturation spatial pattern, which was partially related to the topographic index, was very patchy throughout the catchment, suggesting the influence of other factors associated with past agricultural activities, including changes in local topography and soil properties. The relationship between water table levels and stream flow was weak, especially during the wetting‐up period, suggesting little connection between ground water and the hydrological response, at least at some locations. The results suggest that in drier and human‐disturbed environments, such as sub‐Mediterranean mountains, saturation patterns cannot be represented only by the general topography of the catchment. They also suggest that groundwater storage and runoff is not a succession of steady‐state flow conditions, as assumed in most hydrological models. Copyright © 2013 John Wiley & Sons, Ltd.     

Divergence and flow direction as indicators of subsurface heterogeneity and stage‐dependent storage in alluvial floodplains

Assuming homogeneity in alluvial aquifers is convenient, but limits our ability to accurately predict stream‐aquifer interactions. Research is needed on (i) identifying the presence of focused, as opposed to diffuse, groundwater discharge/recharge to streams and (ii) the magnitude and role of large‐scale bank and transient storage in alluvial floodplains relative to changes in stream stage. The objective of this research was to document and quantify the effect of stage‐dependent aquifer heterogeneity and bank storage relative to changes in stream stage using groundwater flow divergence and direction. Monitoring was performed in alluvial floodplains adjacent to the Barren Fork Creek and Honey Creek in northeastern Oklahoma. Based on results from subsurface electrical resistivity mapping, observation wells were installed in high and low electrical resistivity subsoils. Water levels in the wells were recorded real time using pressure transducers (August to October 2009). Divergence was used to quantify heterogeneity (i.e. variation in hydraulic conductivity, porosity, and/or aquifer thickness), and flow direction was used to assess the potential for large‐scale (100 m) bank or transient storage. Areas of localized heterogeneity appeared to act as divergence zones allowing stream water to quickly enter the groundwater system, or as flow convergence zones draining a large groundwater area. Maximum divergence or convergence occurred with maximum rates of change in flow rates or stream stage. Flow directions in the groundwater changed considerably between base and high flows, suggesting that the floodplains acted as large‐scale bank storage zones, rapidly storing and releasing water during passage of a storm hydrograph. During storm events at both sites, the average groundwater direction changed by at least 90° from the average groundwater direction during baseflow. Aquifer heterogeneity in floodplains yields hyporheic flows that are more responsive and spatially and temporally complex than would be expected compared to more common assumptions of homogeneity. Copyright © 2012 John Wiley & Sons, Ltd.     

Unsaturated zone fracture flow contributions to stream flow: evidence for the process in South Africa and its importance

Understanding hydrological processes has always been important to the development and successful application of conceptual hydrological models. It can also contribute to informed water resources management, particularly in the context of understanding the potential impacts of both land use and climate change. Improved conceptual and quantitative understanding of near‐surface hydrological processes emerged through field studies during the 1960s to1980s; however, there remains a degree of ambiguity about the processes that link surface water and groundwater. This is especially the case in South Africa where a great deal of confusion has arisen about the source of the ‘baseflow’ signal in stream flow observations. This paper suggests that fracture flow within the unsaturated zone could have a lateral component and therefore re‐emerge and contribute to stream flow in catchments with relatively steep topography. The implication is that ‘baseflows’ could be made up of groundwater contributions (caused by intersection of the water table with stream channels) as well as an unsaturated zone flow component. Evidence for the existence of the process is presented on the basis of small‐scale observations and interpretations of stream flow observations. The potential importance of the process relates to interpreting different methods of recharge estimation, assessing the impacts of groundwater abstraction on stream flow, as well as the application and interpretation of the results of hydrological models. The conclusions are that the process does exist, but that there is less than conclusive evidence for its importance. There is therefore a need for further studies that can quantify the scale of the process and therefore its importance. Only then will it be possible to develop a consistent understanding of the processes of surface water and groundwater interaction and therefore manage water resources in a truly integrated manner. Copyright © 2009 John Wiley & Sons, Ltd.     

Origin and palaeo‐environments of calcareous sediments in the Moshaweng dry valley,southeast Botswana

Quaternary sedimentation in the Moshaweng dry valley of southeastern Botswana is evaluated on the basis of geomorphological evolution and sedimentological analyses. Stratigraphic evidence reveals an upper surface (1095 m) containing abundant sil‐calcrete, an intermediate surface (1085 m) in which sil‐calcrete underlies nodular calcrete and lower (1075 m) surface in which sil‐calcrete and nodular calcrete are interbedded. This subdivision is reflected in the geochemical composition of the sediments which show an overall trend of decreasing SiO₂ content (and increasing CaCO₃ content) with depth from the highest to the lowest surface levels. The calcretes and sil‐calcretes represent modifications of pre‐existing detrital Kalahari Group sand and basal Kalahari pebbles which thinned over a Karoo bedrock high. Modification took place during wet periods when abundant Ca⁺⁺‐rich groundwater flowed along the structurally aligned valley system. With the onset of drier conditions, water table fluctuations led to the precipitation of nodular calcretes in the phreatic layer to a depth of about 20 m. A major geochemical change resulted in the preferential silicification of the nodular calcrete deposits. Conditions for silica mobilization may be related to drying‐induced salinity and in situ geochemical differentiation brought about by pebble dissociation towards the top of the sediment pile. As calcretization and valley formation progressed to lower levels, silica release took place on a diminishing scale. Thermoluminescence dating infers a mid‐Pleistocene age for sil‐calcrete formation suggesting that valley evolution and original calcrete precipitation are much older. Late stage dissolution of CaCO₃ from pre‐existing surface calcretes or sil‐calcretes led to the formation of pedogenic case‐hardened deposits during a time of reduced flow through the Moshaweng system possibly during the upper or late Pleistocene. Copyright © 2002 John Wiley & Sons, Ltd.     

Petroleum NAPL Depletion Estimates and Selection of Marker Constituents from Compositional Analysis

Spills and releases of hydrocarbons may result in zones of nonaqueous phase liquids (NAPL) within soils and groundwater. The NAPL will change, or “weather” over time due to a range of physical, chemical, and biological processes. Hydrocarbon constituents in environmental samples collected from NAPL-impacted groundwater wells, sediments, or soils vary in composition over time due to weathering. The changing composition can be used to estimate mass depletion rates and trends for the bulk NAPL and for individual constituent chemicals relative to marker constituents which are less susceptible to weathering. Methods for the selection of marker constituents and for quantitatively and conservatively estimating NAPL depletion rates and trends over time are shown. Estimates are included for two sites with different NAPL mixtures present (crude oil and gasoline/diesel-range product), for which depletion of half the initial total NAPL is estimated at 13.6 ± 2.9 years and 7.3 ± 1.8 years respectively, and with no active NAPL remediation at either site. Similar methods for oil or NAPL depletion estimates have often relied on a prior-identified suite of presumed-conserved marker constituents. The method presented here includes steps which identify the best set of analyzed candidate marker constituents in a NAPL mixture. This can confirm prior-selected markers but is particularly useful for NAPL mixtures in which no prior-identified marker constituents are present.     

Fine‐scale characteristics of groundwater flow in a peatland

Fine‐scale dynamics of groundwater flow were studied in a 1·5 ha peatland in central New York. Measurements of the hydraulic head throughout a detailed network of piezometer clusters revealed spatial and temporal variability in the direction of groundwater flow at a very fine (within a few metres) scale of analysis. Within the small wetland, there were areas of groundwater recharge, discharge and lateral flow. Such patterns of groundwater flow frequently reversed or changed due to fluctuations of only a few centimetres in hydraulic head. Specific conductance, deuterium signatures and calcium concentrations of groundwater corroborated the groundwater flow patterns determined with hydraulic head measurements and illustrated the influence of source water chemistry and evaporation on different layers in the peat column. The control of peat chemistry by such fine‐scale groundwater flow may have important implications for plant community composition and diversity in groundwater‐fed peatlands. Copyright © 1999 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.