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The typically elevated natural attenuation capacity of riverbed-hyporheic zones is expected to decrease chlorinated hydrocarbon (CHC) groundwater plume discharges to river receptors through dechlorination reactions. The aim of this study was to assess physico-chemical processes controlling field-scale variation in riverbed-hyporheic zone dechlorination of a TCE groundwater plume discharge to an urban river reach. The 50-m long pool-riffle-glide reach of the River Tame in Birmingham (UK) studied is a heterogeneous high energy river environment. The shallow riverbed was instrumented with a detailed network of multilevel samplers. Freeze coring revealed a geologically heterogeneous and poorly sorted riverbed. A chlorine number reduction approach provided a quantitative indicator of CHC dechlorination. Three sub-reaches of contrasting behaviour were identified. Greatest dechlorination occurred in the riffle sub-reach that was characterised by hyporheic zone flows, moderate sulphate concentrations and pH, anaerobic conditions, low iron, but elevated manganese concentrations with evidence of sulphate reduction. Transient hyporheic zone flows allowing input to varying riverbed depths of organic matter are anticipated to be a key control. The glide sub-reach displayed negligible dechlorination attributed to the predominant groundwater baseflow discharge condition, absence of hyporheic zone, transition to more oxic conditions and elevated sulphate concentrations expected to locally inhibit dechlorination. The tail-of-pool-riffle sub-reach exhibited patchy dechlorination that was attributed to sub-reach complexities including significant flow bypass of a low permeability, high organic matter, silty unit of high dechlorination potential. A process-based conceptual model of reach-scale dechlorination variability was developed. Key findings of practitioner relevance were: riverbed-hyporheic zone CHC dechlorination may provide only a partial, somewhat patchy barrier to CHC groundwater plume discharges to a surface water receptor; and, monitoring requirements to assess the variability in CHC attenuation within a reach are expected to be onerous. Further research on transient hyporheic zone dechlorination is recommended., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Pumped groundwater sampling evaluations often assume that horizontal head gradients predominate and the sample comprises an average of water quality variation over the well screen interval weighted towards contributing zones of higher hydraulic conductivity (a permeability-weighted sample). However, the pumping rate used during sampling may not always be sufficient to overcome vertical flows in wells driven by ambient vertical head gradients. Such flows are reported in wells with screens between 3 and 10m in length where lower pumping rates are more likely to be used during sampling. Here, numerical flow and particle transport modeling is used to provide insight into the origin of samples under ambient vertical head gradients and under a range of pumping rates. When vertical gradients are present, sample provenance is sensitive to pump intake position, pumping rate and pumping duration. The sample may not be drawn from the whole screen interval even with extended pumping times. Sample bias is present even when the ambient vertical flow in the wellbore is less than the pumping rate. Knowledge of the maximum ambient vertical flow in the well does, however, allow estimation of the pumping rate that will yield a permeability-weighted sample. This rate may be much greater than that recommended for low-flow sampling. In practice at monitored sites, the sampling bias introduced by ambient vertical flows in wells may often be unrecognized or underestimated when drawing conclusions from sampling results. It follows that care should be taken in the interpretation of sampling data if supporting flow investigations have not been undertaken., (Copyright © 2014. Published by Elsevier B.V.)

Forced gradient tracer tests between two boreholes can be used to study contaminant transport processes at the small field scale or investigate the transport properties of an aquifer. Full depth tests, in which tracer samples are collected just from the discharge of the abstraction borehole, often give rise to breakthrough curves with multiple peaks that are usually attributed to different flow paths through the aquifer that can rarely be identified from the test results alone. Tests in selected levels of the aquifer, such as those between packer-isolated sections of the boreholes, are time consuming, expensive; and the identification of major transport pathways is not guaranteed. We present a method for simultaneously conducting multiple tracer tests covering the full depth of the boreholes, in which tracer sampling and monitoring is carried out by a novel multilevel sampling system allowing high frequency and cumulative sampling options. The method is applied to a tracer test using fluorescein conducted in the multilayered sandstone aquifer beneath the city of Birmingham, UK, producing six well-defined tracer breakthrough curves., (© 2013, National Ground Water Association.)

Measurements have been made of diffusion coefficients (D(i)=-mass flux/concentration gradient) using a double reservoir, steady-state method with two tracers, CaBr(2) and amino-G-acid, on intact samples of Triassic red-bed sandstone from northwest England. Diffusibility (D'=D(i)/diffusion coefficient in water) averages 0.124, ranging between 0.075 and 0.215 (porosity 0.1 to 0.24), very similar for the two tracers. Implied tortuosities (actual path length/straight line length) average 1.21 (range 1.06 to 1.47), with constrictivities close to 1. In comparison with limited red-bed sandstone data from elsewhere, these D' values are up to 4 times greater, and tortuosity correspondingly lower. Re-interpretation of formation factor data from previous studies on shallow sandstone samples also from northwest England confirms that diffusibility is significantly higher in these sandstones than others from similar palaeoenvironment/stratigraphic units. The lower tortuosities appear to result from the relatively high permeability, open fabric of the rock, properties likely to be present in shallow sandstone systems used for water supply. It is concluded that diffusion rates may, in some shallow freshwater-containing continental sandstone systems, be significantly greater than is implied by estimates of sandstone diffusibility current in the literature., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The objective of this study was to determine if there is a nanoscale surface film on aquifer-like materials exposed to deep groundwaters, as has previously been found on surfaces exposed to surface and soil waters. Such surface films will modify surface properties that are so important in determining the mobility of many groundwater pollutants. Muscovite mica was used because a) it is a good analogue for the main sorbing phases of many clastic aquifers and b) its cleavage planes are atomically flat allowing high resolution imaging. Freshly-cleaved muscovite plates were exposed to groundwater from a sandstone aquifer for 30 min, and surface properties (morphology, coverage, roughness and tip-substrate force interactions) were measured using atomic force microscopy (AFM). A patchy surface film of several nanometres in depth, incorporating larger separate particles, was found on the mica surface. This film was associated with significantly increased roughness values and AFM probe-sample interaction forces compared with pure water and inorganic (synthetic groundwater) solution controls. Although the results reported are preliminary in nature, if confirmed, such films are likely to affect sorption reactions, surface-facilitated redox interactions, non-aqueous phase liquid wetting angles, and colloid-pathogen-rock attachment, and will thus be of importance in understanding natural attenuation and migration of dissolved, non-aqueous and particulate phases in groundwaters.

A field study involving high-resolution core sampling of a 0.5-2 m thick clay bed was undertaken at a contaminated former industrial facility in the UK to establish the nature and significance of preferential contaminant flowpaths. In contrast to most previous research, the focus was upon a buried aquitard, in this case a Holocene lagoonal clay located 6 m below ground surface and overlain by a sand aquifer impacted by historic nonaqueous phase liquid hydrocarbon spills. The study, involving 11 cores over a 630 by 150 m area, demonstrated that the presence of paleo- (i.e., preupper sand) rootholes controlled the degree of dissolved-phase benzene penetration into the aquitard. Where homogeneous, largely paleoroot-free clay is present (hydraulic conductivity 3 x 10(-5) m/d.), contaminant concentrations in the clay decline rapidly with depth: modeling showed the dominant transport process to be diffusion. In other cores, elevated benzene concentrations deep in the clay require advection to have occurred, presumably along preferential pathways. The latter were shown by thin sectioning, core slice mapping and 3-D X-ray tomography to be organic matter lined rootholes of < 2 mm aperture. The significance of such preferential pathways was confirmed quantitatively by measuring hydraulic conductivity (0.04 m/d) and calculating flux, the latter being over 10 times greater than expected from steady state diffusion. Our study hence demonstrates paleoenvironmental control of modern-day contaminant transport through a clay aquitard. It is suggested that many subaerial unconformities in mudrocks, especially those associated with even rudimentary paleosol development would lead to permeability enhancement and therefore afford substantially reduced protection against migrating contaminants. In contaminated site investigations, it is hence necessary to consider the aquitard paleoenvironment and not just the main rock type present.

The potential hydraulic behaviour of the fracture network in a major Triassic sandstone aquifer in the UK has been evaluated. The properties of the fracture network were determined using results from detailed scan line surveys at 10 sites, television and geophysical borehole logging, and packer testing. Six sets of discontinuities common to all sites were identified and statistically characterised (dip, strike, orientation, density, size, and estimated transmissivity). A discrete fracture network model was then used stochastically to investigate the properties of the network. In general, the network is poorly connected: it is estimated that 9% of the discontinuities intersecting boreholes are transmissive. The hydraulic behaviour of the network is generally dominated by one sub-horizontal bedding plane fracture set, although when present, a relatively infrequent north-south striking, sub-vertical set modifies the bulk flow properties significantly. Ignoring this latter set, the network's minimum representative volume is about 35 x 35 x 35 m. The upscaled permeability is anisotropic, being typically 23 times greater in the horizontal than in the vertical. Tortuosity in the north-south direction is around 1.6.

An attempt has been made to estimate quantitatively cation concentration changes as estuary water invades a Triassic Sandstone aquifer in northwest England. Cation exchange capacities and selectivity coefficients for Na(+), K(+), Ca(2+), and Mg(2+) were measured in the laboratory using standard techniques. Selectivity coefficients were also determined using a method involving optimized back-calculation from flushing experiments, thus permitting better representation of field conditions; in all cases, the Gaines-Thomas/constant cation exchange capacity (CEC) model was found to be a reasonable, though not perfect, first description. The exchange parameters interpreted from the laboratory experiments were used in a one-dimensional reactive transport mixing cell model, and predictions compared with field pumping well data (Cl and hardness spanning a period of around 40 years, and full major ion analyses in approximately 1980). The concentration patterns predicted using Gaines-Thomas exchange with calcite equilibrium were similar to the observed patterns, but the concentrations of the divalent ions were significantly overestimated, as were 1980 sulphate concentrations, and 1980 alkalinity concentrations were underestimated. Including representation of sulphate reduction in the estuarine alluvium failed to replicate 1980 HCO(3) and pH values. However, by including partial CO(2) degassing following sulphate reduction, a process for which there is 34S and 18O evidence from a previous study, a good match for SO(4), HCO(3), and pH was attained. Using this modified estuary water and averaged values from the laboratory ion exchange parameter determinations, good predictions for the field cation data were obtained. It is concluded that the Gaines-Thomas/constant exchange capacity model with averaged parameter values can be used successfully in ion exchange predictions in this aquifer at a regional scale and over extended time scales, despite the numerous assumptions inherent in the approach; this has also been found to be the case in the few other published studies of regional ion exchanging flow.

The chemical attenuation of inorganic contaminants in methanogenic landfill leachate, spiked with heavy metals (Cd, Cd, Ni and Zn), by two UK clay liner materials was compared in laboratory columns over 15 months. Ammonium was attenuated by ion-exchange but this attenuation was finite and when exhausted, NH4 passed through the liners at concentrations found in the leachate. The breakthrough behaviour of NH4 could be described by a simple distribution coefficient. Heavy metals were attenuated by sorption and precipitation of metal sulphide and carbonate compounds near the top of the liner. Adequate SO4 and CaCO3 in the liner is necessary to ensure the long term retention of heavy metals, and pH buffering agents added to stabilise reactive metal fractions should be admixed with the liner. Some metals may not be chemically attenuated by clay liners due to the formation of stable complexes with organic and/or colloidal fractions in leachate. Flushing of the liners with oxygenated water after leachate caused mobilisation of attenuated contaminants. Sorbed NH4 was released by the liners but groundwater loadings were manageable. Re-oxidation of metal sulphides under these conditions resulted in the release of heavy metals from the liners when the pH buffering capacity was poor. Contaminant attenuation by the clay liners was similar and the attenuation of NH4 and heavy metals could be predicted from the geochemical properties of the liner using simple tests. A conceptual model of clay liner performance is presented. Chemical attenuation of inorganic pollutants can be included in containment liner design to produce a dual reactive-passive barrier for landfills.