On the use of mean groundwater age, life expectancy and capture probability for defining aquifer vulnerability and time-of-travel zones for source water protection.

Protection and sustainability of water supply wells requires the assessment of vulnerability to contamination and the delineation of well capture zones. Capture zones, or more generally, time-of-travel zones corresponding to specific contaminant travel times, are most commonly delineated using advective particle tracking. More recently, the capture probability approach has been used in which a probability of capture of P=1 is assigned to the well and the growth of a probability-of-capture plume is tracked backward in time using an advective-dispersive transport model. This approach accounts for uncertainty due to local-scale heterogeneities through the use of macrodispersion. In this paper, we develop an alternative approach to capture zone delineation by applying the concept of mean life expectancy E (time remaining before being captured by the well), and we show how life expectancy E is related to capture probability P. Either approach can be used to delineate time-of-travel zones corresponding to specific travel times, as well as the ultimate capture zone. The related concept of mean groundwater age A (time since recharge) can also be applied in the context of defining the vulnerability of a pumped aquifer. In the same way as capture probability, mean life expectancy and groundwater age account for local-scale uncertainty or unresolved heterogeneities through macrodispersion, which standard particle tracking neglects. The approach is tested on 2D and 3D idealized systems, as well as on several watershed-scale well fields within the Regional Municipality of Waterloo, Ontario, Canada.

High-pressure injection of dissolved oxygen for hydrocarbon remediation in a fractured dolostone aquifer.

A field experiment was completed at a fractured dolomite aquifer in southwestern Ontario, Canada, to assess the delivery of supersaturated dissolved oxygen (supersaturated with respect to ambient conditions) for enhanced bioremediation of petroleum hydrocarbons in groundwater. The injection lasted for 1.5h using iTi's gPro® oxygen injection technology at pressures of up to 450 kPa and at concentrations of up to 34 mg O2/L. A three-dimensional numerical model for advective-dispersive transport of dissolved oxygen within a discretely-fractured porous medium was calibrated to the observed field conditions under a conservative (no-consumption) scenario. The simulation demonstrated that oxygen rapidly filled the local intersecting fractures as well as the porous matrix surrounding the injection well. Following injection, the local fractures were rapidly flushed by the natural groundwater flow system but slow back-diffusion ensured a relatively longer residence time in the matrix. A sensitivity analysis showed significant changes in behaviour with varying fracture apertures and hydraulic gradients. Applying the calibrated model to a 7-day continuous injection scenario showed oxygen residence times (at the 3mg/L limit), within a radius of 2-4m from the injection well, of up to 100 days. This study has demonstrated that supersaturated dissolved oxygen can be effectively delivered to this type of a fractured and porous bedrock system at concentrations and residence times potentially sufficient for enhanced aerobic biodegradation.

A new method to characterize hydraulic short-circuits in defective borehole seals.

A new approach has been developed to detect, characterize, and quantify hydraulic short-circuits in boreholes with faulty seals. The methodology, applicable to an aquifer-aquitard-aquifer system, involves a series of successive, constant-rate pumping tests in the lower aquifer while determining the leakage rate with a simultaneous nonreactive tracer test. During each pumping step, the tracer is injected under constant concentration and constant hydraulic head from a piezometer in the upper aquifer. If a seal defect exists, the tracer will follow the leak and will be recovered from the pumped water. The theoretical equations relate the leakage rate, the pumping rate, the concentration of the injected tracer, and the recovered concentration. Leakage rates can be determined for any pumping rate. The theory is tested using numerical analysis and a full-scale field test.

Well vulnerability: a quantitative approach for source water protection.

The concept of vulnerability of drinking water sources is reviewed, and a quantitative approach for assessing well vulnerability for complex three-dimensional ground water systems is developed. The approach focuses on the relative expected impact of potential contaminant sources at unknown locations within a well capture zone, providing relative measures of intrinsic well vulnerability, including the expected times of arrival of a contaminant, the dispersion-related reduction in concentration, the time taken to breach a certain quality objective, and the corresponding exposure times. Thus, the result of the analysis includes the usual advective travel time information used in conventional wellhead protection analysis, plus a set of selected quantitative measures expressing the expected impact. The technique is based on adjoint theory and combines forward- and backward-in-time transport modeling using a standard numerical flow and transport code. The methodology is demonstrated using the case study of a complex glacial multiaquifer system in Ontario. The new approach will be useful in helping water managers develop more physically based and quantitative wellhead protection strategies.

Numerical investigation of road salt impact on an urban wellfield.

The impact of road salt on a wellfield in a complex glacial moraine aquifer system is studied by numerical simulation. The moraine underlies an extensive urban and industrial landscape, which draws its water supply from >20 wellfields, several of which are approaching or have exceeded the drinking water limit for chloride. The study investigates the mechanisms of road salt infiltration, storage, and transport in the subsurface and assesses the effectiveness of mitigation measures designed to reduce the impact. The three-dimensional transport model accounts for increases in salt loading, as well as growth of the urbanized area and road network over the past 50 years. The simulations, which focus on one impacted wellfield, show chloride plumes originating mainly at arterial roads and migrating through aquitard windows into the water supply aquifers. The results suggest that the aquifer system contains a large and heterogeneously distributed mass of chloride and that concentrations in the aquifer can be substantially higher than the concentrations in the well water. Future impact scenarios indicate that although the system responds rapidly to reductions in salt loading, the residual chloride mass may take decades to flush out, even if road salting were discontinued. The implications with respect to urban wellfields in typical snow-belt areas are discussed.

An analytical solution for ground water transit time through unconfined aquifers.

An exact, closed-form analytical solution is developed for calculating ground water transit times within Dupuit-type flow systems. The solution applies to steady-state, saturated flow through an unconfined, horizontal aquifer recharged by surface infiltration and discharging to a downgradient fixed-head boundary. The upgradient boundary can represent, using the same equation, a no-flow boundary or a fixed head. The approach is unique for calculating travel times because it makes no a priori assumptions regarding the limit of the water table rise with respect to the minimum saturated aquifer thickness. The computed travel times are verified against a numerical model, and examples are provided, which show that the predicted travel times can be on the order of nine times longer relative to existing analytical solutions.

Numerical simulations of pyrite oxidation and acid mine drainage in unsaturated waste rock piles.

Numerical simulations of layered, sulphide-bearing unsaturated waste rock piles are presented to illustrate the effect of coupled processes on the generation of acid mine drainage (AMD). The conceptual 2D systems were simulated using the HYDRUS model for flow and the POLYMIN model for reactive transport. The simulations generated low-pH AMD which was buffered by sequential mineral dissolution and precipitation. Sulphide oxidation rates throughout the pile varied by about two orders of magnitude (0.004-0.4 kg m-3 year-1) due to small changes in moisture content and grain size. In the fine-grained layers, the high reactive surface area induced high oxidation rates, even though capillary forces kept the local moisture content relatively high. In waste rock piles with horizontal layers, most of the acidity discharged through vertical preferential flow channels while with inclined fine grained layers, capillary diversion channeled the AMD to the outer slope boundary, keeping the pile interior relatively dry. The simulation approach will be useful for helping evaluate design strategies for controlling AMD from waste rock.

Delineation of three-dimensional well capture zones for complex multi-aquifer systems.

The delineation of well capture zones is a basic component of ground water protection. The conventional methodology for capture zone delineation is backward advective particle tracking, often applied under the assumption of a two-dimensional aquifer. The suitability of the conventional approach for complex heterogeneous multi-aquifer systems was investigated, using the Waterloo Moraine aquifer system as an example. It was found that the conventional approach produces irregular particle tracks that require judgment to interpret in a meaningful way, and it can raise questions that may affect the credibility of the capture zone delineation. As an alternative, the potentially powerful but little-used backward-in-time advective-dispersive transport approach was investigated. A key advantage of this approach is its capability to represent local heterogeneities through the dispersion term. The dispersion process has a natural smoothing effect that results in unambiguous capture zones without the need for interpretation, thus enhancing credibility. The question of capture zone validation is also addressed. The meaning of a three-dimensional capture zone is considered, and it is shown that a fully three-dimensional representation of the system is crucial for valid results. The distinction between the maximum extent capture zone and the surface capture zone is also explained. In the case of complex heterogeneous systems, advective particle tracking can be used as an initial screening tool, whereas the more realistic backward-transport modeling approach can be used for final capture-zone delineation.

Humic acid enhanced remediation of an emplaced diesel source in groundwater. 2. Numerical model development and application.

A pilot scale experiment for humic acid-enhanced remediation of diesel fuel, described in Part 1 of this series, is numerically simulated in three dimensions. Groundwater flow, enhanced solubilization of the diesel source, and reactive transport of the dissolved contaminants and humic acid carrier are solved with a finite element Galerkin approach. The model (BIONAPL) is calibrated by comparing observed and simulated concentrations of seven diesel fuel components (BTEX and methyl-, dimethyl- and trimethylnaphthalene) over a 1500-day monitoring period. Data from supporting bench scale tests were used to estimate contaminant-carrier binding coefficients and to simulate two-site sorption of the carrier to the aquifer sand. The model accurately reproduced the humic acid-induced 10-fold increase in apparent solubility of trimethylnaphthalene. Solubility increases on the order of 2-5 were simulated for methylnaphthalene and dimethylnaphthalene, respectively. Under the experimental and simulated conditions, the residual 500-ml diesel source was almost completely dissolved and degraded within 5 years. Without humic acid flushing, the simulations show complete source dissolution would take about six times longer.

Modelling the closure-related geochemical evolution of groundwater at a former uranium mine.

A newly developed reactive transport model was used to evaluate the potential effects of mine closure on the geochemical evolution in the aquifer downgradient from a mine site. The simulations were conducted for the Königstein uranium mine located in Saxony, Germany. During decades of operation, uranium at the former mine site had been extracted by in situ acid leaching of the ore underground, while the mine was maintained in a dewatered condition. One option for decommissioning is to allow the groundwater level to rise to its natural level, flooding the mine workings. As a result, pore water containing high concentrations of dissolved metals, radionuclides, and sulfate may be released. Additional contamination may arise due to the dissolution of minerals contained in the aquifer downgradient of the mine. On the other hand, dissolved metals may be attenuated by reactions within the aquifer. The geochemical processes and interactions involved are highly non-linear and their impact on the quality of the groundwater and surface water downstream of the mine is not always intuitive. The multicomponent reactive transport model MIN3P, which can describe mineral dissolution-precipitation reactions, aqueous complexation, and oxidation-reduction reactions, is shown to be a powerful tool for investigating these processes. The predictive capabilities of the model are, however, limited by the availability of key geochemical parameters such as the presence and quantities of primary and secondary mineral phases. Under these conditions, the model can provide valuable insight by means of sensitivity analyses.

Modeling preferential flow in reactive barriers: implications for performance and design.

Reactive barriers are passive and in situ ground water treatment systems. Heterogeneities in hydraulic conductivity (K) within the aquifer-reactive barrier system will result in higher flux rates, and reduced residence times, through portions of the barrier. These spatial variations in residence time will affect the treatment capacity of the barrier. A numerical flow model was used to evaluate the effects of spatial variations in K on preferential flow through barriers. The simulations indicate that the impact of heterogeneities in K will be a function of their location and distribution; the more localized the high K zone, the greater the preferential flow. The geometry of the reactive barrier will also strongly influence flow distribution. Aquifer heterogeneities will produce greater preferential flow in thinner barriers compared to thicker barriers. If the barrier K is heterogeneous, greater preferential flow will occur in thicker barriers. The K of the barrier will affect the flow distribution; decreasing the K of the barrier can result in more even distribution of flow. Results indicate that less variable flow will be attained utilizing thicker, homogeneous barriers. The addition of homogeneous zones to thinner barriers will be effective at redistributing flow only if installed immediately adjacent to both the up- and downgradient faces of the barrier.

Influence of transient flow on contaminant biodegradation.

The rate of biodegradation in contaminated aquifers depends to a large extent on dispersive mixing processes that are now generally accepted to result from spatial variations in the velocity field. It has been shown, however, that transient flow fields can also contribute to dispersive mixing. The influence of transient flow on biodegrading contaminants is particularly important since it can enhance mixing with electron acceptors, further promoting the reactive process. Using numerical simulations, the effect of transient flow on the behavior of a biodegradable contaminant is evaluated here both with respect to the development of apparently large horizontal transverse dispersion and also with respect to enhanced mixing between the substrate (electron donor) and electron acceptor. The numerical model BIO3D, which solves for advective-dispersive transport coupled with Monod-type biodegradation of substrates in the presence of an electron acceptor, was used for the simulations. The model was applied in a two-dimensional plan view mode considering a single substrate. Transient flow fields were found to yield larger apparent transverse dispersion because the longitudinal dispersivity also acts transverse to the mean flow direction. In the reactive case, the transient flow field increases substrate-oxygen mixing, which in turn enhances the overall rate of biodegradation. The results suggest that in the case of moderate changes of flow directions, a steady-state flow field can be justified, thereby avoiding the higher computational costs of a fully transient simulation. The use of a higher transverse horizontal dispersivity in a steady flow field can, under these conditions, adequately forecast plume development.