muFlowReacT: A Library to Solve Multiphase Multicomponent Reactive Transport on Unstructured Meshes.

In this paper we present a new reactive transport code for the efficient simulation of groundwater quality problems. The new code couples the two previously existing tools OpenFoam and PhreeqcRM. The major objective of the development was to transfer and expand the capabilities of the MODFLOW/MT3DMS-family of codes, especially their outstanding ability to suppress numerical dispersion, to a versatile and computationally efficient code for unstructured grids. Owing to the numerous, previously existing transport solvers contained in OpenFoam, the newly developed code achieves this objective and provides a solid basis for future expansions of the code capabilities. The flexibility of the OpenFoam framework is illustrated by the addition of diffusional processes for gaseous compounds in the unsaturated zone and the advection of gases (multiphase transport). The code capabilities and accuracy are illustrated through several examples: (1) a simple 2D case for conservative solute transport under saturated conditions, (2) a gas diffusion case with reactions in the unsaturated zone, (3) a hydrogeologically complex 3D reactive transport problem, and finally (4) the injection of CO2 into a deep aquifer with acidification being buffered by carbonate minerals.

Identifying remedial solutions through optimal bioremediation design under real-world field conditions.

Over more than a century of intense industrial production and associated accidental release, petroleum products (e.g., gasoline, diesel, fuel oil) have contaminated a significant portion of the world's groundwater resources. Groundwater remediation is generally a complex task, especially where aquifers and the associated contaminant distribution are highly heterogeneous. The ability to predict the efficiency of such remediation is of crucial importance, as the costs are strongly linked to the treatment design and duration. In this study, a coupled simulation-optimization (S/O) framework, consisting of a process-based reactive transport simulation model linked with particle swarm optimization (PSO) was developed. It was subsequently applied for the design of a real-world in situ bio-treatment of a BTEX contaminated aquifer in France. In the application, the optimization framework was used to simultaneously determine optimal well locations and their optimal injection rates, both constituting key elements of the enhanced biodegradation design problem. The optimization of the treatment efficiency was examined in terms of three different regulatory objectives, (1) minimization of the residual NAPL mass of the key contaminant, i.e., benzene, in the source zone, (2) reduction of the maximum concentration of benzene in groundwater, and (3) minimization of the time required to reduce the benzene concentration in groundwater to below a threshold value. Our analysis of potential, optimal remediation strategies showed that: (i) the complexity of the biodegradation behavior at real sites may favor very different remediation options as a result of varying remediation targets, (ii) the long term behavior of the contaminants after the end of the active treatment period, which is often neglected, showed to have a significant influence on remediation design that requires increased attention, (iii) PSO has shown to be a very efficient algorithm in the context of the present study. The insights that can be gained from such a framework will provide decision support to select the most suitable remediation strategy while facing different regulatory objectives.

Elucidating the fate of a mixed toluene, DHM, methanol, and i-propanol plume during in situ bioremediation.

Organic pollutants such as solvents or petroleum products are widespread contaminants in soil and groundwater systems. In-situ bioremediation is a commonly used remediation technology to clean up the subsurface to eliminate the risks of toxic substances to reach potential receptors in surface waters or drinking water wells. This study discusses the development of a subsurface model to analyse the performance of an actively operating field-scale enhanced bioremediation scheme. The study site was affected by a mixed toluene, dihydromyrcenol (DHM), methanol, and i-propanol plume. A high-resolution, time-series of data was used to constrain the model development and calibration. The analysis shows that the observed failure of the treatment system is linked to an inefficient oxygen injection pattern. Moreover, the model simulations also suggest that additional contaminant spillages have occurred in 2012. Those additional spillages and their associated additional oxygen demand resulted in a significant increase in contaminant fluxes that remained untreated. The study emphasises the important role that reactive transport modelling can play in data analyses and for enhancing remediation efficiency.

Fate of arsenic, phosphate and ammonium plumes in a coastal aquifer affected by saltwater intrusion.

A severe groundwater contamination with extensive plumes of arsenic, phosphate and ammonium was found in a coastal aquifer beneath a former fertilizer production plant. The implementation of an active groundwater remediation strategy, based on a comprehensive pump and treat scheme, now prevents the migration of the dissolved contaminants into the marine environment. However, due to the site's proximity to the coastline, a seawater wedge was induced by the pumping scheme. Additionally the groundwater flow and salinity patterns were also strongly affected by leakage from the site's sewer system and from a seawater-fed cooling canal. The objective of this study was to elucidate the fate of arsenic and its co-contaminants over the site's history under the complex, coupled hydrodynamic and geochemical conditions that prevail at the site. A detailed geochemical characterisation of samples from sediment cores and hydrochemical data provided valuable high-resolution information. The obtained data were used to develop various conceptual models and to constrain the development and calibration of a reactive transport model. The reactive transport simulations were performed for a sub-domain (two-dimensional transect) of an earlier developed three-dimensional flow and variable density solute transport model. The results suggest that in the upper sub-oxic zone the influx of oxygenated water promoted As attenuation via co-precipitation with Al and Fe oxides and copper hydroxides. In contrast, in the deeper aquifer zone, iron reduction, associated with the release of adsorbed As and the dissolution of As bearing phases, provided and still provides to date a persistent source for groundwater pollution. The presented monitoring and modelling approach could be broadly applied to coastal polluted sites by complex contaminant mixture containing As.

Modelling the fate of styrene in a mixed petroleum hydrocarbon plume.

Severe petroleum hydrocarbon contamination (styrene and the BTEX compounds: benzene, toluene, ethylbenzene and the isomers of xylene) from leaking sewers was detected in a Quaternary aquifer below a chemical plant in the Padana Plain, Italy. From 1994, active pump and treat remediation has been employed. The site is bordered by canals which, in combination with variable pumping rates and groundwater flow directions, control groundwater levels. In this study we sought to determine the fate of styrene at the site within a mixed styrene/BTEX plume where the hydraulic boundaries induced strong seasonal variations in flows. In order to determine the fate of styrene, detailed field investigations provided intensive depth profile information. This information was then incorporated into a staged flow and reactive transport modelling. Three sets of measurements were obtained from sampling multilevel samplers (MLSs) under different hydraulic conditions at the site. These included measurements of BTEX, styrene, all major ions, pH and redox potential. A three-dimensional transient flow model was developed and calibrated to simulate an unconfined sandy aquifer with a variable flow field. Subsequently a reactive, multi-component transport model was employed to simulate the fate of dissolved BTEX and styrene along a selected flow line at the site. Each petroleum hydrocarbon compound was transported as independent species. Different, kinetically controlled degradation rates and a toxicity effect were simulated to explain the observed, selective degradation of pollutants in groundwater. Calibration of the model was accomplished by comparison with the three different sets of measurements obtained from the MLS devices. The results from various scenarios show that the detailed simulation of geochemical changes can be very useful to improve the site's conceptual model.

A critical evaluation of combined engineered and aquifer treatment systems in water recycling.

Australian experience at five research sites where stormwater and reclaimed water have been stored in aquifers prior to reuse, have yielded valuable information about water treatment processes in anaerobic and aerobic aquifers. One of these sites is the stormwater to potable water ASTR project at the City of Salisbury, a demonstration project within the broader EC project 'RECLAIM WATER'. A framework for characterising the effectiveness of such treatment for selected organic chemicals, natural organic matter, and pathogens is being developed for inclusion in new Australian Guidelines for Management of Aquifer Recharge. The combination of pre-treatments (including passive systems such as reed beds) and aquifer treatment effectiveness in relation to source waters and intended uses of recovered water will be described. Advantages and disadvantages of various types of pre-treatments in relation to effectiveness and sustainability of managed aquifer recharge will be discussed taking account of aquifer characteristics. These observations will be consolidated into a draft set of principles to assist in selection of engineered treatments compatible with passive treatment in aquifers.

Predictive modelling of dispersion controlled reactive plumes at the laboratory-scale.

A model-based interpretation of laboratory-scale experimental data is presented. Hydrolysis experiments carried out using thin glass tanks filled with glass beads to construct a hypothetical and inert, homogeneous porous medium were analysed using a 2D numerical model. A new empirical formula, based upon results for non-reactive (tracer) experiments is used to calculate transversal dispersivity values for a range of grain sizes and any flow velocities. Combined with effective diffusion coefficients calculated from Stokes-Einstein type equations, plume lengths arising from mixing between two solutes can be predicted accurately using numerical modelling techniques. Moreover, pH and ion concentration profiles lateral to the direction of flow of the mixing species can be determined at any given point downstream, without the need for result fitting. In our case, this approach does not lead to overpredictions of lateral mixing, as previously reported when using parameters derived from non-reactive tracer experiments to describe reactive solute transport. The theory is based on the assumption of medium homogeneity.

MODFLOW/MT3DMS-based reactive multicomponent transport modeling.

This paper presents a three-dimensional, MODFLOW/MT3DMS-based reactive multicomponent transport model for saturated porous media. Based on a split-operator technique, the model, referred to as PHT3D, couples the transport simulator MT3DMS and the geochemical modeling code PHREEQC-2. Through the flexible, generic nature of PHREEQC-2, PHT3D can handle a broad range of equilibrium and kinetically controlled reactive processes, including aqueous complexation, mineral precipitation/dissolution, and ion exchange. The diversity of potential applications is demonstrated through simulation of five existing literature benchmarks and a new three-dimensional sample problem. The model might be applied to simulate the geochemical evolution of pristine and contaminated aquifers as well as their cleanup. The latter problem class includes the natural and enhanced attenuation/remediation schemes of a wide range of organic and inorganic contaminants. Processes/reactions not included in the standard PHREEQC-2 database but typical for this type of application (e.g., NAPL dissolution, microbial growth/decay) can be defined and included via the extensible PHREEQC-2 database file.

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions.

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.