Evaporation loss along the Calueque-Oshakati Canal in the Cuvelai-Etosha Basin (Northern Namibia): evidence from stable isotopes and hydrochemistry.

Since 1973, Kunene River water has been carried from the Calueque reservoir in Angola along a 160 km open concrete canal to the town of Oshakati in the central part of the Cuvelai-Etosha Basin and has been supplying drinking water to the most densely populated rural area of Namibia. Despite its importance for the region, intra-seasonal water quality and the technical condition of the canal are not routinely checked. Water samples were collected during four field campaigns right before the onset of the rainy season (November 2013 and 2014), and after the rainy season (June 2014 and May 2015), at 16 sites along the canal for stable water isotopes (deuterium, oxygen-17 and oxygen-18) and hydrochemical analyses. The isotope patterns and chemical composition of the canal water is discussed in comparison to local rain, Kunene source water, surface water and groundwater. Clear isotope enrichment indicates evaporative loss of water. A Craig-Gordon model was used to estimate water loss. The loss increases with distance from the source with a maximum of up to 10 %, depending on the season. The results are discussed in context of water availability, vulnerability and water resources management in this water-scarce area.

Spatiotemporal evolution of iron and sulfate concentrations during riverbank filtration: Field observations and reactive transport modeling.

Riverbank filtration is a commonly-used technology that improves water quality by passing river water through aquifers. In this study, a riverbank filtration site in Busan, South Korea, was investigated to understand the spatiotemporal evolution of high iron and sulfate concentrations observed in the riverbank-filtered water. Discrepancies between the nonreactive transport results and field measurements suggest that iron-sulfate-related geochemical reactions play a major role in the spatiotemporal evolution of the hydrochemical properties. Pyrite oxidation was hypothesized to be the main process driving the release of iron and sulfate. To test this hypothesis, a reactive transport model was developed, that implemented pyrite oxidation as a kinetic process and subsequent ferrous iron oxidation and ferric iron precipitation as equilibrium processes. The model accurately captured the temporal evolution of sulfate; however, iron concentrations were underestimated. Sensitivity tests revealed that adjusting reaction constants significantly improved the prediction of iron concentrations. The results of this study suggest that pyrite oxidation can affect the hydrochemistry of riverbank-filtered water and highlight the potential limitations of using theoretical reaction constants in field modeling applications.

How water isotopes (18O, 2H, 3H) within an island freshwater lens respond to changes in rainfall.

Coastal aquifers provide an important source of water globally. Understanding how groundwater responds to changes in rainfall recharge is important for sustainable development. To this end, we investigate how water isotopes (18O, 2H, 3H) and chloride (Cl) concentrations within an island freshwater lens respond under varying rainfall conditions in a region experiencing climate change. Uniquely, this study presents a three year dataset of groundwater collected seasonally between May 2013 and August 2016 from ten wells. Variation in all tracers was observed. The Cl and tritium (3H) show opposing seasonal variation in some sections of the lens, with higher Cl observed in the austral summer when less rainfall occurs and evapotranspiration is highest. The opposite occurs in the austral winter months when 3H increases from atmospheric input via rainfall recharge, and Cl is diluted. An overall decline in 3H values and enrichment in stable water isotopes over the study period was also observed. This study shows that understanding groundwater of freshwater lenses should not rely on a single sampling campaign because seasonal variability is large. The identification of a dual recharge regime, with contributions from both winter rainfall and episodic events, has important implications for understanding the future fate of the freshwater lens on Rottnest Island. The finding that episodic rainfall is a major contributor to groundwater recharge is important and can only be assessed with a multi-year isotope dataset for groundwater and rainfall.

Modelling size constraints on carbonate platform formation in groundwater upwelling zones.

Carbonate depositional systems related to groundwater upwelling are ubiquitous around the world and form ecologically and culturally important features of many landscapes. Spring carbonate deposits record past climatic and hydrological conditions. The reconstruction of past processes using spring carbonate proxies requires fundamental understanding of the factors that control their geometry. In this work, we show that the spatial extent of spring carbonate platforms is amenable to quantitative prediction by simulating the early growth stage of their formation for the iconic mound springs in the central Australian outback. We exploit their well-defined, circular geometry to demonstrate the existence of two size-limiting regimes: one controlled by the spring flow rate and the other by the concentration of lattice ions. Deviations between modelled and observed size metrics are attributable to diminishing spring flow rates since formation, enabling assessment of the relative vulnerability of springs to further hydrological change.

Carbon dynamics in a Late Quaternary-age coastal limestone aquifer system undergoing saltwater intrusion.

This study investigates the inorganic and organic aspects of the carbon cycle in groundwaters throughout the freshwater lens and transition zone of a carbonate island aquifer and identifies the transformation of carbon throughout the system. We determined 14C and 13C carbon isotope values for both DIC and DOC in groundwaters, and investigated the composition of DOC throughout the aquifer. In combination with hydrochemical and 3H measurements, the chemical evolution of groundwaters was then traced from the unsaturated zone to the deeper saline zone. The data revealed three distinct water types: Fresh (F), Transition zone 1 (T1) and Transition zone 2 (T2) groundwaters. The 3H values in F and T1 samples indicate that these groundwaters are mostly modern. 14CDOC values are higher than 14CDIC values and are well correlated with 3H values. F and T1 groundwater geochemistry is dominated by carbonate mineral recrystallisation reactions that add dead carbon to the groundwater. T2 groundwaters are deeper, saline and characterised by an absence of 3H, lower 14CDOC values and a different DOC composition, namely a higher proportion of Humic Substances relative to total DOC. The T2 groundwaters are suggested to result from either the slow circulation of water within the seawater wedge, or from old remnant seawater caused by past sea level highstands. While further investigations are required to identify the origin of the T2 groundwaters, this study has identified their occurrence and shown that they did not evolve along the same pathway as fresh groundwaters. This study has also shown that a combined approach using 14C and 13C carbon isotope values for both DIC and DOC and the composition of DOC, as well as hydrochemical and 3H measurements, can provide invaluable information regarding the transformation of carbon in a groundwater system and the evolution of fresh groundwater recharge.

Groundwater flow estimation using temperature-depth profiles in a complex environment and a changing climate.

Obtaining reliable estimates of vertical groundwater flows remains a challenge but is of critical importance to the management of groundwater resources. When large scale land clearing or groundwater extraction occurs, methods based on water table fluctuations or water chemistry are unreliable. As an alternative, a number of methods based on temperature-depth (T-z) profiles are available to provide vertical groundwater flow estimates from which recharge rates may be calculated. However, methods that invoke steady state assumptions have been shown to be inappropriate for sites that have experienced land surface warming. Analytical solutions that account for surface warming are available, but they typically include unrealistic or restrictive assumptions (e.g. no flow initial conditions or linear surface warming). Here, we use a new analytical solution and associated computer program (FAST) that provides flexible initial and boundary conditions to estimate fluxes using T-z profiles from the Willunga Super Science Site, a complex, but densely instrumented groundwater catchment in South Australia. T-z profiles from seven wells (ranging from high elevation to near sea level) were utilised, in addition to mean annual air temperatures at nearby weather stations to estimate boundary conditions, and thermal properties were estimated from down borehole geophysics. Temperature based flux estimates were 5 to 23mmy-1, which are similar to those estimated using chloride mass balance. This study illustrates that T-z profiles can be studied to estimate recharge in environments where more commonly applied methods fail.

A Spatially Periodic Solute Boundary for MT3DMS and PHT3D.

The assumption of spatial repetition is commonly made when producing bedform scale models of the hyporheic zone. Two popular solute transport codes, MT3DMS and PHT3D, do not currently provide the necessary boundary condition required to simulate spatial periodicity in hyporheic zone transport problems. In this study, we develop a spatially periodic boundary (SPB) for solutes that is compatible with a SPB that was previously developed for MODFLOW to simulate the flow component of spatially periodic problems. The approach is ideal for simulating groundwater flow and transport patterns under repeating surface features, such as ripples or dunes on the bottom of a lake or stream. The appropriate block-centered finite-difference approach to implement the boundary is presented and the necessary source code modifications are discussed. The performance of the solute SPB, operating in conjunction with the groundwater flow SPB, is explored through comparison of a multi-bedform hyporheic-zone model with a single bedform variant. The new boundary conditions perform well in situations where both dispersive effects and lateral seepage flux in the underflow regime beneath the hyporheic zone are minimal.

PHT3D-UZF: A Reactive Transport Model for Variably-Saturated Porous Media.

A modified version of the MODFLOW/MT3DMS-based reactive transport model PHT3D was developed to extend current reactive transport capabilities to the variably-saturated component of the subsurface system and incorporate diffusive reactive transport of gaseous species. Referred to as PHT3D-UZF, this code incorporates flux terms calculated by MODFLOW's unsaturated-zone flow (UZF1) package. A volume-averaged approach similar to the method used in UZF-MT3DMS was adopted. The PHREEQC-based computation of chemical processes within PHT3D-UZF in combination with the analytical solution method of UZF1 allows for comprehensive reactive transport investigations (i.e., biogeochemical transformations) that jointly involve saturated and unsaturated zone processes. Intended for regional-scale applications, UZF1 simulates downward-only flux within the unsaturated zone. The model was tested by comparing simulation results with those of existing numerical models. The comparison was performed for several benchmark problems that cover a range of important hydrological and reactive transport processes. A 2D simulation scenario was defined to illustrate the geochemical evolution following dewatering in a sandy acid sulfate soil environment. Other potential applications include the simulation of biogeochemical processes in variably-saturated systems that track the transport and fate of agricultural pollutants, nutrients, natural and xenobiotic organic compounds and micropollutants such as pharmaceuticals, as well as the evolution of isotope patterns.

Spatial periodic boundary condition for MODFLOW.

Small-scale hyporheic zone (HZ) models often use a spatial periodic boundary (SPB) pair to simulate an infinite repetition of bedforms. SPB's are common features of commercially available multiphysics modeling packages. MODFLOW's lack of this boundary type has precluded it from being effectively utilized in this area of HZ research. We present a method to implement the SPB in MODFLOW by development of the appropriate block-centered finite-difference expressions. The implementation is analogous to MODFLOW's general head boundary package. The difference is that the terms on the right hand side of the solution equations must be updated with each iteration. Consequently, models that implement the SPB converge best with solvers that perform both inner and outer iterations. The correct functioning of the SPB condition in MODFLOW is verified by two examples. This boundary condition allows users to build HZ-bedform models in MODFLOW, facilitating further research using related codes such as MT3DMS and PHT3D.

Offshore fresh groundwater reserves as a global phenomenon.

The flow of terrestrial groundwater to the sea is an important natural component of the hydrological cycle. This process, however, does not explain the large volumes of low-salinity groundwater that are found below continental shelves. There is mounting evidence for the global occurrence of offshore fresh and brackish groundwater reserves. The potential use of these non-renewable reserves as a freshwater resource provides a clear incentive for future research. But the scope for continental shelf hydrogeology is broader and we envisage that it can contribute to the advancement of other scientific disciplines, in particular sedimentology and marine geochemistry.

The impact of low-temperature seasonal aquifer thermal energy storage (SATES) systems on chlorinated solvent contaminated groundwater: modeling of spreading and degradation.

Groundwater systems are increasingly used for seasonal aquifer thermal energy storage (SATES) for periodic heating and cooling of buildings. Its use is hampered in contaminated aquifers because of the potential environmental risks associated with the spreading of contaminated groundwater, but positive side effects, such as enhanced contaminant remediation, might also occur. A first reactive transport study is presented to assess the effect of SATES on the fate of chlorinated solvents by means of scenario modeling, with emphasis on the effects of transient SATES pumping and applicable kinetic degradation regime. Temperature effects on physical, chemical, and biological reactions were excluded as calculations and initial simulations showed that the small temperature range commonly involved (ΔT<15 °C) only caused minor effects. The results show that a significant decrease of the contaminant mass and (eventually) plume volume occurs when degradation is described as sediment-limited with a constant rate in space and time, provided that dense non-aqueous phase liquid (DNAPL) is absent. However, in the presence of DNAPL dissolution, particularly when the dissolved contaminant reaches SATES wells, a considerably larger contaminant plume is created, depending on the balance between DNAPL dissolution and mass removal by degradation. Under conditions where degradation is contaminant-limited and degradation rates depend on contaminant concentrations in the aquifer, a SATES system does not result in enhanced remediation of a contaminant plume. Although field data are lacking and existing regulatory constraints do not yet permit the application of SATES in contaminated aquifers, reactive transport modeling provides a means of assessing the risks of SATES application in contaminated aquifers. The results from this study are considered to be a first step in identifying the subsurface conditions under which SATES can be applied in a safe or even beneficial manner.

Simulating MODFLOW-based reactive transport under radially symmetric flow conditions.

Radially symmetric flow and solute transport around point sources and sinks is an important specialized topic of groundwater hydraulics. Analysis of radial flow fields is routinely used to determine heads and flows in the vicinity of point sources or sinks. Increasingly, studies also consider solute transport, biogeochemical processes, and thermal changes that occur in the vicinity of point sources/sinks. Commonly, the analysis of hydraulic processes involves numerical or (semi-) analytical modeling methods. For the description of solute transport, analytical solutions are only available for the most basic transport phenomena. Solving advanced transport problems numerically is often associated with a significant computational burden. However, where axis-symmetry applies, computational cost can be decreased substantially in comparison with full three-dimensional (3D) solutions. In this study, we explore several techniques of simulating conservative and reactive transport within radial flow fields using MODFLOW as the flow simulator, based on its widespread use and ability to be coupled with multiple solute and reactive transport codes of different complexity. The selected transport simulators are MT3DMS and PHT3D. Computational efficiency and accuracy of the approaches are evaluated through comparisons with full 2D/3D model simulations, analytical solutions, and benchmark problems. We demonstrate that radial transport models are capable of accurately reproducing a wide variety of conservative and reactive transport problems provided that an adequate spatial discretization and advection scheme is selected. For the investigated test problems, the computational load was substantially reduced, with the improvement varying, depending on the complexity of the considered reaction network.

Closed-form approximations for two-dimensional groundwater age patterns in a fresh water lens.

Simple closed-form approximations are presented for calculating the steady-state groundwater age distribution in two-dimensional vertical cross sections of idealized fresh water lenses overlying salt water, for aquifers that are vertically semi-infinite and of finite thickness. The approximations are developed on the basis of existing one-dimensional analytical solutions for travel-time calculation in fresh water lenses and approximate streamline formulations. The two-dimensional age distributions based on the closed-form solutions match convincingly with numerical simulations. As expected, notable deviations from the numerical solution are encountered at the groundwater flow divide and when submarine groundwater discharge occurs. Ratios of recharge over hydraulic conductivities are varied to explore how the magnitude of the deviations changes, and it is found that the approximate closed-form solutions perform well over a range of conditions found in natural systems.

Process-based reactive transport model to quantify arsenic mobility during aquifer storage and recovery of potable water.

Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.

Tidal boundary conditions in SEAWAT.

SEAWAT, a U.S. Geological Survey groundwater flow and transport code, is increasingly used to model the effects of tidal motion on coastal aquifers. Different options are available to simulate tidal boundaries but no guidelines exist nor have comparisons been made to identify the most effective approach. We test seven methods to simulate a sloping beach and a tidal flat. The ocean is represented in one of the three ways: directly using a high hydraulic conductivity (high-K) zone and indirect simulation via specified head boundaries using either the General Head Boundary (GHB) or the new Periodic Boundary Condition (PBC) package. All beach models simulate similar water fluxes across the upland boundary and across the sediment-water interface although the ratio of intertidal to subtidal flow is different at low tide. Simulating a seepage face results in larger intertidal fluxes and influences near-shore heads and salinity. Major differences in flow occur in the tidal flat simulations. Because SEAWAT does not simulate unsaturated flow the water table only rises via flow through the saturated zone. This results in delayed propagation of the rising tidal signal inland. Inundation of the tidal flat is delayed as is flow into the aquifer across the flat. This is severe in the high-K and PBC models but mild in the GHB models. Results indicate that any of the tidal boundary options are fine if the ocean-aquifer interface is steep. However, as the slope of that interface decreases, the high-K and PBC approaches perform poorly and the GHB boundary is preferable.

Evaluation of conceptual and numerical models for arsenic mobilization and attenuation during managed aquifer recharge.

Managed Aquifer Recharge (MAR) is promoted as an attractive technique to meet growing water demands. An impediment to MAR applications, where oxygenated water is recharged into anoxic aquifers, is the potential mobilization of trace metals (e.g., arsenic). While conceptual models for arsenic transport under such circumstances exist, they are generally not rigorously evaluated through numerical modeling, especially at field-scale. In this work, geochemical data from an injection experiment in The Netherlands, where the introduction of oxygenated water into an anoxic aquifer mobilized arsenic, was used to develop and evaluate conceptual and numerical models of arsenic release and attenuation under field-scale conditions. Initially, a groundwater flow and nonreactive transport model was developed. Subsequent reactive transport simulations focused on the description of the temporal and spatial evolution of the redox zonation. The calibrated model was then used to study and quantify the transport of arsenic. In the model that best reproduced field observations, the fate of arsenic was simulated by (i) release via codissolution of arsenopyrite, stoichiometrically linked to pyrite oxidation, (ii) kinetically controlled oxidation of dissolved As(III) to As(V), and (iii) As adsorption via surface complexation on neo-precipitated iron oxides.

Using hydraulic head measurements in variable-density ground water flow analyses.

The use of hydraulic head measurements in ground water of variable density is considerably more complicated than for the case of constant-density ground water. A theoretical framework for dealing with these complications does exist in the current literature but suffers from a lack of awareness among many hydrogeologists. When corrections for density variations are ignored or not properly taken into account, misinterpretation of both ground water flow direction and magnitude may result. This paper summarizes the existing theoretical framework and provides practical guidelines for the interpretation of head measurements in variable-density ground water systems. It will be argued that, provided that the proper corrections are taken into account, fresh water heads can be used to analyze both horizontal and vertical flow components. To avoid potential confusion, it is recommended that the use of the so-called environmental water head, which was initially introduced to facilitate the analysis of vertical ground water flow, be abandoned in favor of properly computed fresh water head analyses. The presented methodology provides a framework for determining quantitatively when variable-density effects on ground water flow need to be taken into account or can be justifiably neglected. Therefore, we recommend that it should become part of all hydrogeologic analyses in which density effects are suspected to play a role.