Structural Uncertainty Due to Fault Timing: A Multimodel Case Study from the Perth Basin.

Faults can fundamentally change a groundwater flow regime and represent a major source of uncertainty in groundwater studies. Much research has been devoted to uncertainty around their location and their barrier-conduit behavior. However, fault timing is one aspect of fault uncertainty that appears to be somewhat overlooked. Many faulted models feature consistent layer offsets, thereby presuming that block faulting has occurred recently and almost instantaneously. Additionally, barrier and/or conduit behavior is often shown to extend vertically through all layers when a fault may in fact terminate well below-ground surface. In this study, we create three plausible geological interpretations for a transect in the Perth Basin. Adjacent boreholes show stratigraphic offsets and thickening which indicate faulting; however, fault timing is unknown. Flow modeling demonstrates that the model with the most recent faulting shows profoundly different flow patterns due to aquifer juxtaposition. Additionally, multiple realizations with stochastically generated parameter sets for layer, fault core, and fault damage zone conductivity show that fault timing influences flow more than layer or fault zone conductivity. Finally, fault conduit behavior that penetrates aquitards has significant implications for transport, while fault barrier behavior has surprisingly little. This research advocates for adequate data collection where faults may cause breaches in aquitards due to layer offsets or conduit behavior in the damage zone. It also promotes the use of multiple geological models to address structural uncertainty, and highlights some of the hurdles in doing so such as computational expense and the availability of seamless geological-flow modeling workflows.

Quantifying Carbon Cycling across the Groundwater-Stream-Atmosphere Continuum Using High-Resolution Time Series of Multiple Dissolved Gases.

The quantification of carbon cycling across the groundwater-stream-atmosphere continuum (GSAC) is crucial for understanding regional and global carbon cycling. However, this quantification remains challenging due to highly coupled carbon exchange and turnover in the GSAC. Here, we disentangled carbon cycling processes in a representative groundwater-stream-atmosphere transect by obtaining and numerically simulating high-resolution time series of dissolved He, Ar, Kr, O2, CO2, and CH4 concentrations. The results revealed that groundwater contributed ∼60% of CO2 and ∼30% of CH4 inputs to the stream, supporting stream CO2 and CH4 emissions to the atmosphere. Furthermore, diurnal variations in stream metabolism (-0.6 to 0.6 mol O2 m-2 day-1) induced pronounced carbonate precipitation during the day and dissolution at night. The significant diurnal variability of biogeochemical processes emphasizes the importance of high-resolution time series investigations of carbon dynamics. This study shows that dissolved gases are promising environmental tracers for discerning and quantifying carbon cycling across the GSAC with high spatiotemporal resolution. Our high-resolution carbon exchange and turnover quantification provides a process-oriented and mechanistic understanding of carbon cycling across the GSAC.

Revisiting MODFLOW's Capability to Model Flow Through Sedimentary Structures.

Sedimentary structures have unique geometries and anisotropic hydraulic conductivity, both of which control groundwater flow. Traditional finite-difference simulators (e.g., MODFLOW) have not been able to correctly represent irregular, dipping and anisotropic structures due their use of a simplified conductivity tensor, causing many modelers to turn toward finite-element codes with their sophisticated meshing capabilities. However, the release of MODFLOW 6 with its flexible discretization and multipoint flux approximation scheme prompts us to revisit its capability to compute flow through complex sedimentary structures. Through the use of a novel benchmark and case study, we show that when versions previous to MODFLOW 6 are applied to dipping structures, modeled fluxes and hence flow through the system, can be significantly over or underestimated. For example, effective conductivity for a 30° dipping layer with a 100:1 conductivity ratio is reduced to only 2% of its inputted value. We show that MODFLOW 6, with its XT3D capability and flexible discretization options is far superior to its predecessors, allowing flow through complex sedimentary structures to be simulated more accurately. However, on vertically offset grids, which have been available in all versions of MODFLOW and are often used in practice, loss of accuracy is still a concern when the vertical offset is large, that is, the dip of the sedimentary layer is steep, particularly if the layer is much more conductive than the surrounding material. The hypothesis that vertically offset grids lack sufficient hydraulic connectivity between adjacent model layers to accurately simulate the steeply dipping, highly heterogeneous case is a topic for further investigation.

Fate of trace organic compounds in the hyporheic zone: Influence of microbial metabolism.

The hyporheic zone (HZ) is considered a hydrodynamically-driven bioreactor with significant pollutant removal capacities and can therefore not only improve wholestream water quality but also preserve human and ecosystem health. Microbial metabolism is hypothesized to play a key role in pollutant transformation in hyporheic sediments of natural streams. However, previous work investigating the influence of microbial metabolism on pollutant transformation has been predominantly laboratory studies. The key challenge for field studies is the appropriate determination of net microbial metabolism, i.e. information on the actual exposure times to specific microbial processes in the investigated system. The present study uses reactive fluorescent tracers to determine microbial metabolism and ultimately its influence on pollutant transformation, e.g. for trace organic compounds, in hyporheic sediments under natural conditions. In particular, the reactive fluorescent tracers resazurin and its main transformation product resorufin were used to determine the microbial metabolism of facultative or obligate aerobes. The influence of the derived microbial metabolism on the transformation of 20 trace organic compounds, such as pharmaceuticals, including 3 parent-daughter pairs, was examined. The present findings validate laboratory results on the microbially-mediated transformation of the anticonvulsant gabapentin to its main transformation product gabapentin lactam under natural conditions. All other TrOCs investigated did not show a clear link between TrOC reactivity to the microbial metabolism informed by the resazurin-resorufin-system. Overall, the present study not only demonstrates the use of the fluorescent tracer-system resazurin and resorufin for determining microbial metabolism of facultative or obligate aerobes but also generally highlights the potential of reactive fluorescent tracers to disentangle specific reactive properties and ultimately their influence on the fate of pollutants in natural HZs.

Determining hyporheic removal rates of trace organic compounds using non-parametric conservative transport with multiple sorption models.

Assessing the transport and reactive processes of contaminants in freshwater streams is crucial in managing water resources sustainably. Particularly the hyporheic zone, the sediment-water interface where surface water and groundwater mix, may possess significant contaminant removal capacities due to its myriad physical, chemical, and microbiological processes. However, modelling approaches aiming at assessing the hyporheic zone's reactivity are either based on simple assumptions, such as, predefining the shape of the residence times distribution (RTD) function, or are computationally not feasible due to a too detailed system characterisation. In addition, parent-daughter reactions of contaminants are barely investigated. The present study introduces a numerical modelling framework for assessing hyporheic reactions of contaminant transformation reactions based on a non-parametric residence time approach combined with multiple sorption models and first-order removal reactions. The proposed framework uses natural electrical conductivity fluctuations to determine conservative transport properties and is demonstrated by interpreting time series of hyporheic point measurements of trace organic compounds, such as pharmaceuticals, and their transformation products using two commonly-used sorption models, namely the simple retardation and the first-order kinetic sorption model. The developed approach gives similar reaction rate coefficient estimates for all contaminants considered for both sorption models tested. The findings highlight that (i) the accurate shape of the RTD is most certainly important for reactive parameter determination and (ii) the daughter reaction rate coefficient may be underestimated if its parent transformation is ignored. The model provides reactive parameter estimates of contaminant transformation reactions with high parameter identifiability and informs which specific parent-daughter-pathway has occurred.

Including Vertical Fault Structures in Layered Groundwater Flow Models.

Accurate representation of groundwater flow and solute transport requires a sound representation of the underlying geometry of aquifers. Faults can have a significant influence on the structure and connectivity of aquifers, which may allow permeable units to connect, and aquifers to seal when juxtaposed against lower permeability units. Robust representation of groundwater flow around faults remains challenging despite the significance of faults for flow and transport. We present a methodology for the inclusion of faults utilizing the unstructured grid features of MODFLOW-USG and MODFLOW 6. The method focuses on the representation of fault geometries using non-neighbor connections between juxtaposed layers. We present an illustration of the method for a synthetic fluvial aquifer. The combined impact of the heterogeneous aquifer and fault offset is clearly visible where channel features at different depths in the aquifer were connected at the fault. These results highlight the importance of representing fault features in groundwater flow models.

Effects of Intraborehole Flow on Purging and Sampling Long-Screened or Open Wells.

Hydraulic head differences across the screened or open interval of a well significantly influence the sampled water mixture. Sample bias can occur due to an insufficient pumping rate and/or due to native groundwater displacement by intraborehole flow (IBF). Proper understanding of the sampled water mixture is crucial for accurate interpretation of environmental tracers and groundwater chemistry data, and hence groundwater characterization. This paper uses numerical modeling to quantify sample bias caused by IBF in an un-pumped high-yield well, and the influence of pumping rate and heterogeneity on the volume of pumpage required to purge an IBF plume. The results show that (1) the pumping rate must be at least an order of magnitude greater than the IBF rate to achieve permeability-weighted yield, (2) purge volume was 2.2 to 20.6 times larger than the IBF plume volume, with the ratio depending on plume location relative to hydraulic conductivity and head distributions, and (3) after an example 1000-day un-pumped period, purging required removal of at least three orders of magnitude more water than the common practice of three to five well volumes. These results highlight the importance of knowing the borehole flow regime to identify IBF inflow and outflow zones, estimate IBF rates, and to develop a strategic sampling approach.

Hyporheic Exchange Controls Fate of Trace Organic Compounds in an Urban Stream.

First-order half-lives for 26 trace organic compounds (TrOCs) were determined in the hyporheic zone (HZ) and along a 3 km reach of a first-order stream in South Australia during both dry and wet seasons. Two salt tracer experiments were conducted and evaluated using a transient storage model to characterize seasonal differences in stream residence time and transient storage. Lagrangian and time-integrated surface water sampling were conducted to calculate half-lives in the surface water. Half-lives in the HZ were calculated using porewater samples obtained from a modified mini-point sampler and hyporheic residence times measured via active heat-pulse sensing. Half of the investigated TrOCs (e.g., oxazepam, olmesartan, candesartan) were not significantly removed along both the investigated river stretch and the sampled hyporheic flow paths. The remaining TrOCs (e.g., metformin, guanylurea, valsartan) were found to be significantly removed in the HZ and along the river stretch with relative removals in the HZ correlating to reach-scale relative removals. Using the modeled transport parameters, it was estimated that wet season reach-scale removal of TrOCs was predominately caused by removal in the HZ when the intensity of hyporheic exchange was also higher. Factors that increase HZ exchange are thus likely to promote in-stream reactivity of TrOCs.

Limitations of the use of environmental tracers to infer groundwater age.

Apparent ages obtained from the measured concentrations of environmental tracers have the potential to inform recharge rates, flow rates, and assist in the calibration of groundwater models. A number of studies have investigated sources of error in the relationships between the apparent ages, and the age assumed by models to relate this quantity to an aquifer property (e.g., recharge). These studies have also provided a number of techniques for correcting the known biases of apparent ages. In this paper, we review some of the concepts of age bias. We then demonstrate this bias through the use on four numerical examples, and assess the accuracy of correction methods in overcoming this bias. We examine this for CFCs, SF6, 3H/3He, 39Ar, and 14C. We demonstrate that in our four simple steady-state aquifer examples, bias occurs for a wide range of environmental tracers and flow configurations. When applying correction methods, we found that the values obtained are limited by the model assumptions. Models accounting for exchange with aquitards represent whole mobile zones and not discrete well screens. Mean transit times (comparable to mean ages) obtained from lumped parameter models deviate from actual values as the assumed distribution varies from the actual distribution. Methods that use multiple tracer ages are limited to ranges where both tracers report apparent ages. Our findings suggest that the incorporation of environmental tracer data into the understanding of groundwater systems requires approaches such as the direct use of concentrations, or the simulation of full age distributions.

Bias of apparent tracer ages in heterogeneous environments.

The interpretation of apparent ages often assumes that a water sample is composed of a single age. In heterogeneous aquifers, apparent ages estimated with environmental tracer methods do not reflect mean water ages because of the mixing of waters from many flow paths with different ages. This is due to nonlinear variations in atmospheric concentrations of the tracer with time resulting in biases of mixed concentrations used to determine apparent ages. The bias of these methods is rarely reported and has not been systematically evaluated in heterogeneous settings. We simulate residence time distributions (RTDs) and environmental tracers CFCs, SF6 , (85) Kr, and (39) Ar in synthetic heterogeneous confined aquifers and compare apparent ages to mean ages. Heterogeneity was simulated as both K-field variance (σ(2) ) and structure. We demonstrate that an increase in heterogeneity (increase in σ(2) or structure) results in an increase in the width of the RTD. In low heterogeneity cases, widths were generally on the order of 10 years and biases generally less than 10%. In high heterogeneity cases, widths can reach 100 s of years and biases can reach up to 100%. In cases where the temporal variations of atmospheric concentration of individual tracers vary, different patterns of bias are observed for the same mean age. We show that CFC-12 and CFC-113 ages may be used to correct for the mean age if analytical errors are small.