Hydrogeophysical characterization of anisotropy in the Biscayne Aquifer using geophysical methods

The anisotropy of the Biscayne Aquifer which serves as the source of potable water for Miami-Dade County was investigated by applying geophysical methods. Electrical resistivity imaging, self potential and ground penetration radar techniques were employed in both regional and site specific studies. In the regional study, electrical anisotropy and resistivity variation with depth were investigated with azimuthal square array measurements at 13 sites. The observed coefficient of electrical anisotropy ranged from 1.01 to 1.36. The general direction of measured anisotropy is uniform for most sites and trends W-E or SE-NW irrespective of depth. Measured electrical properties were used to estimate anisotropic component of the secondary porosity and hydraulic anisotropy which ranged from 1 to 11% and 1.18 to 2.83 respectively. 1-D sounding analysis was used to models the variation of formation resistivity with depth. Resistivities decreased from NW (close to the margins of the everglades) to SE on the shores of Biscayne Bay. Porosity calculated from Archie's law, ranged from 18 to 61% with higher values found along the ridge. Higher anisotropy, porosities and hydraulic conductivities were on the Atlantic Coastal Ridge and lower values at low lying areas west of the ridge. The cause of higher anisotropy and porosity is attributed to higher dissolution rates of the oolitic facies of the Miami Formation composing the ridge. The direction of minimum resistivity from this study is similar to the predevelopment groundwater flow direction indicated in published modeling studies. Detailed investigations were carried out to evaluate higher anisotropy at West Perrine Park located on the ridge and Snapper Creek Municipal well field where the anisotropy trend changes with depth. The higher anisotropy is attributed to the presence of solution cavities oriented in the E-SE direction on the ridge. Similarly, the change in hydraulic anisotropy at the well field might be related to solution cavities, the surface canal and groundwater extraction wells.^

Modélisation de l'évolution hydroclimatique des flux et stocks d'eau verte et d'eau bleue du bassin versant de la Garonne

La gestion intégrée de la ressource en eau implique de distinguer les parcours de l’eau qui sont accessibles aux sociétés de ceux qui ne le sont pas. Les cheminements de l’eau sont nombreux et fortement variables d’un lieu à l’autre. Il est possible de simplifier cette question en s’attardant plutôt aux deux destinations de l’eau. L’eau bleue forme les réserves et les flux dans l’hydrosystème : cours d’eau, nappes et écoulements souterrains. L’eau verte est le flux invisible de vapeur d’eau qui rejoint l’atmosphère. Elle inclut l’eau consommée par les plantes et l’eau dans les sols. Or, un grand nombre d’études ne portent que sur un seul type d’eau bleue, en ne s’intéressant généralement qu’au devenir des débits ou, plus rarement, à la recharge des nappes. Le portrait global est alors manquant. Dans un même temps, les changements climatiques viennent impacter ce cheminement de l’eau en faisant varier de manière distincte les différents composants de cycle hydrologique. L’étude réalisée ici utilise l’outil de modélisation SWAT afin de réaliser le suivi de toutes les composantes du cycle hydrologique et de quantifier l’impact des changements climatiques sur l’hydrosystème du bassin versant de la Garonne. Une première partie du travail a permis d’affiner la mise en place du modèle pour répondre au mieux à la problématique posée. Un soin particulier a été apporté à l’utilisation de données météorologiques sur grille (SAFRAN) ainsi qu’à la prise en compte de la neige sur les reliefs. Le calage des paramètres du modèle a été testé dans un contexte differential split sampling, en calant puis validant sur des années contrastées en terme climatique afin d’appréhender la robustesse de la simulation dans un contexte de changements climatiques. Cette étape a permis une amélioration substantielle des performances sur la période de calage (2000-2010) ainsi que la mise en évidence de la stabilité du modèle face aux changements climatiques. Par suite, des simulations sur une période d’un siècle (1960-2050) ont été produites puis analysées en deux phases : i) La période passée (1960-2000), basée sur les observations climatiques, a servi de période de validation à long terme du modèle sur la simulation des débits, avec de très bonnes performances. L’analyse des différents composants hydrologiques met en évidence un impact fort sur les flux et stocks d’eau verte, avec une diminution de la teneur en eau des sols et une augmentation importante de l’évapotranspiration. Les composantes de l’eau bleue sont principalement perturbées au niveau du stock de neige et des débits qui présentent tous les deux une baisse substantielle. ii) Des projections hydrologiques ont été réalisées (2010-2050) en sélectionnant une gamme de scénarios et de modèles climatiques issus d’une mise à l’échelle dynamique. L’analyse de simulation vient en bonne part confirmer les conclusions tirées de la période passée : un impact important sur l’eau verte, avec toujours une baisse de la teneur en eau des sols et une augmentation de l’évapotranspiration potentielle. Les simulations montrent que la teneur en eau des sols pendant la période estivale est telle qu’elle en vient à réduire les flux d’évapotranspiration réelle, mettant en évidence le possible déficit futur des stocks d’eau verte. En outre, si l’analyse des composantes de l’eau bleue montre toujours une diminution significative du stock de neige, les débits semblent cette fois en hausse pendant l’automne et l’hiver. Ces résultats sont un signe de l’«accélération» des composantes d’eau bleue de surface, probablement en relation avec l’augmentation des évènements extrêmes de précipitation. Ce travail a permis de réaliser une analyse des variations de la plupart des composantes du cycle hydrologique à l’échelle d’un bassin versant, confirmant l’importance de prendre en compte toutes ces composantes pour évaluer l’impact des changements climatiques et plus largement des changements environnementaux sur la ressource en eau.

A systems approach to cardiovascular health and disease with a focus on aortic wave dynamics

Cardiovascular diseases (CVDs) have reached an epidemic proportion in the US and worldwide with serious consequences in terms of human suffering and economic impact. More than one third of American adults are suffering from CVDs. The total direct and indirect costs of CVDs are more than $500 billion per year. Therefore, there is an urgent need to develop noninvasive diagnostics methods, to design minimally invasive assist devices, and to develop economical and easy-to-use monitoring systems for cardiovascular diseases. In order to achieve these goals, it is necessary to gain a better understanding of the subsystems that constitute the cardiovascular system. The aorta is one of these subsystems whose role in cardiovascular functioning has been underestimated. Traditionally, the aorta and its branches have been viewed as resistive conduits connected to an active pump (left ventricle of the heart). However, this perception fails to explain many observed physiological results. My goal in this thesis is to demonstrate the subtle but important role of the aorta as a system, with focus on the wave dynamics in the aorta.

The operation of a healthy heart is based on an optimized balance between its pumping characteristics and the hemodynamics of the aorta and vascular branches. The delicate balance between the aorta and heart can be impaired due to aging, smoking, or disease. The heart generates pulsatile flow that produces pressure and flow waves as it enters into the compliant aorta. These aortic waves propagate and reflect from reflection sites (bifurcations and tapering). They can act constructively and assist the blood circulation. However, they may act destructively, promoting diseases or initiating sudden cardiac death. These waves also carry information about the diseases of the heart, vascular disease, and coupling of heart and aorta. In order to elucidate the role of the aorta as a dynamic system, the interplay between the dominant wave dynamic parameters is investigated in this study. These parameters are heart rate, aortic compliance (wave speed), and locations of reflection sites. Both computational and experimental approaches have been used in this research. In some cases, the results are further explained using theoretical models.

The main findings of this study are as follows: (i) developing a physiologically realistic outflow boundary condition for blood flow modeling in a compliant vasculature; (ii) demonstrating that pulse pressure as a single index cannot predict the true level of pulsatile workload on the left ventricle; (iii) proving that there is an optimum heart rate in which the pulsatile workload of the heart is minimized and that the optimum heart rate shifts to a higher value as aortic rigidity increases; (iv) introducing a simple bio-inspired device for correction and optimization of aortic wave reflection that reduces the workload on the heart; (v) deriving a non-dimensional number that can predict the optimum wave dynamic state in a mammalian cardiovascular system; (vi) demonstrating that waves can create a pumping effect in the aorta; (vii) introducing a system parameter and a new medical index, Intrinsic Frequency, that can be used for noninvasive diagnosis of heart and vascular diseases; and (viii) proposing a new medical hypothesis for sudden cardiac death in young athletes.

Hydrogeophysical Characterization of Anisotropy in the Biscayne Aquifer Using Geophysical Methods

The anisotropy of the Biscayne Aquifer which serves as the source of potable water for Miami-Dade County was investigated by applying geophysical methods. Electrical resistivity imaging, self potential and ground penetration radar techniques were employed in both regional and site specific studies. In the regional study, electrical anisotropy and resistivity variation with depth were investigated with azimuthal square array measurements at 13 sites. The observed coefficient of electrical anisotropy ranged from 1.01 to 1.36. The general direction of measured anisotropy is uniform for most sites and trends W-E or SE-NW irrespective of depth. Measured electrical properties were used to estimate anisotropic component of the secondary porosity and hydraulic anisotropy which ranged from 1 to 11% and 1.18 to 2.83 respectively. 1-D sounding analysis was used to models the variation of formation resistivity with depth. Resistivities decreased from NW (close to the margins of the everglades) to SE on the shores of Biscayne Bay. Porosity calculated from Archie's law, ranged from 18 to 61% with higher values found along the ridge. Higher anisotropy, porosities and hydraulic conductivities were on the Atlantic Coastal Ridge and lower values at low lying areas west of the ridge. The cause of higher anisotropy and porosity is attributed to higher dissolution rates of the oolitic facies of the Miami Formation composing the ridge. The direction of minimum resistivity from this study is similar to the predevelopment groundwater flow direction indicated in published modeling studies. Detailed investigations were carried out to evaluate higher anisotropy at West Perrine Park located on the ridge and Snapper Creek Municipal well field where the anisotropy trend changes with depth. The higher anisotropy is attributed to the presence of solution cavities oriented in the E-SE direction on the ridge. Similarly, the change in hydraulic anisotropy at the well field might be related to solution cavities, the surface canal and groundwater extraction wells.

A NOVEL MODELING AND STATE OF CHARGE ESTIMATION SCHEME FOR LITHIUM-ION BATTERIES

Lithium Ion (Li-Ion) batteries have got attention in recent decades because of their undisputable advantages over other types of batteries. They are used in so many our devices which we need in our daily life such as cell phones, lap top computers, cameras, and so many electronic devices. They also are being used in smart grids technology, stand-alone wind and solar systems, Hybrid Electric Vehicles (HEV), and Plug in Hybrid Electric Vehicles (PHEV). Despite the rapid increase in the use of Lit-ion batteries, the existence of limited battery models also inadequate and very complex models developed by chemists is the lack of useful models a significant matter. A battery management system (BMS) aims to optimize the use of the battery, making the whole system more reliable, durable and cost effective. Perhaps the most important function of the BMS is to provide an estimate of the State of Charge (SOC). SOC is the ratio of available ampere-hour (Ah) in the battery to the total Ah of a fully charged battery. The Open Circuit Voltage (OCV) of a fully relaxed battery has an approximate one-to-one relationship with the SOC. Therefore, if this voltage is known, the SOC can be found. However, the relaxed OCV can only be measured when the battery is relaxed and the internal battery chemistry has reached equilibrium. This thesis focuses on Li-ion battery cell modelling and SOC estimation. In particular, the thesis, introduces a simple but comprehensive model for the battery and a novel on-line, accurate and fast SOC estimation algorithm for the primary purpose of use in electric and hybrid-electric vehicles, and microgrid systems. The thesis aims to (i) form a baseline characterization for dynamic modeling; (ii) provide a tool for use in state-of-charge estimation. The proposed modelling and SOC estimation schemes are validated through comprehensive simulation and experimental results.

Novel analytical and numerical methods for solving fractional dynamical systems

During the past three decades, the subject of fractional calculus (that is, calculus of integrals and derivatives of arbitrary order) has gained considerable popularity and importance, mainly due to its demonstrated applications in numerous diverse and widespread fields in science and engineering. For example, fractional calculus has been successfully applied to problems in system biology, physics, chemistry and biochemistry, hydrology, medicine, and finance. In many cases these new fractional-order models are more adequate than the previously used integer-order models, because fractional derivatives and integrals enable the description of the memory and hereditary properties inherent in various materials and processes that are governed by anomalous diffusion. Hence, there is a growing need to find the solution behaviour of these fractional differential equations. However, the analytic solutions of most fractional differential equations generally cannot be obtained. As a consequence, approximate and numerical techniques are playing an important role in identifying the solution behaviour of such fractional equations and exploring their applications. The main objective of this thesis is to develop new effective numerical methods and supporting analysis, based on the finite difference and finite element methods, for solving time, space and time-space fractional dynamical systems involving fractional derivatives in one and two spatial dimensions. A series of five published papers and one manuscript in preparation will be presented on the solution of the space fractional diffusion equation, space fractional advectiondispersion equation, time and space fractional diffusion equation, time and space fractional Fokker-Planck equation with a linear or non-linear source term, and fractional cable equation involving two time fractional derivatives, respectively. One important contribution of this thesis is the demonstration of how to choose different approximation techniques for different fractional derivatives. Special attention has been paid to the Riesz space fractional derivative, due to its important application in the field of groundwater flow, system biology and finance. We present three numerical methods to approximate the Riesz space fractional derivative, namely the L1/ L2-approximation method, the standard/shifted Gr¨unwald method, and the matrix transform method (MTM). The first two methods are based on the finite difference method, while the MTM allows discretisation in space using either the finite difference or finite element methods. Furthermore, we prove the equivalence of the Riesz fractional derivative and the fractional Laplacian operator under homogeneous Dirichlet boundary conditions – a result that had not previously been established. This result justifies the aforementioned use of the MTM to approximate the Riesz fractional derivative. After spatial discretisation, the time-space fractional partial differential equation is transformed into a system of fractional-in-time differential equations. We then investigate numerical methods to handle time fractional derivatives, be they Caputo type or Riemann-Liouville type. This leads to new methods utilising either finite difference strategies or the Laplace transform method for advancing the solution in time. The stability and convergence of our proposed numerical methods are also investigated. Numerical experiments are carried out in support of our theoretical analysis. We also emphasise that the numerical methods we develop are applicable for many other types of fractional partial differential equations.

Australia and New Zealand CBNG development and environmental implications

Following the success of Coalbed Natural Gas (CBNG) operations in the United States, companies in Australia and New Zealand have been actively exploring and developing this technology for the last two decades. In particular, the Bowen and Surat basins in Queensland, Australia, have undergone extensive CBNG development. Unfortunately, awareness of potential environmental problems associated with CBNG abstraction has not been widespread and legislation has at times struggled to keep up with rapid development. In Australia, the combined CBNG resource for both the Bowen and Surat basins has been estimated at approximately 10,500 PJ with gas content as high as 10 m3/tonne of coal. There are no official estimates for the magnitude of the CBNG resource in New Zealand but initial estimates suggest this could be up to 1,300 PJ with gas content ranging from 1 to 5 m3/tonne of coal. In Queensland, depressurization of the Walloon Coal Measures to recover CBNG has the potential to induce drawdown in adjacent deep aquifer systems through intraformational groundwater flow. In addition, CBNG operators have been disposing their co-produced water by using large unlined ponds, which is not the best practice for managing co-produced water. CBNG waters in Queensland have the typical geochemical signature associated with CBNG waters (Van Voast, 2003) and thus have the potential to impair soils and plant growth where land disposal is considered. Water quality from exploration wells in New Zealand exhibit the same characteristics although full scale production has not yet begun. In general, the environmental impacts that could arise from CBNG water extraction depend on the aquifer system, the quantity and quality of produced water, and on the method of treatment and disposal being used. Understanding these impacts is necessary to adequately manage CBNG waters so that environmental effects are minimized; if properly managed, CBNG waters can be used for beneficial applications and can become a valuable resource to stakeholders.

Krylov subspace approximations for the exponential Euler method: Error estimates and the harmonic Ritz approximant

We study Krylov subspace methods for approximating the matrix-function vector product φ(tA)b where φ(z) = [exp(z) - 1]/z. This product arises in the numerical integration of large stiff systems of differential equations by the Exponential Euler Method, where A is the Jacobian matrix of the system. Recently, this method has found application in the simulation of transport phenomena in porous media within mathematical models of wood drying and groundwater flow. We develop an a posteriori upper bound on the Krylov subspace approximation error and provide a new interpretation of a previously published error estimate. This leads to an alternative Krylov approximation to φ(tA)b, the so-called Harmonic Ritz approximant, which we find does not exhibit oscillatory behaviour of the residual error.

Logan Basin Water Resource Plan : environmental assessment of the southern Moreton Bay islands. Technical Advisory Panel Report: Stage 1.

This report is a technical assessment of the hydrological environment of the southern Moreton Bay islands and follows the terms of reference supplied by the then Queensland Department of Natural Resources and Water. The terms of reference describe stage 1 as a condition assessment and stage 2 as an assessment of the implications of water planning scenarios on future condition. This report is the first stage of a two-stage investigation whose primary purpose is to identify and assess groundwater dependent ecosystems (GDEs) and the groundwater flow regimes necessary to support them. Within this context, the groundwaters themselves are also considered and comment made on their condition. Information provided in this report will inform an amendment to the Logan Basin Water Resource Plan to incorporate the southern Moreton Bay islands. The study area is the water resource plan amendment area, which includes North and South Stradbroke islands and the smaller islands between these and the mainland, including the inhabited smaller rocky islands—namely, Macleay, Russell, Karragarra, Lamb and Coochiemudlo islands. This assessment is largely a desktop study based on existing information, but incorporates some field observations, input from experts in specific areas and community representatives, and the professional experience and knowledge of the authors. This report reviews existing research and information on the southern Moreton Bay area with an emphasis on North Stradbroke Island, as it represents the largest and most regionally significant groundwater resource in southern Moreton Bay. The report provides an assessment of key waterrelated environmental features, their condition and their degree of dependence on groundwater. This report also assesses the condition and status of ecosystems within this region. In addition, the report identifies information gaps, uncertainties and potential impacts; reviews groundwater models that have been developed for North Stradbroke Island; and makes recommendations on monitoring and research needs.

Modelling sea water intrusion in coastal aquifers using heterogeneous computing

The objective of this PhD research program is to investigate numerical methods for simulating variably-saturated flow and sea water intrusion in coastal aquifers in a high-performance computing environment. The work is divided into three overlapping tasks: to develop an accurate and stable finite volume discretisation and numerical solution strategy for the variably-saturated flow and salt transport equations; to implement the chosen approach in a high performance computing environment that may have multiple GPUs or CPU cores; and to verify and test the implementation. The geological description of aquifers is often complex, with porous materials possessing highly variable properties, that are best described using unstructured meshes. The finite volume method is a popular method for the solution of the conservation laws that describe sea water intrusion, and is well-suited to unstructured meshes. In this work we apply a control volume-finite element (CV-FE) method to an extension of a recently proposed formulation (Kees and Miller, 2002) for variably saturated groundwater flow. The CV-FE method evaluates fluxes at points where material properties and gradients in pressure and concentration are consistently defined, making it both suitable for heterogeneous media and mass conservative. Using the method of lines, the CV-FE discretisation gives a set of differential algebraic equations (DAEs) amenable to solution using higher-order implicit solvers. Heterogeneous computer systems that use a combination of computational hardware such as CPUs and GPUs, are attractive for scientific computing due to the potential advantages offered by GPUs for accelerating data-parallel operations. We present a C++ library that implements data-parallel methods on both CPU and GPUs. The finite volume discretisation is expressed in terms of these data-parallel operations, which gives an efficient implementation of the nonlinear residual function. This makes the implicit solution of the DAE system possible on the GPU, because the inexact Newton-Krylov method used by the implicit time stepping scheme can approximate the action of a matrix on a vector using residual evaluations. We also propose preconditioning strategies that are amenable to GPU implementation, so that all computationally-intensive aspects of the implicit time stepping scheme are implemented on the GPU. Results are presented that demonstrate the efficiency and accuracy of the proposed numeric methods and formulation. The formulation offers excellent conservation of mass, and higher-order temporal integration increases both numeric efficiency and accuracy of the solutions. Flux limiting produces accurate, oscillation-free solutions on coarse meshes, where much finer meshes are required to obtain solutions with equivalent accuracy using upstream weighting. The computational efficiency of the software is investigated using CPUs and GPUs on a high-performance workstation. The GPU version offers considerable speedup over the CPU version, with one GPU giving speedup factor of 3 over the eight-core CPU implementation.

How long does it take for aquifer recharge or aquifer discharge processes to reach steady state?

Groundwater flow models are usually characterized as being either transient flow models or steady state flow models. Given that steady state groundwater flow conditions arise as a long time asymptotic limit of a particular transient response, it is natural for us to seek a finite estimate of the amount of time required for a particular transient flow problem to effectively reach steady state. Here, we introduce the concept of mean action time (MAT) to address a fundamental question: How long does it take for a groundwater recharge process or discharge processes to effectively reach steady state? This concept relies on identifying a cumulative distribution function, $F(t;x)$, which varies from $F(0;x)=0$ to $F(t;x) \to \infty$ as $t\to \infty$, thereby providing us with a measurement of the progress of the system towards steady state. The MAT corresponds to the mean of the associated probability density function $f(t;x) = \dfrac{dF}{dt}$, and we demonstrate that this framework provides useful analytical insight by explicitly showing how the MAT depends on the parameters in the model and the geometry of the problem. Additional theoretical results relating to the variance of $f(t;x)$, known as the variance of action time (VAT), are also presented. To test our theoretical predictions we include measurements from a laboratory–scale experiment describing flow through a homogeneous porous medium. The laboratory data confirms that the theoretical MAT predictions are in good agreement with measurements from the physical model.

Analysis and modelling of the hydraulic conductivity in aquitards : application to the Galilee Basin and the Great Artesian Basin, Australia

In large sedimentary basins with layers of different rocks, the groundwater flow between aquifers depends on the hydraulic conductivity (K) of the separating low-permeable rocks, or aquitards. Three methods were developed to evaluate K in aquitards for areas with limited field data: • Coherence and harmonic analysis: estimates the regional-scale K based on water-level fluctuations in adjacent aquifers. • Cokriging and Bayes' rule: infers K from downhole geophysical logs. • Fluvial process model: reproduces the lithology architecture of sediment formations which can be converted to K. These proposed methods enable good estimates of K and better planning of further drillholes.

Three-dimensional geological modelling of the Galilee and central Eromanga basins, Australia: New insights into aquifer/aquitard geometry and potential influence of faults on inter-connectivity

Study region The Galilee and Eromanga basins are located in central Queensland, Australia. Both basins are components of the Great Artesian Basin which host some of the most significant groundwater resources in Australia. Study focus This study evaluates the influence of regional faults on groundwater flow in an aquifer/aquitard interbedded succession that form one of the largest Artesian Basins in the world. In order to assess the significance of regional faults as potential barriers or conduits to groundwater flow, vertical displacements of the major aquifers and aquitards were studied at each major fault and the general hydraulic relationship of units that are juxtaposed by the faults were considered. A three-dimensional (3D) geological model of the Galilee and Eromanga basins was developed based on integration of well log data, seismic surfaces, surface geology and elevation data. Geological structures were mapped in detail and major faults were characterised. New hydrological insights for the region Major faults that have been described in previous studies have been confirmed within the 3D geological model domain and a preliminary assessment of their hydraulic significance has been conducted. Previously unknown faults such as the Thomson River Fault (herein named) have also been identified in this study.

Seasonal and spatial variations in rare earth elements to identify inter-aquifer linkages and recharge processes in an Australian catchment

With the aim of elucidating the seasonal behaviour of rare earth elements (REEs), surface and groundwaters were collected under dry and wet conditions in different hydrological units of the Teviot Brook catchment (Southeast Queensland, Australia). Sampled waters showed a large degree of variability in both REE abundance and normalised patterns. Overall REE abundance ranged over nearly three orders of magnitude, and was consistently lower in the sedimentary bedrock aquifer (18ppt<∑REE<477ppt) than in the other hydrological systems studied. Abundance was greater in springs draining rhyolitic rocks (∑REE=300 and 2054ppt) than in springs draining basalt ranges (∑REE=25 and 83ppt), yet was highly variable in the shallow alluvial groundwater (16ppt<∑REE<5294ppt) and, to a lesser extent, in streamwater (85ppt<∑REE<2198ppt). Generally, waters that interacted with different rock types had different REE patterns. In order to obtain an unbiased characterisation of REE patterns, the ratios between light and middle REEs (R(M/L)) and the ratios between middle and heavy REEs (R(H/M)) were calculated for each sample. The sedimentary bedrock aquifer waters had highly evolved patterns depleted in light REEs and enriched in middle and heavy REEs (0.17groundwater flow during the wet season (decrease from R(M/L)=0.81 and 0.56 to R(M/L)=0.46 and 0.17). Results from this study suggest that REEs may be usefully applied as indicators of recharge processes and inter-aquifer mixing. They also underline the importance of conducting seasonal sampling campaigns to capture possible short-term variations in REE patterns and abundance, which is essential to enable a better understanding of hydrological and hydrochemical processes in complex geological settings