Biased monitoring of fresh water-salt water mixing zone in coastal aquifers

In coastal aquifers, significant vertical hydraulic gradients are formed where fresh water and underlying salt water discharge together upward to the seafloor. Monitoring boreholes may act as "short circuits" along these vertical gradients, connecting between the higher and the lower hydraulic head zones. When a sea tide is introduced, the fluctuations of both the water table and the depth of the mixing zone are also biased due to this effect. This problem is intensified in places of long-screen monitoring boreholes, which are common in many places in the world. For example, all approximately 500 boreholes of the fresh water-salt water mixing zone in the coastal aquifer of Israel are installed with 10 to 50 m long screens. We present field measurements of these fluctuations, along with a three-dimensional numerical model. We find that the in-well fluctuation magnitude of the mixing zone is an order of magnitude larger than that in the porous media of the actual aquifer. The primary parameters that affect the magnitude of this bias are the anisotropy of the aquifer conductivity and the borehole hydraulic parameters. With no sea tide, borehole interference is higher for the anisotropic case because the vertical hydraulic gradients are high. When tides are introduced, the amplitude of the mixing zone fluctuation is higher for the isotropic case because the overall effective hydraulic conductivity is greater than the conductivity in the anisotropic case. In the aquifer, the fresh water-salt water mixing zone fluctuations are dampened, and tens of meters inland from the shoreline, the fluctuations are on the order of few centimeters.     

Continuum-scale convective mixing in geological CO2 sequestration in anisotropic and heterogeneous saline aquifers

Deep saline aquifers are important geological formations for CO₂ sequestration. It has been known that dissolution of CO₂ increases brine density, which results in downward density-driven convection and consequently greatly enhances CO₂ sequestration. In this study, a continuum-scale lattice Boltzmann model is used to investigate convective mixing of CO₂ in saline aquifers. It is found that increasing permeability in either the vertical or horizontal direction accelerates the development of convective mixing. In a heterogeneous aquifer, increasing heterogeneity hampers the onset of convective mixing, because the heterogeneous permeability field results in a large portion of low-velocity region which reduces the instability of the system. The critical time for the onset of instability depends mainly on the coefficient of variation (COV) of the permeability field, and is insensitive to the correlation length. This implies that within the scale of critical time, mass transport is dominated by diffusion, and thus depends mainly on fine-scale heterogeneity controlled by COV. We derived an empirical formula for estimating the critical time, which leads to good estimates for all combinations of COV and correlation length. Fingering, channeling, and dispersion are the three mechanisms for mass transport. In dispersion, dissolved mass is approximately proportional to the square root of time, while in fingering and channeling it is approximately proportional to time. Mass transport by channeling depends significantly on permeability structure, while by fingering it is controlled by gravitational instability. It is also found that larger volumes of CO₂ can be stored in heterogeneous aquifers because of higher mass dissolution rates.     

Evaluation of an upscaled model for DNAPL dissolution kinetics in heterogeneous aquifers

Estimates of contaminant fluxes from DNAPL sources as a function of time and DNAPL mass reduction are important to assess the long-term sustainability and costs of monitored natural attenuation and to determine the benefits of partial source removal. We investigate the accuracy of the upscaled mass transfer function (MTF) proposed by Parker and Park [Parker JC, Park E. Modeling field-scale dense nonaqueous phase liquid dissolution kinetics in heterogeneous aquifers. WRR 2004;40:W05109] to describe field-scale dissolved phase fluxes from DNAPL sources for a range of scenarios generated using high-resolution 3-D numerical simulations of DNAPL infiltration and long-term dissolved phase transport. The results indicate the upscaled MTF is capable of accurately describing field-scale DNAPL dissolution rates as a function of time. For finger-dominated source regions, an empirical mass depletion exponent in the MTF takes on values greater than one which results in predicted mass flux rates that decrease continuously with diminishing DNAPL mass over time. Lens-dominated regions exhibit depletion exponents less than one, which results in more step-function like mass flux versus time behavior. Mass fluxes from DNAPL sources exhibiting both lens- and finger-dominated subregions were less accurately described by the simple MTF, but were well described by a dual-continuum model of the same form for each subregion. The practicality of calibrating a dual-continuum model will likely depend on the feasibility of obtaining spatially resolved field measurements of contaminant fluxes or concentrations associated with the subregions using multilevel sampling or some other means.     

A time dependent mixing model to close PDF equations for transport in heterogeneous aquifers

Probability density function (PDF) methods are a promising alternative to predicting the transport of solutes in groundwater under uncertainty. They make it possible to derive the evolution equations of the mean concentration and the concentration variance, used in moment methods. The mixing model, describing the transport of the PDF in concentration space, is essential for both methods. Finding a satisfactory mixing model is still an open question and due to the rather elaborate PDF methods, a difficult undertaking. Both the PDF equation and the concentration variance equation depend on the same mixing model. This connection is used to find and test an improved mixing model for the much easier to handle concentration variance. Subsequently, this mixing model is transferred to the PDF equation and tested. The newly proposed mixing model yields significantly improved results for both variance modelling and PDF modelling.     

Organic carbon inputs,common ions and degassing: rethinking mixing dissolution in coastal eogenetic carbonate aquifers

Caves deliver freshwater from coastal carbonate landscapes to estuaries but how these caves form and grow remains poorly understood. Models suggest fresh and salt water mixing drives dissolution in eogenetic limestone, but have rarely been validated through sampling of mixing waters. Here we assess controls on carbonate mineral saturation states using new and legacy geochemical data that were collected in vertical profiles through three cenotes and one borehole in the Yucatan Peninsula. Results suggest saturation states are primarily controlled by carbon fluxes rather than mixing. Undersaturation predicted by mixing models that rely on idealized end members is diminished or eliminated when end members are collected from above and below actual mixing zones. Undersaturation due to mixing is limited by CO₂ degassing from fresh water in karst windows, which results in calcite supersaturation. With respect to saline groundwater, controls on capacity for mixing dissolution were more varied. Oxidation of organic carbon increased pCO₂ of saline groundwater in caves (pCO₂ = 10^–2.06 to 10^–0.96 atm) relative to matrix porosity (10^–2.39 atm) and local seawater (10^–3.12 atm). The impact of increased pCO₂ on saturation state, however, depended on the geochemical composition of the saline water and the magnitude of organic carbon oxidation. Carbonate undersaturation due to mixing was limited where gypsum dissolution (Cenote Angelita) or sulfate reduction (Cenote Calica) increased concentrations of common ions (Ca²⁺ or HCO₃^?, respectively). Maximum undersaturation was found to occur in mixtures including saline water that had ion concentrations and ratios similar to seawater, but with moderately elevated pCO₂ (Cenote Eden). Undersaturation, however, was dominated by the initial undersaturation of the saline end member, mixing was irrelevant. Our results add to a growing body of literature that suggests oxidation of organic carbon, and not mixing dissolution, is the dominant control on cave formation and enlargement in coastal eogenetic karst aquifers. Copyright © 2016 John Wiley & Sons, Ltd.     

Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.     

Studies on reaction kinetics in magnetic oxide minerals

Summary Reactions within spinel-type oxides are examined by consideration of (i) the law of mass-action and its limits, (ii) the structural field situation (Mössbaufr) and the (high- or low-) spin state, (iii) the cation site preferences. The conditions for electron transport, cation and vacancy diffusion during oxidation are determined. Effects of defect diffusion on domain-wall mobility and ordering processes during thermal influences are discussed.     

Groundwater ages in coastal aquifers

The interpretation of groundwater ages in coastal aquifers requires an improved understanding of relationships between age distributions and the processes accompanying dispersive, density-dependent flow and transport. This study uses numerical modeling to examine the influence of mixing and a selection of other hydrogeological factors on steady-state age distributions in coastal aquifers. Three methods of age estimation are compared: the piston flow age, the direct age, and the tracer-based age. These are applied to various forms of the Henry problem, as well as to three variants of a larger, hypothetical coastal aquifer. Circulation of water within the seawater wedge results in markedly higher ages in the transition zone than in the underlying saltwater or overlying freshwater. Piston flow ages show a sharp increase where the freshwater and saltwater systems meet, whereas direct- and tracer-based simulations result in a smoother age distribution, as expected. Greater degrees of mixing result in larger differences between piston flow and direct or tracer-based ages, and bring about lower ages in the saltwater wedge. Tracer-based ages are preferred over direct- and piston flow ages for comparison with field data, especially in cases with wide transition zones. Despite the relatively simple conditions used for the simulations, complex age distributions with depth were obtained. Hence, the assessment of ages in field cases will be difficult, particularly where accurate ages in the transition zone are sought.     

Periodic forcing in composite aquifers

Observations of periodic components of measured heads have long been used to estimate aquifer diffusivities. The estimations are often made using well-known solutions of linear differential equations for the propagation of sinusoidal boundary fluctuations through homogeneous one-dimensional aquifers. Recent field data has indicated several instances where the homogeneous aquifer solutions give inconsistent estimates of aquifer diffusivity from measurements of tidal lag and attenuation. This paper presents new algebraic solutions for tidal propagation in spatially heterogeneous one-dimensional aquifers. By building on existing solutions for homogeneous aquifers, comprehensive solutions are presented for composite aquifers comprising of arbitrary (finite) numbers of contiguous homogeneous sub-aquifers and subject to sinusoidal linear boundary conditions. Both Cartesian and radial coordinate systems are considered. Properties of the solutions, including rapid phase shifting and attenuation effects, are discussed and their practical relevance noted. Consequent modal dispersive effects on tidal waveforms are also examined via tidal constituent analysis. It is demonstrated that, for multi-constituent tidal forcings, measured peak heights of head oscillations can seem to increase, and phase lags seem to decrease, with distance from the forcing boundary unless constituents are separated and considered in isolation.     

Well recharge in idealized rectangular aquifers

Analytical solutions for groundwater flow in rectangular aquifers are presented in the case of a single-well recharge. The problem concerns the impact of a seasonal recharge scheme of variable duration on aquifers with various boundary conditions. The results obtained from these idealized aquifers can be used in a preliminary assessment of the groundwater response to artificial recharge schemes.     

Optimal and sustainable extraction of groundwater in coastal aquifers

Four examples are investigated for the optimal and sustainable extraction of groundwater from a coastal aquifer under the threat of seawater intrusion. The objectives and constraints of these management scenarios include maximizing the total volume of water pumped, maximizing the profit of selling water, minimizing the operational and water treatment costs, minimizing the salt concentration of the pumped water, and controlling the drawdown limits. The physical model is based on the density-dependent advective-dispersive solute transport model. Genetic algorithm is used as the optimization tool. The models are tested on a hypothetical confined aquifer with four pumping wells located at various depths. These solutions establish the feasibility of simulating various management scenarios under complex three-dimensional flow and transport processes in coastal aquifers for the optimal and sustainable use of groundwater.     

A study on the reaction kinetics of mineral surface adsorption in mix system

The experimental results on adsorption of ions pb²⁺, Zn²⁺ and Ag⁺ onto mineral surfaces in a mix system show that the reaction kinetics of adions adsorbed onto mineral surfaces was mainly controlled by their diffusion rates in solution. The concentration variations can be fit for the second-order rate equation with good determined coefficients r = 0.800 5—0.979 7. In the near neutral solution, the concentration of exchanged ions K⁺ and Na⁺ related to reaction time can be described by the fint-order rate equation with r = 0.855 7–0.997 7. Meanwhile, the complex diffusionexchange rate equation is suitable for describing the ca^{2 +} concentration variation, as ions Pb^{2 +} and Zn²⁺ were adions. Experimental data show that the amount of ions K⁺, Na⁺and Ca²⁺ release is much more than that of adion decrement in solution. This fact may suggest that the complexstion reaction of adions Pb²⁺, Z²⁺ and Ag⁺ with the mineral surfaces was the major reaction process while adions were not entering the phyllosilicate interlayers or CaCO₃ lattice to exchange the ions K⁺, Na⁺ and Ca²⁺ at room temperature. Project supported by the National Natural Science Foundation of China (Grant No. 49773206) and the Natural Science Foundation of Guangdong Province (Grant No. 960504)     

Non-Darcian groundwater flow in leaky aquifers

Abstract

A simplified method has been developed for solving leaky aquifer non-Darcian flow hydraulics. The principle of volumetric approach is combined with the confined-aquifer, time-dependent drawdown equation in an observation well. The groundwater flow in the leaky aquifer is assumed to obey a non-Darcian flow law of exponential type. The results are obtained in the form of type-curve expressions from which the necessary bundles of curves are drawn for a set of selective non-Darcian flow aquifer parameters. Although application of the methodology appears as rather limited but it provides a scientific contribution and extension of leaky aquifer theory towards nonlinear flow conditions. The methodology developed herein is applied to some actual field data from the eastern sedimentary basin in the Kingdom of Saudi Arabia.     

Agricultural pollutant penetration and steady state in thick aquifers

The leakage of pollutants from agricultural lands to aquifers has increased greatly, driven by increasing fertilizer and pesticide use. Because this increase is recent, ground water pollutant concentrations, loads, and exports may also be increasing as pollutants penetrate more deeply into aquifers. We established in an aquifer profile a ground water recharge and pollutant leakage chronology in an agricultural landscape where 30 m of till blankets a 57-m thick sandstone aquifer. Pollutant concentrations increased from older ground water (1963) at the aquifer base to younger ground water (1985) at its top, a signal of increasing pollutant leakage. Nitrate-N increased from 0.9 to 13.2 mg/L, implying that leakage increased from 1.9 to 16.5 kg/ha/year. Nitrate load and export could increase from 130% to 230% before reaching a steady state in 20 to 40 years. Chloride increases were similar. Pesticide residues alachlor ethane sulfonic acid (ESA), metolachlor ESA, and atrazine residues partially penetrated the aquifer profile. Their concentration-age-date patterns exhibited an initial increase and then a leveling corresponding to the timing of product adoption and leveling of demand. Unlike NO(3), projecting pesticide residue steady states is complicated by the phasing in and out of pesticide products over time; for example, neither alachlor nor atrazine is currently used in the area, and newer products, which have not had time to transit to the aquifer, have been adopted. The circumstances that resulted in the lack of a pollutant steady state are not rare; thus, the lack of steady states in agricultural region aquifers may not be uncommon.     

Spectral analysis of water level fluctuations in aquifers

 The water level of a seawater gauging station and 18 groundwater wells coupled with atmospheric pressure in southwestern Taiwan are analyzed by using spectral analysis in time and frequency domain. The semidiurnal component is found to be the most significant signal from the measurement of water level and atmospheric pressure, and the diurnal component is less distinctive in part of water level and atmospheric pressure record. Although auto-spectral and cross-spectral density functions are significant in atmospheric pressure and water level, the pressure variations do not significantly affect the seawater and the majority of groundwater level in the study area with amplitude of time series observations. The astronomical tidal components are likely the main factor causing seawater and groundwater level to fluctuate in Pingtung, Taiwan. Time lags are estimated from 20 min to a few hours in aquifers. It concludes that the disturbance on groundwater levels from the effect of oceanic astronomical tide is different from the varying hydrogeological characteristics of aquifer. In this study, the spectral analysis of water level in time and frequency domains gives strong indications of sensitive variations to water level fluctuation. This research is supported by the Institute of Nuclear Energy Research (INER), AEC, Taiwan, Republic of China, under a fund from Executive Yuan. The authors thank Taiwan Central Weather Bureau and Taiwan Provincial Government Water Resources Department for providing useful data.