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Geochemical modeling is an important tool in environmental studies, and in the areas of subsurface and surface hydrology, pedology, water resources management, mining geology, geothermal resources, hydrocarbon geology, and related areas dealing with the exploration and extraction of natural resources. The book fills a gap in the literature through its discussion of geochemical modeling, which simulates the chemical and physical processes affecting the distribution of chemical species in liquid, gas, and solid phases. Geochemical modeling applies to a diversity of subsurface environments, from the vadose zone close to the Earth's surface, down to deep-seated geothermal reservoirs.The book is addressed to students, teachers, other professionals, and to the institutions involved in water, geothermal and hydrocarbon resources, mining, and environmental management. The book should prove useful to undergraduate and graduate students, postgraduates, professional geologists and geophysicists, engineers, environmental scientists, soil scientists, hydrochemists, and others interested in water and geochemistry.

Understanding responses of stream discharge to precipitation in a watershed is important in gaining insights into watershed hydrology and estimating hydraulic parameters. Transfer functions in the spectral domain are commonly used to quantify the relationship between precipitation and discharge, and estimate watershed hydraulic parameters. However, previous models have not adequately accounted for the impact of the unsaturated zone. To address this, we have developed a novel analytical model that considers the effect of the unsaturated zone to obtain transfer functions within watersheds. These transfer functions are derived by the spectral method and verified through numerical simulations. The results indicate that the transfer functions are influenced significantly by the relative hydraulic conductivity exponent αk in the moisture characteristic curve. A higher αk results in a lower transfer function, indicating more robust filtering of hydrological signals. A thicker unsaturated zone results in lower transfer functions at higher frequencies. The traditional transfer functions, which neglect the retention capacity of the unsaturated zone, tend to overestimate hydrological responses at high frequencies. Our transfer functions agree well with integrated watershed‐scale flow models and are also applied to observed data from four watersheds in Iowa, providing reasonable estimates for the hydraulic parameters. This study contributes to a deeper understanding of watershed behavior and offers an enhanced tool for estimating hydraulic parameters with practical applications. Key Points Transfer functions are proposed to quantify hydrological signal filtration considering unsaturated flow described by Richards equation Thicker unsaturated zones or higher conductivity exponents enhance the filtration of hydrological signals Unsaturated zone generally possesses a stronger ability to filter watershed hydrological signals than that of saturated zone

Hydrologic models such as the USEPA Stormwater Management Model (SWMM) are commonly used to assess the design and performance of green infrastructure (GI). To accurately represent GI performance models used in design need to be able to address both the hydrology/hydraulics of the catchment and the GI unsaturated (vadose) zone hydrology. While hydrologic models, such as SWMM, address the need for catchment hydrology/hydraulics, they often simplify the unsaturated zone hydrology. This paper presents a methodology utilizing existing components of SWMM to represent unsaturated zone hydrology in an accessible format that does not require adjustments to the SWMM source code. The methodology simulated the unsaturated soil water movement by considering flow caused by differences of soil matric head and flow caused by gravity between soil layers with finite depth/length. The flow flux related to the soil matric head is a function of soil water diffusivity (D) and the soil moisture gradient, where D can be represented by a pump curve in SWMM. The flow flux related to gravity was controlled by unsaturated hydraulic conductivity (K) only and was also simulated by a pump. The methodology was compared to another variably saturated model, HYDRUS, with theoretical soils (with single layers of sand, loam, silt, and clay, as well as dual-layer scenarios). Field data was used to compare the methodology to HYDRUS and the SWMM LID (Low Impact Development) module. In all comparisons the presented methodology and HYDRUS delivered similar results for the vadose zone response to a storm event, while the LID module of SWMM exhibited slower water movement. The results showed that under natural conditions, the approximation of the presented methodology yielded satisfactory results to simulate flow through the unsaturated vadose zone.

If properly applied, karst hydrological models are a valuable tool for karst water resource management. If they are able to reproduce the relevant flow and storage processes of a karst system, they can be used for prediction of water resource availability when climate or land use are expected to change. A common challenge to apply karst simulation models is the limited availability of observations to identify their model parameters. In this study, we quantify the value of information when water quality data (NO3− and SO42−) is used in addition to discharge observations to estimate the parameters of a process-based karst simulation model at a test site in southern Spain. We use a three-step procedure to (1) confine an initial sample of 500 000 model parameter sets by discharge and water quality observations, (2) identify alterations of model parameter distributions through the confinement, and (3) quantify the strength of the confinement for the model parameters. We repeat this procedure for flow states, for which the system discharge is controlled by the unsaturated zone, the saturated zone, and the entire time period including times when the spring is influenced by a nearby river. Our results indicate that NO3− provides the most information to identify the model parameters controlling soil and epikarst dynamics during the unsaturated flow state. During the saturated flow state, SO42− and discharge observations provide the best information to identify the model parameters related to groundwater processes. We found reduced parameter identifiability when the entire time period is used as the river influence disturbs parameter estimation. We finally show that most reliable simulations are obtained when a combination of discharge and water quality date is used for the combined unsaturated and saturated flow states.

In this study, we investigate the use of ground-penetrating radar (GPR) time-lapse monitoring of artificial soil infiltration experiments. The aim is to evaluate this protocol in the context of estimating the hydrodynamic unsaturated soil parameter values and their associated uncertainties. The originality of this work is to suggest a statistical parameter estimation approach using Markov chain Monte Carlo (MCMC) methods to have direct estimates of the parameter uncertainties. Using the GPR time data from the moving wetting front only does not provide reliable results. Thus, we propose to use additional information from other types of reflectors to optimize the quality of the parameter estimation. Water movement and electromagnetic wave propagation in the unsaturated zone are modeled using a one-dimensional hydrogeophysical model. The GPR travel time data are analyzed for different reflectors: a moving reflector (the infiltration wetting front) and three fixed reflectors located at different depths in the soil. Global sensitivity analysis (GSA) is employed to assess the influence of the saturated hydraulic conductivity Ks, the saturated and residual water contents θs and θr, and the Mualem–van Genuchten shape parameters α and n of the soil on the GPR travel time data of the reflectors. Statistical calibration of the soil parameters is then performed using the MCMC method. The impact of the type of reflector (moving or fixed) is then evaluated by analyzing the calibrated model parameters and their confidence intervals for different scenarios. GSA results show that the sensitivities of the GPR data to the hydrodynamic soil parameters are different between moving and fixed reflectors, whereas fixed reflectors at various depths have similar sensitivities. Ks has a similar and strong influence on the data of both types of reflectors. Concerning the other parameters, for the wetting front, only θs and α have an influence, and only at long time steps since the total variance is zero at the very beginning of the experiment. On the other hand, for the fixed reflectors, the total variance is not zero at the very start and the parameters θs, θr, α and n can have an influence from the very beginning of the infiltration. Results of parameter estimation show that the use of calibration data from the moving or fixed reflectors alone does not enable a good identification of all soil parameters. With the moving reflector, the error between the estimated mean value and the exact target value for θr and α is 9 % and 45 %, respectively, and less than 3 % for the other parameters. The best reduction of the size of the parameter distribution is obtained for n, with a posterior distribution 9 times smaller than the prior one. For the others, this reduction ratio varies between 1 and 5. For the fixed reflectors, the estimated mean values are far from the target values for α, θr and n, representing for a reflector located at 120 cm 15 %, 27 %, and 121 %, respectively. On the other hand, when both data are combined, all soil parameters can be well estimated with narrow confidence intervals. For instance, when using both data from the moving wetting front and a fixed reflector located at 120 cm for calibration, the estimated mean values of the errors of all parameters are less than 5 %. Moreover, all parameter distributions are well reduced, with a maximum reduction for Ks, leading to a posterior distribution being 46 times smaller than the prior one, and the worst but still satisfactory being for θr for which the posterior distribution is 8 times smaller than the prior one. The methodology was applied to fine, medium, and coarse sands with very good results, particularly for the finest soil. The thickness of the unsaturated zone was also tested (0.5, 1, and 2 m) and a better estimation of the hydrodynamic parameters is obtained when the water table is deeper. In addition, the height of water applied in the infiltrometry test influences the speed of the test without affecting the performance of the proposed method.

The present study is aimed to formulate a numerical model to simulate hydrogeochemical reactions controlling pyrite oxidation in unsaturated aquifers under non-uniform flow conditions. A coupled flow and multi-component transport model is solved using a finite difference scheme to simulate the concentration distribution of oxygen (O 2 ), ferrous (Fe 2+ ), ferric (Fe 3+ ), sulphate (SO 4 2− ) and hydrogen (H + ) ions. An attempt is made to quantify the transport characteristics of pyrite oxidation ions by analysing the spatial moments of concentration profiles. The simulation results suggest that the variable flow rate in the vertical direction significantly enhances the pyrite oxidation near the ground surface. Peak concentration of Fe 2+ , Fe 3+ , and SO 4 2− near the ground surface is found to be approximately 2–3 times higher in the case of variable flow. The pH level near the ground surface drops considerably when variable flow conditions exist in the unsaturated zone. The variation in flow parameters such as porosity, and water saturation and reaction parameters such as oxygen diffusion rate and the oxygen consumption rate are found to affect the mass and mobility of Fe 2+ , Fe 3+ , and SO 4 2− considerably. Although there has been substantial research on hydrogeochemical events associated with pyrite oxidation in the past, there has been very less focus on the transport qualities of the ions produced in groundwater. The mobility assessment of pyrite oxidation ions in aquifer presented in the study is beneficial to understand the groundwater quality risk associated with mining and to plan and implement effective remediation strategies for the restoration of affected aquifers.

When the soil at the plant roots is poorly ventilated due to few pores, the root system will grow short and shallow, leading to poor growth. In this paper, we developed a shockwave soil-loosening device. It can first drill a hollow drill bit containing multi-directional holes into the soil near the roots of the crops and then generate high-pressure gas to impact the soil outside the drill bit to increase the soil pores. Therefore, this can quickly improve soil aeration. We conducted numerical simulations of shockwave loosening to explore how 3.4 atm shockwaves are emitted from the drill bit’s porous nozzles and analyze the behavior and efficiency of shockwave loosening. We also performed visual observation experiments of shockwave multi-directional impact in a transparent acrylic water tank. Furthermore, we used eight pressure sensors to automatically measure the range of shockwave impact and found that when the storage tank volume was 5000 cm3, we could achieve a soil loosening range of 30 cm. Finally, this shockwave-loosening mechanism ensures that the soil surface will not be damaged during the loosening process, thus avoiding large-scale tillage disturbance of the soil. This will reduce carbon emissions stored in soil and released into the atmosphere.

Nitrate pollution in groundwater, which is mainly from agricultural activities, remains an international problem. It threatens the environment, economics and human health. There is a rising trend in nitrate concentrations in many UK groundwater bodies. Research has shown it can take decades for leached nitrate from the soil to discharge into groundwater and surface water due to the ‘store’ of nitrate and its potentially long travel time in the unsaturated and saturated zones. However, this time lag is rarely considered in current water nitrate management and policy development. The aim of this study was to develop a catchment-scale integrated numerical method to investigate the nitrate lag time in the groundwater system, and the Eden Valley, UK, was selected as a case study area. The method involves three models, namely the nitrate time bomb—a process-based model to simulate the nitrate transport in the unsaturated zone (USZ), GISGroundwater—a GISGroundwater flow model, and N-FM—a model to simulate the nitrate transport in the saturated zone. This study answers the scientific questions of when the nitrate currently in the groundwater was loaded into the unsaturated zones and eventually reached the water table; is the rising groundwater nitrate concentration in the study area caused by historic nitrate load; what caused the uneven distribution of groundwater nitrate concentration in the study area; and whether the historic peak nitrate loading has reached the water table in the area. The groundwater nitrate in the area was mainly from the 1980s to 2000s, whilst the groundwater nitrate in most of the source protection zones leached into the system during 1940s–1970s; the large and spatially variable thickness of the USZ is one of the major reasons for unevenly distributed groundwater nitrate concentrations in the study area; the peak nitrate loading around 1983 has affected most of the study area. For areas around the Bowscar, Beacon Edge, Low Plains, Nord Vue, Dale Springs, Gamblesby, Bankwood Springs, and Cliburn, the peak nitrate loading will arrive at the water table in the next 34 years; statistical analysis shows that 8.7 % of the Penrith Sandstone and 7.3 % of the St Bees Sandstone have not been affected by peak nitrate. This research can improve the scientific understanding of nitrate processes in the groundwater system and support the effective management of groundwater nitrate pollution for the study area. With a limited number of parameters, the method and models developed in this study are readily transferable to other areas.

For computationally efficient modeling of unsaturated–saturated flow in regional scales, the quasi-three-dimensional (3-D) scheme that considers one-dimensional (1-D) soil water flow and 3-D groundwater flow is an alternative method. However, it is still practically challenging for regional-scale problems due to the highly nonlinear and intensive input data needed for soil water modeling and the reliability of the coupling scheme. This study developed a new quasi-3-D model coupled to the UBMOD 1-D soil water balance model with the MODFLOW 3-D hydrodynamic model. A new implementation method of the iterative scheme was developed in which the vertical net recharge and unsaturated zone depth were used as the exchange information. A modeling framework was developed to organize the coupling scheme of the soil water model and the groundwater model and to handle the pre- and post-processing information. The strength and weakness of the coupled model were evaluated by using two published studies. The comparison results show that the coupled model is satisfactory in terms of computational accuracy and mass balance error. The influences of spatial and temporal discretization as well as the stress period on the model accuracy were discussed. Additionally, the coupled model was used to evaluate groundwater recharge in a real-world study. The measured groundwater table and soil water content were used to calibrate the model parameters, and the groundwater recharge data from a 2-year tracer experiment were used to evaluate the recharge estimation. The field application further shows the practicability of the model. The developed model and the modeling framework provide a convenient and flexible tool for evaluating unsaturated–saturated flow systems at the regional scale.

The aim of this study is to present a framework that provides new ways to characterize the spatio-temporal variability of lateral exchanges for water flow and solute transport in a karst conduit network during flood events, treating both the diffusive wave equation and the advection–diffusion equation with the same mathematical approach, assuming uniform lateral flow and solute transport. A solution to the inverse problem for the advection–diffusion equations is then applied to data from two successive gauging stations to simulate flows and solute exchange dynamics after recharge. The study site is the karst conduit network of the Fourbanne aquifer in the French Jura Mountains, which includes two reaches characterizing the network from sinkhole to cave stream to the spring. The model is applied, after separation of the base from the flood components, on discharge and total dissolved solids (TDSs) in order to assess lateral flows and solute concentrations and compare them to help identify water origin. The results showed various lateral contributions in space – between the two reaches located in the unsaturated zone (R1), and in the zone that is both unsaturated and saturated (R2) – as well as in time, according to hydrological conditions. Globally, the two reaches show a distinct response to flood routing, with important lateral inflows on R1 and large outflows on R2. By combining these results with solute exchanges and the analysis of flood routing parameters distribution, we showed that lateral inflows on R1 are the addition of diffuse infiltration (observed whatever the hydrological conditions) and localized infiltration in the secondary conduit network (tributaries) in the unsaturated zone, except in extreme dry periods. On R2, despite inflows on the base component, lateral outflows are observed during floods. This pattern was attributed to the concept of reversal flows of conduit–matrix exchanges, inducing a complex water mixing effect in the saturated zone. From our results we build the functional scheme of the karst system. It demonstrates the impact of the saturated zone on matrix–conduit exchanges in this shallow phreatic aquifer and highlights the important role of the unsaturated zone on storage and transfer functions of the system.