Use of geochemical mass balance modelling to evaluate the role of weathering in determining stream chemistry in five mid-atlantic watersheds on different lithologies

The importance of mineral weathering was assessed and compared for five mid-Atlantic watersheds receiving similar atmospheric inputs but underlain by differing bedrock. Annual solute mass balances and volume-weighted mean solute concentrations were calculated for each watershed for each year of record. In addition, primary and secondary mineralogy were determined for each of the watersheds through analysis of soil samples and thin sections using petrographic, scanning electron microscope, electron microprobe and X-ray diffraction techniques. Mineralogical data were also compiled from the literature. These data were input to NETPATH, a geochemical program that calculates the masses of minerals that react with precipitation to produce stream water chemistry. The feasibilities of the weathering scenarios calculated by NETPATH were evaluated based on relative abundances and reactivities of minerals in the watershed. In watersheds underlain by reactive bedrocks, weathering reactions explained the stream base cation loading. In the acid-sensitive watersheds on unreactive bedrock, calculated weathering scenarios were not consistent with the abundance of reactive minerals in the underlying bedrock, and alternative sources of base cations are discussed. © 1997 John Wiley & Sons, Ltd.     

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.     

A Permanent Multilevel Monitoring and Sampling System in the Coastal Groundwater Mixing Zones

To study the spatial and temporal variability of water dynamics and chemical reactions within the coastal groundwater mixing zones (CGMZs), high‐resolution periodical and spatial groundwater sampling within CGMZs is needed. However, current samplers and sampling systems may require heavy driving machines to install. There is also possible contamination from the metal materials for current samplers and sampling systems. Here, a permanent multilevel sampling system is designed to sample coastal groundwater within CGMZs. This cost‐effective system consists of metal‐free materials and can be installed easily. The system is tested in Po Sam Pai and Tingkok, Tolo Harbor and Hong Kong. Major ions, nutrients, stable isotopes and radium and radon isotopes were analyzed and the data provided scientific information to study the fresh‐saltwater interface fluctuations, and temporal variations and spatial heterogeneity of geochemical processes occurred within CGMZs. The reliable spatial and temporal data from the sampling system demonstrate that the system functions well and can provide scientific data for coastal aquifer studies.     

Advances in interpretation of subsurface processes with time‐lapse electrical imaging

Electrical geophysical methods, including electrical resistivity, time‐domain induced polarization, and complex resistivity, have become commonly used to image the near subsurface. Here, we outline their utility for time‐lapse imaging of hydrological, geochemical, and biogeochemical processes, focusing on new instrumentation, processing, and analysis techniques specific to monitoring. We review data collection procedures, parameters measured, and petrophysical relationships and then outline the state of the science with respect to inversion methodologies, including coupled inversion. We conclude by highlighting recent research focused on innovative applications of time‐lapse imaging in hydrology, biology, ecology, and geochemistry, among other areas of interest. Copyright © 2014 John Wiley & Sons, Ltd.     

Bivariate Gaussian mixture–based equivalent linearization method for stochastic seismic analysis of nonlinear structures

To address challenges in stochastic seismic analysis of nonlinear structures, this paper further develops a recently proposed Gaussian mixture–based equivalent linearization method (GM‐ELM). The GM‐ELM uses a Gaussian mixture distribution model to approximate the probabilistic distribution of a nonlinear system response. Using properties of the Gaussian mixture model, GM‐ELM can decompose the non‐Gaussian response of a nonlinear system into multiple Gaussian responses of linear single–degree of freedom oscillators. With the set of the equivalent linear systems identified by GM‐ELM, response statistics as crossing rate and first‐passage probability can be computed conveniently using theories of linear random vibration analysis. However, the original version of GM‐ELM may lead to an inaccurate estimate because of the heuristic parameters of the linear system introduced to supplement insufficient information. To overcome this limitation and define unique equivalent linear systems, this paper proposes a further developed version of GM‐ELM, which uses a mixture of bivariate Gaussian densities instead of univariate models. Moreover, to facilitate the use of elastic response spectra for estimating the mean peak responses of a nonlinear structure, a new response spectrum combination rule is proposed for GM‐ELM. Two numerical examples of hysteretic structural systems are presented in this paper to illustrate the application of the bivariate GM‐ELM to nonlinear stochastic seismic analysis. The analysis results obtained by the bivariate GM‐ELM are compared with those obtained by the univariate GM‐ELM, the conventional equivalent linearization method, the tail equivalent linearization method, and Monte Carlo simulation. The supporting source code and data are available for download at https://github.com/yisangri/GitHub‐bGM‐ELM‐code.git     

Broad‐Scale Evidence That pH Influences the Balance Between Microbial Iron and Sulfate Reduction

Understanding basic controls on aquifer microbiology is essential to managing water resources and predicting impacts of future environmental change. Previous theoretical and laboratory studies indicate that pH can influence interactions between microorganisms that reduce ferric iron and sulfate. In this study, we test the environmental relevance of this relationship by examining broad‐scale geochemical data from anoxic zones of aquifers. We isolated data from the U.S. Geological Survey National Water Information System for 19 principal aquifer systems. We then removed samples with chemical compositions inconsistent with iron‐ and sulfate‐reducing environments and evaluated the relationships between pH and other geochemical parameters using Spearman's rho rank correlation tests. Overall, iron concentration and the iron‐sulfide concentration ratio of groundwater share a statistically significant negative correlation with pH (P < 0.0001). These relationships indicate that the significance of iron reduction relative to sulfate reduction tends to increase with decreasing pH. Moreover, thermodynamic calculations show that, as the pH of groundwater decreases, iron reduction becomes increasingly favorable relative to sulfate reduction. Hence, the relative significance of each microbial reaction may vary in response to thermodynamic controls on microbial activity. Our findings demonstrate that trends in groundwater geochemistry across different regional aquifer systems are consistent with pH as a control on interactions between microbial iron and sulfate reduction. Environmental changes that perturb groundwater pH can affect water quality by altering the balance between these microbial reactions.     

Three‐dimensional modelling of controlled‐source electromagnetic surveys using an edge finite‐element method with a direct solver

A fully three‐dimensional finite‐element algorithm has been developed for simulating controlled‐source electromagnetic surveys. To exploit the advantages of geometric flexibility, frequency‐domain Maxwell's equations of the secondary electric field were discretised using edge‐based finite elements while the primary field was calculated analytically for a horizontally layered‐earth model. The resulting system of equations for the secondary field was solved using a parallel version of direct solvers. The accuracy of the algorithm was successfully verified by comparisons with integral‐equations and iterative solutions, and the applicability to models containing large conductivity contrasts was verified against published data. The advantages of geometry‐conforming meshes have been demonstrated by comparing different mesh systems to simulate an inclined sheet model. A comparison of the performance between direct and iterative solvers demonstrated the superior efficiency of direct solvers, particularly for multisource problems.     

WATEQB – BASICA REVISION OF WATEQF FOR IBM PERSONAL COMPUTERS

Abstract. WATEQB is a BASICA revision for IBM PC of WATEQF, a geochemical model for chemical equilibrium and saturation of natural waters. This model computes the speciation of inorganic ions and complex species in solution for a given water analysis.
WATEQB is identical to the FORTRAN IV version from the standpoint of chemical process; however, the structure of the program differs from the original version. The structure of the program is not complex and allows the user to try some new modifications, if necessary.
Due to the limited memory of personal computers and in contrast to the large volume of the original version of the program, the author has created four data files, one of which is of random access type. Reading the thermochemical data is possible through these four data files.
This paper demonstrates how to set up the input data to execute WATEQB and describes the program rather than the model. The users of WATEQB will increase as personal computers become more common.     

Application of a confluence‐based sediment‐fingerprinting approach to a dynamic sedimentary catchment,New Zealand

Fine sediment is a dynamic component of the fluvial system, contributing to the physical form, chemistry and ecological health of a river. It is important to understand rates and patterns of sediment delivery, transport and deposition. Sediment fingerprinting is a means of directly determining sediment sources via their geochemical properties, but it faces challenges in discriminating sources within larger catchments. In this research, sediment fingerprinting was applied to major river confluences in the Manawatu catchment as a broad‐scale application to characterizing sub‐catchment sediment contributions for a sedimentary catchment dominated by agriculture. Stepwise discriminant function analysis and principal component analysis of bulk geochemical concentrations and geochemical indicators were used to investigate sub‐catchment geochemical signatures. Each confluence displayed a unique array of geochemical variables suited for discrimination. Geochemical variation in upstream sediment samples was likely a result of the varying geological source compositions. The Tiraumea sub‐catchment provided the dominant signature at the major confluence with the Upper Manawatu and Mangatainoka sub‐catchments. Subsequent downstream confluences are dominated by the upstream geochemical signatures from the main stem of Manawatu River. Variability in the downstream geochemical signature is likely due to incomplete mixing caused in part by channel configuration. Results from this exploratory investigation indicate that numerous geochemical elements have the ability to differentiate fine sediment sources using a broad‐scale confluence‐based approach and suggest there is enough geochemical variation throughout a large sedimentary catchment for a full sediment fingerprint model. Combining powerful statistical procedures with other geochemical analyses is critical to understanding the processes or spatial patterns responsible for sediment signature variation within this type of catchment. Copyright © 2015 John Wiley & Sons, Ltd.     

Hydrogeochemistry of shallow groundwater in an upland Scottish catchment

The hydrogeochemistry of shallow groundwater has been characterized in the Allt a'Mharcaidh catchment in the Scottish Cairngorms in order to: (i) assess the spatial and temporal variation in groundwater chemistry; (ii) identify the hydrogeochemical processes regulating its evolution; and (iii) examine the influence of groundwater on the quality and quantity of stream flow. Shallow groundwater in superficial drift deposits is circumneutral (pH∽7·1) and base cation concentrations are enriched compared with precipitation and drainage water from overlying podzolic soils. Modelling with NETPATH suggests that the dominant geochemical processes that account for this are the dissolution of plagioclase, K-feldspar and biotite. Groundwater emerging as springs from weathered granite underlying high altitude (>900 m) alpine soils shows similar characteristics, though weathering rates are lower, probably as a result of reduced residence times and lower temperatures. Chemical hydrograph separation techniques using acid neutralizing capacity (ANC) and Si as tracers show that groundwater is the dominant source of baseflow in the catchment and also buffers the chemistry of stream water at high flows: groundwater may account for as much as 50–60% of annual runoff in the catchment. Climate and land use in the Cairngorms are vulnerable to future changes, which may have major implications for hydrogeological processes in the area. © 1998 John Wiley & Sons, Ltd.     

In situ characterization of grain‐scale fluvial morphology using Terrestrial Laser Scanning

The grain‐scale morphology of fluvial sediments is an important control on the character and dynamics of river systems; however current understanding of its role is limited by the difficulties of robustly quantifying field surface morphology. Terrestrial Laser Scanning (TLS) offers a new methodology for the rapid acquisition of high‐resolution and high‐precision surface elevation data from in situ sediments. To date, most environmental and fluvial applications of TLS have focused on large‐scale systems, capturing macroscale morphologies. Application of this new technology at scales necessary to characterize the complexity of grain‐scale fluvial sediments therefore requires a robust assessment of the quality and sources of errors in close‐range TLS data. This paper describes both laboratory and field experiments designed to evaluate close‐range TLS for sedimentological applications and to develop protocols for data acquisition. In the former, controlled experiments comprising high‐resolution scans of white, grey and black planes and a sphere were used to quantify the magnitude and source of three‐dimensional (3D) point errors resulting from a combination of surface geometry, reflectivity effects and inherent instrument precision. Subsequently, a methodology for the collection and processing of grain‐scale TLS data is described through an application to a coarse grained gravel system, the River Feshie (D₅₀ 32 to 63 mm). This stepwise strategy incorporates averaging repeat scans and filtering scan artefact and non‐surface points using local 3D search algorithms. The sensitivity of the results to the filter parameter values are assessed by careful internal validation of Digital Terrain Models (DTMs) created from the resulting point cloud data. The transferability of this methodology is assessed through application to a second river, Bury Green Brook, dominated by finer gravel (D₅₀ 18 to 33 mm). The factor limiting the resolution of DTMs created from this second dataset was found to be the relative sizes of the laser footprint and smallest grains. Copyright © 2009 John Wiley & Sons, Ltd.     

Time domain identification of hybrid base isolation systems using free vibration tests

A procedure for the dynamic identification of the physical parameters of coupled base isolation systems is developed in the time domain. The isolation systems considered include high damping rubber bearings (HDRB) and low friction sliding bearings (LFSB). A bi‐linear hysteretic model is used alone or in parallel with a viscous damper to describe the behavior of the HDRB system, while a constant Coulomb friction device is used to model the LFSB system. After deriving the analytical dynamical solution for the coupled system under an imposed initial displacement, this is used in combination with the least‐squares method and an iterative procedure to identify the physical parameters of a given base isolation system belonging to the class described by the models considered. Performance and limitations of the proposed procedure are highlighted by numerical applications. The procedure is then applied to a real base isolation system using data from static and dynamic tests performed on a building at Solarino. The results of the proposed identification procedure have been compared to available laboratory data and the agreement is within ±10%. However, the need for improvement both in models and testing procedures also emerges from the numerical applications and results obtained. Copyright © 2010 John Wiley & Sons, Ltd.     

Sorption of Iron on Surfaces: Modelling,Data Evaluation,and Measurement Uncertainty

Assessment of the likely outcome of engineered invention strategies in acid mine drainage often involves complex geochemical modelling activities. Geochemical modelling is based on chemical thermodynamic data. In addition sorption models, kinetical reaction rates and transport tools are included into the modelling codes because the interactions between solution components and surfaces, reaction time and transport are considered important features characterising the site‐specific situation. In the determination of both thermodynamic data and sorption coefficients, speciation calculations play an important role. By applying the probabilistic speciation code Ljungskile to some simplified acid mine drainage scenarios, the strong impact of chemical speciation on the complete measurement uncertainty budget of geochemical modelling predictions is shown. The complete measurement uncertainty budget in combination with other metrological concepts like traceability is an essential element of quality assurance for experimental data. The elements of quality assurance are provided by international agreements and normative documents on national and international levels. The following discussion will focus on some metrological issues of sorption data.     

Groundwater—Surface waters interactions at slope and catchment scales: implications for landsliding in clay‐rich slopes

Understanding water infiltration and transfer in soft‐clay shales slopes is an important scientific issue, especially for landsliding. Geochemical investigations are carried out at the Super‐Sauze and Draix‐Laval landslides, both developed in the Callovo‐Oxfordian black marls, with the objective to define the origin of the groundwater. In situ investigations, soil leaching experiments and geochemical modeling are combined to identify the boundaries of the hydrological systems. At Super‐Sauze, the observations indicate that an external water flow occurs in the upper part of the landslide at the contact between the weathered black marls and the overlying formations, or at the landslide basement through a fault network. Such external origin of water is not observed at the local scale of the Draix‐Laval landslide but is detected at the catchment scale with the influence of deep waters in the streamwater quality of low river flows. Hydrogeological conceptual models are proposed emphasizing the role of the interactions between local (slope) and regional (catchment) flow systems. The observations suggest that this situation is a common case in the Alpine area. Expected consequences of the regional flows on slope stability are discussed in term of rise of pore water pressures and physicochemical weathering of the clay shales.     

Petrogenesis of the Ulsan carbonate rocks from the south-eastern Kyongsang Basin, South Korea

Abstract The petrogenesis of the Ulsan carbonate rocks in the Mesozoic Kyongsang Basin of South Korea, which have previously been interpreted as limestone of Paleozoic age, is reconsidered in the present study. Within the Kyongsang Basin, a small volume of carbonate rocks, containing a magnetite deposit and spatially associated ultramafic rocks, is surrounded by sedimentary, volcanic and granitic rocks of the Mesozoic age. The simple cross‐cutting relationships and other outcrop features of the area indicate that the carbonate rocks are an intrusive phase and younger than the other surrounding Mesozoic rocks. The Ulsan carbonates have low concentrations of rare earth elements (REE) and trace elements with the carbon and oxygen isotope values in the range of δ¹³C_PDB = 2.4 to 4.0‰ and δ¹⁸O_SMOW = 17.0 to 19.5‰. Outcrop evidence and geochemical signatures indicate that the Ulsan carbonates were formed from crustal carbonate melts, which were generated by the melting/fluxing of crustal carbonate materials, caused by the emplacement‐related processes of alkaline A‐type granitic rocks. Compared to typical mantle‐derived carbonatites associated with silica‐undersaturated, strongly peralkaline systems, the relatively small size and geochemical characteristics of the Ulsan carbonates reflect carbonatite genesis in a silica‐saturated, weakly alkali intrusive system. Major deep‐seated tectonic fractures formed by the collapse of the cauldron or the rift system associated with the opening of the East Sea (Japan Sea) might have facilitated the ascent of the crustal carbonate melts.     

Influence of partial confinement and Holocene river formation on groundwater flow and dissolution in the Florida carbonate platform

Much of what is known about groundwater circulation and geochemical evolution in carbonate platforms is based on platforms that are fully confined or unconfined. Much less is known about groundwater flow paths and geochemical evolution in partially confined platforms, particularly those supporting surface water. In north‐central Florida, sea level rise and a transition to a wetter climate during the Holocene formed rivers in unconfined portions of the Florida carbonate platform. Focusing on data from the Santa Fe River basin, we show river formation has led to important differences in the hydrological and geochemical evolution of the Santa Fe River basin relative to fully confined or unconfined platforms. Runoff from the siliciclastic confining layer drove river incision and created topographic relief, reorienting the termination of local and regional groundwater flow paths from the coast to the rivers in unconfined portions of the platform. The most chemically evolved groundwater occurs at the end of the longest and deepest flow paths, which discharge near the center of the platform because of incision of the Santa Fe River at the edge of the confining unit. This pattern of discharge of mineralized water differs from fully confined or unconfined platforms where discharge of the most mineralized water occurs at the coast. Mineralized water flowing into the Santa Fe River is diluted by less evolved water derived from shorter, shallower flow paths that discharge to the river downstream. Formation of rivers shortens flow path lengths, thereby decreasing groundwater residence times and allowing freshwater to discharge more quickly to the oceans in the newly formed rivers than in platforms that lack rivers. Similar dynamic changes to groundwater systems should be expected to occur in the future as climate change and sea level rise develop surface water on other carbonate platforms and low lying coastal aquifer systems. Copyright © 2012 John Wiley & Sons, Ltd.     

New Insights from Well Responses to Fluctuations in Barometric Pressure

Hydrologists have long recognized that changes in barometric pressure can produce changes in water levels in wells. The barometric response function (BRF) has proven to be an effective means to characterize this relationship; we show here how it can also be utilized to glean valuable insights into semi‐confined aquifer systems. The form of the BRF indicates the degree of aquifer confinement, while a comparison of BRFs between wells sheds light on hydrostratigraphic continuity. A new approach for estimating hydraulic properties of aquitards from BRFs has been developed and verified. The BRF is not an invariant characteristic of a well; in unconfined or semi‐confined aquifers, it can change with conditions in the vadose zone. Field data from a long‐term research site demonstrate the hydrostratigraphic insights that can be gained from monitoring water levels and barometric pressure. Such insights should be of value for a wide range of practical applications.     

Spatial analysis of sand dunes with a new global topographic dataset: new approaches and opportunities

On June 29, 2009, version 1 of the ASTER GDEM (Advanced Spaceborne Thermal Emission and Reflection Radiometer Global Digital Elevation Model) was made available at no cost or restrictions to users worldwide via electronic download. The ASTER GDEM provides expanded spatial coverage and better resolution than other global digital elevation models (DEMs). In this paper we demonstrate how the ASTER GDEM provides new opportunities for investigating large aeolian sand dunes in three‐dimensions. Two dune‐specific spatial analysis methods are presented to illustrate potential applications of these data for discriminating dune generations and quantifying spatial variations of sediment supply. Moreover, we review how existing and emerging fields of dune pattern analysis and simulation modeling will be able to make significant advances through application of these data, potentially leading to future progress in studies of dune morphodynamics, environmental controls, and paleoenvironmental reconstructions. Copyright © 2010 John Wiley & Sons, Ltd.     

Modified passive capillary samplers for collecting samples of snowmelt infiltration for stable isotope analysis in remote,seasonally inaccessible watersheds 2: field evaluation

Twelve modified passive capillary samplers (M‐PCAPS) were installed in remote locations within a large, alpine watershed located in the southern Rocky Mountains of Colorado to collect samples of infiltration during the snowmelt and summer rainfall seasons. These samples were collected in order to provide better constraints on the isotopic composition of soil‐water endmembers in the watershed. The seasonally integrated stable isotope composition (δ¹⁸O and δ²H) of soil‐meltwater collected with M‐PCAPS installed at shallow soil depths < 10 cm was similar to the seasonally integrated isotopic composition of bulk snow taken at the soil surface. However, meltwater which infiltrated to depths > 20 cm evolved along an isotopic enrichment line similar to the trendline described by the evolution of fresh snow to surface runoff from snowmelt in the watershed. Coincident changes in geochemistry were also observed at depth suggesting that the isotopic and geochemical composition of deep infiltration may be very different from that obtained by surface and/or shallow‐subsurface measurements. The M‐PCAPS design was also used to estimate downward fluxes of meltwater during the snowmelt season. Shallow and deep infiltration averaged 8·4 and 4·7 cm of event water or 54 and 33% of the measured snow water equivalent (SWE), respectively. Finally, dominant shallow‐subsurface runoff processes occurring during snowmelt could be identified using geochemical data obtained with the M‐PCAPS design. One soil regime was dominated by a combination of slow matrix flow in the shallow soil profile and fast preferential flow at depth through a layer of platy, volcanic rocks. The other soil regime lacked the rock layer and was dominated by slow matrix flow. Based on these results, the M‐PCAPS design appears to be a useful, robust methodology to quantify soil‐water fluxes during the snowmelt season and to sample the stable isotopic and geochemical composition of soil‐meltwater endmembers in remote watersheds. Copyright © 2009 John Wiley & Sons, Ltd.     

Modeling Variably Saturated Multispecies Reactive Groundwater Solute Transport with MODFLOW‐UZF and RT3D

A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated‐Zone Flow (UZF1) package and MODFLOW. Referred to as UZF‐RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS‐1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one‐dimensional, two‐dimensional, and three‐dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF‐RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run‐time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic‐wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF‐RT3D can be used for large‐scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary‐pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run‐time and the ability to include site‐specific chemical species and chemical reactions make UZF‐RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large‐scale subsurface systems.