Hydrochemical tracers in the middle Rio Grande Basin,USA: 2. Calibration of a groundwater-flow model

The calibration of a groundwater model with the aid of hydrochemical data has demonstrated that low recharge rates in the Middle Rio Grande Basin may be responsible for a groundwater trough in the center of the basin and for a substantial amount of Rio Grande water in the regional flow system. Earlier models of the basin had difficulty reproducing these features without any hydrochemical data to constrain the rates and distribution of recharge. The objective of this study was to use the large quantity of available hydrochemical data to help calibrate the model parameters, including the recharge rates. The model was constructed using the US Geological Surveys software MODFLOW, MODPATH, and UCODE, and calibrated using ¹⁴C activities and the positions of certain flow zones defined by the hydrochemical data. Parameter estimation was performed using a combination of nonlinear regression techniques and a manual search for the minimum difference between field and simulated observations. The calibrated recharge values were substantially smaller than those used in previous models. Results from a 30,000-year transient simulation suggest that recharge was at a maximum about 20,000 years ago and at a minimum about 10,000 years ago.

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Resumen La calibración de un modelo de aguas subterráneas con el apoyo de datos hidroquímicos ha demostrado que la recarga relativamente baja en la cuenca media del Río Grande es probablemente responsable de una depresión de aguas subterráneas en el centro de la cuenca y de la presencia de una cantidad considerable de agua del Río Grande en el acuífero del Grupo Santa Fe. Los modelos propuestos con anterioridad para la cuenca tenían dificultades para reproducir estas características ya que no tenían datos hidroquímicos que permitieran delimitar los ritmos y distribución de recarga. El objetivo del presente estudio consistió en utilizar una gran cantidad de datos hidroquímicos disponibles para ayudar a calibrar los parámetros del modelo, incluyendo los ritmos de recarga. El modelo se construyó utilizando los modelos MODFLOW, MODPATH, y UCODE del USGS, mientras que la calibración se realizó en base a concentraciones de ¹⁴C y a la posición de ciertas zonas definidas con los datos hidroquímicos. La estimación de parámetros se realizó en base a una combinación de técnicas de regresiones no lineares y a una búsqueda a viva fuerza del error mínimo entre los datos observados y los simulados. Los valores de recarga calibrados fueron significativamente más bajos que los estimados en los modelos anteriores. Los resultados de una simulación transitoria de 30,000 años sugieren que la recarga durante la última glacial máxima (LGM) fue diez veces el ritmo moderno, pero que la recarga que ocurrió inmediatamente después de la LGM fue más baja que el ritmo moderno.

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Résumé Le calibrage dun modèle hydrogéologique avec laide de données hydrochimiques a démontré que la recharge relativement faible dans le Grand Bassin du Middle Rio est vraisemblablement responsable dune dépression des eaux souterraines dans le centre du bassin et de la présence dune quantité substantielle deau du Rio Grande dans laquifère du Groupe de Santa Fe. Les modèles antérieurs avaient des difficultés à reproduire ses conclusions sans laide de données hydrochimiques pour contraindre les taux et la distribution de la recharge. Lobjectif de cette étude était dutiliser une grande quantité de données hydrochimiques permettant de calibrer les paramètres du modèle, et notamment les taux de recharge. Le modèle a été construit avec les logiciels MODFLOW, MODPATH et UCODE, et calibré en utilisant les concentrations en ¹⁴C et la position de certaines zones définies par les données hydrochimiques. Lestimation de certains paramètres a été réalisée en utilisant une combinaison de techniques de régression non linéaire et une méthode de recherche exhaustive (Brute Force Search) de lerreur minimum entre les résultats des observations et les simulations. Les valeurs de la recharge calibrée sont substantiellement plus basses que celles estimées dans les modèles antérieurs. Les résultats dune simulation en régime transitoire sur 30.000 ans suggèrent que la recharge au maximum de la dernière glaciation (last glacial maximum, LGM) était 10 fois supérieure au taux actuel, mais que la recharge qui a suivit la LGM était plus bas que la recharge actuelle.

     

NETPATH-WIN: An interactive user version of the mass-balance model, NETPATH

NETPATH‐WIN is an interactive user version of NETPATH, an inverse geochemical modeling code used to find mass‐balance reaction models that are consistent with the observed chemical and isotopic composition of waters from aquatic systems. NETPATH‐WIN was constructed to migrate NETPATH applications into the Microsoft WINDOWS® environment. The new version facilitates model utilization by eliminating difficulties in data preparation and results analysis of the DOS version of NETPATH, while preserving all of the capabilities of the original version. Through example applications, the note describes some of the features of NETPATH‐WIN as applied to adjustment of radiocarbon data for geochemical reactions in groundwater systems.     

Comparison of age distributions estimated from environmental tracers by using binary-dilution and numerical models of fractured and folded karst: Shenandoah Valley of Virginia and West Virginia, USA

Measured concentrations of environmental tracers in spring discharge from a karst aquifer in the Shenandoah Valley, USA, were used to refine a numerical groundwater flow model. The karst aquifer is folded and faulted carbonate bedrock dominated by diffuse flow along fractures. The numerical model represented bedrock structure and discrete features (fault zones and springs). Concentrations of ³H, ³He, ⁴He, and CFC-113 in spring discharge were interpreted as binary dilutions of young (0–8  years) water and old (tracer-free) water. Simulated mixtures of groundwater are derived from young water flowing along shallow paths, with the addition of old water flowing along deeper paths through the model domain that discharge to springs along fault zones. The simulated median age of young water discharged from springs (5.7  years) is slightly older than the median age estimated from ³H/³He data (4.4  years). The numerical model predicted a fraction of old water in spring discharge (0.07) that was half that determined by the binary-dilution model using the ³H/³He apparent age and ³H and CFC-113 data (0.14). This difference suggests that faults and lineaments are more numerous or extensive than those mapped and included in the numerical model.     

Global investment and future minerals production

The global minerals industry experienced several structural adjustments during the 1980s. The changes were accompanied by shifts in investment by region, commodity, and type of project. Planned increases in production capacity in the 1990s and beyond suggest that a highly-significant amount of capital will be required to finance long-term expansion, notwithstanding an increasingly capital-scarce environment. This paper examines recent trends of investment in the global minerals industry, and describes likely investment flows in the future. The authors focus on the investment requirements in transitional economies for the major metals.     

Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity,and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

We have calculated the total individual ion activity coefficients of carbonate and calcium, and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of and are $\text{0.038 ± 0.002}$ and $\text{0.173 ± 0.010}$, respectively. These values of and are independent of liquid junction errors and internally consistent with the value . By defining and on a common scale (), the product is independent of the assigned value of and may be determined directly from thermodynamic measurements in seawater. Using the value and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978, Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.     

First application of MC2-AQ to multiscale air quality modelling over Europe

A three-dimensional air quality model (MC2-AQ) developed for studying oxidant chemistry on regional to urban scales over North America was adapted and implemented for European conditions. The modelling system is based on the Canadian Mesoscale Compressible Community (MC2) Model, a non-hydrostatic meteorological model, to which modules permitting on-line calculations of chemical transformations, anthropogenic and biogenic emissions, and deposition were added. The transport of chemical species is done on the same grid and with the same advection, convection, and diffusion schemes as are used for the meteorological fields. The developed model is highly flexible and was adapted to different scales by allowing for self-nesting. In this paper we present model results for a high-ozone episode, June 18–26, 2000, over Europe. The modelling system was able to reproduce general characteristics (growth, extent, and dissipation) of the pollution episode. Accumulation of ozone precursors during weak wind and high-temperature synoptic conditions was essential for episode formation. Subsequent episode development and advancement across Europe was driven by frontal systems. A stationary front associated with a low-pressure system over Ukraine prevented the further eastward transport of the polluted air mass. The episode was terminated after the passage of a cold front advecting relatively clean Atlantic air mass.     

GC profiles of oils reflect organic maturity rather than depositional environment of parent source rock: examples from Central Australia

Abstract

Review and analysis of 1332 gas chromatography (GC) n-alkane traces of oils from the Cooper and Eromanga basins indicate the shape of any GC trace profile is primarily controlled by the degree of organic maturity (early, peak or late) at which the oils were expelled from the parent source rock, rather than indicating the depositional environment, and hence organic composition, of that source rock. The depositional environment of a source rock may still be inferred, however, from the position of the n-alkane maximum on the GC traces of early expulsion oils in association with the pour point of the oil. Departures of GC trace profiles from the standard early, peak or late expulsion profiles can indicate mixing of oils of different maturities, while variations in the GC trace profiles of oils within adjacent reservoir units may indicate phase separation of the parent liquid, or possible seal breach by an accumulation that exceeds the capacity of its overlying seal.

1. KEY POINTS

2. GC trace profiles of 1332 oils from across the Cooper and Eromanga basins of central Australia have been reviewed.

3. Organic maturity, rather than organic composition, of the parent source rock controls the shape of any GC trace profile.

4. All early maturity oils display a consistent GC trace profile shape that is different from all peak maturity oils and different again from all late maturity oils.

5. Depositional environment of the source rocks within a basin can be inferred from the relative pour points of the resultant oils.

     

Horizontal and Vertical Well Comparison for In Situ Air Sparging

A laboratory study was conducted to determine the effectiveness ol vertical and horizontal well configurations for ground water remediation using in situ air sparging. A lexan lank was designed and constructed to allow both the visualization of air flow and quantitative measurement of the distribution of air flow. Two media, sand and glass beads. were tested with both Vertical and horizontal air sources. In each case, most of the air traveled through preferential channels as continuous flow rather than as discrete bubbles as reported in other studies. Liven though glass beads were selected to have the same grain-size distribution as the sand, air flow was quite different through the two media. Results show that glass beads are not a suitable material for modeling air flow through natural sediments. In this study, the horizontal well proved to be more effective than the vertical well by impacting more of the media with a uniform distribution of air throughout the media. The vertical well resulted in a nonuniform distribution of air flow with most of the air concentrated directly above the well.