Hydrochemical tracers in the middle Rio Grande Basin,USA: 1. Conceptualization of groundwater flow

Chemical and isotopic data for groundwater from throughout the Middle Rio Grande Basin, central New Mexico, USA, were used to identify and map groundwater flow from 12 sources of water to the basin, evaluate radiocarbon ages, and refine the conceptual model of the Santa Fe Group aquifer system.Hydrochemical zones, representing groundwater flow over thousands to tens of thousands of years, can be traced over large distances through the primarily siliciclastic aquifer system. The locations of the hydrochemical zones mostly reflect the modern predevelopment hydraulic-head distribution, but are inconsistent with a trough in predevelopment water levels in the west-central part of the basin, indicating that this trough is a transient rather than a long-term feature of the aquifer system. Radiocarbon ages adjusted for geochemical reactions, mixing, and evapotranspiration/dilution processes in the aquifer system were nearly identical to the unadjusted radiocarbon ages, and ranged from modern to more than 30 ka. Age gradients from piezometer nests ranged from 0.1 to 2 year cm^–1 and indicate a recharge rate of about 3 cm year^–1 for recharge along the eastern mountain front and infiltration from the Rio Grande near Albuquerque. There has been appreciably less recharge along the eastern mountain front north and south of Albuquerque.

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Resumen Se utilizaron datos químicos e isotópicos de agua subterránea a lo largo de la cuenca central del río Grande, Nuevo México, EEUU, para identificar y mapear el flujo de agua subterránea de 12 fuentes de agua a la cuenca para evaluar edades por medio de radio carbon y para refinar el modelo conceptual del sistema acuífero del Grupo Santa Fé. Se puede establecer zonas hidrotérmicas que representan el flujo de agua subterránea a lo largo de miles a miles de decenas de años en grandes distancias a través del sistema acuífero principalmente siliclástico. Las ubicaciones de las zonas hidroquímicas mayormente reflejan la distribucion de la cabeza hidráulica pre-desarollo moderna pero son inconsistentes con una depresión en los niveles de agua pre-desarollo en la zona central oeste de la cuenca. Esto indica que esta depresión es un rasgo transitorio y no un rasgo de largo plazo del sistema acuífero. Las edades de radio carbon ajustadas para los procesos de reaciones geoquímicas, de mezclado y de evapotranspiración-dilución son casi idénticas a los edades de radio carbon no ajustadas oscilan en un rango desde la modernidad a 30 mil años. Las gradientes de edad de nidos de piezometros van de 0.1 a 2 años cm^–1 e indican un sitio de recarga de aproximadamente 3 cm/yr para la recarga a lo largo del frente montañoso oriental e infiltración del río Grande cerca de Albuquerque. Se aprecia una recarga menor a lo largo del frente oriental de montañas al norte y al sur de Albuquerque.

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Résumé Des données sur les éléments chimiques et les isotopes présents dans leau souterraine prélevée à divers endroits dans le bassin moyen du Rio Grande, au centre du Nouveau-Mexique (É-U), ont permis de déterminer lexistence et létendue de douze sources deau régionales dans le bassin, dévaluer les âges radiocarbones et de raffiner le modèle conceptuel du système aquifère du groupe de Santa Fe. Des zones hydro-chimiques qui représentent lécoulement de leau souterraine depuis des dizaines de milliers dannées peuvent être suivies sur de longues distances à travers laquifère principalement siliclastique. La position des zones hydro-chimiques reflète principalement la distribution moderne des charges hydrauliques mais est incohérente avec une dépression dans le niveau deau dans la partie centre-ouest du bassin, ce qui indique que cette dépression est un élément transitoire du système aquifère plutôt quun élément à long terme. Les âges radiocarbones ajustés aux réactions géochimiques et aux processus de mélange et dévapotranspiration/dilution qui ont lieu dans laquifère sont presque identiques aux âges non ajustés et varient de la période moderne jusquà 30 ka. Les gradients dâge établis à partir des nids de piézomètres sétendent de 0.1 à 2 a cm^–1 et suggèrent un taux de recharge denviron 3 cm a^–1 le long du front des montagnes à lest et pour linfiltration provenant du Rio Grande près dAlbuquerque. Il y a eu substantiellement moins de recharge le long du front des montagnes à lest, au nord et au sud dAlbuquerque.

     

The solubilities of calcite,aragonite and vaterite in CO2-H2O solutions between 0 and 90°C,and an evaluation of the aqueous model for the system CaCO3-CO2-H2O

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO^2?₃: $\text{Log K}{}_{\mathrm{C}}\text{= ?171.9065 ? 0.077993T +}\text{2839.319}\text{T}\text{+ 71.595 log T}$$\text{Log K}{}_{\mathrm{A}}\text{= ?171.9773 ? 0.077993T +}\text{2903.293}\text{T}\text{+71.595 log T}$$\text{Log K}{}_{\mathrm{V}}\text{= ?172.1295 ? 0.077993T +}\text{3074.688}\text{T}\text{+ 71.595 log T}$ where T is in ^oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃ association constant was measured potentiometrically to be between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are $\text{log K}{}_{\mathrm{H}}\text{= 108.3865 + 0.01985076T ?}\text{6919.53}\text{T}\text{? 40.45154 log T +}\text{669365.}\text{T}{}^2$, $\text{log K}{}_1\text{= ?356.3094 ? 0.06091964T +}\text{21834.37}\text{T}\text{+ 126.8339 log T —}\text{1684915.}\text{T}{}^2$ and logK₂ = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.