Global Groundwater Solute Composition and Concentrations.

Informed analysis of policies related to food security, global climate change, wetland ecology, environmental nutrient flux, element cycling, groundwater weathering, continental denudation, human health, and others depends to a large extent on quantitative estimates of solute mass fluxes into and out of all global element pools including the enigmatic global aquifer systems. Herein for the first time, we proffer the mean global solute concentration of all major and selected minor and trace solutes in the active groundwater that represents 99% of liquid fresh water on Earth. Concentrations in this significant element pool have yielded to a geospatial machine learning kNN-nearest neighbors' algorithm with numerous geospatial predictors utilizing a large new lithology/climate/aquifer age/elevation based solute database. The predicted concentrations are consistent with traditional solute ratios, concentrations, and thermodynamic saturation indices.

Isotopically Enriched Geogenic δ81 Br and δ37 Cl: Primary Evidence for the Ascending Brine Model.

Mass balance calculations and hydrodynamics of groundwater flow suggest that the solutes in brines of the coastal sabkha aquifer from the Emirate of Abu Dhabi are derived largely from ascending geologic brines into the sabkha from the underlying formations. Solute interpretation for the ascending brine model (ABM) was based on two independent but secondary lines of evidence (solute ratios and solute fluxes). In the current study, direct primary evidence for this ABM was provided through analyses of δ81 Br, δ37 Cl, and 87 Sr/86 Sr. Different solute histories of geologic brine and sea water provide an "isotopic fingerprint" that can uniquely distinguish between the two possible sources. Samples from the coastal sabkha aquifer of Abu Dhabi were determined to have a mean δ81 Br of 1.17‰ that is statistically equal, at the 95% confidence level, to the mean of 1.11‰ observed in the underlying geologic brine and statistically different than sea water. Similarly, the δ37 Cl in sabkha brine has a mean of 0.25‰ and is statistically equal to a mean of 0.21‰ in the underlying geologic brines at the 95% confidence level and statistically different from sea water. Also, dissolved strontium isotope data are consistent with the ABM and even with the complex set of processes in the sabkha, the variance in strontium isotope results is similar to the geologic brine. These observations provide primary direct evidence consistent that the major source of these solutes (and presumably others in the aquifer) is from discharging geologic brines, not from adjacent sea water.

Density-Driven Free-Convection Model for Isotopically Fractionated Geogenic Nitrate in Sabkha Brine.

Subsurface brines with high nitrate (NO3- ) concentration are common in desert environments as atmospheric nitrogen is concentrated by the evaporation of precipitation and little nitrogen uptake. However, in addition to having an elevated mean concentration of ∼525 mg/L (as N), NO3- in the coastal sabkhas of Abu Dhabi is enriched in 15 N (mean δ15 N ∼17‰), which is an enigma. A NO3- solute mass balance analysis of the sabkha aquifer system suggests that more than 90% of the nitrogen is from local atmospheric deposition and the remainder from ascending brine. In contrast, isotopic mass balances based on Δ17 O, δ15 N, and δ18 O data suggest approximately 80 to 90% of the NO3- could be from ascending brine. As the sabkha has essentially no soil, no vegetation, and no anthropogenic land or water use, we propose to resolve this apparent contradiction with a density-driven free-convection transport model. In this conceptual model, the density of rain is increased by solution of surface salts, transporting near-surface oxygenated NO3- bearing water downward where it encounters reducing conditions and mixes with oxygen-free ascending geologic brines. In this environment, NO3- is partially reduced to nitrogen gas (N2 ), thus enriching the remaining NO3- in heavy isotopes. The isotopically fractionated NO3- and nitrogen gas return to the near-surface oxidizing environment on the upward displacement leg of the free-convection cycle, where the nitrogen gas is released to the atmosphere and new NO3- is added to the system from atmospheric deposition. This recharge/recycling process has operated over many cycles in the 8000-year history of the shallow aquifer, progressively concentrating and isotopically fractionating the NO3- .

The response of playa and sabkha hydraulics and mineralogy to climate forcing.

Dry playa lakes and sabkhat often represent the terminus of large ground water flow systems and act as integrators of both upgradient (recharge) and downgradient discharge (evaporation). Ground water levels beneath playa/sabkha systems show a variety of surprising responses driven by large evaporation demands and chemical processes not typically encountered in more humid regions. When the water table is very close to the land surface, almost instantaneous rises can be observed with little observed change in either upgradient ground water recharge or potential evaporation. Conversely, when water tables are several meters below the playa surface, water table responses to interannual variability of recharge can be damped and lag significantly behind such changes. This review of the dynamics of shallow water tables in playa lakes and sabkhat discusses the pertinent hydraulic and solute processes and extracts a simple but comprehensive model based on soil physics for predicting the water table response to either upstream recharge changes or changes in potential evaporation at the playa/sabkha. Solutes and associated authigenic minerals are also shown to be important in discriminating both the causes and effects of water level fluctuations.

A fresh water odyssey: some observations on the global resource.

Appreciable increases in the human population are expected to continue in the next 50 to 100 years. This population will require additional water for nonfungible (nonexchangeable) uses such as irrigated agriculture, livestock watering, domestic supply, and ecosystem support. Because most of the world's easily captured water is already identified and allocated, society must improve efficiency, change the present allocations, and/or develop new sources to meet the expected demands. As the global economy expands, apparently unrelated changes in policy or technology may have large, unexpected consequences for water resources. Foreshadowing these changes in stress on these resources will be the result of nonlinear thinking. Whereas policy cannot create new water, it can provide strategies to promote more efficient use of present water and foster an environment in which important technological improvements can be made. This manuscript provides a brief overview of some of the physical and policy considerations relating to fresh water resources.

Role of ground water in geomorphology, geology, and paleoclimate of the Southern High Plains, USA.

Study of ground water in the Southern High Plains is central to an understanding of the geomorphology, deposition of economic minerals, and climate change record in the area. Ground water has controlled the course of the Canadian and Pecos rivers that isolated the Southern High Plains from the Great Plains and has contributed significantly to the continuing retreat of the westward escarpment. Evaporative and dissolution processes are responsible for current plateau topography and the development of the signature 20,000 small playa basins and 40 to 50 large saline lake basins in the area. In conjunction with eolian processes, ground water transport controls the mineralogy of commercially valuable mineral deposits and sets up the distribution of fine efflorescent salts that adversely affect water quality. As the water table rises and retreats, lunette and tufa formation provides valuable paleoclimate data for the Southern High Plains. In all these cases, an understanding of ground water processes contributes valuable information to a broad range of geological topics, well beyond traditional interest in water supply and environmental issues.

Radon (222Rn) in ground water of fractured rocks: a diffusion/ion exchange model.

Ground waters from fractured igneous and high-grade sialic metamorphic rocks frequently have elevated activity of dissolved radon (222Rn). A chemically based model is proposed whereby radium (226Ra) from the decay of uranium (238U) diffuses through the primary porosity of the rock to the water-transmitting fracture where it is sorbed on weathering products. Sorption of 226Ra on the fracture surface maintains an activity gradient in the rock matrix, ensuring a continuous supply of 226Ra to fracture surfaces. As a result of the relatively long half-life of 226Ra (1601 years), significant activity can accumulate on fracture surfaces. The proximity of this sorbed 226Ra to the active ground water flow system allows its decay progeny 222Rn to enter directly into the water. Laboratory analyses of primary porosity and diffusion coefficients of the rock matrix, radon emanation, and ion exchange at fracture surfaces are consistent with the requirements of a diffusion/ion-exchange model. A dipole-brine injection/withdrawal experiment conducted between bedrock boreholes in the high-grade metamorphic and granite rocks at the Hubbard Brook Experimental Forest, Grafton County, New Hampshire, United States (42 degrees 56'N, 71 degrees 43'W) shows a large activity of 226Ra exchanged from fracture surfaces by a magnesium brine. The 226Ra activity removed by the exchange process is 34 times greater than that of 238U activity. These observations are consistent with the diffusion/ion-exchange model. Elutriate isotopic ratios of 223Ra/226Ra and 238U/226Ra are also consistent with the proposed chemically based diffusion/ion-exchange model.

Eolian transport of geogenic hexavalent chromium to ground water.

A conceptual model of eolian transport is proposed to address the widely distributed, high concentrations of hexavalent chromium (Cr(+6)) observed in ground water in the Emirate of Abu Dhabi, United Arab Emirates. Concentrations (30 to more than 1000 microg/L Cr(+6)) extend over thousands of square kilometers of ground water systems. It is hypothesized that the Cr is derived from weathering of chromium-rich pyroxenes and olivines present in ophiolite sequence of the adjacent Oman (Hajar) Mountains. Cr(+3) in the minerals is oxidized to Cr(+6) by reduction of manganese and is subsequently sorbed on iron and manganese oxide coatings of particles. When the surfaces of these particles are abraded in this arid environment, they release fine, micrometer-sized, coated particles that are easily transported over large distances by wind and subsequently deposited on the surface. During ground water recharge events, the readily soluble Cr(+6) is mobilized by rain water and transported by advective flow into the underlying aquifer. Chromium analyses of ground water, rain, dust, and surface (soil) deposits are consistent with this model, as are electron probe analyses of clasts derived from the eroding Oman ophiolite sequence. Ground water recharge flux is proposed to exercise some control over Cr(+6) concentration in the aquifer.