International audienceAquifer overexploitation could significantly impact crop production in the United States because 60% of irrigation relies on groundwater. Groundwater depletion in the irrigated High Plains and California Central Valley accounts for ∼50% of groundwater depletion in the United States since 1900. A newly developed High Plains recharge map shows that high recharge in the northern High Plains results in sustainable pumpage, whereas lower recharge in the central and southern High Plains has resulted in focused depletion of 330 km3 of fossil groundwater, mostly recharged during the past 13,000 y. Depletion is highly localized with about a third of depletion occurring in 4% of the High Plains land area. Extrapolation of the current depletion rate suggests that 35% of the southern High Plains will be unable to support irrigation within the next 30 y. Reducing irrigation withdrawals could extend the lifespan of the aquifer but would not result in sustainable management of this fossil groundwater. The Central Valley is a more dynamic, engineered system, with north/south diversions of surface water since the 1950s contributing to ∼7× higher recharge. However, these diversions are regulated because of impacts on endangered species. A newly developed Central Valley Hydrologic Model shows that groundwater depletion since the 1960s, totaling 80 km3, occurs mostly in the south (Tulare Basin) and primarily during droughts. Increasing water storage through artificial recharge of excess surface water in aquifers by up to 3 km3 shows promise for coping with droughts and improving sustainability of groundwater resources in the Central Valley

Reduction/oxidation (redox) conditions in 15 principal aquifer (PA) systems of the United States, and their impact on several water quality issues, were assessed from a large data base collected by the National Water-Quality Assessment Program of the USGS. The logic of these assessments was based on the observed ecological succession of electron acceptors such as dissolved oxygen, nitrate, and sulfate and threshold concentrations of these substrates needed to support active microbial metabolism. Similarly, the utilization of solid-phase electron acceptors such as Mn(IV) and Fe(III) is indicated by the production of dissolved manganese and iron. An internally consistent set of threshold concentration criteria was developed and applied to a large data set of 1692 water samples from the PAs to assess ambient redox conditions. The indicated redox conditions then were related to the occurrence of selected natural (arsenic) and anthropogenic (nitrate and volatile organic compounds) contaminants in ground water. For the natural and anthropogenic contaminants assessed in this study, considering redox conditions as defined by this framework of redox indicator species and threshold concentrations explained many water quality trends observed at a regional scale. An important finding of this study was that samples indicating mixed redox processes provide information on redox heterogeneity that is useful for assessing common water quality issues. Given the interpretive power of the redox framework and given that it is relatively inexpensive and easy to measure the chemical parameters included in the framework, those parameters should be included in routine water quality monitoring programs whenever possible.

[1] In 2000-2002, three rangeland and six irrigated sites were instrumented to assess the storage and transit time of chemicals in thick (15 to 50 m) unsaturated zones (UZ) in the High Plains. These processes are likely to influence relations between land use and groundwater quality, yet they have not been documented systematically in the High Plains. Land use and climate were important controls on the size of subsoil chloride, nitrate, and pesticide compound reservoirs. The reservoirs under irrigated cropland generally were larger than those under rangeland because more chemicals were applied to cropland than to rangeland. In some cases, chloride and nitrate reservoirs under rangeland were larger than those under cropland, presumably because of long-term evaporative concentration near the base of the root zone. Natural salts mobilized by irrigation return flow accounted for as much as 60 and 80% of the nitrate and chloride reservoirs, respectively, under some cropland, as indicated by detailed chemical profiles and . Advective chemical transit times in the UZ under cropland ranged from about 50 to 375 years, longer than any of the instrumented fields had been irrigated, yet agrichemicals were detected at the water table at four of the six sites. The data provide evidence for the existence of slow and fast paths for water movement in the UZ, with larger subsoil chemical reservoirs occurring in areas dominated by slow paths. Implications of these findings with respect to water quality in the aquifer are significant because they indicate that the amount of chemical mass reaching the aquifer could increase with time as chemicals that still reside under irrigated fields reach the water table.

The distribution of microbially mediated terminal electron-accepting processes (TEAPs) was investigated in four hydrologically diverse groundwater systems by considering patterns of electron acceptor (nitrate, sulfate) consumption, intermediate product (hydrogen (H2)) concentrations, and final product (ferrous iron, sulfide, and methane) production. In each hydrologic system a determination of predominant TEAPs could be arrived at, but the level of confidence appropriate for each determination differed. In a portion of the lacustrine aquifer of the San Joaquin Valley, for example, all three indicators (sulfate concentrations decreasing, H2 concentrations in the 1-2 nmol range, and sulfide concentrations increasing along flow paths identified sulfate reduction as the predominant TEAP, leading to a high degree of confidence in the determination. In portions of the Floridan aquifer and a petroleum hydrocarbon-contaminated aquifer, sulfate reduction and methanogenesis are indicated by production of sulfide and methane, and hydrogen concentrations in the 1-4 nmol and 5-14 nmol range, respectively. However, because electron acceptor consumption could not be documented in these systems, less confidence is warranted in the TEAP determination. In the Black Creek aquifer, no pattern of sulfate consumption and sulfide production were observed, but H2 concentrations indicated sulfate reduction as the predominant TEAP. In this case, where just a single line of evidence is available, the least confidence in the TEAP diagnosis is justified. Because this methodology is based on measurable water chemistry parameters and upon the physiology of microbial electron transfer processes, it provides a better description of predominant redox processes in groundwater systems than more traditional Eh-based methods. IntroductionEvaluating oxidation-reduction processes is fundamental to understanding the hydrochemistry of groundwater systems. Redox reactions affect the speciation and mobility of dissolved constituents, especially metals and organic compounds, that are important from a water quality and health perspective. In spite of this importance, methods for evaluating redox conditions in anaerobic groundwater systems remain problematic. The early expectation that platinum electrode measurements [Sato, 1960] or measurement of redox couples could be used quantitatively to define an equilibrium redox potential (Eh) of groundwater has not been realized. This reflects the fact that the basic assumption of thermodynamic equilibrium is not appropriate for most hydrologic systems [Thorstenson, 1984;Lindberg and RunnelIs, 1984].The introduction of a kinetic, as apposed to an equilibrium, framework for describing microbially mediated terminal electron-accepting processes (TEAPs) in groundwater systems Paper number 94WR02525. 0043-1397/95/94 WR-025 25 $ 05.00 native way to describe redox processes in groundwater systems. At the most basic level, microbially mediated redox processes proceed sequentially so that electron donors and acceptors are con...

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