Humans have exerted large-scale changes on the terrestrial biosphere, primarily through agriculture; however, the impacts of such changes on the hydrologic cycle are poorly understood. The purpose of this study was to test the hypothesis that the conversion of natural rangeland ecosystems to agricultural ecosystems impacts the subsurface portion of the hydrologic cycle by changing groundwater recharge and flushing salts to underlying aquifers. The hypothesis was examined through point and areal studies investigating the effects of land use/land cover (LU/LC) changes on groundwater recharge and solute transport in the Amargosa Desert (AD) in Nevada and in the High Plains (HP) in Texas, US. Studies use the fact that matric (pore-water-pressure) potential and environmental-tracer profiles in thick unsaturated zones archive past changes in recharging fluxes. Results show that recharge is related to LU/LC as follows: discharge through evapotranspiration (i.e., no recharge; upward fluxes o0.1 mm yr À1 ) in natural rangeland ecosystems (low matric potentials; high chloride and nitrate concentrations); moderate-to-high recharge in irrigated agricultural ecosystems (high matric potentials; lowto-moderate chloride and nitrate concentrations) (AD recharge: $ 130-640 mm yr À1 ); and moderate recharge in nonirrigated (dryland) agricultural ecosystems (high matric potentials; low chloride and nitrate concentrations, and increasing groundwater levels) (HP recharge: $ 9-32 mm yr À1 ). Replacement of rangeland with agriculture changed flow directions from upward (discharge) to downward (recharge). Recent replacement of rangeland with irrigated ecosystems was documented through downward displacement of chloride and nitrate fronts. Thick unsaturated zones contain a reservoir of salts that are readily mobilized under increased recharge related to LU/LC changes, potentially degrading groundwater quality. Sustainable land use requires quantitative knowledge of the linkages between ecosystem change, recharge, and groundwater quality.

A large reservoir of bioavailable nitrogen (up to approximately 10(4) kilograms of nitrogen per hectare, as nitrate) has been previously overlooked in studies of global nitrogen distribution. The reservoir has been accumulating in subsoil zones of arid regions throughout the Holocene. Consideration of the subsoil reservoir raises estimates of vadose-zone nitrogen inventories by 14 to 71% for warm deserts and arid shrublands worldwide and by 3 to 16% globally. Subsoil nitrate accumulation indicates long-term leaching from desert soils, impelling further evaluation of nutrient dynamics in xeric ecosystems. Evidence that subsoil accumulations are readily mobilized raises concern about groundwater contamination after land-use or climate change.

ABSTRACT:In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with fieldscale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site.Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO 2 (aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.

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A substantial reservoir (up to 1 kg ha(-1)) of natural perchlorate is present in diverse unsaturated zones of the arid and semi-arid southwestern United States. The perchlorate co-occurs with meteoric chloride that has accumulated in these soils throughout the Holocene [0 to 10-15 ka (thousand years ago)] and possibly longer periods. Previously, natural perchlorate widely believed to be limited to the Atacama Desert, now appears widespread in steppe-to-desert ecoregions. The perchlorate reservoir becomes sufficiently large to affect groundwater when recharge from irrigation or climate change flushes accumulated salts from the unsaturated zone. This new source may help explain increasing reports of perchlorate in dry region agricultural products and should be considered when evaluating overall source contributions.

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