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Our recent steady‐state mass‐balance modeling suggests that most global carbonic‐acid weathering of silicate rocks occurs in the vadose zone of aquifer systems not on the surface by atmospheric CO2. That is, the weathering solute flux is nearly equal to the total global continental riverine carbon flux, signifying little atmospheric weathering by carbonic acid. This finding challenges previous carbon models that utilize silicate weathering as a control of atmospheric CO2 levels. A robust analysis utilizing global estimates of groundwater carbon concentration generated by a geospatial machine learning algorithm was coupled with recharge flux in a geographic information system environment to yield a total global groundwater carbon flux of between 0.87 and 0.96 Pg C/year to the surface environment. On discharging to the surface, the carbon is speciated between 0.01 and 0.11 Pg C/year as CaCO3; 0.35 and 0.38 Pg C/year as CO2 gas; and 0.49 and 0.51 Pg C/year as dissolved HCO3−. This total weathering carbon flux was calculated for direct ocean discharge (0.030 Pg C/year); endorheic basins (0.046 Pg C/year); cold‐wet exorheic basins (0.058 Pg C/year); warm‐dry exorheic basins (0.072 Pg C/year); cold‐dry exorheic basins (0.115 Pg C/year); and warm‐wet exorheic basins (0.448 Pg C/year). [ABSTRACT FROM AUTHOR]

The estimated current global mean nitrogen concentration (geogenic + anthropogenic) in the active continental freshwater aquifer element pool is 1.1 mg/L as N, or between four and five times greater than the assumed geogenic mean. This concentration, combined with groundwater flux, generates a continental mass flux of 17 Tg N/y (teragrams of nitrogen, as N, per year) as a result of direct ocean discharge (0.67 Tg N/y), endorheic basins (1.2 Tg N/y), and cold‐wet (0.82 Tg N/y); cold‐dry (1.4 Tg N/y); warm‐dry (1.6 Tg N/y); and warm‐wet (11 Tg N/y) exorheic basins. These values are derived from a geospatial machine learning algorithm and combined groundwater‐modeled recharge in an ArcGIS environment. This active continental freshwater aquifer mass flux is between 35% and 40% of the continental integrated riverine system discharge, thus a significant component of the Earth's active continental freshwater nitrogen budget. We estimate the active continental freshwater aquifer volume to be between 1.4 and 2.8 million km3 suggesting a legacy of between 1.5 and 3.1 Pg as N (petagrams nitrogen as N) with mean residences of 90–180 years. Plain Language Summary: Globally, the current average nitrogen concentration in groundwater is 1.1 mg/L, or more than 4 times the estimated natural uncontaminated value. This nitrogen contributes between 35% and 40% of the total nitrogen carried in the rivers on Earth. A freshwater aquifer volume of between 1.4 and 2.8 million km3 combined with a concentration of 1.1 mg/L results in a mass legacy of between 1.5 and 3.1 Pg as N with a mean residence time of between 90 and 180 years.. Key Points: The current nitrogen concentration in the active global aquifer element pool is 1.1 mg/L as N or 4 to 5 times the estimated geogenic meanA mass flux of 17 Tg N/y (Tetragrams of nitrogen, as N, per year) and is between 35% and 40% of the total nitrogen riverine fluxThe current global mass legacy is between 1.5 and 3.1 billion tons with a residence time of 90–180 years. [ABSTRACT FROM AUTHOR]

While the physical processes governing groundwater flow are well understood, and the computational resources now exist for solving the governing equations in three dimensions over continental‐scale domains, there remains substantial uncertainty about the subsurface distribution of the properties that control groundwater flow and transport for much of the contiguous United States (CONUS). The transmissivity of the shallow subsurface is a key parameter for the simulation of water table position, shallow groundwater flow, and base‐flow discharge, but is not well‐characterized at large regional to continental scales. We used a process‐based inversion of CONUS‐extent groundwater information to generate national data sets of (a) the transmissivity of the shallow groundwater system, (b) the depth to the water table, (c) groundwater discharge as base‐flow, and (d) long‐term average water content in the unsaturated zone. CONUS‐extent coverage was developed in the form of 75 subdomain models, with the spatial distribution of long‐term average transmissivity for each subdomain model calibrated against water‐levels derived from U.S. Geological Survey (USGS) observation wells, NHDPlusV2 first‐order perennial streams, and National Wetlands Inventory (NWI) freshwater wetlands. Estimated transmissivities were lower in the western CONUS than the eastern CONUS, and across the CONUS both transmissivity and depth to water correlate with recharge, elevation, and topographic slope. These generated data sets provide spatially distributed, long‐term average estimates of subsurface properties and hydrological states that we anticipate will complement other environmental modeling efforts as explanatory variables, boundary conditions, or transport pathways. Plain Language Summary: We developed a simulation of the shallow groundwater system for the contiguous United States (CONUS) and compared it to large data sets of water table measurements in order to generate a map of surficial transmissivity, which is a property that controls the flow of water between its entrance into the groundwater system and its discharge to streams and rivers. Better maps of this property are one ingredient to improved understanding of how the landscape stores and releases water at large spatial scales. Key Points: Calibrated simulations of the shallow groundwater system were used to estimate the CONUS‐extent spatial distribution of transmissivityCorrelations were explored between the estimated transmissivities and recharge, elevation, and topographic slopeSimulated depth to water and groundwater discharge were used to derive unsaturated zone properties and long‐term average base‐flow on the NHDPlusV2 stream network [ABSTRACT FROM AUTHOR]

Numerous studies have documented the linkages between agricultural nitrogen loads and surface water degradation. In contrast, potential water quality improvements due to agricultural best management practices are difficult to detect because of the confounding effect of background nitrate removal rates, as well as the groundwater‐driven delay between land surface action and stream response. To characterize background controls on nitrate removal in two agricultural catchments, we calibrated groundwater travel time distributions with subsurface environmental tracer data to quantify the lag time between historic agricultural inputs and measured baseflow nitrate. We then estimated spatially distributed loading to the water table from nitrate measurements at monitoring wells, using machine learning techniques to extrapolate the loading to unmonitored portions of the catchment to subsequently estimate catchment removal controls. Multiple models agree that in‐stream processes remove as much as 75% of incoming loads for one subcatchment while removing <20% of incoming loads for the other. The use of a spatially variable loading field did not result in meaningfully different optimized parameter estimates or model performance when compared with spatially constant loading derived directly from a county‐scale agricultural nitrogen budget. Although previous studies using individual well measurements have shown that subsurface denitrification due to contact with a reducing argillaceous confining unit plays an important role in nitrate removal, the catchment‐scale contribution of this process is difficult to quantify given the available data. Nonetheless, the study provides a baseline characterization of nitrate transport timescales and removal mechanisms that will support future efforts to detect water quality benefits from ongoing best management practice implementation. [ABSTRACT FROM AUTHOR]

The article discusses the importance of understanding the travel time of groundwater and the movement of contaminants through aquifers. It suggests the use of a new term, "transportivity," to describe the combined influence of porosity and saturated thickness on travel time calculations. The article also explores the relationship between transportivity and the mean residence time of discharging water in groundwater systems. It concludes by drawing an analogy between transmissivity and transportivity, highlighting their fundamental properties in aquifers. [Extracted from the article]

Dual-domain transport is an alternative conceptual and mathematical paradigm to advection-dispersion for describing the movement of dissolved constituents in groundwater. Here we test the use of a dual-domain algorithm combined with advective pathline tracking to help reconcile environmental tracer concentrations measured in springs within the Shenandoah Valley, USA. The approach also allows for the estimation of the three dual-domain parameters: mobile porosity, immobile porosity, and a domain exchange rate constant. Concentrations of CFC-113, SF6, 3H, and 3He were measured at 28 springs emanating from carbonate rocks. The different tracers give three different mean composite piston-flow ages for all the springs that vary from 5 to 18 years. Here we compare four algorithms that interpret the tracer concentrations in terms of groundwater age: piston flow, old-fraction mixing, advective-flow path modeling, and dual-domain modeling. Whereas the second two algorithms made slight improvements over piston flow at reconciling the disparate piston-flow age estimates, the dual-domain algorithm gave a very marked improvement. Optimal values for the three transport parameters were also obtained, although the immobile porosity value was not well constrained. Parameter correlation and sensitivities were calculated to help quantify the uncertainty. Although some correlation exists between the three parameters being estimated, a watershed simulation of a pollutant breakthrough to a local stream illustrates that the estimated transport parameters can still substantially help to constrain and predict the nature and timing of solute transport. The combined use of multiple environmental tracers with this dual-domain approach could be applicable in a wide variety of fractured-rock settings. [ABSTRACT FROM AUTHOR]

A method is presented for using dissolved CFCs or SF6 to estimate the apparent age of stream base flow by indirectly estimating the mean concentration of the tracer in the inflowing groundwater. The mean value is estimated simultaneously with the mean residence times of the gas and water in the stream by sampling the stream for one or both age tracers, along with dissolved nitrogen and argon at a single location over a period of approximately 12-14 h. The data are fitted to an equation representing the temporal in-stream gas exchange as it responds to the diurnal temperature fluctuation. The efficacy of the method is demonstrated by collecting and analyzing samples at six different stream locations across parts of northern Virginia, USA. The studied streams drain watersheds with areas of between 2 and 122 km2 during periods when the diurnal stream temperature ranged between 2 and 5°C. The method has the advantage of estimating the mean groundwater residence time of discharge from the watershed to the stream without the need for the collection of groundwater infiltrating to streambeds or local groundwater sampled from shallow observation wells near the stream. [ABSTRACT FROM AUTHOR]

Sanford, Ward E. and David L. Selnick, 2012. Estimation of Evapotranspiration Across the Conterminous United States Using a Regression with Climate and Land-Cover Data. Journal of the American Water Resources Association (JAWRA) 1-14. DOI: 10.1111/jawr.12010 Abstract: Evapotranspiration (ET) is an important quantity for water resource managers to know because it often represents the largest sink for precipitation ( P) arriving at the land surface. In order to estimate actual ET across the conterminous United States (U.S.) in this study, a water-balance method was combined with a climate and land-cover regression equation. Precipitation and streamflow records were compiled for 838 watersheds for 1971-2000 across the U.S. to obtain long-term estimates of actual ET. A regression equation was developed that related the ratio ET/ P to climate and land-cover variables within those watersheds. Precipitation and temperatures were used from the PRISM climate dataset, and land-cover data were used from the USGS National Land Cover Dataset. Results indicate that ET can be predicted relatively well at a watershed or county scale with readily available climate variables alone, and that land-cover data can also improve those predictions. Using the climate and land-cover data at an 800-m scale and then averaging to the county scale, maps were produced showing estimates of ET and ET/ P for the entire conterminous U.S. Using the regression equation, such maps could also be made for more detailed state coverages, or for other areas of the world where climate and land-cover data are plentiful. [ABSTRACT FROM AUTHOR]

A hybrid finite element, integrated finite difference numerical model is developed for the simulation of double-diffusive and multicomponent flow in two and three dimensions. The model is based on a multidimensional, density-dependent, saturated-unsaturated transport model (SUTRA), which uses one governing equation for fluid flow and another for solute transport. The solute-transport equation is applied sequentially to each simulated species. Density coupling of the flow and solute-transport equations is accounted for and handled using a sequential implicit Picard iterative scheme. High-resolution data from a double-diffusive Hele-Shaw experiment, initially in a density-stable configuration, is used to verify the numerical model. The temporal and spatial evolution of simulated double-diffusive convection is in good agreement with experimental results. Numerical results are very sensitive to discretization and correspond closest to experimental results when element sizes adequately define the spatial resolution of observed fingering. Numerical results also indicate that differences in the molecular diffusivity of sodium chloride and the dye used to visualize experimental sodium chloride concentrations are significant and cause inaccurate mapping of sodium chloride concentrations by the dye, especially at late times. As a result of reduced diffusion, simulated dye fingers are better defined than simulated sodium chloride fingers and exhibit more vertical mass transfer. [ABSTRACT FROM AUTHOR]

Examines the corrections for diffusion in carbon-14 dating of groundwater. Validity of solution for steady-state radionuclide transport through fractured rock; Ratio to the rate of distribution to the rate of decay of carbon-14; Development of an age-correction formula.

Thermodynamic models of aqueous solutions have indicated that the mixing of seawater and calcite-saturated fresh groundwater can produce a water that is undersaturated with respect to calcite. Mixing of such waters in coastal carbonate aquifers could lead to significant amounts of limestone dissolution. The potential for such dissolution in coastal saltwater mixing zones is analyzed by coupling the results from a reaction simulation model (PHREEQE) with a variable density groundwater flow and solute transport model. Idealized cross sections of coastal carbonate aquifers are simulated to estimate the potential for calcite dissolution under a variety of hydrologic and geochemical conditions. Results show that limestone dissolution in mixing zones is strongly dependent on groundwater flux and nearly independent of the dissolution kinetics of calcite. The amount of dissolution varies within a mixing zone, depending on the properties, physical dimensions, and boundary conditions of the aquifer system. Nearly all of the dissolution occurs in the fresher side of the mixing zone, with the maximum dissolution occurring in water that is fresher than that predicted solely by geochemical reaction models. The greatest porosity and permeability development occur at the toe and at the top of the mixing zone. If permeability increases as porosity increases, asymmetry in the dissolution causes the mixing zone to migrate landward over time. Dissolution rates indicated by the model show that this mechanism can produce significant increases in porosity and permeability over time spans on the order of tens of thousands of years. Given the comparatively long span of geologic time, this process may be largely responsible for porosity and permeability development observed in those carbonate rocks through which a freshwater-saltwater mixing zone had at one time migrated. [ABSTRACT FROM AUTHOR]

Eolian processes associated with saline lakes are shown to be important in determining solute concentration in groundwater in arid and semiarid areas. Steady state mass balance analyses of chloride in the groundwater at Double Lakes, a saline lake basin in the southern High Plains of Texas, United States, suggest that approximately 4.5 × 105 kg of chloride is removed from the relatively small (4.7 km2) basin floor each year by deflation. This mass enters the groundwater down the wind gradient from the lake, degrading the water quality. The estimates of mass transport were independently determined by evaluation of solutes in the unsaturated zone and by solute mass balance calculations of groundwater flux. Transport of salts from the lake was confirmed over a short term (2 years) by strategically placed dust collectors. Results consistent with those at Double Lake were obtained from dune surfaces collected upwind and downwind from a sabkha near the city of Abu Dhabi in the United Arab Emirates. The eolian transport process provides an explanation of the degraded groundwater quality associated with the 30-40 saline lake basins on the southern half of the southern High Plains of Texas and New Mexico and in many other arid and semiarid areas. [ABSTRACT FROM AUTHOR]

A correction to the article "Estimation of Evapotranspiration Across the Coterminous United States Using a Regression with Climate and Land-Cover Data," in volume 49, April 2013 issue of the "Journal of the American Water Resources Association," is presented.