High levels of arsenic in well water are causing widespread poisoning in Bangladesh. In a typical aquifer in southern Bangladesh, chemical data imply that arsenic mobilization is associated with recent inflow of carbon. High concentrations of radiocarbon-young methane indicate that young carbon has driven recent biogeochemical processes, and irrigation pumping is sufficient to have drawn water to the depth where dissolved arsenic is at a maximum. The results of field injection of molasses, nitrate, and low-arsenic water show that organic carbon or its degradation products may quickly mobilize arsenic, oxidants may lower arsenic concentrations, and sorption of arsenic is limited by saturation of aquifer materials.

[1] We describe the upscaled groundwater flow and solute transport characteristics of two-dimensional hydraulic conductivity fields with three fundamentally different spatial textures and consider the conditions under which physical mobile-immobile domain mass transfer occurs in these fields. All three fields have near-identical lognormal univariate conductivity distributions, as well as near-identical isotropic spatial covariance functions. They differ in the pattern by which high-or low-conductivity regions are connected: the first field has connected high-conductivity structures; the second is multivariate logGaussian and, hence, has connected structures of intermediate value; and the third has connected regions of low conductivity. We find substantially different flow and transport behaviors in the three different fields. Flow and transport in the multivariate log-Gaussian field are consistent with stochastic theory. The field with connected high-conductivity paths has an effective conductivity greater than the geometric mean and large variations in fluid velocity. It produces significant mass transfer behavior (i.e., tailing) when the conductivity variance is large and, depending on the system parameters, this mass transfer is driven by either diffusion or advection. In the field with connected low-conductivity regions, the effective conductivity is below the geometric mean and transport is well characterized by the advection-dispersion model with a dispersivity smaller than that in the multivariate log-Gaussian field. Thus, physical mobile-immobile domain mass transfer may occur in smooth hydraulic conductivity fields with univariate log-Gaussian density functions if the variability in conductivity is sufficient and the high values are more connected than modeled by the multivariate log-Gaussian distribution.

Groundwater transport models that accurately describe spreading of nonreactive solutes in an aquifer can poorly predict concentrations of reactive solutes. The dispersive term in the advection-dispersion equation can overpredict pore-scale mixing, and thereby overpredict homogeneous chemical reaction. We quantified this experimentally by imaging instantaneous colorimetric reactions between solutions of aqueous CuSO4 and EDTA4- within a 30-cm long translucent chamber packed with cryolite sand that closely matched the optical index of refraction of water. A charge-coupled device camera was used to quantify concentrations of blue CuEDTA2- within the chamber as it was produced by mixing of the two reactants at different flow rates. We compared these experimental results with a new analytic solution for instantaneous bimolecular reaction coupled with advection and dispersion of the product and reactants. For all flow rates, the concentrations of CuEDTA2- recorded in the experiments were about 20% less than predicted by the analytic solution, thereby demonstrating that models assuming complete mixing at the pore scale can overpredict reaction during transport.

Ground water of both terrestrial and marine origin flows into coastal surface waters as submarine groundwater discharge, and constitutes an important source of nutrients, contaminants and trace elements to the coastal ocean. Large saline discharges have been observed by direct measurements and inferred from geochemical tracers, but sufficient seawater inflow has not been observed to balance this outflow. Geochemical tracers also suggest a time lag between changes in submarine groundwater discharge rates and the seasonal oscillations of inland recharge that drive groundwater flow towards the coast. Here we use measurements of hydraulic gradients and offshore fluxes taken at Waquoit Bay, Massachusetts, together with a modelling study of a generalized coastal groundwater system to show that a shift in the freshwater-saltwater interface-controlled by seasonal changes in water table elevation-can explain large saline discharges that lag inland recharge cycles. We find that sea water is drawn into aquifers as the freshwater-saltwater interface moves landward during winter, and discharges back into coastal waters as the interface moves seaward in summer. Our results demonstrate the connection between the seasonal hydrologic cycle inland and the saline groundwater system in coastal aquifers, and suggest a potentially important seasonality in the chemical loading of coastal waters.

Abstract. We present a model of solute transport that explains the large-scale behavior of the solute tracer-test plumes at the Macrodispersion Experiment (MADE) site as the result of advection and rate-limited mass transfer between mobile and small-scale immobile domains. This model does not consider the process of dispersion and yet provides an alternative explanation of the evolution of the observed concentration profiles.Compared to the macrodispersion model, the mass transfer model better represents the change in mobile dissolved mass with time, the peak of the concentration profile, and the profile asymmetry. Specifically, unlike the macrodispersion model, the mass transfer model explains the facts that the observed mass of the plume was greater than the injected mass in early snap shots of the plume and less than the injected mass at late times. We suggest that the injected mass advects through the mobile domain and diffuses into and out of the immobile domain. The immobile domain consists of a combination of low-permeability zones on the scale of centimeters to decimeters (the Darcy-scale immobile domain), and intragranular porosity, dead-end pores, and surface sorption (the pore-scale immobile domain). We suggest that the mobile domain was sampled preferentially when water was extracted. Therefore, at early times, relatively clean water in the immobile domain was not sampled and incorrectly assumed to contain high solute concentrations. Similarly, the mass at late times was underestimated because solute trapped in the pore-scale immobile domain was not extracted during sampling and therefore ignored. The combination of advection and slow mass transfer is consistent with the fact that the peak of the plume migrated only -5 m by the termination of the experiment, as well as the different behavior of bromide and tritium tracers. IntroductionTwo natural gradient tests have been conducted at the Columbus Air Force Base in northeastern Mississippi (Figure 1) We contend that a combination of physical nonequilibrium mass transfer (molecular diffusion into and out of low permeability areas) and chemical sorption can explain much of the behavior of the plumes at the Mississippi site. Declining mobile mass and extreme asymmetric spreading are both typical of transport subject to rate-limited mass transfer when the capacity coefficient (ratio of immobile to mobile mass at equilibrium) is large and when the timescale of mass transfer is similar to the timescale of the experiment. Thus, we suggest that the mass transfer model provides an alternative to the macrodispersion model that may better explain the key features of large-scale spreading of the solute plumes. We present our model of plume evolution and analyze the behavior of the solute mass, advection, and spreading. The paper is organized as follows: we introduce the MADE site and the controversy regarding processes that dominate plume evolution (this section); we present the mass transfer model (section 2); we apply the mass transfer model to the MADE plumes ...

Arsenic (As) mobility and transport in the environment are strongly influenced by arsenic's associations with solid phases in soil and sediment. We have tested a sequential extraction procedure intended to differentiate the following pools of solid phase arsenic: loosely and strongly adsorbed As; As coprecipitated with metal oxides or amorphous monosulfides; As coprecipitated with crystalline iron (oxyhydr)oxides; As oxides; As coprecipitated with pyrite; and As sulfides. Additions of As-bearing phases to wetland and riverbed sediment subsamples were quantitatively recovered by the following extractants of the sequential extraction procedure: As adsorbed on goethite, 1 M NaH2PO4; arsenic trioxide (As2O3), 10 M HF; arsenopyrite (FeAsS), 16 N HNO3; amorphous As sulfide, 1 N HCI, 50 mM Ti-citrate-EDTA, and 16 N HNO3; and orpiment (As2S3), hot concentrated HNO3/H2O2. Wet sediment subsamples from both highly contaminated wetland peat and less As-rich sandy riverbed sediment were used to test the extraction procedure for intra-method reproducibility. The proportional distribution of As among extractant pools was consistent for subsamples of the wetland and for subsamples of the riverbed sediments. In addition, intermethod variability between the sequential extraction procedure and a single-step hot concentrated HNO3/H2O2 acid digestion was investigated. The sum of the As recovered in the different extractant pools was not significantly different than results for the acid digestion.

Stabilizing the concentration of atmospheric CO 2 may require storing enormous quantities of captured anthropogenic CO 2 in near-permanent geologic reservoirs. Because of the subsurface temperature profile of terrestrial storage sites, CO 2 stored in these reservoirs is buoyant. As a result, a portion of the injected CO 2 can escape if the reservoir is not appropriately sealed. We show that injecting CO 2 into deep-sea sediments <3,000-m water depth and a few hundred meters of sediment provides permanent geologic storage even with large geomechanical perturbations. At the high pressures and low temperatures common in deep-sea sediments, CO 2 resides in its liquid phase and can be denser than the overlying pore fluid, causing the injected CO 2 to be gravitationally stable. Additionally, CO 2 hydrate formation will impede the flow of CO 2 (l) and serve as a second cap on the system. The evolution of the CO 2 plume is described qualitatively from the injection to the formation of CO 2 hydrates and finally to the dilution of the CO 2 (aq) solution by diffusion. If calcareous sediments are chosen, then the dissolution of carbonate host rock by the CO 2 (aq) solution will slightly increase porosity, which may cause large increases in permeability. Karst formation, however, is unlikely because total dissolution is limited to only a few percent of the rock volume. The total CO 2 storage capacity within the 200-mile economic zone of the U.S. coastline is enormous, capable of storing thousands of years of current U.S. CO 2 emissions.

The origin of dissolved arsenic in the Ganges Delta has puzzled researchers ever since the report of widespread arsenic poisoning two decades ago. Today, microbially mediated oxidation of organic carbon is thought to drive the geochemical transformations that release arsenic from sediments, but the source of the organic carbon that fuels these processes remains controversial. At a typical site in Bangladesh, where groundwater-irrigated rice fields and constructed ponds are the main sources of groundwater recharge, we combine hydrologic and biogeochemical analyses to trace the origin of contaminated groundwater. Incubation experiments indicate that recharge from ponds contains biologically degradable organic carbon, whereas recharge from rice fields contains mainly recalcitrant organic carbon. Chemical and isotopic indicators as well as groundwater simulations suggest that recharge from ponds carries this degradable organic carbon into the shallow aquifer, and that groundwater flow, drawn by irrigation pumping, transports pond water to the depth where dissolved arsenic concentrations are greatest. Results also indicate that arsenic concentrations are low in groundwater originating from rice fields. Furthermore, solute composition in arsenic-contaminated water is consistent with that predicted using geochemical models of pond-water-aquifer-sediment interactions. We therefore suggest that the construction of ponds has influenced aquifer biogeochemistry, and that patterns of arsenic contamination in the shallow aquifer result from variations in the source of water, and the complex three-dimensional patterns of groundwater flow.