Approximately 300 kg/day of food-grade CO 2 was injected through a perforated pipe placed horizontally 2-2.3 m deep during July 9-August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO 2 . As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1-6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO 2 injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO 2 injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO 2 leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO 2 intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0-5.6), alkalinity (400-1,330 mg/l as HCO 3 ), and electrical conductance (600-1,800 lS/cm) following CO 2 injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90-240 mg/l), Mg (25-70 mg/l), Fe (5-1,200 ppb), and Mn (5-1,400 ppb) following CO 2 injection. These chemical changes could provide early detection of CO 2 leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorptionion exchange resulting from lowered pH values following CO 2 injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO 2 injection. CO 2 injection, however, is responsible for detection of BTEX (e.g. benzene, 0-0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.

Two parallel metallic rods were used as a wave guide to measure the dielectric constant and electrical conductivity of soils having different electrical conductivities but the same water content. Measurements showed that the two parameters were sufficiently independent to permit simultaneous determinations of water content and bulk electrical conductivity.

A multiplexing time domain reflectoinetry (TDR) system for real‐time monitoring of volumetric soil moisture content was developed. The system was tested at a remote field site in the Hubbard Brook Experimental Forest in New Hampshire. The average value of soil moisture content in the top 500 mm of soil was measured every 4 hours for 1 year at 12 locations within a 12‐ by 18‐m plot. The system functioned well except when the air temperature dropped below −15°C, which caused the data logger tape recorder to stop. Calibrations run on undisturbed soil cores did not compare well with published curves developed for mineral soils, probably because of high soil organic matter content. The standard error of estimate of soil moisture content, indicated by the calibrations, was 0.02 cm3/cm3. The standard deviation of repeated moisture content measurements made in the field was 0.003 cm3/cm3. The effect of cable length on the TDR signal was investigated. It was found that long cables tend to attenuate the signal, ultimately making the measurement impractical. However, cable length had little effect on the calibration up to a length of 27 m. The coefficient of variation of the moisture content measurements taken at any given time ranged from 0.12 to 0.21 during the test period. As predicted by a stochastic analysis of soil moisture flow in heterogeneous soil, the spatial variability of the measurements decreased as average soil moisture increased.

Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O 2 and elevated concentrations of Mn 21 , Fe 21 , CH 4 , and Ca 21 over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH 4 and CO 2 gas phases, and sorption of Fe, Mn, and H 1 . Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH 4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO 2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

a b s t r a c tA field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer was conducted near Bozeman, Montana, during the summer of 2008, to investigate the potential groundwater quality impacts in the case of leakage of CO 2 from deep geological storage. As an essential part of the Montana State University Zero Emission Research and Technology (MSU-ZERT) field program, food-grade CO 2 was injected over a 30 day period into a horizontal perforated pipe a few feet below the water table of a shallow aquifer. The impact of elevated CO 2 concentrations on groundwater quality was investigated by analyzing water samples taken before, during, and following CO 2 injection, from observation wells located in the vicinity of the injection pipe, and from two distant monitoring wells. Field measurements and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of naturally occurring major and trace element species.The geochemical data were evaluated using principal component analysis (PCA) to (1) understand potential correlations between aqueous species, and (2) to identify minerals controlling the chemical composition of the groundwater prior to CO 2 injection. These evaluations were used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents, and to simulate these processes using a multicomponent reaction path model. Reasonable agreement between observed and modeled data suggests that (1) calcite dissolution was the primary pH buffer, yielding increased Ca +2 concentrations in the groundwater, (2) increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions, (3) the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions, and (4) the dissolution of reactive Fe minerals (presumed ferrihydrite and fougerite, from thermodynamic analyses) could explain increases in total Fe concentration.