Measurement of dissolved H2, O2, and CO2 in groundwater using passive samplers for gas chromatographic analyses.

A simple in-situ passive dissolved gas groundwater sampler, comprised of a short length of silicone tubing attached to a gastight or other syringe, was adapted and tested for in-situ collection of equilibrium gas samples. Sampler retrieval after several days of immersion in groundwater allowed the direct injection of the sample onto a gas chromatograph (GC), simplifying field collection and sample handling over the commonly used "bubble stripping" method for H2 analyses. A GC was modified by sequencing a thermal conductivity (TC) detector followed by a reductive gas (RG) detector so that linear calibration of H2 over the range 0.2-200,000 ppmv was attained using a 0.5-mL gas sample; inclusion of the TC detector allowed the simultaneous quantification of other fixed gases (O2, CO2, He, and Ne) to which the RG detector was not responsive. Uptake kinetics for H2 and He indicated that the passive sampler reached equilibrium within 12 h of immersion in water. Field testing of these passive samplers revealed unusually large equilibrium gas-phase H2 concentrations in groundwater, ranging from 0.1 to 13.9%, by volume, in 11 monitoring wells surrounding four former radiological wastewater disposal ponds at the Y-12 plant in Oak Ridge, Tennessee.

Permeable environmental leaching capsules (PELCAPs) for in situ evaluation of contaminant immobilization in soil.

We encapsulated radioisotope-spiked soil within a water-permeable polyacrylamide matrix cast in a small cylindrical geometry (approximately to 5 cm3) to measure the persistence of immobilized soil contaminants. As a proof-of-principle, soils contained within these permeable environmental leaching capsules (PELCAPs) were labeled with either 85Sr or 134Cs and were leached in both laboratory tests and continuously in situ with ground and streamwaters at two field sites on the Oak Ridge reservation. Groups of PELCAPs were retrieved, assayed nondestructively for radioisotopes via gamma spectroscopy, and then replaced in ground and surface water repeatedly over a 6-month period. PELCAPs that contained no soil readily and quantitatively leached either 85Sr or 134Cs into laboratory extractants or ground or surface water with effective diffusion coefficients (D(eff)) of (1.14 +/- 0.06) and (4.8 +/- 0.2) x 10(-6) cm2/s, respectively. PELCAPs containing untreated soil readily leached > 90% of 85Sr but < 1% of 134Cs during field leaching at both sites, whereas thermally treated soils quantitatively retained both isotopes under all conditions. Permeable polymer encapsulation methods, such as PELCAPs, offer the potential capability to conveniently test large numbers of soils and soil treatments for contaminant release and uptake under actual field environmental conditions.

Fixation of radionuclides in soil and minerals by heating.

Heating of fine sand-sized common mineral powders (quartz, feldspar, or calcite) or a soil (from the Department of Energy's Hanford site) up to 1000 degrees C, in contact with sorbed radioisotopes (85Sr, 57Co, 134Cs, or U), markedly increased each isotope's immobilization. A sequential extraction procedure was applied after heating the materials to assess the changes in each isotope's functional form among water-soluble, cation-exchangeable, acid-soluble, and residual phases. The overall immobilization effects were consistent with rapid high temperature ionic diffusion from the initially contaminated surfaces into the mineral matrices; subsequent diffusion out of mineral particles at ambient temperature, as measured by the sequential extraction behavior, would be such a slow process that the radionuclides may be considered sequestered from further potential environmental mobilization. In the Hanford soil, the effect was found to follow an Arrhenius-type relationship with treatment temperature up to 1000 degrees C for 57Co, 85Sr, and U, and immobilization was independent of previous thermal treatment of the materials. Although 134Cs exhibited its largest immobilization in the Hanford soil after heating to 1000 degrees C, the large immobilization of 134Cs at all temperature and even in unheated Hanford soil made it difficult to observe a strong temperature dependence. A general and promising technique for environmental remediation of contaminated soil by high-temperature heating without melting can be extrapolated directly from the empirical leaching information.

Chemical equilibria model of strontium-90 adsorption and transport in soil in response to dynamic alkaline conditions.

Strontium-90 is a major hazardous contaminant of radioactive wastewater and its processing sludges at many Department of Energy (DOE) facilities. In the past, such contaminated wastewater and sludge have been disposed in soil seepage pits, lagoons, or cribs often under highly perturbed alkaline conditions (pH > 12) where 90Sr solubility is low and its adsorption to surrounding soil is high. As natural weathering returns these soils to near-neutral or slightly acidic conditions, the adsorbed and precipitated calcium and magnesium phases, in which 90Sr is carried, change significantly in both nature and amounts. No comprehensive computational method has been formulated previously to quantitatively simulate the dynamics of 90Sr in the soil-groundwater environment under such dynamic and wide-ranging conditions. A computational code, the Hydrologic Utility Model for Demonstrating Integrated Nuclear Geochemical Environmental Responses (HUMDINGER), was composed to describe the changing equilibria of 90Sr in soil based on its causative chemical reactions including soil buffering, pH-dependent cation-exchange capacity, cation selectivity, and the precipitation/dissolution of calcium carbonate, calcium hydroxide, and magnesium hydroxide in response to leaching groundwater characteristics including pH, acid-neutralizing capacity, dissolved cations, and inorganic carbonate species. The code includes a simulation of one-dimensional transport of 90Sr through a soil column as a series of soil mixing cells where the equilibrium soluble output from one cell is applied to the next cell. Unamended soil leaching and highly alkaline soil treatments, including potassium hydroxide, sodium silicate, and sodium aluminate, were simulated and compared with experimental findings using large (10 kg) soil columns that were leached with 90Sr-contaminated groundwater after treatment. HUMDINGER's simulations were in good agreement with dynamic experimental observations of soil exchange capacity, exchangeable cations, total 90Sr, and pH values of layers within the soil columns and of column effluents.