Publications

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Injection of CO{sub 2}-laden flue gas can decrease the potential for silica and calcite scale formation in cooling tower blowdown by lowering solution pH to decrease equilibrium calcite solubility and kinetic rates of silica polymerization. Flue gas injection might best inhibit scale formation in power plant cooling towers that use impaired makeup waters - for example, groundwaters that contain relatively high levels of calcium, alkalinity, and silica. Groundwaters brought to the surface for cooling will degas CO{sub 2} and increase their pH by 1-2 units, possibly precipitating calcite in the process. Recarbonation with flue gas can lower the pHs of these fluids back to roughly their initial pH. Flue gas carbonation probably cannot lower pHs to much below pH 6 because the pHs of impaired waters, once outgassed at the surface, are likely to be relatively alkaline. Silica polymerization to form scale occurs most rapidly at pH {approx} 8.3 at 25 C; polymerization is slower at higher and lower pH. pH 7 fluids containing {approx}220 ppm SiO{sub 2} require > 180 hours equilibration to begin forming scale whereas at pH 8.3 scale formation is complete within 36 hours. Flue gas injection that lowers pHs to {approx} 7 should allow substantially higher concentration factors. Periodic cycling to lower recoveries - hence lower silica concentrations - might be required though. Higher concentration factors enabled by flue gas injection should decrease concentrate volumes and disposal costs by roughly half.

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Decommissioning high level nuclear waste tanks will leave small amounts of residual sludge clinging to the walls and floor of the structures. The permissible amount of material left in the tanks depends on the radionuclide release characteristics of the sludge. At present, no systematic process exists for assessing how much of the remaining inventory will migrate, and which radioisotopes will remain relatively fixed. Working with actual sludges is both dangerous and prohibitively expensive. Consequently, methods were developed for preparing sludge simulants and doping them with nonradioactive surrogates for several radionuclides and RCRA metals of concern in actual sludges. The phase chemistry of these mixes was found to be a reasonable match for the main phases in actual sludges. Preliminary surrogate release characteristics for these sludges were assessed by lowering the ionic strength and pH of the sludges in the manner that would occur if normal groundwater gained access to a decommissioned tank. Most of the Se, Cs and Tc in the sludges will be released into the first pulse of groundwater passing through the sludge. A significant fraction of the other surrogates will be retained indefinitely by the sludges. This prolonged sequestration results from a combination coprecipitated and sorbed into or onto relatively insoluble phases such as apatite, hydrous oxides of Fe, Al, Bi and rare earth oxides and phosphates. The coprecipitated fraction cannot be released until the host phase dissolves or recrystallizes. The sorbed fraction can be released by ion exchange processes as the pore fluid chemistry changes. However, these releases can be predicted based on a knowledge of the fluid composition and the surface chemistry of the solids. In this regard, the behavior of the hydrous iron oxide component of most sludges will probably play a dominant role for many cationic radionuclides while the hydrous aluminum oxides may be more important in governing anion releases.

A number of Hanford tanks have leaked high level radioactive wastes (HLW) into the surrounding unconsolidated sediments. The disequilibrium between atmospheric C0{sub 2} or silica-rich soils and the highly caustic (pH > 13) fluids is a driving force for numerous reactions. Hazardous dissolved components such as {sup 133}Cs, {sup 79}Se, {sup 99}Tc may be adsorbed or sequestered by alteration phases, or released in the vadose zone for further transport by surface water. Additionally, it is likely that precipitation and alteration reactions will change the soil permeability and consequently the fluid flow path in the sediments. In order to ascertain the location and mobility/immobility of the radionuclides from leaked solutions within the vadose zone, the authors are currently studying the chemical reactions between: (1) tank simulant solutions and Hanford soil fill minerals; and (2) tank simulant solutions and C0{sub 2}. The authors are investigating soil-solution reactions at: (1) elevated temperatures (60--200 C) to simulate reactions which occur immediately adjacent a radiogenically heated tank; and (2) ambient temperature (25 C) to simulate reactions which take place further from the tanks. The authors studies show that reactions at elevated temperature result in dissolution of silicate minerals and precipitation of zeolitic phases. At 25 C, silicate dissolution is not significant except where smectite clays are involved. However, at this temperature CO{sub 2} uptake by the solution results in precipitation of Al(OH){sub 3} (bayerite). In these studies, radionuclide analogues (Cs, Se and Re--for Tc) were partially removed from the test solutions both during high-temperature fluid-soil interactions and during room temperature bayerite precipitation. Altered soils would permanently retain a fraction of the Cs but essentially all of the Se and Re would be released once the plume was past and normal groundwater came in contact with the contaminated soil. Bayerite, however, will retain significant amounts of all three radionuclides.

{sup 137}Cs was dispersed globally by cold war activities and, more recently, by the Chernobyl accident. Engineered extraction of {sup 137}Cs from soils and groundwaters is exceedingly difficult. Because the half life of {sup 137}Cs is only 30.2 years, remediation might be more effective (and less costly) if {sup 137}Cs bioavailability could be demonstrably limited for even a few decades by use of a reactive barrier. Essentially permanent isolation must be demonstrated in those few settings where high nuclear level wastes contaminated the environment with {sup 135}Cs (half life 2.3x10{sup 6} years) in addition to {sup 137}Cs. Clays are potentially a low-cost barrier to Cs movement, though their long-term effectiveness remains untested. To identify optimal clays for Cs retention Cs resorption was measured for five common clays: Wyoming Montmorillonite (SWy-1), Georgia Kaolinites (KGa-1 and KGa-2), Fithian Illite (F-Ill), and K-Metabentonite (K-Mbt). Exchange sites were pre-saturated with 0.16 M CsCl for 14 days and readily exchangeable Cs was removed by a series of LiNO{sub 3} and LiCl washes. Washed clay were then placed into dialysis bags and the Cs release to the deionized water outside the bags measured. Release rates from 75 to 139 days for SWy-1, K-Mbt and F- 111 were similar; 0.017 to 0.021% sorbed Cs released per day. Both kaolinites released Cs more rapidly (0.12 to 0.05% of the sorbed Cs per day). In a second set of experiments, clays were doped for 110 days and subjected to an extreme and prolonged rinsing process. All the clays exhibited some capacity for irreversible Cs uptake so most soils have some limited ability to act as a natural barrier to Cs migration. However, the residual loading was greatest on K-Mbt ({approximately} 0.33 wt% Cs). Thus, this clay would be the optimal material for constructing artificial reactive barriers.

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