Evaluating the impact of drying on leaching from a solidified/stabilized waste using a monolithic diffusion model.

The release rates of constituents of potential concern from solidified/stabilized cementitious waste forms are potentially impacted by drying, which, however, is not well understood. This study aimed to identify the impacts of drying on subsequent leaching from Cast Stone as an example of a solidified cementitious waste form. The release fluxes of constituents from monoliths after aging under 100, 68, 40, and 15 % relative humidity for 16, 32, and 48 weeks, respectively, were derived from mass transfer tank leaching tests following EPA Method 1315. A monolithic diffusion model was calibrated based on the leaching test results to simulate the leaching of major and redox-sensitive constituents from monoliths after drying. The reduction in physical retention of constituents (tortuosity-factor) in the unsaturated zone was identified as the primary impact from drying on subsequent leaching. Fluxes of both major (i.e., OH-, Na, K, Ca, Si, and Al) and redox-sensitive constituents (i.e., Tc, Cr, Fe, and S) from monoliths during leaching were well described by the model. The drying-induced reduction of tortuosity-factor and concomitant changes in porewater pH and redox conditions can significantly change the subsequent release fluxes of pH- and redox- sensitive constituents.

Impact of oxidation and carbonation on the release rates of iodine, selenium, technetium, and nitrogen from a cementitious waste form.

Evaluation of the long-term retention mechanisms and potential release rates for the primary constituents of potential concern (COPCs) (i.e., Tc, I, Se, and nitrate) is necessary to determine if Cast Stone, a radioactive waste form, can meet performance objectives under near-surface disposal scenarios. Herein, a mineral and parameter set accounting for the solubility of I and Se in Cast Stone was developed based on pH-dependent and monolithic diffusion leaching test results, to extend a geochemical speciation model previously developed. The impact of oxidation and carbonation as environmental aging processes on the retention properties of Cast Stone for primary COPCs was systematically estimated. Physically, the effective diffusion coefficients of 4 COPCs in Cast Stone were increased after carbonation and/or oxidation, reflecting an increase in permeability to diffusion. Chemically, i) pH & pe conditions in the original Cast Stone were favorable for the stabilization of Tc, but not for I, Se, and N; ii) oxidation (with/without carbonation) of Cast Stone changed the pe & pH conditions to be detrimental for Tc stabilization; and iii) carbonation (with/without oxidation) of Cast Stone modified the pH & pe conditions to be beneficial for the stabilization of I (in system with Ag added) and Se.

Application and uncertainty of a geochemical speciation model for predicting oxyanion leaching from coal fly ash under different controlling mechanisms.

Three primary mechanisms (adsorption to iron oxides or analogous surfaces, co-precipitation with Ca, and substitution in ettringite) controlling oxyanion retention in coal fly ashes (CFAs) were identified by differentiating the leaching behavior of As, B, Cr, Mo, Se, and V from 30 CFAs. Fidelity evaluation of geochemical speciation modeling focused on six reference CFAs representing a range of CFA compositions, whereby different leaching-controlling mechanisms of oxyanions were systematically considered. For three reference CFAs with low Ca and S content, calibration of adsorption reactions for the diffuse double-layer model for hydrous ferric oxides improved the simultaneous prediction of oxyanion leaching, which reduced uncertainties in Se and V predictions caused by nonideal adsorption surfaces and competitive adsorption effects. For two reference CFAs with intermediate Ca content, the solubility constants for Ca-arsenates from literature and postulated phases of B, Cr, Se, and V were used to describe co-precipitation of oxyanions with Ca-bearing minerals under alkaline conditions. For the reference CFA with high Ca and S content, an ettringite solid solution was used to capture the simultaneous retention of all oxyanions at pH> 9.5. Overall, the simultaneous leaching predictions of oxyanions from a wide range of CFAs were improved by calibration of adsorption reactions and controlling solid phases.

Impact of carbonation on leaching of constituents from a cementitious waste form for treatment of low activity waste at the DOE Hanford site.

Carbonation can be a major aging process during disposal of alkaline cementitious waste forms and can impact constituent leaching by changes in material alkalinity, pore structure, and controlling mineral phases. The effect of carbonation on the leaching of major and trace constituents from Cast Stone, a cementitious waste form developed to treat high salt content low activity waste, was studied through a combination of leaching experiments and reactive transport simulations. Diffusive transport of constituents in the waste form was evaluated using reactive transport modeling of diffusion-controlled leaching test results and a geochemical speciation model derived from pH-dependent leaching. Comparisons between Cast Stone materials aged under nitrogen, air, and 2% carbon dioxide in nitrogen showed that carbonation impacts solubility, physical retention and observed diffusivity of major and trace constituents. Carbonation under 2% CO2 decreased the diffusion-controlled leaching of chromium by two orders of magnitude. Modeling results suggest that carbonation may also decrease solubility of technetium while changes to microstructure by carbonation increases effective diffusivity of constituents in Cast Stone.

The influence of redox conditions on aqueous-solid partitioning of arsenic and selenium in a closed coal ash impoundment.

A closed coal ash impoundment case study characterized the effects of field redox conditions on arsenic and selenium partitioning through monitoring of porewater and subsurface gas in conjunction with geochemical speciation modeling. When disposed coal ash materials and porewater were recovered for testing, oxidation led to lower arsenic and higher selenium concentrations in leaching test extracts compared to porewater measurements. Multiple lines of evidence suggest multiple mechanisms of arsenic retention are plausible and the concurrent presence of several redox processes and conditions (e.g., methanogenesis, sulfate reduction, and Fe(III)-reduction) controlled by spatial gradients and dis-equilibrium. Geochemical speciation modeling indicated that, under reducing field conditions, selenium was immobilized through the formation of insoluble precipitates Se(0) or FeSe while arsenic partitioning was affected by a progression of reactions including changes in arsenic speciation, reduction in adsorption due to dissolution and recrystallization of hydrous ferric oxides, and precipitation of arsenic sulfide minerals.

Demonstration of the use of test results from the Leaching Environmental Assessment Framework (LEAF) to develop screening-level leaching assessments.

Environmental management often benefits from leaching assessment as a predictive tool for estimating constituent leaching from solid and waste materials. The Leaching Environmental Assessment Framework (LEAF) provides both validated tests methods for characterizing materials and a methodology for developing screening assessments based on material characterization results. The use of LEAF data in a screening-level environmental assessment approach is demonstrated through a hypothetical case study of copper/lead smelter soil remediation. The LEAF test methods characterize leaching behavior from a wide range of materials as either constituent liquid-solid partitioning as functions of pH and liquid-to-solid ratio (L/S) or as a rate of constituent mass transport. In this study, leaching characteristics of a contaminated smelter soil and the same soil treated by solidification/stabilization with Portland cement were compared to hypothetical environmental thresholds. Screening assessments were developed for total content, available content, and maximum concentrations over relevant pH domains and L/S ranges. Assessment ratios for barium, beryllium, and fluoride indicated that estimated leaching would be less than thresholds in both materials and these constituents were removed from further analysis. Similarly, chromium (in soil) and zinc (in solidified material) were screened from further analysis. For the remaining constituents, scenario-based assessment could refine estimated leaching concentrations by considering anticipated conditions of leaching scenario.

Methodology for scenario-based assessments and demonstration of treatment effectiveness using the Leaching Environmental Assessment Framework (LEAF).

A methodology for developing scenario-based leaching assessments as part of the Leaching Environmental Assessment Framework (LEAF) is illustrated using a hypothetical management/treatment scenario of contaminated soil from a copper and lead smelter. Scenario assessments refine the process beyond screening-level assessments by considering site- and scenario-specific information about the disposal or utilization environment. LEAF assessments assume (i) granular materials leach at local equilibrium with percolating water, while (ii) monolithic materials (e.g., low permeability solidified/stabilized soils) leach by diffusion-based mass transport toward surrounding contact water. Leaching concentrations, estimated using LEAF leaching test data and estimated or measured scenario information, are compared to threshold values. Demonstration results indicate that leaching from untreated soil is significantly (>10x) greater from solidified/stabilized soil than treated material, except for highly soluble constituents (Cl-, NO3-2) or when constituents have similar equilibrium concentrations in both materials (As, Pb). Comparison between wet and dry environments show that while dry environments lead to lower COPC mass-based rates of leaching, the leaching concentrations may be higher due to lower liquid-to-solid ratios. The presented assessment methodology can be used to evaluate treatment effectiveness when both physical and chemical retention characteristics of the material are altered.

Effect of coal combustion fly ash use in concrete on the mass transport release of constituents of potential concern.

Concerns about the environmental safety of coal combustion fly ash use as a supplemental cementitious material have necessitated comprehensive evaluation of the potential for leaching concrete materials containing fly ash used as a cement replacement. Using concrete formulations representative of US residential and commercial applications, test monoliths were made without fly ash replacement (i.e., controls) and with 20% or 45% of the portland cement fraction replaced by fly ash from four coal combustion sources. In addition, microconcrete materials were created with 45% fly ash replacement based on the commercial concrete formulation but with no coarse aggregate and an increased fine aggregate fraction to maintain aggregate-paste interfacial area. All materials were cured for 3 months prior to mass transport-based leach testing of constituents of potential concern (i.e., Sb, As, B, Ba, Cd, Cr, Mo, Pb, Se, Tl and V) according to EPA Method 1315. The cumulative release results were consistent with previously tested samples of concretes and mortars from international sources. Of the 11 constituents tested, only Sb, Ba, B, Cr and V were measured in quantifiable amounts. Microconcretes without coarse aggregate were determined to be conservative surrogates for concrete in leaching assessment since cumulative release from microconcretes were only slightly greater than the associated concrete materials. Relative to control materials without fly ash, concretes and microconcretes with fly ash replacement of cement had increased 28-d and 63-d cumulative release for a limited number 10 comparison cases: 2 cases for Sb, 7 cases for Ba and 1 case for Cr. The overall results suggest minimal leaching impact from fly ash use as a replacement for up to 45% of the cement fraction in typical US concrete formulations; however, scenario-specific assessment based on this leaching evaluation should be used to determine if potential environmental impacts exist.

pH-dependent leaching of constituents of potential concern from concrete materials containing coal combustion fly ash.

Current concerns about the environmental safety of coal combustion fly ash have motivated this evaluation of the impact of fly ash use as a cement replacement in concrete materials on the leaching of constituents of potential concern. The chemical effects of fly ash on leaching were determined through characterization of liquid-solid partitioning using EPA Method 1313 for four fly ash materials as well as concrete and microconcrete materials containing 0% (control materials), 25% and 45% replacement of portland cement with the fly ash source. All source materials, concrete formulations and replacement levels are representative of US concrete industry practices. Eluate concentrations as a function of pH were compared to a broader range of available testing results for international concretes and mortars for which the leaching characteristics of the component fly ashes were unknown. The chemistry of the hydrated cement fraction was found to dominate the liquid-solid partitioning resulting in reduced leaching concentrations of most trace metals compared to concentrations from fly ash materials alone. Compared to controls, eluate concentrations of Sb, As, B, Cr, Mo, Se, Tl and V from concrete products containing fly ash were essentially the same as the eluate concentrations from control materials produced without fly ash replacement indicating little to no significant impact on aqueous partitioning.

Evaluating the fate of metals in air pollution control residues from coal-fired power plants.

Changes in emissions control at U.S. coal-fired power plants will shift metals content from the flue gas to the air pollution control (APC) residues. To determine the potential fate of metals that are captured through use of enhanced APC practices, the leaching behavior of 73 APC residues was characterized following the approach of the Leaching Environmental Assessment Framework. Materials were tested over pH conditions and liquid-solid ratios expected during management via land disposal or beneficial use. Leachate concentrations for most metals were highly variable over a range of coal rank, facility configurations, and APC residue types. Liquid-solid partitioning (equilibrium) as a function of pH showed significantly different leaching behavior for similar residue types and facility configurations. Within a facility, the leaching behavior of blended residues was shown to follow one of four characteristic patterns. Variability in metals leaching was greater than the variability in totals concentrations by several orders of magnitude, inferring that total content is not predictive of leaching behavior. The complex leaching behavior and lack of correlation to total contents indicates that release evaluation under likely field conditions is a better descriptor of environmental performance than totals content or linear partitioning approaches.

Comparison of the release of constituents from granular materials under batch and column testing.

Column leaching testing can be considered a better basis for assessing field impact data than any other available batch test method and thus provides a fundamental basis from which to estimate constituent release under a variety of field conditions. However, column testing is time-intensive compared to the more simplified batch testing, and may not always be a viable option when making decisions for material reuse. Batch tests are used most frequently as a simple tool for compliance or quality control reasons. Therefore, it is important to compare the release that occurs under batch and column testing, and establish conservative interpretation protocols for extrapolation from batch data when column data are not available. Five different materials (concrete, construction debris, aluminum recycling residue, coal fly ash and bottom ash) were evaluated via batch and column testing, including different column flow regimes (continuously saturated and intermittent unsaturated flow). Constituent release data from batch and column tests were compared. Results showed no significant difference between the column flow regimes when constituent release data from batch and column tests were compared. In most cases batch and column testing agreed when presented in the form of cumulative release. For arsenic in carbonated materials, however, batch testing underestimates the column constituent release for most LS ratios and also on a cumulative basis. For cases when As is a constituent of concern, column testing may be required.