Andrew C. Garrabrants

Changes in constituent equilibrium leaching and pore water characteristics of a Portland cement mortar as a result of carbonation

Two equilibrium-based characterization protocols were applied to ground samples of a cement-based material containing metal oxide powders in both noncarbonated and carbonated states. The effects of carbonation were shown through comparison of (i) material buffering capacity, (ii) constituent equilibrium as a function of leachate pH, and (iii) constituent solubility and release as a function of liquid-to-solid (LS) ratio. As expected, the material alkalinity was significantly neutralized during carbonation. In addition, carbonation of the cement material led to the formation of calcium carbonate and a corresponding increase in arsenic release across the entire pH range. The solubility as a function of pH for lead and copper was lower in the alkaline pH range (pH>9) for carbonated samples compared with the parent material. When solubility and release as a function of LS ratio was compared, carbonation was observed to decrease calcium solubility, sodium and potassium release, and ionic strength. In response to carbonate solid formation, chloride and sulfate release as a function of LS ratio was observed to increase. Trends in constituent concentration as a function of LS ratio were extrapolated to estimate pore water composition at a 0.06 mL/g LS ratio. Significant differences were observed upon comparison of estimated pore water composition to leachate concentrations extracted at LS ratio of 5 mL/g. These differences show that practical laboratory extractions cannot be assumed directly representative of pore water concentrations.

THE EFFECTS OF CARBONATION AND DRYING DURING INTERMITTENT LEACHING ON THE RELEASE OF INORGANIC CONSTITUENTS FROM A CEMENT-BASED MATRIX

A Portland cement mortar was submitted to cycles of intermittent wetting (IW) in which tank leaching was interspersed with periods of storage in either an inert or a reactive atmosphere. Relative humidity (RH) (23%, 48% and 98%) was maintained during storage to control the drying process. The effects of IW were qualified by comparing flux and cumulative release of matrix constituents (Ca, OH, Na, K and Cl) to that of continuous water saturation. The carbonation process was associated with the degree of drying occurring due to storage. Cumulative release of most major constituents was suppressed in samples storage under 100% CO2 in comparison to the inert atmosphere (100% N2). Results suggest that accurate long-term performance assessment must account for the potential impact of phenomena associated with IW.

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.

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.

ENVIRONMENTAL ASSESSMENT OF WASTE MATRICES CONTAMINATED WITH ARSENIC

The use of equilibrium-based and mass transfer-based leaching tests has been proposed to provide an integrated assessment of leaching processes from solid wastes. The objectives of the research presented here are to (i) validate this assessment approach for contaminated soils and cement-based matrices, (ii) evaluate the use of diffusion and coupled dissolution-diffusion models for estimating constituent release, and (iii) evaluate model parameterization using results from batch equilibrium leaching tests and physical characterization. The test matrices consisted of (i) a soil contaminated with arsenic from a pesticide production facility, (ii) the same soil subsequently treated by a Portland cement stabilization/solidification (S/S) process, and (iii) a synthetic cement-based matrix spiked with arsenic(III) oxide. Results indicated that a good assessment of contaminant release from contaminated soils and cement-based S/S treated wastes can be obtained by the integrated use of equilibrium-based and mass transfer-based leaching tests in conjunction with the appropriate release model. During the time scale of laboratory testing, the release of arsenic from the contaminated soil matrix was governed by diffusion and the solubility of arsenic in the pore solution while the release of arsenic from the cement-based matrices was mainly controlled by solubilization at the interface between the matrix and the bulk leaching solution. In addition, results indicated that (i) estimation of the activity coefficient within the matrix pore water is necessary for accurate prediction of constituent release rates and (ii) inaccurate representation of the factors controlling release during laboratory testing can result in significant errors in release estimates.

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.

Modeling Moisture Transport from a Portland Cement-Based Material During Storage in Reactive and Inert Atmospheres

Abstract Monolithic samples of a cement mortar were stored in reactive (100% CO2) and inert (100% N2) atmospheres at three levels of relative humidity (23, 48, and 98%). Atmospheric conditions were monitored and the mass of each sample was measured periodically over a period of 88 days. Carbonation depth of split samples was delineated using 1% phenolphthalein solution. In addition, a solid–liquid isotherm was developed by drying smaller monoliths over eight hygroscopic salt solutions in 100% N2 until a constant mass was obtained. Isotherm experimental data was used to parameterize a two-regime moisture transport model based on previously developed drying approaches. This first-order model accounts for both funicular moisture transport and isothermally controlled drying in a fixed porous matrix. Kinetic drying data for the cement mortar was described adequately by simulation of mean relative saturation as a function of drying time and external relative humidity. Comparison of moisture transport in the inert atmosphere to that in the reactive atmosphere indicates that matrix drying had a substantial effect on the carbonation depth; however, drying was seemingly independent of the carbonation process.

The effect of storage in an inert atmosphere on the release of inorganic constituents during intermittent wetting of a cement-based material.

Monolithic waste materials (e.g. Portland cement treated wastes) in many field scenarios do not remain continuously saturated, but experience intermittent wetting interspersed with periods of storage in an unsaturated environment. During storage, the matrix may loss moisture to the environment, promoting precipitation or redistribution of species. In addition, the matrix may react with the surrounding atmosphere through carbonation or oxidation. Upon subsequent leaching, changes in the chemical and physical composition incurred over the storage interval can influence the release of inorganic species. Current assessment approaches, which use continuous leaching data to project release over some assessment interval, do not allow for changes in leachability resulting from intermittent wetting and storage. Thus, this study evaluates the effect of storage intervals in an inert atmosphere on subsequent release of inorganic species from a synthetic Portland cement matrix. Tank leaching in deionized water was interspersed with storage at three relative humidity (RH) levels (nominally 0, 50 and 100% RH) in a 100% nitrogen atmosphere. Leaching data from the three intermittent wetting cases were compared to continuous leaching for the release of structural species (Ca, OH), highly soluble species (Na, K, Cl) and pH-dependent species (As, Cd, Pb). The RH of storage environment, which acted as a boundary condition for the drying process, influenced the precipitation of species within dried pores and relaxation of pH and concentration gradients within water-filled regions. Gradient relaxation resulted from continued mass transport within saturated pores over the storage interval and was most evident when storage was conducted at 98% RH. However, when storage RH promoted drying of the matrix, the effect of gradient relaxation was balanced by precipitation. When release was normalized to total leaching time, relaxation of concentration gradients of highly soluble species resulted in greater cumulative release for the intermittently wetted cases than in the case of continuous leaching. The release of pH-dependent constituents was controlled by relaxation of the pH gradient and species solubility as a function of local pore water pH. Application of a current assessment protocol to estimate intermittent wetting release resulted in either over or underestimation of actual cumulative release, depending on the nature of the constituent of interest. These results imply that long-term constituent release from Portland cement-based waste forms should not be made by simple correction of saturated release assessments because alterations to the matrix leachability induced by the storage environment need to be considered.

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.