Multiple-scale dynamic leaching of a municipal solid waste incineration ash.

Predicting the impact on the subsurface and groundwater of a pollutant source, such as municipal solid waste (MSW) incineration ash, requires a knowledge of the so-called "source term". The source term describes the manner in which concentrations in dissolved elements in water percolating through waste evolve over time, for a given percolation scenario (infiltration rate, waste source dimensions, etc.). If the source term is known, it can be coupled with a model that simulates the fate and transport of dissolved constituents in the environment of the waste (in particular in groundwater), in order to calculate potential exposures or impacts. The standardized laboratory upward-flow percolation test is generally considered a relevant test for helping to define the source term for granular waste. The LIMULE project (Multiple-Scale Leaching) examined to what extent this test, performed in very specific conditions, could help predict the behaviour of waste at other scales and for other conditions of percolation. Three distinct scales of percolation were tested: a laboratory upward-flow percolation column (30 cm), lysimeter cells (1-2 m) and a large column (5 m) instrumented at different depths. Comparison of concentration data collected from the different experiments suggests that for some non-reactive constituents (Cl, Na, K, etc.), the liquid versus solid ratio (L/S) provides a reasonable means of extrapolating from one scale to another; if concentration data are plotted versus this ratio, the curves coincide quite well. On the other hand, for reactive elements such as chromium and aluminium, which are linked by redox reactions, the L/S ratio does not provide a means of extrapolation, due in particular to kinetic control on reactions. Hence extrapolation with the help of coupled chemistry-transport modelling is proposed.

Pollutants leaching behaviour from solidified wastes: a selection of adapted various models.

Leaching tests are essential in the environmental assessment of stabilized wastes. Research programmes were conducted on their interpretation in order to develop tools for the evaluation of long term release of pollutants contained in solidified wastes. Models for the leaching of porous materials are discussed in this paper according to the specificity of the chemical species (i.e. transport model with total dissolution of species-diffusional model; transport model with progressive dissolution of species due to limitation of solubility-shrinking core model; and the model coupling transport and chemical phenomena). The leaching behaviour of pollutants (i.e. lead) solidified in a cement matrix was studied under different chemical conditions. Results have shown that the release of species whose solubilities depend on the physico-chemical conditions, and especially the pH (e.g. amphoteric metals), is governed by the solubility of the species in the pore water at local conditions and by the pH evolution within the matrix. A coupled dissolution/diffusion model was developed to describe the release of chemically complex species contained in a porous medium in contact with water. Leaching tests of cement matrices and artificial porous matrices containing calcium hydroxide and pollutants were conducted in order to validate the coupled dissolution/diffusion model. A good assessment of the retention of some pollutants contained in cement matrices could then be obtained by the association of two tests: solubilization of the pollutants related to the chemical context (pH) under steady state conditions and monolithic long term dynamic leaching tests in order to characterize the evolution of the chemical context (pH) and consequently the release of pollutants. The objective is to integrate this approach in the standardization process (CEN TC 292- WG 6, in progress).

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.

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.

Leaching assessment of road materials containing primary lead and zinc slags.

Characterisation of the leaching behaviour of waste-containing materials is a crucial step in the environmental assessment for reuse scenarios. In our research we applied the multi-step European methodology ENV 12-920 to the leaching assessment of road materials containing metallurgical slag. A Zn slag from an imperial smelting furnace (ISF) and a Pb slag from a lead blast furnace (LBF) are investigated. The two slags contain up to 11.2 wt% of lead and 3.5 wt% of zinc and were introduced as a partial substitute for sand in two road materials, namely sand-cement and sand-bitumen. At the laboratory scale, a leaching assessment was performed first through batch equilibrium leaching tests. Second, the release rate of the contaminants was evaluated using saturated leaching tests on monolithic material. Third, laboratory tests were conducted on monolithic samples under intermittent wetting conditions. Pilot-scale tests were conducted for field testing of intermittent wetting conditions. The results show that the release of Pb and Zn from the materials in a saturated scenario was controlled by the pH of the leachates. For the intermittent wetting conditions, an additional factor, blocking of the pores by precipitation during the drying phase is proposed. Pilot-scale leaching behaviour only partially matched with the laboratory-scale test results: new mass transfer mechanisms and adapted laboratory leaching tests are discussed.

Modeling of solid/liquid/gas mass transfer for environmental evaluation of cement-based solidified waste.

A physicochemical and transport model has been developed for the long term prediction of environmental leaching behavior of porous materials containing inorganic waste solidified with hydraulic binders and placed in a reuse scenario. The reuse scenario considered in the paper is a storage tank open to the atmosphere including material leaching with water and carbonation through the leachate contact with air. The model includes three levels: (i) the physicochemical pollution source term (chemical equilibria in the pore water and diffusion in the porous system); (ii) chemical equilibria and mass transfer in the tank; and (iii) gas/liquid transfer of carbon dioxide. The model was applied to the case of a material obtained through solidification of Air Pollution Control (APC) residues from Municipal Solid Waste Incinerator (MSWI). The simulation results are in good agreement with two scale experimental data: laboratory and field tests. Experimental data and simulations show the main trends for release of elements contained in the material: (i) the release of alkaline metals and chloride is not significantly influenced by carbonation and (ii) the release of Ca and Pb is governed by chemical equilibria in pore water and diffusion, while their speciation in the leachate is determined by pH and the presence of carbonate ions.