Comparison of percolation to batch and sequential leaching tests: Theory and data

Leaching tests are becoming more relevant in assessing solid waste material, particularly with respect to groundwater risks. In the field, water infiltration is the dominant leaching mechanism, which is simulated in the lab with batch and column tests. In this study, we compared percolation, through analytical solutions of the advection–dispersion equation, to laboratory batch and sequential leaching tests. The analytical solutions are supported with comprehensive data from various field and laboratory leaching of different solutes from waste materials and soils collected in long-term joint research projects funded by the German Federal Ministry for Education and Research and the Federal Environment Agency. The comparison of theory and data is facilitated if concentrations and cumulative release are plotted versus the liquid–solid ratios (LS). Both theory and data indicate that leaching behaviour is independent of duration and physical dimensions of the leaching tests. This holds even if field lysimeters are compared to laboratory columns of different size, different flow velocities as well as different contact times. In general, laboratory batch tests over predict effluent concentrations (for LS < K_d). Leaching of solutes from solid samples of certain materials (e.g. chloride from incineration ashes or sulphate from demolition waste) in column and lysimeter tests compares very well and agrees with the analytical solutions. Overall, reproducibility and agreement with theory of column tests are better than batch tests, presumably because the latter are prone to artefacts (e.g. in liquid–solid separation steps). Theory and data fit surprisingly well, despite the fact that the theory is based on the local equilibrium assumption; non-linear sorption and chemical reactions in the solid waste materials are not considered.     

Evaluation of leaching and extraction procedures for soil and waste

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.     

Leachate from land disposal of coal fly ash

The results of large-scale lysimeter tests in which two pulverized coal fly ashes (PCFA) have been exposed to natural weather conditions for up to seven years are presented and compared with those of laboratory leaching tests. Laboratory column leaching tests on PCFA show good reproducibility, and comparisons between lysimeter and laboratory leaching results are promising for several salt ions and trace elements in the leachate when expressed in terms of the leachate to solids ratio (L/S). A long-term disposal strategy which takes into account the largely insoluble nature of PCFA is suggested.     

Leaching behaviour of hazardous demolition waste

Demolition wastes are generally disposed of in unlined landfills for inert waste. However, demolition wastes are not just inert wastes. Indeed, a small fraction of demolition waste contains components that are hazardous to human health and the environment, e.g., lead-based paint, mercury-contained in fluorescent lamps, treated wood, and asbestos. The objective of this study is to evaluate the release potential of pollutants contained in these hazardous components when they are mixed with inert wastes in unlined landfills. After identification of the different building products which can contain hazardous elements and which can be potentially pollutant in landfill scenario, we performed leaching tests using three different lysimeters: one lysimeter containing only inert wastes and two lysimeters containing inert wastes mixed with hazardous demolition wastes. The leachates from these lysimeters were analysed (heavy metals, chlorides, sulphates fluoride, DOC (Dissolved Organic Carbon), phenol index, and PAH). Finally, we compared concentrations and cumulative releases of elements in leachates with the limits values of European regulation for the acceptance of inert wastes at landfill. Results indicate that limit values are exceeded for some elements. We also performed a percolation column test with only demolition hazardous wastes to evaluate the specific contribution of these wastes in the observed releases.     

Evaluation of heavy metal leaching from spent household batteries disposed in municipal solid waste

Batch leaching tests and simulated landfill lysimeter tests were performed to evaluate the contents of heavy metals leached from spent batteries in the municipal solid waste. The toxicity characteristic leaching procedure was utilized to perform the batch leaching tests of 36 spent batteries. Four lysimeters were prepared with battery contents ranging from 0% to 100% by weight for column tests, and the experiments were performed at ambient temperature. The age of all the batteries used in the study ranged from freshly disposed up to approximately 3 years old. The results from the batch tests showed that the type of battery influenced the heavy metal concentrations in the leached solutions. The lysimeter experiment results illustrated that at lower pH levels more metals are leached than at higher pH levels. The increasing amount of batteries disposed in landfills can contribute to the leaching of more metals, especially Mn and Zn, into the environment. These results indicate that the direct disposal of spent household batteries into a MSW landfill can increase the heavy metal contents in the landfill leachate.     

Effect of contact time on the release of contaminants from granular waste materials during column leaching experiments

When reusing or disposing of contaminated granular waste materials there is a need to evaluate how the contaminants will interact on the pathway soil–groundwater and the effect this interaction will have on the surrounding environment. While column testing can provide a closer approximation to field percolation conditions than batch testing, there is still a need to develop column testing procedures that consider the requirements of practical testing time frames. This study evaluates the effect of different column contact times (2.5, 5, and 16 h) on the release of inorganic constituents from bottom ash and demolition waste, two commonly reused granular materials. Leaching data for representative constituents of concern, such as copper, chromium, sulfate and chloride, as well as pH and electrical conductivity was compared for all different contact times studied.Results for the materials investigated in this study showed that variations in contact time have no significant effect on the release of the selected constituents and leaching parameters at low liquid to solid ratios. However, after a liquid to solid ratio of 1 L/kg, the effect is more noticeable, and higher contact times show lower pH values as well as a reduction in the release of constituents of concern from bottom ash. In the case of demolition waste, the variation of contact time did not have a strong effect on the leaching behavior.     

Leaching of inorganic contaminants from cement-based waste materials as a result of carbonation during intermittent wetting

Characterization of the leaching behavior of wastes is a crucial step in the environmental assessment for reuse or disposal scenarios. The release of inorganic contaminants from waste materials is typically evaluated by tank leaching of continuously water-saturated material. However, materials, in many field or management scenarios, experience cyclic wetting and drying under varied environmental conditions (i.e. variable relative humidity, atmospheric CO2 or CO2 from biologic activities). During periods of storage in an unsaturated environment, many processes may occur that can influence the release potential and release rate of inorganic constituents. The research presented here was carried out to examine how the phenomena of carbonation during drying influence the release of inorganic contaminants from Portland cement-based materials during cyclic wetting and storage. Batch equilibrium leaching tests were used to determine constituent solubility as a function of pH. Dynamic leaching tests on monolithic material were carried out to determine the rate of constituent release as a function of leaching time and intermittent storage conditions. This paper presents the results observed for three typical waste constituents, arsenic, cadmium and lead.     

Evaluation of carbonization as a thermal pretreatment method for landfilling by column leaching tests

To evaluate carbonization as a thermal pretreatment method for landfilling, the releasing characteristics of organic and inorganic constituents from carbonization residue derived from shredded residue of bulky waste was investigated by means of batch and column leaching tests. Shredded residue of bulky waste itself and its incineration ash were tested together to compare pretreatment methods. In batch leaching tests at a liquid/solid ratio of 10, the release of organic carbon from carbonization residue was at a remarkably low level. Besides, carbonization contributed to immobilize heavy metals such as chromium, cadmium, and lead within its residue. In column tests, the discharges of organic constituents were lowest from carbonization residue under aerobic conditions due to microbial activity. The leaching of Cd, Cr, Pb, and Cu from carbonization residue was suppressed under anaerobic conditions; however, this suppression effect tended to be weaker under aerobic conditions. From the results showing that the total releasing amounts of organic and inorganic constituents from carbonization residue are so low as to be comparable to that of incineration ash, carbonization can be considered as one of the thermal pretreatment methods of organic wastes.     

Lysimeter washing of MSW incinerator bottom ash

Stockpiled municipal waste incinerator bottom ash is frequently considered for utilization as a construction material. Two 360 kg lysimeter experiments were conducted to study percolation washing of contaminants from stockpiled MSW bottom ash. One lysimeter was leached with a concentrated sodium hydroxide solution, as a possible pre-treatment for improvement of the bottom ash characteristics prior to utilization, while the other was leached using distilled water. The lysimeter leachate was analysed, and at the end of the 2-year leaching period, the bottom ash from each lysimeter was subjected to several laboratory tests to assess the effect of the treatments. The laboratory tests showed that distilled water leachability of both treated ashes was an order of magnitude lower than that of fresh ash, but long-term contaminant leachability under acidic conditions had not changed. Although alkaline washing clearly resulted in greater contaminant removal than did distilled water washing, the chemical properties of the alkaline-leached bottom ash were not significantly different from those of the water-leached ash.     

Treatment of copper industry waste and production of sintered glass-ceramic.

Copper waste is iron-rich hazardous waste containing heavy metals such as Cu, Zn, Co, Pb. The results of leaching tests show that the concentration of these elements exceeds the Turkish and EPA regulatory limits. Consequently, this waste cannot be disposed of in its present form and therefore requires treatment to stabilize it or make it inert prior to disposal. Vitrification was selected as the technology for the treatment of the toxic waste under investigation. During the vitrification process significant amounts of the toxic organic and inorganic chemical compounds could be destroyed, and at the same time, the metal species are immobilized as they become an integral part of the glass matrix. The copper flotation waste samples used in this research were obtained from the Black Sea Copper Works of Samsun, Turkey. The samples were vitrified after being mixed with other inorganic waste and materials. The copper flotation waste and their glass-ceramic products were characterized by X-ray analysis (XRD), scanning electron microscopy and by the toxicity characteristic leaching procedure test. The products showed very good chemical durability. The glass-ceramics fabricated at 850 degrees C/2 h have a large application potential especially as construction and building materials.     

Investigation on the humification of municipal solid waste incineration residue and its effect on the leaching behavior of dioxins

In this study, we investigated the humification of municipal solid waste incineration residue through identification of extracted humic substances, and examined the leachability of dioxins by batch leaching test. The samples were incineration residues excavated from lysimeters 6-8 years after being filled. The results of investigation of humic substances showed that the top layers from the surface to a depth of 30-70 cm contained more humic substances than the other layers judging from the color of the samples and optical characteristics of the extracts. In particular, humification in the lysimeter filled with a small amount of compost had progressed through all the layers, not only the top one. The tests revealed that the leaching concentrations of dioxins increased with advanced humification and showed relatively good correlation to dissolved organic carbon (DOC) of leachate at each lysimeter. Humification advances from the surface first, and DOC generated from the humification may preferentially carry down the highly chlorinated dioxin compounds such as O8CDD as DOC-dioxin complexes. Comparing the content and leaching concentration according to depth, we observed not only a decrease in dioxin content but also an increase in leaching of the highly chlorinated dioxins at deeper layers in the lysimeters with the compost. This tendency seemed to result from biological activities.     

Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

Effect of drying on leaching testing of treated municipal solid waste incineration APC-residues

Air-pollution-control (APC) residues from waste incinerators are hazardous waste according to European legislation and must be treated prior to landfilling. Batch and column leaching data determine which type of landfill can receive the treated APC-residues. CEN standards are prescribed for the batch and column leaching test; however, these standards do not specify whether or not the residue samples should be dried prior to the leaching testing. Laboratory tests were performed in parallel (dried/non-dried) on treated APC-residue samples and evaluated with respect to Cr, Cd, Cu, Pb and Zn leaching. The effect of drying of the wet APC-residue samples was particularly dramatic regarding the leaching of Cr. Drying resulted in 10-100 times more Cr leaching in both batch and columns test. Drying also affected the leaching of Cd, Cu and Pb. Initial Cd leaching was up to 100 times higher in column tests with dried APC-residue than in tests with wet residues. The effect of drying appeared to be a combination of decreasing the reduction capacity of the sample (Cr), decreasing pH (Cd, Cu) and in column tests also a wash-out of salts (probably affecting Cd and Pb). If the leaching tests are intended to mimic landfill conditions, the results of this paper suggest that the tests should be done on wet, non-dried residue samples, although this may be less practical than testing dried samples.     

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.     

On equilibration of pore water in column leaching tests

Column leaching tests are closer to natural conditions than batch shaking tests and in the last years have become more popular for assessing the release potential of pollutants from a variety of solids such as contaminated soils, waste, recycling and construction materials. Uncertainties still exist regarding equilibration of the percolating water with the solids, that might potentially lead to underestimation of contaminant concentrations in the effluent. The intention of this paper is to show that equilibration of pore water in a finite bath is fundamentally different from release of a certain fraction of the pollutant from a sample and that equilibrium is reached much faster at low liquid-to-solid ratios typical for column experiments (<0.25) than in batch tests with much higher liquid-to-solid ratios (e.g. 2–10). Two mass transfer mechanisms are elucidated: First-order type release (film diffusion) and intraparticle diffusion. For the latter, mass transfer slows down with time and sooner or later non-equilibrium conditions are observed at the column outlet after percolation has been started. Time scales of equilibrium leaching can be estimated based on a comparison of column length with the length of the mass transfer zone, which is equivalent to a Damköhler number approach. Mass transfer and diffusion coefficients used in this study apply to mass transfer mechanisms limited by diffusion in water, which is typical for release of organic compounds but also for dissolution of soluble minerals such as calcite, gypsum or similar. As a conclusion based on these theoretical considerations column tests (a) equilibrate much faster than batch leaching tests and (b) the equilibrium concentrations are maintained in the column effluent even for slow intraparticle diffusion limited desorption for extended periods of time (>days). Since for equilibration the specific surface area is crucial, the harmonic mean of the grain size is relevant (small grain sizes result in high concentrations even after short pre-equilibration of a column). The absolute time scales calculated with linear sorption and aqueous diffusion aim at organic compounds and are not valid for sparingly soluble mineral phases (e.g. metal oxides and silicates). However, the general findings on how different liquid-to-solid ratios and specific surface area influence equilibration time scales also apply to other mass transfer mechanisms.     

SERIAL BATCH TESTS PERFORMED ON MUNICIPAL SOLID WASTE INCINERATION BOTTOM ASH AND ELECTRIC ARC FURNACE SLAG,IN COMBINATION WITH COMPUTER MODELLING

To predict long-term behaviour of wastes, knowledge is needed about the mechanisms controlling the leaching. The serial batch leaching test, developed in this study, is a version of an ordinary column test that allows sampling at different places in the column. In this study the results from the experiment are compared with computer simulations made with the coupled geochemical and transport program CHEM- FRONTS. The experiments showed that some elements, for example potassium, are easily leached, while the leaching of others, for example iron, is slower. The leaching of some elements is solubility controlled whereas others are controlled by dissolution kinetics. The comparison between the experiments and the computer simulations shows good agreement for most elements. A flow through system has been simulated for the steel slag based on the results from the experiments and the computer simulation thereof. The latter simulation gives an idea of the long-term leaching behaviour of the steel slag. The conclusion of the work is that a combination of serial batch leaching test and computer simulation with a geochemical transport program can give good information about the long-term leaching of waste materials.     

Comparison of batch leaching tests and influence of pH on the release of metals from construction and demolition wastes

Construction and demolition wastes are suitable for use in road construction. However, leaching characterization of recycled materials is required to determine their pollutant potential and the consequence of their application in different scenarios. The motivation of this paper is derived from the increasing use of different leaching test methods. In Europe, the confusion resulting from the wide variety of tests used to evaluate environmental properties of construction materials implies that an evaluation of the current practices and the attempt to consolidate the approaches are required.Two equilibrium-based leaching tests (the Dutch test and the European standard) were conducted to assess the environmental impact of four recycled aggregates. Three natural limestone aggregates were used as controls. Both tests measure the potential release of hazardous elements under extreme conditions using different leaching parameters (L/S ratio, pH value and contact time). The results proved that pH is the most relevant factor on the assessment of the differences between leaching methods due to its strong control on the pollutant release.To classify the materials according to their environmental effects, the concentration limit values of the metals imposed by Council Decision 2003/33/EC were used as a reference. The comparison allowed the classification of the recycled aggregates as inert wastes, with the exception of the MR-2 aggregate, which was classified as non-hazardous material.     

Occurrence of organic pollutants in recovered soil fines from construction and demolition waste

The objective of this study was to characterize recovered soil fines from construction and demolition (C&D) waste recycling facilities for trace organic pollutants. Over a period of 18 months, five sampling trips were made to 14 C&D waste recycling facilities in Florida. Screened soil fines were collected from older stockpiles and newly generated piles at the sites. The samples were analyzed for the total concentration (mg/kg) of a series of volatile organic compound (VOCs) and semi-volatile organic compounds (semi-VOCs). The synthetic precipitation leaching procedure (SPLP) test was also performed to evaluate the leachability of the trace organic chemicals. During the total analysis only a few volatile organic compounds were commonly found in the samples (trichlorofluoromethane, toluene, 4-isopropyltoluene, trimethylbenzene, xylenes, and methylene chloride). A total of nine VOCs were detected in the leaching test. Toluene showed the highest leachability among the compounds (61.3-92.0%), while trichlorofluoromethane, the most commonly detected compound from both the total and leaching tests, resulted in the lowest leachability (1.4-39.9%). For the semi-VOC analysis, three base-neutral semi-VOC compounds (bis(2-ethylhexyl)phthalate, butyl benzyl phthalate, and di-n-butyl phthalate) and several PAHs (acenaphthene, pyrene, fluoranthene, and phenanthrene) were commonly detected in C&D fines samples. These compounds also leached during the SPLP leaching test (0.1-25%). No acid extractable compounds, pesticides, or PCBs were detected. The results of this study were further investigated to assess risk from land applied recovered soil fines by comparing total and leaching concentrations of recovered soil fines samples to risk-based standards. The results of this indicate that the organic chemicals in recovered soil fines from C&D debris recycling facilities were not of a major concern in terms of human risk and leaching risk to groundwater under reuse and contact scenarios.     

Screening tests for hazard classification of complex waste materials – Selection of methods

In this study we describe the development of an alternative methodology for hazard characterization of waste materials. Such an alternative methodology for hazard assessment of complex waste materials is urgently needed, because the lack of a validated instrument leads to arbitrary hazard classification of such complex waste materials. False classification can lead to human and environmental health risks and also has important financial consequences for the waste owner. The Hazardous Waste Directive (HWD) describes the methodology for hazard classification of waste materials. For mirror entries the HWD classification is based upon the hazardous properties (H1–15) of the waste which can be assessed from the hazardous properties of individual identified waste compounds or – if not all compounds are identified – from test results of hazard assessment tests performed on the waste material itself. For the latter the HWD recommends toxicity tests that were initially designed for risk assessment of chemicals in consumer products (pharmaceuticals, cosmetics, biocides, food, etc.). These tests (often using mammals) are not designed nor suitable for the hazard characterization of waste materials. With the present study we want to contribute to the development of an alternative and transparent test strategy for hazard assessment of complex wastes that is in line with the HWD principles for waste classification. It is necessary to cope with this important shortcoming in hazardous waste classification and to demonstrate that alternative methods are available that can be used for hazard assessment of waste materials. Next, by describing the pros and cons of the available methods, and by identifying the needs for additional or further development of test methods, we hope to stimulate research efforts and development in this direction. In this paper we describe promising techniques and argument on the test selection for the pilot study that we have performed on different types of waste materials. Test results are presented in a second paper.As the application of many of the proposed test methods is new in the field of waste management, the principles of the tests are described. The selected tests tackle important hazardous properties but refinement of the test battery is needed to fulfil the a priori conditions.     

Incorporation of gypsum waste in ceramic block production: Proposal for a minimal battery of tests to evaluate technical and environmental viability of this recycling process

Civil engineering-related construction and demolition debris is an important source of waste disposed of in municipal solid waste landfills. After clay materials, gypsum waste is the second largest contributor to the residential construction waste stream. As demand for sustainable building practices grows, interest in recovering gypsum waste from construction and demolition debris is increasing, but there is a lack of standardized tests to evaluate the technical and environmental viability of this solid waste recycling process. By recycling gypsum waste, natural deposits of gypsum might be conserved and high amounts of the waste by-product could be reused in the civil construction industry. In this context, this paper investigates a physical property (i.e., resistance to axial compression), the chemical composition and the ecotoxicological potential of ceramic blocks constructed with different proportions of clay, cement and gypsum waste, and assesses the feasibility of using a minimal battery of tests to evaluate the viability of this recycling process. Consideration of the results for the resistance to axial compression tests together with production costs revealed that the best formulation was 35% of plastic clay, 35% of non-plastic clay, 10% of Portland cement and 20% of gypsum waste, which showed a mean resistance of 4.64 MPa. Energy dispersive X-ray spectrometry showed calcium and sulfur to be the main elements, while quartz, gypsum, ettringite and nacrite were the main crystalline compounds found in this formulation. Ecotoxicity tests showed that leachate from this formulation is weakly toxic toward daphnids and bacteria (EC_20% = 69.0 and 75.0, respectively), while for algae and fish the leachate samples were not toxic at the EC_50% level. Overall, these results show that the addition of 20% of gypsum waste to the ceramic blocks could provide a viable substitute for clay in the ceramics industry and the tests applied in this study proved to be a useful tool for the technical and environmental evaluation of this recycling process, bacterial and daphnid tests being more sensitive than algae and fish tests.