Stabilization/solidification of MSW incineration residues from facilities with different air pollution control systems. Durability of matrices versus carbonation

This paper discusses the stabilisation/solidification process with Portland cement applied to municipal solid waste incineration residues. Two types of residues were considered: fly ash (FA) produced in an electrostatic precipitator, and air pollution control (APC) residues from a semi-dry scrubber process. Cement pastes with different percentages of FA and APC residues were characterised according to their physical properties, the effect of the hydration products and their leaching behaviour. Portland pastes prepared with APC residues showed a rapid setting velocity in comparison with setting time for those pastes substituted with FA residues. Portland cement hydration was retarded in FA pastes. Leaching test results showed that heavy metals (such as Zn, Pb and Cd) and sulphates are immobilised within the paste, whereas chlorides are only partially retained. The carbonation process increases the leachability of S04(2-) and heavy metals such as Zn and Cr.     

Leaching of mercury-containing cement monoliths aged for one year

A directive from the Swedish Government states that waste containing more than 1% of mercury shall be permanently deposited. The stabilization of mercury by conversion to a sparingly soluble compound like the sulphide is crucial to ensure long-term immobilization in a permanent storage. Immobilization by the solidification/stabilization (S/S) method and possible formation of HgS from mercury oxide or elemental mercury by reaction with a sulphur source (S or FeS) is investigated by a modified version of the NEN 7345 Dutch tank-leaching test. The diffusion of mercury during 11 months from 1-year-old mercury containing monoliths of Portland and slag cement is demonstrated. In a geologic repository under conditions representative of deep granitic bedrock (bicarbonate buffered to pH 8.6), a favourable monolith combination is slag cement with addition of the iron sulphide troilite. The apparent diffusion coefficient of mercury is estimated.     

Heavy metal leaching from hydroxide, sulphide and silicate stabilised/solidified wastes

A synthetic, mixed-metal solution has been stabilised by treatment with sodium hydroxide, sodium sulphide, and sodium silicate, respectively. The three stabilised filter cakes have subsequently been solidified using additions of ordinary Portland cement and pulverised fuel ash (PFA) which are typically used in UK solidification operations. Both the stabilised filter cakes and the solidified wastes have been subjected to an equilibrium extraction test, a modified TCLP test, and a series of single-extraction, batch leach tests using an increasingly acidic leachant. Metal release was found to be primarily dependent on the pH of the leachate. Under mildly acidic conditions, the percentages leached from the stabilised and the stabilised/solidified wastes were comparable for most metals. A high-volume fraction of these solidified wastes is occupied by the stabilised filter cake. When they are broken up and tested in single-extraction leach tests, the primary effect of the cementitious additives is to increase the pH of the leachate so that most heavy metals remain insoluble. When tested under acidic leachate conditions, copper, lead, and mercury were found to be particularly well retained within sodium sulphide stabilised wastes. Under similar test conditions, cadmium was leached at very low levels from the sodium silicate stabilised waste.     

Evaluation of a Slag and Portland Cement Mix to Simulate Treatment of Acidic Waste via Solidification/Stabilization in a Deep Soil Mix Application

Site investigations at an oil and gas facility identified a highly acidic waste referred to as residual acid tar that resulted in the transport of dissolved nickel toward the point of compliance at concentrations that exceeded site environmental screening levels. Solidification/stabilization (S/S) via deep soil mixing was selected as the remedial approach and a mixture of ground granulated blast furnace slag cement and Portland cement was subjected to treatability testing to evaluate the reagent mix's ability to achieve treatment objectives. Results from the treatability test showed a cement mix dose of 21 percent was sufficient to raise the pH above the target of 6.0 and reduce dissolved nickel concentrations to below site screening levels in leachate from treated samples of residual acid tar and material impacted by residual acid tar. Cement mix doses of 21 percent or greater were sufficient to achieve target strengths in the unimpacted shallow overburden. However, none of the doses tested were able to achieve target strengths in the residual acid tar or peaty material impacted by the residual acid tar. Results showed soil strengths increased significantly when the pH in leachate from the treated samples approached 12, suggesting the presence of organic acids related to the peaty soils may interfere with the cement set. Recommendations from the study include additional treatability testing to evaluate pre‐treatment with hydrated lime to satisfy acid neutralization requirements prior to dosing with the cement mix. ©2016 Wiley Periodicals, Inc.     

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.     

An ecotoxic risk assessment of residue materials produced by the plasma pyrolysis/vitrification (PP/V) process

Plasma is the fourth state of matter, following the three states of solid, liquid and gas. Experience has amply demonstrated that solids exposed to the oxygen-deficient plasma flame are converted to liquid, and liquid exposed to the same flame is converted to gas. A low amount of vitrified solid residue material usually remains at the end of this process. Plasma pyrolysis/vitrification (PP/V) has been demonstrated as a safe, efficient, cost-effective technology for the treatment of wastes, including hazardous wastes. Besides the low amounts of gaseous byproducts that PP/V produces, the solid vitrified residue presents a low leachability of pollutants. Studies have been performed in many countries in order to assess the leachability of chemical substances. But from the results of identified studies, none has reported results on the ecotoxicological properties of the leachates. The aim of this study was to contribute to the assessment of ecotoxic risk of four different vitrified materials. Vitrified samples of contaminated soils, municipal solid wastes, and incinerator bottom ashes were submitted to the European leaching pre-standard test number prEN 12457-2. The leachates were analyzed for 22 chemical parameters. The biological characterization comprised the assessment of bioluminescence inhibition of Photobacterium phosphoreum bacterium, growth inhibition of Pseudokirchneriella subcapitata algae and the germination inhibition of Lactuca sativa vegetable. The chemical and ecotoxicological results were analyzed according to the French proposal of Criteria on the Evaluation Methods of Waste Toxicity (CEMWT) and a Toxicity Classification System (TCS). The chemical and ecotoxicological results indicated a low leachability of pollutants and a low toxicity level of leachates. All samples studied were as below the TCS class 1 level (no significant toxicity observed) and as non-ecotoxic for CEMWT. Therefore, the environmental ecotoxic risk of the analyzed vitrified samples was determined to be very low.     

Modelling the effects of waste components on cement hydration

Ordinary Portland Cement (OPC) is often used for the solidification/stabilization (S/S) of waste containing heavy metals and salts. These waste components will precipitate in the form of insoluble compounds on to unreacted cement clinker grains preventing further hydration. In this study the long term effects of the presence of contaminants in solidified waste is examined by numerically simulating cement hydration after precipitation of metal salts on the surface of cement grains. A cement hydration model was extended in order to describe pore water composition and the effects of cement grain coating. Calculations were made and the strength development predicted by the model was found to agree qualitatively with experimental results found in literature. The complete model is useful in predicting the strength and leaching resistance of solidified products and developing solidification recipes based on cement.     

Critical evaluation of the use of the hydroxyapatite as a stabilizing agent to reduce the mobility of Zn and Ni in sewage sludge amended soils

The leachability of zinc (Zn) and nickel (Ni) was investigated in various soil types amended with sewage sludge and sewage sludge treated with hydroxyapatite. Sandy, clay and peat soils were investigated. For leachability tests, plastic columns (diameter 9 cm, height 50 cm) were filled with moist samples up to a height of 25 cm. Sewage sludge (1 kg) was mixed with 4.6 kg of clay and sandy soils and with 6.7 kg of peat soil. For sewage sludge mixtures treated with hydroxyapatite, 0.5 kg of the hydroxyapatite was added to 1 kg of the sewage sludge. Neutral (pH 7) and acid precipitation (pH 3.5) were applied. Acid precipitation was prepared from concentrated HNO(3), H(2)SO(4) and fresh doubly distilled water. The amount of precipitation corresponded to the average annual precipitation for the city of Ljubljana, Slovenia. It was divided into eight equal portions and applied sequentially on the top of the columns. The results indicated that the leachabilities of Zn in sewage sludge amended peat and clay soils were low (below 0.3% of total Zn content) and of Ni in sewage sludge amended sandy, clay and peat soil below 1.9% of total Ni content. In sewage sludge amended sandy soil, the leachability of Zn was higher (11% of Zn content). The pH of precipitation had no influence on the leachability of either metal. Treatment of sewage sludge with hydroxyapatite efficiently reduced the leachability of Zn in sewage sludge amended sandy soil (from 11% to 0.2% of total Zn content). In clay and peat sewage sludge amended soils, soil characteristics rather than hydroxyapatite treatment dominate Zn mobility.     

The effect of using a geotextile in a monolithic (evapotranspiration) alternative landfill cover on the resulting water balance

This paper examines the potential effects of a geotextile layer used in a lysimeter pan experiment conducted in a monolithic (evapotranspiration) soil cover trial on its resulting water balance performance. The geotextile was added to the base of the lysimeter to serve as a plant root barrier in order to delineate the root zone depth. Both laboratory data and numerical modelling results indicated that the geotextile creates a capillary barrier under certain conditions and retains more water in the soil above the soil/geotextile interface than occurs without a geotextile. The numerical modelling results also suggested that the water balance of the soil cover could be affected by an increase in plant transpiration taking up this extra water retained above the soil/geotextile interface. This finding has a practical implication on the full-scale monolithic cover design, as the absence of the geotextile in the full-scale cover may affect the associated water balance and hence cover performance. Proper consideration is therefore required to assess the final monolithic cover water balance performance if its design is based on the lysimeter results.     

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.     

Use of co-combustion bottom ash to design an acoustic absorbing material for highway noise barriers

The present study aims to determine and evaluate the applicability of a new product consisting of coal bottom ash mixed with Portland cement in the application of highway noise barriers. In order to effectively recycle the bottom ash, the influence of the grain particle size of bottom ash, the thickness of the panel and the combination of different layers with various particle sizes have been studied, as well as some environmental properties including leachability (EN-12457-4, NEN-7345) and radioactivity tests. Based on the obtained results, the acoustic properties of the final composite material were similar or even better than those found in porous concrete used for the same application. According to this study, the material produced presented no environmental risk.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

电动力学作用下多溴联苯醚在土壤中的迁移特性

以4,4′-二溴联苯醚(BDE-15)为研究对象,探讨了电极电压、初始土壤pH、β-环糊精加入量、NaCl加入量等工艺条件对多溴联苯醚在土壤中迁移效果的影响。实验结果表明:在电极电压为5~15V范围内,随着电极电压的升高,土壤中BDE-15的迁移效果增强;初始土壤为酸性时、加入β-环糊精或NaCl后,土壤中BDE-15的迁移效果均增强。本实验选择的最佳工作条件为:电极电压15V,初始土壤pH3,β-环糊精的加入量3g,NaCl加入量5g。     

Leaching of heavy metals from solidified waste using Portland cement and zeolite as a binder

This study investigated the properties of solidified waste using ordinary Portland cement (OPC) containing synthesized zeolite (SZ) and natural zeolite (NZ) as a binder. Natural and synthesized zeolites were used to partially replace the OPC at rates of 0%, 20%, and 40% by weight of the binder. Plating sludge was used as contaminated waste to replace the binder at rates of 40%, 50% and 60% by weight. A water to binder (w/b) ratio of 0.40 was used for all of the mixtures. The setting time and compressive strength of the solidified waste were investigated, while the leachability of the heavy metals was determined by TCLP. Additionally, XRD, XRF, and SEM were performed to investigate the fracture surface, while the pore size distribution was analyzed with MIP. The results indicated that the setting time of the binders marginally increased as the amount of SZ and NZ increased in the mix. The compressive strengths of the pastes containing 20 and 40wt.% of NZ were higher than those containing SZ. The compressive strengths at 28 days of the SZ solidified waste mixes were 1.2-31.1MPa and those of NZ solidified waste mixes were 26.0-62.4MPa as compared to 72.9MPa of the control mix at the same age. The quality of the solidified waste containing zeolites was better than that with OPC alone in terms of the effectiveness in reducing the leachability. The concentrations of heavy metals in the leachates were within the limits specified by the US EPA. SEM and MIP revealed that the replacement of Portland cement by zeolites increased the total porosity but decreased the average pore size and resulted in the better containment of heavy ions from the solidified waste.     

Caesium sorption by hydrated cement as a function of degradation state: experiments and modelling

To provide reliable K(d) data for Cs required for the performance assessment of cement-based radioactive waste repositories, two complementary approaches were followed. First, Cs sorption was determined on a range of hydrated cement paste (HCP) and mortar samples of CEM I and CEM V for different degradation states and solution compositions, as well as on some single mineral phases. Second, a surface complexation-diffuse layer model previously developed by Pointeau et al. [Pointeau, I., Marmier, N., Fromage, F., Fedoroff, M., Giffaut, E., 2001. Cs and Pb uptake by CSH phases of hydrated cement. Material Research Society Symposium Proceedings, 663, 105-113] for Cs sorption on synthetic CSH phases was simplified to facilitate its application to whole HCP and mortars or concrete, following re-assessment of the model parameters. All measurements were compared with model predictions. The sorption data obtained on the different solid phases as a function of conditions corroborate that CSH minerals are the main sorbing phase for Cs in HCP. The data also clearly show the important influence of pH and the dissolved concentration of Na, K and Ca on K(d). It is further suggested that a decrease of pH is concomitant with a decrease of the Ca/Si ratio and a corresponding increase in surface sites with high affinity for Cs and, thus, K(d). Elevated concentrations of cations able to compete with Cs for these sites lead to a decrease of K(d), on the other hand. The simplified model was applied to the sorption measurements performed within this study as well as to a variety of literature data, mainly K(d) values for a variety of fresh HCP and mortar or concrete samples based on different samples of Ordinary Portland Cement as well as blended cements. The results show that the model can be applied reasonably well to a very large variety of conditions in terms of solid and solution compositions that cover a range of K(d) values from 10(-4) to ca. 3.2m(3)/kg. The large scatter typically observed for Cs sorption, especially on fresh HCP samples prepared from different formulations, can be explained quantitatively by the variable concentrations of Na and K in the respective solutions, which compete with Cs for fixation sites. On the other hand, the comparatively uniform conditions in degraded HCP typically render the prediction of K(d) values less uncertain than in case of fresh HCP.     

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.     

Treatment of organic-contaminated industrial wastes using cement-based stabilization/solidification—I. Microstructural analysis of cement-organic interactions

The major deficiencies in cement-based stabilization/solidification (S/S) processes are their inability to treat inorganic wastes contaminated with organic material or organic wastes. In general, organic compounds are poorly retained in a cement matrix and frequently have a detrimental, poorly understood, effect upon cement hydration and strength development. These interactions need to be understood as fully as possible, however, if S/S processes are to be developed in ways which will assure the long-term integrity of the resultant products.The work presented in this paper investigates some fundamental aspects of the interactions of two organic compounds, 3-chlorophenol and chloronaphthalene, with a cement matrix. Phenolic compounds have previously been shown to have a detrimental effect upon the macrostructural properties of ordinary Portland cement (OPC), for example, the strength, setting rate and leachability (Montgomery et al. 1988). Microstructural studies in this work have shown that 3-chlorophenol inhibits the hydration of tricalcium silicate (C₃S in cement chemists' notation), with up to 90% of the C₃S remaining after 28 days for highly dosed 3-chlorophenol/OPC samples. The formation of ettringite was found to be increased by the presence of 3-chlorophenol and its conversion to monosulphate inhibited. Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analysis of the samples showed that 3-chlorophenol crystallized in the cement matrix to form discrete crystals containing calcium and phenol. In contrast, chloronaphthalene had no observable effect on hydration reactions. In a subsequent paper, detailed studies will be presented showing how these deleterious effects can be minimized by the use of organophilic clays as a pre-solidification adsorbent.     

Leachability of automotive shredder residues burned in a fluidized bed system

This paper presents the results of the study of a combustible fraction of automotive shredder residues (CASRs) and the corresponding ashes generated by combustion on a fluidized bed pilot with the aim to understand the influence of thermal treatment regarding properties for final disposal, such as landfilling. The chemical composition was evaluated and the leachability behaviour of ashes and CASR was investigated using the three more commonly used tests: the European Standard EN 12457, the US TCLP-EPA 1311 and the Dutch availability test EA NEN 7371. Different results were obtained depending on the specific conditions of the methods employed. It was found that both the CASR and the ashes contained large amounts of toxic metals and other undesirable elements, such as Cl and S. For the CASR, in addition to the leachability of organic matter above the limit set for hazardous materials, the release of heavy metals, either under alkaline and acidic conditions was significant, revealing the serious risks associated to the landfilling practices still being undertaken worldwide. Release of organic matter from ashes was insignificant, but solubility of sulphates increased and chlorides exceed the hazardous limits in the case of fly ashes. Toxic metals were found to leach from the ashes only under acidic conditions, except Pb and Cu which also leached from finer ashes at alkaline pH. Cr also leached from ashes at alkaline pH values. Both the Dutch availability and TCLP revealed much higher leaching intensities than the European Standard due to the acidity of leachants. However, it was found that ashes may be more resistant to acidification because they exhibit much higher acid neutralization capacity (ANC) than the untreated CASR. The study undertaken shows that thermal valorisation of the combustible fraction of ASR may avoid the risks associated with their landfilling; however, care has to be taken with the ashes because they also behave as hazardous residues. Although, the mass reduction provided by thermal treatment may make landfilling less expensive, a more profitable reutilization of the ashes should be developed.     

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.     

Physical and mechanical properties of cement-based products containing incineration bottom ash

This paper presents the results of a wider experimental programme conducted in the framework of the NNAPICS ("Neural Network Analysis for Prediction of Interactions in Cement/Waste Systems") project funded by the European Commission and a number of industrial partners under Brite-EuRamIII. Based on the fact that bottom ashes from waste incineration are classified as non-hazardous wastes according to the European Waste Catalogue, the aim of the present work was to investigate the feasibility of addressing the potential use of such residues in cement-based mixtures. This issue was suggested by the analysis of the properties of different bottom ashes coming from Italian municipal and hospital solid waste incinerators, which showed a chemical composition potentially suitable for such applications. Different mixes were prepared by blending bottom ash with ordinary Portland cement in different proportions and at different water dosages. The solidified products were tested for setting time and bulk density, unconfined compressive strength and evaporable water content at different curing times. The results of the experimental campaign were analysed through a statistical procedure (analysis of variance), in order to investigate the effect of mixture composition (waste replacement level and water dosage) on the product properties.