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.     

An alternative method for the treatment of waste produced at a dye and a metal-plating industry using natural and/or waste materials.

The aim of this study was to develop cost-effective, appropriate solidification technologies for treating hazardous industrial wastes that are currently disposed of in ways that may threaten the quality of local groundwater. One major objective was to use materials other than cement, and preferably materials that are themselves wastes, as the solidification additives, namely using wastes to treat wastes or locally available natural material. This research examines the cement-based and lime-based stabilization/solidification (S/S) techniques applied for waste generated at a metal-plating industry and a dye industry. For the lime-based S/S process the following binder mixtures were used: cement kiln dust/ lime, bentonite/lime and gypsum/lime. For the cement-based S/S process three binder mixtures were used: cement kiln dust/cement, bentonite/cement and gypsum/cement. The leachability of the wastes was evaluated using the toxicity characteristic leaching procedure. The applicability and optimum weight ratio of the binder mixtures were estimated using the unconfined compressive strength test. The optimum ratio mixtures were mixed with waste samples in different ratios and cured for 28 days in order to find the S/S products with the highest strength and lowest leachability at the same time. The results of this work showed that the cement-and lime-based S/S process, using cement kiln dust and bentonite as additives can be effectively used in order to treat industrial waste.     

Leaching toxicity and heavy metal bioavailability of medical waste incineration fly ash

The aim of this study was to provide a comprehensive risk assessment for medical waste incineration fly ash from another aspect through various leaching methods. The differences and connections between leaching concentrations achieved via the toxicity characteristic leaching procedure (TCLP), the physiologically based extraction test (PBET) and the sequential extraction procedure were also described. Heavy metal contents of the used medical waste incineration fly ash were 1.7–31 times higher than that from Japan, indicating poor medical waste management in China. The fly ash leaching concentration in the TCLP test exceeded the regulation value and can be characterized as hazardous waste under current regulations. However, the PBET concentrations were only 1/10 of the TCLP value or even lower, and the calculated ingested contents of all heavy metals were lower than tolerable daily intake, demonstrating that TCLP might have overestimated the environment risk to some degree. The leaching metal content of TCLP ranged from exchangeable to residual forms, and the leaching percentage varied from 7.75 to 92.55 %, while the content for PBET was equal to or lower than the exchangeable form.     

脱硫废水生化处理初探

火电厂烟气脱硫过程产生的废水中污染物主要包括悬浮物、过饱和的亚硫酸盐、硫酸盐以及重金属等，燃煤电厂烟气系统增设脱硝装置后，进入脱硫废水的氨氮、总氮含量急剧增加。通过对国内外多个电厂的脱硫废水处理系统运行情况的调研及分析，采用厌氧氨氧化工艺作为废水脱氮方式是可行的。     

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique.     

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

Immobilization of copper flotation waste using red mud and clinoptilolite

The flash smelting process has been used in the copper industry for a number of years and has replaced most of the reverberatory applications, known as conventional copper smelting processes. Copper smelters produce large amounts of copper slag or copper flotation waste and the dumping of these quantities of copper slag causes economic, environmental and space problems. The aim of this study was to perform a laboratory investigation to assess the feasibility of immobilizing the heavy metals contained in copper flotation waste. For this purpose, samples of copper flotation waste were immobilized with relatively small proportions of red mud and large proportions of clinoptilolite. The results of laboratory leaching demonstrate that addition of red mud and clinoptilolite to the copper flotation waste drastically reduced the heavy metal content in the effluent and the red mud performed better than clinoptilolite. This study also compared the leaching behaviour of metals in copper flotation waste by short-time extraction tests such as the toxicity characteristic leaching procedure (TCLP), deionized water (DI) and field leach test (FLT). The results of leach tests showed that the results of the FLT and DI methods were close and generally lower than those of the TCLP methods.     

The influence of mix parameters and binder choice on the carbonation of cement solidified wastes

This paper explores the kinetics of carbonation of cement-based solidified hazardous waste. This study is part of a wide investigation into the effects of carbonation on solidified waste forms. Two commercially produced heavy metal wastes were solidified with three different types of Portland cement and two mineral admixtures and carbonated under controlled conditions. Measurements of the uptake of carbon dioxide were made for the different mixes and areas showing the degree of carbonation for each cement system were defined. The effects of water/binder ratio, waste and binder type on both total uptake of carbon dioxide and rate of carbonation were investigated and are discussed.     

Solidification/stabilization Process For Steel Foundry Dust Using Cement Based Binders: Influence Of Processing Variables

The influence of processing variables: mixing time, waste/binder ratio and water/solid ratio on the solidification/stabilization process of steel foundry dust has been studied. The characterization of the final product was based on the Toxic Characterization Leaching Procedure (TCLP) followed by the biotoxicity (bioluminescence assay) and concentration of the metals, Cr, Cd, Pb and Zn in the leachates. The final product characteristics depend mainly on the waste/binder ratio, as a function of the metal hydroxide solubilities. The results of this work allow one to establish the optimization of a solidification/stabilization process for steel foundry dust.     

Metal releases from a municipal solid waste incineration air pollution control residue mixed with compost

The influence of 10 wt.% mature compost was tested on the heavy metal leachate emissions from a calcium-rich municipal solid waste incineration air pollution control residue (MSWI APC). Apart from elongated columns (500 and 1250 mm), an otherwise norm compliant European percolation test setup was used. More than 99% of the metals Al, As, Cd, Cr, Cu, Fe and Ni were left in the APC residue after leaching to a liquid-to-solid ratio (L/S) of 10. Apparent short-term effects of elevated leachate DOC concentrations on heavy metal releases were not detected. Zn and Pb leachate concentrations were one order of magnitude lower for L/S 5 and 10 from the pure APC residue column, which suggests a possible long-term effect of compost on the release of these elements. Prolonging the contact time between the pore water and the material resulted in elevated leachate concentrations at L/S 0.1 to L/S 1 by a factor of 2. Only Cr and Pb concentrations were at their maxima in the first leachates at L/S 0.1. Equilibrium speciation modelling with the PHREEQC code suggested portlandite (Ca(OH)2) to control Ca solubility and pH.     

Sustainable alkali-activated binders with municipal solid waste incineration ashes as sand or fly ash replacement

The present study investigates the feasibility of using two types of municipality solid wastes incineration ashes, namely, fly ash and bottom ash in the production of sustainable alkali-activated binder. The ashes are collected from the incineration plant and characterized to determine their particle size distribution, specific gravity, chemical composition, and heavy metals content. The ashes are then used as either fly ash or sand replacement with five replacement ratios 0%, 5%, 10%, 15%, and 20% to produce the binder. The produced binder are characterized in terms of strength, workability, density, water absorption, thermal conductivity and stability, chemical composition, and heavy metals content. The results reflect the ability of producing sustainable alkali-activated binder with small dosage of MSWI ashes as either fly ash or sand replacement without negatively affecting its strength, workability, density, and water absorption. The ashes enhance the thermal insulation capability of the binder.

     

Effects of limestone addition and sintering on heavy metal leaching from hazardous waste incineration slag

Hazardous waste incineration (HWI) in rotary kilns and the disposal of the residual slag on landfills play an important role in German waste treatment. In order to save disposal costs the elution behaviour of HWI-slag should be further optimised. Quality-improved slag may be disposed off on cheaper landfill sites still applying to landfill regulations. In a new process-integrated approach hazardous waste is mixed with limestone, which initiates chemical reactions with heavy metals in the rotary kiln yielding new compounds of different solubility. In this work HWI-slag/limestone mixtures are thermally treated and then examined by elution tests. Experimental data indicate that the heavy metals pertinent to landfill class assignment of a HWI-slag share a solubility minimum at a CaO-content of about 15%. Such improved HWI-slags are allowed to be disposed off on cheaper landfill sites. Furthermore, a new combination of thermodynamic calculation methods is applied to predict heavy metal solubility for different process conditions. Used models hold the opportunity to explain the tendencies of heavy metal leaching and propose plausible chemical reactions. With it, a new tool to examine the impact of temperature treatment and slag composition on heavy metal elution from HWI-slag is presented.     

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.     

Solidification/stabilization of ash from medical waste incineration into geopolymers

In the present work, bottom and fly ash, generated from incinerated medical waste, was used as a raw material for the production of geopolymers. The stabilization (S/S) process studied in this paper has been evaluated by means of the leaching and mechanical properties of the S/S solids obtained. Hospital waste ash, sodium hydroxide, sodium silicate solution and metakaolin were mixed. Geopolymers were cured at 50 °C for 24 h. After a certain aging time of 7 and 28 days, the strength of the geopolymer specimens, the leachability of heavy metals and the mineralogical phase of the produced geopolymers were studied. The effects of the additions of fly ash and calcium compounds were also investigated. The results showed that hospital waste ash can be utilized as source material for the production of geopolymers. The addition of fly ash and calcium compounds considerably improves the strength of the geopolymer specimens (2–8 MPa). Finally, the solidified matrices indicated that geopolymerization process is able to reduce the amount of the heavy metals found in the leachate of the hospital waste ash.     

Towards zero industrial waste: Utilisation of brick dust waste in sustainable construction

Laboratory investigations were carried out to establish the potential utilisation of brick dust (BD) in construction. The dust is a waste material from the cutting of fired clay bricks. Currently, the disposal of the dust is a problem to the brick fabrication company, and hence an environmental pollution concern. The dust was stabilised either used on its own or in combination with Pulverised Fuel Ash (PFA), a by-product material from coal combustion. The traditional stabilisers of lime and/or Portland Cement (PC) were used as controls. The main aim was to use a sustainable stabiliser material, where these stabilisers were partially replaced with Ground Granulated Blastfurnace Slag (GGBS), a by-product material from steel manufacture. Compacted cylinder test specimens were made at typical stabiliser contents and moist cured for up to 56 days prior to testing for compressive and California Bearing Ratio (CBR) strength tests, and to linear expansion during moist curing and subsequent soaking in water. The results obtained showed that partial substitution of the dust with PFA resulted in stronger material compared to using it on its own. The blended stabilisers achieved better performance. These results suggest technological, economic as well as environmental advantages of using the brick dust and similar industrial by-products to achieve sustainable infrastructure development with near zero industrial waste.     

The effects of the mechanical–chemical stabilization process for municipal solid waste incinerator fly ash on the chemical reactions in cement paste

A water extraction process can remove the soluble salts present in municipal solid waste incinerator (MSWI) fly ash, which will help to increase the stability of the synthetic materials produced from the MSWI fly ash. A milling process can be used to stabilize the heavy metals found in the extracted MSWI fly ash (EA) leading to the formation of a non-hazardous material. This milled extracted MSWI fly ash (MEA) was added to an ordinary Portland cement (OPC) paste to induce pozzolanic reactions. The experimental parameters included the milling time (96 h), water to binder ratios (0.38, 0.45, and 0.55), and curing time (1, 3, 7 and 28 days). The analysis procedures included inductively coupled plasma atomic emission spectroscopy (ICP/AES), BET, mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR) imaging. The results of the analyses indicate that the milling process helped to stabilize the heavy metals in the MEA, with an increase in the specific surface area of about 50 times over that of OPC. The addition of the MEA to the OPC paste decreased the amount of Ca(OH)₂ and led to the generation of calcium–silicate–hydrates (C–S–H) which in turned increased the amount of gel pores and middle sized pores in the cement. Furthermore, a comparison shows an increase in the early and later strength over that of OPC paste without the addition of the milled extracted ash. In other words, the milling process could stabilize the heavy metals in the MEA and had an activating effect on the MEA, allowing it to partly substitute OPC in OPC paste.     

Evaluating waste disposal systems

Waste disposal systems conventionally exhibit many problems, such as difficulties in finding final disposal sites for incinerator residues and the issue of how to recycle waste materials. Some new technologies have been developed to solve such problems, including ash melting and gasification melting. Furthermore, to improve the power generation efficiency of waste treatment facilities so that their energy is used more efficiently, combined stoker/gas turbine power generation (super waste power generation) technology has been developed. Through examination of two cases in this study, environmental impacts and costs were determined using lifecycle assessment (LCA) and lifecycle cost (LCC) methods in a model city. In case 1, a stoker furnace was compared to a combined stoker/gas turbine system. In case 2, a stoker furnace plus ash melting system was compared to a gasification melting system. The results demonstrate that the stoker furnace has a lower environmental impact than the combined stoker/gas turbine system in case 1, and that the stoker plus ash melting system costs less than the gasification melting system in case 2, but both systems had strong impacts on the environment.     

Stabilization/solidification of waste ferrous sulphate from titanium dioxide production by fluidized bed combustion product

A treatment procedure to allow the disposal of waste ferrous sulphate was developed. This waste contains sulphuric acid and originates from titanium dioxide production. The process is based on simultaneous neutralization and stabilization/solidification (S/S) of the waste by means of fluidized bed combustion product (FBC-P). The prepared stabilized waste specimens have a solid matrix and their batch leachates display practically neutral pH and also satisfactory conductivity values. The leachate composition is notable in its absence of toxic metals and even iron.     

Toxicity potentials from waste cellular phones,and a waste management policy integrating consumer,corporate, and government responsibilities

Cellular phones have high environmental impact potentials because of their heavy metal content and current consumer attitudes toward purchasing new phones with higher functionality and neglecting to return waste phones into proper take-back systems. This study evaluates human health and ecological toxicity potentials from waste cellular phones; highlights consumer, corporate, and government responsibilities for effective waste management; and identifies key elements needed for an effective waste management strategy. The toxicity potentials are evaluated by using heavy metal content, respective characterization factors, and a pathway and impact model for heavy metals that considers end-of-life disposal in landfills or by incineration. Cancer potentials derive primarily from Pb and As; non-cancer potentials primarily from Cu and Pb; and ecotoxicity potentials primarily from Cu and Hg. These results are not completely in agreement with previous work in which leachability thresholds were the metric used to establish priority, thereby indicating the need for multiple or revised metrics. The triple bottom line of consumer, corporate, and government responsibilities is emphasized in terms of consumer attitudes, design for environment (DfE), and establishment and implementation of waste management systems including recycling streams, respectively. The key strategic elements for effective waste management include environmental taxation and a deposit-refund system to motivate consumer responsibility, which is linked and integrated with corporate and government responsibilities. The results of this study can contribute to DfE and waste management policy for cellular phones.     

Chemical stability of geopolymers containing municipal solid waste incinerator fly ash

Municipal solid waste incinerators every year produce tons of fly ashes which, differently from coal fly ashes, contain large amounts of toxic substances (heavy metals, dioxins, furans). The stabilization/solidification (S/S) technology known as geopolymerization is proposed with the purpose to bond physically and chemically incinerator fly ashes (IFA) in a solid matrix, in order to reduce pollutant mobility. The chemical stability of geopolymers with Si/Al ratio of 1.8–1.9 and Na/Al ratio of 1.0, synthesized by alkali activation of metakaolin and the addition of 20 wt% of two different kinds of IFA, is presented. The concentration of the alkaline solution, water to solid ratio and curing process have been optimized. The room temperature consolidation of IFA containing geopolymers has been tested for leachability in water for 1 day, accordingly to EN 12457 regulation and extended to 7 days to increase the water attack on solid granules. Leachable metals in the test solution, determined by ICP_AES, fall within limit values set by regulation for non-dangerous waste landfill disposal. Geopolymeric matrix evolution with leaching time has been also evaluated in terms of pH and electrical conductivity increase in solution.