Cement-based stabilization/solidification of oil refinery sludge: Leaching behavior of alkanes and PAHs

Stabilization/solidification is a process widely applied for the immobilization of inorganic constituents of hazardous wastes, especially for metals. Cement is usually one of the most common binders for that purpose. However, limited results have been presented on immobilization of hydrocarbons in cement-based stabilized/solidified petroleum solid waste. In this study, real oil refinery sludge samples were stabilized and solidified with various additions of I42.5 and II42.5 cement (Portland and blended cement, respectively) and subject to leaching. The target analytes were total petroleum hydrocarbons, alkanes and 16 polycyclic aromatic hydrocarbons of the EPA priority pollutant list. The experiments showed that the waste was confined in the cement matrix by macroencapsulation. The rapture of the cement structure led to the increase of leachability for most of the hydrocarbons. Leaching of n-alkanes from II42.5 cement-solidified samples was lower than that from I42.5 solidified samples. Leaching of alkanes in the range of n-C(10) to n-C(27) was lower than that of long chain alkanes (>n-C(27)), regardless the amount of cement addition. Generally, increasing the cement content in the solidified waste samples, increased individual alkane leachability. This indicated that cement addition resulted in destabilization of the waste. Addition of I42.5 cement favored immobilization of anthracene, benzo[a]anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene, benzo[a]pyrene and dibenzo[a,h]anthracene. However, addition of II42.5 favored 5 out of 16, i.e., naphthalene, anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene and dibenzo[a,h]anthracene.     

Stabilization/solidification of lead-contaminated soil using cement and rice husk ash

This paper presents the findings of a study on solidification/stabilization (S/S) of lead-contaminated soil using ordinary Portland cement (OPC) and rice husk ash (RHA). The effects of varying lead concentrations (in the form of nitrates) in soil samples on the physical properties of their stabilized forms, namely unconfined compressive strength (UCS), setting times of early mixtures and changes in crystalline phases as well as chemical properties such as leachability of lead, pH and alkalinity of leachates are studied. Results have indicated that usage of OPC with RHA as an overall binder system for S/S of lead-contaminated soils is more favorable in reducing the leachability of lead from the treated samples than a binder system with standalone OPC. On the other hand, partial replacement of OPC with RHA in the binder system has reduced the UCS of solidified samples.     

Stabilization/solidification (S/S) of mercury-containing wastes using reactivated carbon and Portland cement

Stabilization/solidification (S/S) of mercury-containing solid wastes using activated carbon and cement was investigated in this study. The activated carbon used in the study was a powder reactivated carbon (PAC). The effect of sulfur-treatment of the PAC was also studied. It was found that PAC was effective in stabilizing Hg in the waste surrogate. Pretreatment of the PAC by soaking it in CS(2) significantly improved the mercury adsorption capacity of the PAC. The adsorption equilibrium was reached within 24h. The optimum pH for the reaction was within the range of 5.0-5.5. After mercury stabilization by adsorption on the reactivated carbon, the Hg waste surrogate was mixed with Portland cement for solidification. Surrogates with up to 1000 mg/kg Hg were stabilized and solidified well enough to pass the TCLP test. The adsorption of mercury by reactivated carbon was in accordance with the Freundlich isotherm. Cement solidification of reactivated carbon-stabilized surrogates, significantly reduced the often-reported interference by chloride ions, by forming a barrier outside of the carbon particles. The S/S process using reactivated carbon and cement is an effective and economical technology for treating and disposing mercury-containing solid wastes.     

Solidification/stabilization of arsenic containing solid wastes using portland cement, fly ash and polymeric materials

Stabilization/solidification (S/S) is used as a pre-landfill waste treatment technology that aims to make hazardous industrial wastes safe for disposal. Cement-based solidification/stabilization technology is widely used because it offer assurance of chemical stabilization of many contaminants and produce a stable form of waste. The leaching behavior of arsenic from a solidified/stabilized waste was studied to obtain information about their potential environmental risk. Activated alumina (AA) contaminated with arsenic was used as a waste, which was stabilized/solidified (S/S) using ordinary portland cement (C), fly ash (FA), calcium hydroxide (CH) and various polymeric materials such as polystyrene and polymethyl methacrylate (PMMA). Toxicity characteristics leaching procedure (TCLP) and semi-dynamic leach tests were conducted to evaluate the leaching behavior of arsenic. Formations of calcite along with precipitate formation of calcium arsenite were found to be responsible for low leaching of arsenic from the stabilized/solidified samples. Effective diffusivity of arsenic ion from the matrix and leachablity index was also estimated. Minimum leaching of the contaminant was observed in matrix having AA+C+FA+CH due to the formation of calcite.     

Solidification of radioactively contaminated sludge from industrial water basins by cementing with sorption additives

The possibility of solidification of sludge from industrial water basins by incorporation into Portland cement and slag alkaline binder with sorption additives (Cambrian clay) was examined. The solidified products with respect to their mechanical strength and radionuclide leachability meet the requirements of safe storage both in standard and in the simplest repositories.     

Small hazardous waste generators in developing countries: use of stabilization/solidification process as an economic tool for metal wastewater treatment and appropriate sludge disposal

The aim of this study was to propose a profitable destination for an industrial sludge that can cover the wastewater treatment costs of small waste generators. Optimized stabilization/solidification technology was used to treat hazardous waste from an electroplating industry that is currently released untreated to the environment. The stabilized/solidified (S/S) waste product was used as a raw material to build concrete blocks, to be sold as pavement blocks or used in roadbeds and/or parking lots. The quality of the blocks containing a mixture of cement, lime, clay and waste was evaluated by means of leaching and solubility tests according to the current Brazilian waste regulations. Results showed very low metal leachability and solubility of the block constituents, indicating a low environmental impact. Concerning economic benefits from the S/S process and reuse of the resultant product, the cost of untreated heavy metal-containing sludge disposal to landfill is usually on the order of US$ 150-200 per tonne of waste, while 1tonne of concrete roadbed blocks (with 25% of S/S waste constitution) has a value of around US$ 100. The results of this work showed that the cement, clay and lime-based process of stabilization/solidification of hazardous waste sludge is sufficiently effective and economically viable to stimulate the treatment of wastewater from small industrial waste generators.     

Solidification/stabilization of electric arc furnace dust using coal fly ash. Analysis of the stabilization process

In this paper, the stabilization of electric arc furnace (EAF) dust containing hazardous metals such as Pb, Cd, Cr or Zn is described. The treatment involves a waste solidification/stabilization (S/S) process, using coal fly ash as the fundamental raw material and main binder. The article also contains a brief review of the most important recent publications related to the use of fly ash as S/S agents.The efficacy of the process has been evaluated mainly through leaching tests on the solidified products and compliance with some imposed leachate limits. The concentration of metals leaching from the S/S products was strongly leachate pH dependent; thus, the final pH of the leachate is the most important variable in reaching the limits and, therefore, in meeting the stabilization goals.In this study, the dependence relationship between the leachate pH and the concentrations of metals in the leachate are analyzed; in some cases, this allows us to estimate the speciation of contaminants in the S/S solids and to understand the mechanism responsible for reduced leachability of heavy metals from solidified wastes.     

含砷废渣水泥固化/稳定化技术研究进展

含砷废渣作为一种持久性污染物被广泛关注,固化/稳定化技术是治理含砷废渣的一种行之有效的途径。对硅酸盐水泥基胶凝材料固砷效果以及其固化机理等方面的研究进行了综述,水泥水化过程中产生的大量Ca(OH)_2与可溶性砷酸盐反应生成较为稳定的砷酸钙盐,降低砷的浸出浓度,从而实现砷的有效固化,但其存在污染物包容量小、耐久性差等缺点。本课题组提出了利用地聚物水泥(地聚物材料)固化含砷废渣,通过在地聚物材料水化聚合过程中,以同晶取代的方式实现AsO43-与SiO_4~(4-)、AlO_4~(5-)之间的化学键合,并辅以地聚物材料的高强、耐久性好的优良特性,利用地聚物材料固化含砷废渣实现砷的大容量、持久性地安全稳定固封。     

Stabilization/solidification of hazardous and radioactive wastes with alkali-activated cements

This paper reviews progresses on the use of alkali-activated cements for stabilization/solidification of hazardous and radioactive wastes. Alkali-activated cements consist of an alkaline activator and cementing components, such as blast furnace slag, coal fly ash, phosphorus slag, steel slag, metakaolin, etc., or a combination of two or more of them. Properly designed alkali-activated cements can exhibit both higher early and later strengths than conventional portland cement. The main hydration product of alkali-activated cements is calcium silicate hydrate (CSH) with low Ca/Si ratios or aluminosilicate gel at room temperature; CSH, tobmorite, xonotlite and/or zeolites under hydrothermal condition, no metastable crystalline compounds such as Ca(OH)(2) and calcium sulphoaluminates exist. Alkali-activated cements also exhibit excellent resistance to corrosive environments. The leachability of contaminants from alkali-activated cement stabilized hazardous and radioactive wastes is lower than that from hardened portland cement stabilized wastes. From all these aspects, it is concluded that alkali-activated cements are better matrix for solidification/stabilization of hazardous and radioactive wastes than Portland cement.     

Steel foundry electric arc furnace dust management: stabilization by using lime and Portland cement

The purpose of this study was to determine an appropriate treatment for steel foundry electric arc furnace dust (EAFD) prior to permanent disposal. Lime and Portland cement (PC)-based stabilization was applied to treat the EAFD that contains lead and zinc above the landfilling limits, and is listed by USEPA as hazardous waste designation K061 and by EU as 10 02 07. Three types of paste samples were prepared with EAFD content varying between 0 and 90%. The first type contained the EAFD and Portland cement, the second contained the EAFD, Portland cement, and lime, and the third contained the EAFD and lime. All the samples were subjected to toxicity characteristics leaching procedure (TCLP) after an air-curing period of 28 days. pH changes were monitored and acid neutralization capacity of the samples were examined. Treatment effectiveness was evaluated in terms of reducing the heavy metal leachability to the levels below the USEPA landfilling criteria. An optimum composition for the EAFD stabilization was formulated as 30% EAFD +35% lime +35% Portland cement to achieve the landfilling criteria. The pH interval, where the solubility of the heavy metals in the EAFD was minimized, was found to be between 8.2 and 9.4.     

Performance study of cementitious systems containing zeolite and silica fume: effects of four metal nitrates on the setting time,strength and leaching characteristics

The aim of this study is to investigate the effect of four metal nitrate contaminants, namely chromium, manganese, lead and zinc on the mechanical and leaching characteristics of cement-based materials. For this purpose, three different matrices made of: (i) Portland cement, (ii) Portland cement and silica fume, and (iii) Portland cement and natural zeolite were studied. The effects of metals on the stabilised/solidified (S/S) product characteristics were monitored by measuring: (i) setting time, (ii) compressive strength, (iii) acid neutralisation capacity (ANC), and (iv) solubility of the metal contaminants as a function of pH.The results of both mechanical and leaching tests showed the importance of the contaminant/matrix couple considered. Setting time was accelerated in presence of chromium, while in presence of manganese, lead and zinc it was delayed. However, for the last two contaminants, a 10% replacement of cement by silica fume and zeolite, markedly accelerated the setting time compared to the cement-only matrix. Although the early strength development was adversely affected in presence of all four contaminants, the long-term strength was less affected compared to the control materials. Although the ANC of the materials was not markedly affected by the presence of contaminants, the nature of the matrix did modify the ANC behaviour of the solidified materials. The increased strength and reduced ANC observed in the presence of silica fume are both due to pozzolanic reaction. The type of matrix used for solidification did not affect the solubility of the four metal contaminants. Overall, the results showed that the use of blended cements must be carried out with care and the performance assessment of waste-containing cement-based materials must take into consideration both the mechanical and leaching characteristics of the systems.     

Screening tests for assessing treatability of inorganic industrial wastes by stabilisation/solidification with cement

Stabilisation/solidification with cementitious or pozzolanic binders (S/S) is an option for reducing leachability of contaminants from residual, predominantly inorganic, industrial wastes and contaminated soils before disposal or reuse. Treatment by S/S is complicated by the fact that the presence of impurities, such as the contaminants and bulk matrix components present in industrial wastes, can have deleterious effects on cements. Therefore, careful laboratory development and testing of S/S formulations are required prior to full-scale application, to avoid technology failures, including problems with handling and contaminant retention. An understanding of cement chemistry and contaminant immobilisation mechanisms has been used to propose a series of test methods and performance thresholds for use in efficient evaluation of the treatability of industrial wastes by S/S, and optimising S/S formulations: measurement of stabilised/solidified product workability, bleeding and setting time (for flowable mixtures) or Proctor compaction (for compactable mixtures), together with unconfined compressive strength, leachability in a batch extraction with distilled water, and hydraulic conductivity.     

Leaching of metals from soil contaminated by mining activities

Stabilization/solidification (s/s) is one of the most effective methods of dealing with heavy metal contaminated sites. The ability of lime and cement stabilization to immobilize Pb, Cu and Fe contained in a contaminated soil originating from an old mining and smelting area located along the Mediterranean Sea shore in northern Cyprus was investigated. The stabilization was evaluated by applying leaching tests. A series of tests were conducted to optimize the additive soil ratio for the best immobilization process. Additive/soil=1/15 (m/m) ratio was found to be the optimum for both lime and cement. Application of the US EPA toxicity characteristic leaching procedure (TCLP) on the soil samples treated with lime at additive/soil=1/15 (m/m) mixing ratios showed that Cu and Fe solubility was reduced at 94 and 90%, respectively. The results of cement treatment using the same ratio, reduced the solubility 48 and 71% for Cu and Fe, respectively. The Pb solubility was found to be below the regulatory limit of 5mg/l so no additive treatment was needed. The optimum additive/soil amount (1/15) was selected for more detailed column studies, that were carried out in the acidic pH range. According to the results of column leaching tests, it was found that, the degree of heavy metal leaching is highly dependent on pH.     

Binders for radioactive waste forms made from pretreated calcined sodium bearing waste

Radioactive waste generated during the reprocessing of fuel rods by the U.S. Department of Energy (DOE) is stored in underground tanks at Hanford, Savannah River and INEEL. The liquid fraction commonly referred to as sodium bearing waste (SBW), is a highly alkaline solution containing large amounts of sodium hydroxide, sodium nitrate and sodium nitrite. It has been shown that SBW can be mixed with a reducing agent and metakaolin and then calcined at 500°–700°C to form a calcine containing sodium aluminosilicate phases such as zeolite A, hydroxysodalite and/or cancrinite. Although calcination of the pretreated SBW produces a reasonable waste form in its own right, existing regulations require that granular calcines must be solidified before they can be shipped off site. It is possible to solidify the calcine in a number of ways. The calcine can be mixed with additional metakaolin and NaOH solution followed by mild curing (90°–200°C). The solid that forms (aka hydroceramic) has both strength and suitably low leachability. The current study examines the feasibility of using a more conventional Portland cement binder to solidify the calcine. Although strength was adequate, the leachabilities of the Portland cement solidified samples were higher than those of companion samples made with metakaolin. The zeolitic phases in the calcine acted like pozzolans and reacted with the Ca(OH)₂ in the Portland cement binder forming additional calcium silicate hydrate (C—S—H). Typically C—S—H is unable to host large amounts of sodium ions in its structure, thus a majority of the sodium present in the zeolites became concentrated in the pore solution present in the Portland cement binder and readily entered the leachant during PCT testing. In this instance metakaolin mixed with NaOH proved to be a superior binder for solidification purposes.     

Immobilization of Co(Ⅱ) Ions in Cement Pastes and Their Effects on the Hydration Characteristics

The immobilization of Co(Ⅱ) in various cement matrices was investigated by using the solidification/stabilization(S/S) technique.The different cement pastes used in this study were ordinary Portland cement in absence and presence of water reducing-and water repelling-admixtures as well as blended cement with kaolin.Two ratios of Co(Ⅱ) were used(0.5% and 1.0% by weight of the solid binder).The hydration characteristics of the used cement pastes were tested via the determination of the combined water content,phase composition and compressive strength at different time intervals up to 180 d.The degree of immobilization of the added heavy metal ions was evaluated by determining the leached ion concentration after time intervals extended up to 180 d.The leachability experiments were carried out by using two modes:the static and the semi-dynamic leaching processes.It was noticed that the concentration of the leached Co2+ ions in the static mode of leachability was lower than the solubility of its hydroxide in all the investigated cement pastes.     

Oil palm ash as partial replacement of cement for solidification/stabilization of nickel hydroxide sludge

In this study, solidification/stabilization (S/S) of nickel hydroxide sludge using ordinary Portland cement (OPC) and oil palm ash (OPA) was carried out. The effects of increased substitution of OPA wt% in the S/S mix designs on the treated samples' physical and chemical characteristics were investigated. The physical characteristics studied were unconfined compressive strength (UCS) and changes in crystalline phases while chemical characteristics studied were leachability of nickel and leachate pH. Results indicated the optimum mix design for S/S of nickel hydroxide sludge using both OPC and OPA at B/S(d)=1 in terms of cost-effectiveness and treatment efficiency was 15 wt% OPA, 35 wt% OPC and 50 wt% sludge. The sufficient UCS and low leached nickel concentrations shown for this mix design indicate the viability of using OPA as substitute of OPC as it can significantly reduce cost normally incurred by usage of high amounts of OPC.     

Release of Zn, Ni, Cu, SO4(2-) and CrO4(2-) as a function of pH from cement-based stabilized/solidified refinery oily sludge and ash from incineration of oily sludge

A framework for the evaluation of leaching behavior of inorganic constituents from stabilized/solidified refinery oily sludge and ash produced from incineration of oily sludge with cement was employed. Metal and anion release as a function of pH was investigated. The leaching test consisted of multiple parallel extractions at pH range from 2 to 12. Remarkably good immobilization >98% was observed for metals of solidified ash at pH>6 and >93% of solidified oily sludge at pH>7. Sulfate leaching was high at pH range 2-12. The leaching behavior of metals and anions was simulated by VMINTEQ. The calculations showed that leaching behavior of Zn, Ni and Cu was controlled by chemical equilibrium and surface complexation onto ferrihydrite, at the pH range 2-12. The dominant solid phases that controlled metal leachability were metal hydroxides. The dominant mechanism that described sulfate leaching was found to be chemical equilibrium. Sulfate and also chromate leachability was controlled by Ettringite and Cr(VI)Ettringite as the major minerals affecting their release.     

Solidification and stabilization of asbestos waste from an automobile brake manufacturing facility using cement

Currently, the generated brake lining waste dust, which contains asbestos as its major component, is disposed of into a secure landfill without any additional treatment. As an alternative to this, solidification/stabilization (S/S) disposal of the dust was investigated using Portland cement alone and Portland cement mixed with activated carbon (AC), as the binders. Toxicity Characteristics Leaching Procedure (TCLP) results on the solidified matrix showed that cement was able to immobilize the heavy metals, Ba, Zn, Cr, Pb, Cu and Fe, to within the limits set by the US EPA for TCLP. Addition of AC to the cement reduced the leaching of heavy metals by an additional 4-24% compared to cement alone. The pH of the TCLP leachate extracted from virgin cement, and from dust treated with cement with or without AC was found to increase to 10.9-12.5 as opposed to an initial value of 4.93 for the TCLP extract for the untreated dust. Results of ANS 16.1 (modified) leach protocol revealed that Ba in cement-treated samples showed the highest leach rate, followed by Zn, Pb, Cr, Cu and Fe. The leach rate of heavy metals decreased with progress in time. Cement mixed with AC exhibited similar leach characteristics, however, the leach rate was lower. The linear relationship between the cumulative fraction leached (CFL) and the square root of leaching time in all cement-based samples indicate that a diffusional process is the controlling transport mechanism for the leaching of the heavy metals. The obtained Leachability Indices (L(i)) of 7.6-9.1 and 8.3-9.5 for cement and cement with AC, respectively, were low but exceeded the guidance value of 6, which clearly indicates that all the heavy metals studied are retained well within solid matrices. Cement-based S/S hardening times increased from 30 to 96 h as the dust content increased from 40 to 70 wt.%. The resulting solid matrices exhibited a compressive strength ranging from 1 to 12 MPa, which was well above the specified limit of 414 kPa for such matrices. An economic analysis indicates that the disposal costs for the dust in the only available secure landfill would increase by 40.3% if one were to go for the cement S/S option. Addition of AC to the cement would escalate this by an additional 43.8%. Although the S/S of brake lining dust using cement effectively immobilized the heavy metals of concern, cost considerations may hinder the commercial adaptation of this technique for waste disposal unless new regulatory demands are implemented.     

A SEM and X-ray study for investigation of solidified/stabilized arsenic-iron hydroxide sludge

Despite the fact that the solidification/stabilization of arsenic containing wastes with Portland cement and lime has an extensively documented history of use, the physical and chemical phenomena as a result of the interaction between arsenic and cement components have not been fully characterized. The study investigates the behavior of synthesized arsenic-iron hydroxide sludge, the by-product of arsenic removal by coagulation with ferric chloride, in solidified/stabilized matrices as well as its binding mechanisms by exploring the cementitious matrices in the micro-scale by scanning electron microscopy equipped with energy dispersive X-ray spectrometer (SEM-EDS). It was revealed that arsenic can be chemically fixed into cementitious environment of the solidified/stabilized matrices by three important immobilization mechanisms; sorption onto C-S-H surface, replacing SO4(2-) of ettringite, and reaction with cement components to form calcium-arsenic compounds, the solubility limiting phases.     

Kinetics of transformation of 1,1,1-trichloroethane by Fe(II) in cement slurries

This study examines the applicability of the iron-based degradative solidification/stabilization (DS/S-Fe(II)) process to 1,1,1-trichloroethane (1,1,1-TCA), which is one of common chlorinated aliphatic hydrocarbons (CAHs) of concern at contaminated sites. DS/S-Fe(II) combines contaminant degradation by Fe(II) and immobilization by the hydration reactions of Portland cement. The transformation of 1,1,1-TCA by Fe(II) in 10% Portland cement slurries was studied using a batch slurry reactor system. The effects of Fe(II) dose, pH, and initial concentration of 1,1,1-TCA on the kinetics of 1,1,1-TCA degradation were evaluated. Degradation of 1,1,1-TCA in cement slurries including Fe(II) was very rapid and could be described by a pseudo-first-order rate law. The half-lives for 1,1,1-TCA were measured between 0.4 and 5h when Fe(II) dose ranged from 4.9 to 39.2mM. The pseudo-first-order rate constant increased with pH to a maximum near pH 12.5. A saturation rate equation was able to predict degradation kinetics over a wide range of target organic concentrations and at higher Fe(II) doses. The major transformation product of 1,1,1-TCA in mixtures of Fe(II) and cement was 1,1-dichloroethane (1,1-DCA), which indicates that degradation occurred by a hydrogenolysis pathway. A small amount of ethane was observed. The conversion of 1,1,1-TCA to ethane was better described by a parallel reaction model than by a consecutive reaction model.