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.     

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.     

Microbial influenced degradation of solidified waste binder

Ordinary cement pastes with water/cement (w/c) ratios of 0.2, 0.4 and 0.5 were used to examine the chemical and physical effects of microbial influenced degradation (MID). Samples were exposed to an active culture of Thiobacillus thiooxidans or to sterile media containing sulphuric acid using an intermittent immersion technique. Acid consumption and Ca, Al and Fe releases are presented for an exposure period of 90 days. Exposed samples were also sectioned and analysed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). All cement paste samples were subject to significant degradation in either sterile acid media or the T. thiooxidans lixiviant. Corrosion depths observed from SEM examination of exposed samples were affected by the w/c ratio of the cement. The extent and rate of degradation were not apparent from the calculated rate of hydrogen ion consumption, or the leaching rates of Ca, Al and Fe. It was not possible to distinguish differences in corrosion due to the chemical and microbial influenced degradation from the results obtained to date and further work is focusing on modified procedures to address this.     

Treatment of organic-contaminated industrial wastes using cement-based stabilization/solidification—II. Microstructural analysis of the organophilic clay as a pre-solidification adsorbent

In the preceding paper detailed microstructural studies were presented of some fundamental aspects of the interactions of two organic compounds on a cement matrix. Organophilic clays are now attracting increasing attention as potential presolidification adsorbents to reduce adverse organic-cement interactions in solidification/stabilization (S/S) systems. This paper presents extensive microstructural studies of interactions between an organophilic clay, containing adsorbed organic wastes, and a cement matrix. Such interactions must be as fully understood as possible if the long-term integrity of the organophilic clay/cement mixes, in whatever formulation, is to be assured in S/S applications.A range of mixes was made up with the objective of characterizing the interaction of the organophilic clay with phenolic compounds and cement using microstructural methods. This approach was adopted in order to enable essential comparisons to be made between clay-containing and clay-free S/S mixes, using the same organics in both cases. Microstructural studies of organic-free cement/clay mixes showed that the presence of the clay caused an inhibition of the initial ettringite formation, up to seven days, but once ettringite had begun to form it increased to 140% of that in OPC paste at 28 days. Scanning electron microscopy (SEM) micrographs showed that the whole fracture surface was covered with a mat of needle shaped crystals approximately 1 μm in length. These results indicated that the incorporation of clay into the cement matrix may cause the strength reduction observed in macrostructural studies by altering the cement hydration reaction. Microstructural analysis of the solidified (post-adsorption) 3-chlorophenol showed that its detrimental effects on the cement hydration reaction were minimized, provided that the maximum adsorption capacity of the clay was not exceeded.     

The effect of sodium chloride on the dissolution of calcium silicate hydrate gels

The use of cement based materials will be widespread in the long-term management of radioactive materials in the United Kingdom. One of the applications could be the Nirex reference vault backfill (NRVB) as an engineered barrier within a deep geological repository. NRVB confers alkaline conditions, which would provide a robust chemical barrier through the control of the solubility of some key radionuclides, enhanced sorption and minimised corrosion of steel containers. An understanding of the dissolution of C-S-H gels in cement under the appropriate conditions (e.g., saline groundwaters) is necessary to demonstrate the expected evolution of the chemistry over time and to provide sufficient cement to buffer the porewater conditions for the required time. A programme of experimental work has been undertaken to investigate C-S-H gel dissolution behaviour in sodium chloride solutions and the effect of calcium/silicon ratio (C/S), temperature and cation type on this behaviour. Reductions in calcium concentration and pH values were observed with samples equilibrated at 45 degrees C compared to those prepared at 25 degrees C. The effect of salt cation type on salt-concentration dependence of the dissolution of C-S-H gels was investigated by the addition of lithium or potassium chloride in place of sodium chloride for gels with a C/S of 1.0 and 1.8. With a C/S of 1.0, similar increases in dissolved calcium concentration with increasing ionic strength were recorded for the different salts. However, at a C/S of 1.8, anomalously high calcium concentrations were observed in the presence of lithium.     

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.     

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.     

Efficiency of a blast furnace slag cement for immobilizing simulated borate radioactive liquid waste

The efficiency of a blast furnace slag cement (Spanish CEM III/B) for immobilizing simulated radioactive borate liquid waste [containing H3BO3, NaCl, Na2SO4 and Na(OH)] has been evaluated by means of a leaching attack in de-mineralized water at the temperature of 40 degrees C over 180 days. The leaching was carried out according to the ANSI/ANS-16.1-1986 test. Moreover, changes of the matrix microstructure were characterized through porosity and pore-size distribution analysis carried out by mercury intrusion porosimetry (MIP), X-ray diffraction (XRD) and thermal analysis (TG). The results were compared with those obtained from a calcium aluminate cement matrix, previously published.     

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.     

Immobilization of tritiated water by hydrothermal hot-pressing

Tritium is generally disposed of as an oxide form, and immobilization of tritium oxide with Portland cement is the most popular disposal method. However, the cement solidified body is rather leachable for tritium and is poor in some physical properties. A silicate powder, such as borosilicate glass powder, forms a synthetic rock by the hydrothermal hot-pressing (HHP) technique, making it a technique for immobilization of tritium oxide. Tritium oxide with borosilicate glass powder was solidified by the HHP technique. Leachability of tritium from the produced solidified bodies and the behavior of fixed tritium oxide during the heating were studied and discussed. The amount of tritium oxide fixed by the present procedure was almost the same as that fixed by the ordinary cement solidifying procedure. The diffusivity of tritium from the body by this procedure was much lower than that from the cement body and the compressive strength of the body was higher than that of the cement body.     

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.     

Utilization of gold tailings as an additive in Portland cement.

Mine tailings are formed as an industrial waste during coal and ore mining and processing. In the investigated process, following the extraction of gold from the ore, the remaining tailings are subjected to a two-stage chemical treatment in order to destroy the free cyanide and to stabilize and coagulate heavy metals prior to discharge into the tailings pond. The aim of this study was the investigation of the feasibility of utilization of the tailings as an additive material in Portland cement production. For this purpose, the effects of the tailings on the compressive strength properties of the ordinary Portland cement were investigated. Chemical and physical properties, mineralogical composition, particle size distribution and microstructure of the tailings were determined by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), particle size analyzer (Mastersizer) and scanning electron microscope (SEM). Following the characterization of the tailings, cement mortars were prepared by intergrinding Portland cement with dried tailings. Composition of the cement clinkers were adjusted to contain 5, 15, 25% (wt/wt) dried tailings and also silica fume and fly ash samples (C and F type) were added to clinker in different ratios. The mortars produced with different amounts of tailings, silica fume, fly ashes and also mixtures of them were tested for compressive strength values after 2, 7, 28 and 56 days according to the European Standard (EN 196-1). The results indicated that gold tailings up to 25% in clinker could be beneficially used as an additive in Portland cement production. It is suggested that the gold tailings used in the cement are blended with silica fume and C-type fly ash to obtain higher compressive strength values.     

Recovery of MSWI and soil washing residues as concrete aggregates

The aim of the present work was to study if municipal solid waste incinerator (MSWI) residues and aggregates derived from contaminated soil washing could be used as alternative aggregates for concrete production.Initially, chemical, physical and geometric characteristics (according to UNI EN 12620) of municipal solid waste incineration bottom ashes and some contaminated soils were evaluated; moreover, the pollutants release was evaluated by means of leaching tests. The results showed that the reuse of pre-treated MSWI bottom ash and washed soil is possible, either from technical or environmental point of view, while it is not possible for the raw wastes.Then, the natural aggregate was partially and totally replaced with these recycled aggregates for the production of concrete mixtures that were characterized by conventional mechanical and leaching tests. Good results were obtained using the same dosage of a high resistance cement (42.5R calcareous Portland cement instead of 32.5R); the concrete mixture containing 400 kg/m³ of washed bottom ash and high resistance cement was classified as structural concrete (C25/30 class). Regarding the pollutants leaching, all concrete mixtures respected the limit values according to the Italian regulation.     

Sequestration of metals in active cap materials: A laboratory and numerical evaluation

Active capping involves the use of capping materials that react with sediment contaminants to reduce their toxicity or bioavailability. Although several amendments have been proposed for use in active capping systems, little is known about their long‐term ability to sequester metals. Recent research has shown that the active amendment apatite has potential application for metals‐contaminated sediments. The focus of this study was to evaluate the effectiveness of apatite in the sequestration of metal contaminants through the use of short‐term laboratory column studies in conjunction with predictive, numerical modeling. A breakthrough column study was conducted using North Carolina apatite as the active amendment. Under saturated conditions, a spike solution containing elemental As, Cd, Co, Se, Pb, Zn, and a nonreactive tracer was injected into the column. A sand column was tested under similar conditions as a control. Effluent water samples were periodically collected from each column for chemical analysis. Relative to the nonreactive tracer, the breakthrough of each metal was substantially delayed by the apatite. Furthermore, breakthrough of each metal was substantially delayed by the apatite compared to the sand column. Finally, a simple 1‐D, numerical model was created to qualitatively predict the long‐term performance of apatite based on the findings from the column study. The results of the modeling showed that apatite could delay the breakthrough of some metals for hundreds of years under typical groundwater flow velocities. © 2012 Wiley Periodicals, Inc.     

Cement-based solidification/stabilization of lead-contaminated soil at a utah highway construction site

This article describes portland cement-based solidification/stabilization (S/S) treatment of heavy metal-contaminated soil. The soil was discovered during highway construction in West Jordan, Utah. Environmental Chemical Corporation (ECC) performed an emergency response to remediate the soil under contract with the EPA and the United States Bureau of Reclamation (USBR). The soil was treated by S/S. Treatment of the soil, contaminated with lead and arsenic, involved: (1) excavation, (2) size segregation, (3) reduction of oversized particles, (4) addition and mixture of portland cement and cement kiln dust, and (5) beneficial reuse of the treated soil as a subbase. S/S treatment successfully reduced Toxicity Characteristic Leaching Procedure (TCLP) concentrations of the contaminants to below regulatory levels.     

Cement-clay pastes for stabilization/solidification of 2-chloroaniline

Immobilization of a model liquid organic pollutant, i.e. the 2-chloroaniline (2-CA), into a cement matrix using organoclays as pre-sorbent agents was investigated. Five cement-clay pastes were prepared with different nominal water-to-cement ratios (w/c=0.40, 0.25 and 0.15 wt/wt) and various amounts of waste (waste-to-cement o/c=0.20, 0.60 and 1.00 wt/wt); for comparison, a neat cement paste was also prepared. Dynamic leach tests were performed on solidified monoliths in order to assess the successful immobilization of the 2-CA. In monoliths at constant w/c ratio (0.40) the total amount of pollutant released increases with its initial content, and ranges from 15 to 35% with respect to it. By lowering w/c from 0.40 to 0.15 at constant o/c, the performances improved (<25% released). The microstructure of the hardened cement-clay pastes was characterized by quantitative X-ray diffraction (QXRD) and electronic microscopy (SEM-EDS) techniques; hydration degree was estimated by means of thermogravimetric analysis (TGA) in addition to QXRD. No evidence of any chemical reaction between 2-CA and cement phases was found. Moreover, it was shown that the most important factors affecting the cement hydration process were the total water content, i.e. the one taking also into account the water contained in the wet polluted clay, and the amount of 2-CA not firmly sorbed by the organoclay, and then freely dispersed in the paste.     

Cement based solidification/stabilization of arsenic-contaminated mine tailings

Cement was used to solidify/stabilize the abandoned mine tailings contaminated primarily with arsenic (up to 88 mg/kg) and lead (up to 35 mg/kg). Solidified/stabilized (s/s) forms with a range of cement contents, 5–30 wt%, were evaluated to determine the optimal binder content. Unconfined compression strength test (UCS), Korean standard leaching tests, toxicity characteristic leaching procedures (TCLP), and synthetic precipitation leaching procedure (SPLP) were used for physical and chemical characterization of the s/s forms. Addition of 5% cement was enough for the s/s forms to satisfy the UCS requirements (0.35 MPa). The addition of 7.5% cement remarkably reduced the leachability of arsenic in tailings. However, that of lead tends to increase slightly with increase of cement content due to its amphoteric nature. The discussions were made for determination of optimal binder content and for results from different evaluation procedures.     

Microstructure of Portland cement pastes containing metal nitrate salts

In recent years, Backscattered Scanning Electron microscopy techniques (BSE), coupled with an image analysis system have been recognised as a powerful tool for quantitative analysis. This paper investigates the effect of metal additions (Ba, Cu, Ni, Zn, Cr(III), Pb and Cd) to Portland cement to produce a solidified product which meets the durability criteria quantified by the ratio of hydrated products and porosity. In addition, other indicators of the progress of cement hydration such as the bulk density and evaporable water of the solidified products were also measured. Metal concentrations of 0.1 and 1% per weight of cement at a constant water/cement ratio of 0.4 were examined. The same measurements were conducted on control samples of different water/ cement ratio. The results have shown that the control samples at different W/C ratio showed consistent trend in residual cement porosity, density and evaporable water content. It also showed that low dosage of metal nitrate additions can reduce cement hydration by up to 50% and at the same time reduce the observable porosity. Overall, this work has shown that Scanning Electron Microscopy (SEM) and image analysis are powerful tools and could be used to quantify the observable porosity and cement hydration in solidified systems.     

Glass recycling in cement production--an innovative approach

An innovative approach of using waste glass in cement production was proposed and tested in a laboratory and cement production plant. The laboratory characterization of 32 types of glass show that the chemical composition of glass does not vary significantly with its color or origin but depends on its application. The alkali content of glass, a major concern for cement production varies from 0 to 22%. For the glass bottles mainly found in Hong Kong waste glasses, the alkali content (Na2O) ranges from 10 to 19% with an average around 15%. There is no significant change of the SO2 content in the gas exhaust of the rotary kiln when about 1.8 t/h of glass bottles were loaded along with the 280-290 t/h raw materials. The content of NOx, mainly depends on the temperature of the kiln, does not show significant change either. The SO3 content of the clinker is comparable with that obtained without the loading of glass. The alkaline content shows a slight increase but still within three times the standard deviation obtained from the statistical data of the past year. The detailed analysis of the quality of the cement product shows that there is not any significant impact of glass for the feeding rate tested.     

Laboratory development and field demonstration of self-sealing/self-healing landfill liner

The self-sealing/self-healing (SS/SH) barrier concept is based on the principle that two or more parent materials placed in vertical or horizontal layers will react at their interfaces to form insoluble reaction products. These products constitute a seamless impermeable seal, which is resistant to the transmission of leachate and contaminants. A SS/SH liner formulation was developed in the laboratory and demonstrated at the Sudokwon landfill site in South Korea. Laboratory testing results indicated that a seal with a hydraulic conductivity less than 10(-9) m/s formed after two to four weeks of curing at room temperature, and the seal healed itself after it was fractured. The use of the soil from the Sudokwon landfill site instead of sand as the matrix of the parent materials in the SS/SH liner retarded the sealing and healing of the seal, but did not show an obvious effect on the overall sealing and healing capacity of the seal at early stages. The construction and installation of the field demonstration SS/SH liner were carried out in the same way as for a soil cement liner. The quality of the liner was ensured by the enforcement of quality analysis/quality control procedures during installation. A single sealed ring infiltration test was performed on the field demonstration liner 36 days after the installation was completed. The measurement of water infiltration rate indicated that the liner healed after it was fractured. However, the long-term sealing and healing capacity needs to be further investigated.