Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment

The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO2 as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity - sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1: 1. The concentrations of mercury and other heavy metals in the leachates were below 0.10 mg/L and 5 mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na2CO3 and CO2 may practically apply to cement-based s/s of heavy metal-bearing sediment. (C) 2008 Elsevier B.V. All rights reserved.

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 Si-29 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 oil 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. (C) 2008 Elsevier Ltd. All rights reserved.

Aspects of the in vitro bioactivity of hydraulic calcium (alumino)silicate cement

In response to a burgeoning interest in the prospective clinical applications of hydraulic calcium (alumino)silicate cements, the in vitro bioactivity and dissolution characteristics of a white Portland cement have been investigated. The formation of an apatite layer within 6 h of contact with simulated body fluid was attributed to the rapid dissolution of calcium hydroxide from the cement matrix and to the abundance of pre-existing Si-OH nucleation sites presented by the calcium silicate hydrate phase. A simple kinetic model has been used to describe the rate of apatite formation and an apparent pseudo-second-order rate constant for the removal of HPO42- ions frorn solultion has been calculated (k(2) = 5.8 x 10(-4) g mg(-1)). Aspects of the chemistry of hydraulic cements are also discussed with respect to their potential use in the remedial treatment of living tissue. (C) 2008 Wiley Periodicals, Inc. J Biomed Mater Res 90A: 166-174, 2009

Influence of carbonation on the acid neutralization capacity of cements and cement-solidified/stabilized electroplating sludge

Portland cement (PC) and blended cements containing pulverized fuel ash (PFA) or granulated blast-furnace slag (GGBS) were used to solidify/stabilize an electroplating sludge in this work. The acid neutralization capacity (ANC) of the hydrated pastes increased in the order of PC > PC/GGBS > PC/PFA. The GGBS or PFA replacement (80 wt%) reduced the ANC of the hydrated pastes by 30–50%. The ANC of the blended cement-solidified electroplating sludge (cement/sludge 1:2) was 20–30% higher than that of the hydrated blended cement pastes. Upon carbonation, there was little difference in the ANC of the three cement pastes, but the presence of electroplating sludge (cement/sludge 1:2) increased the ANC by 20%. Blended cements were more effective binders for immobilization of Ni, Cr and Cu, compared with PC, whereas Zn was encapsulated more effectively in the latter. Accelerated carbonation improved the immobilization of Cr, Cu and Zn, but not Ni. The geochemical code PHREEQC, with the edited database from EQ3/6 and HATCHES, was used to calculate the saturation index and solubility of likely heavy metal precipitates in cement-based solidification/stabilization systems. The release of heavy metals could be related to the disruption of cement matrices and the remarkable variation of solubility of heavy metal precipitates at different pH values.

Zinc polycarboxylate dental cement for the controlled release of an active organic substance: proof of concept

The potential of employing zinc polycarboxylate dental cement as a controlled release material has been studied. Benzalkonium chloride was used as the active ingredient, and incorporated at concentrations of 1, 2 and 3% by mass within the cement. At these levels, there was no observable effect on the speed of setting. Release was followed using an ion-selective electrode to determine changes in chloride ion concentration with time. This technique showed that the additive was released when the cured cement was placed in water, with release occurring by a diffusion mechanism for the first 3 h, but continuing beyond that for up to 1 week. Diffusion coefficients were in the range 5.62 × 10(−6) cm(2) s(−1) (for 1% concentration) to 10.90 × 10(−6) cm(2) s(−1) (for 3% concentration). Up to 3% of the total loading of benzalkonium chloride was released from the zinc polycarboxylate after a week, which is similar to that found in previous studies with glass-ionomer cement. It is concluded that zinc polycarboxylate cement is capable of acting as a useful material for the controlled release of active organic compounds.

Water transport in resin-modified glass-ionomer dental cement

Water uptake and water loss have been studied in a commercial resin-modified glass-ionomer cement, Fuji II LC, under a variety of conditions. Uptake was generally non-Fickian, but affected by temperature. At room temperature, the equilibrium water uptake values varied from 2.47 to 2.78% whereas at low temperature (12 degrees C), it varied from 0.85 to 1.18%. Cure time affected uptake values significantly. Water uptake was much lower than in conventional glass-ionomer restorative cements exposed to water vapor. Loss of water under desiccating conditions was found to be Fickian for the first 5 h loss at both 22 and 12 degrees C. Diffusion coefficients were between 0.45 and 0.76 x 10( -7) cm(2)/s, with low temperature diffusion coefficients slightly greater than those at room temperature. Plotting water loss as percentage versus s(-(1/2)) allowed activation energies to be determined from the Arrhenius equation and these were found to be 65.6, 79.8, and 7.7 kJ/mol respectively for 30, 20, and 10 s cure times. The overall conclusion is that the main advantage of incorporating HEMA into resin-modified-glass-ionomers is to alter water loss behavior. Rate of water loss and total amount lost are both reduced. Hence, resin-modified glass-ionomers are less sensitive to water loss than conventional glass-ionomers.

A preliminary investigation of the in vitro bioactivity of white Portland cement

Freshly-mixed and partially-cured ordinary Portland cement (OPC) pastes have been shown to exhibit good biological compatibility with a range of cells and tissue-types; particularly those associated with bone formation. Formulations based on OPC have been used as dental restoratives and are now being investigated for their potential use in orthopaedic repair. Despite the current clinical interest in OPCs, very little is known about their chemistry in the physiological environment. In this respect, research to investigate aspects of the interactions between a white Portland cement (WPC) paste and simulated body fluid (SBF) has been carried out in vitro. Exposure to SBF has been found to promote the precipitation of a layer of 'bone-like' hydroxyapatite on the surface of WPC paste which underpins its ability to integrate with living tissue. The dissolution of portlandite and formation of calcite were also observed on contact with SBF.

Ion release by endodontic grade glass-ionomer cement

Cylindrical specimens (6 mm high x 4 mm diameter) of the endodontic grade glass-ionomer (Ketac Endo) were exposed to various media for 1 week, after which changes in their mass, pH of storage medium, and ion release were determined. In water, this cement was shown to release reasonable amounts of sodium, aluminium and silicon, together with smaller amounts of calcium and phosphorus, as well as taking up 2.41% by mass of water. A comparison with the restorative grade materials (Ketac Molar, ex 3M ESPE and Fuji IX, ex GC) showed both ion release and water uptake to be greater. All three cements shifted pH from 7 to around 6 with no significant differences between them. Other storage media were found to alter the pattern of ion release. Lactic acid caused an increase, whereas both saturated calcium hydroxide and 0.6% sodium hypochlorite, caused decreases. This suppression of ion-release may be significant clinically. Aluminium is the most potentially hazardous of the ions involved but amounts released were low compared with levels previously reported to show biological damage.

The Medway Valley: a Kent landscape transformed

In 1750 the lower Medway Valley, the area between the towns of Maidstone and Rochester, was firmly part of Kent's 'Garden of England'. A century later, this tranquil, agrarian landscape had been transformed into a hive of industry and commerce, through the emergence of papermaking, cement manufacture, brickmaking, brewing, ship and barge building, seed crushing and engineering. The lower Medway Valley became synonymous with the production of Portland cement, stock bricks and the steam engines of Aveling and Porter, yet, by the end of the Second World War, much of this industry was gone. "The Medway Valley: A Kent Landscape Transformed", the first Victoria County History publication in Kent for over 75 years, charts this cyclical story of landscape change. It explores how the quiet, rural landscape of a collection of eight riverside parishes around Rochester was dramatically transformed during industrialization, before returning to its formal rural state. This volume traces the impact of industrial development and decline on the valley and its people. It details changing patterns of work and society, the creation of new settlements and the pivotal role of the river in all aspects of village life reflecting two centuries of change and upheaval.

Reinforcement corrosion initiation and activation times in concrete structures exposed to severe marine environments

The corrosion of steel reinforcement bars in reinforced concrete structures exposed to severe marine environments usually is attributed to the aggressive nature of chloride ions. In some cases in practice corrosion has been observed to commence already within a few years of exposure even with considerable concrete cover to the reinforcement and apparently high quality concretes. However, there are a number of other cases in practice for which corrosion initiation took much longer, even in cases with quite modest concrete cover and modest concrete quality. Many of these structures show satisfactory long-term structural performance, despite having high levels of localized chloride concentrations at the reinforcement. This disparity was noted already more than 50 years ago, but appears still not fully explained. This paper presents a systematic overview of cases reported in the engineering and corrosion literature and considers possible reasons for these differences. Consistent with observations by others, the data show that concretes made from blast furnace cements have better corrosion durability properties. The data also strongly suggest that concretes made with limestone or non-reactive dolomite aggregates or sufficiently high levels of other forms of calcium carbonates have favourable reinforcement corrosion properties. Both corrosion initiation and the onset of significant damage are delayed. Some possible reasons for this are explored briefly.

Accelerated carbonation treatment of industrial wastes

The disposal of industrial waste presents major logistical, financial and environmental issues. Technologies that can reduce the hazardous properties of wastes are urgently required. In the present work, a number of industrial wastes arising from the cement, metallurgical, paper, waste disposal and energy industries were treated with accelerated carbonation. In this process carbonation was effected by exposing the waste to pure carbon dioxide gas. The paper and cement wastes chemically combined with up to 25% by weight of gas. The reactivity of the wastes to carbon dioxide was controlled by their constituent minerals, and not by their elemental composition, as previously postulated. Similarly, microstructural alteration upon carbonation was primarily influenced by mineralogy. Many of the thermal wastes tested were classified as hazardous, based upon regulated metal content and pH. Treatment by accelerated carbonation reduced the leaching of certain metals, aiding the disposal of many as stable non-reactive wastes. Significant volumes of carbon dioxide were sequestrated into the accelerated carbonated treated wastes.

The influence of alkali metal chlorides on the loss of water from glass-ionomer dental cements

The water loss behaviour of a clinical glass-ionomer dental cement has been studied with and without the addition of alkali metal chlorides. Dehydrating conditions were provided by placing specimens in a desiccator over concentrated sulphuric acid. Cements were prepared using either pure water or an aqueous solution of metal chloride (LiCl, NaCl, KCl) at 1.0 mol/dm(3). In addition, NaCl at 0.5 mol/dm(3) was also used to fabricate cements. Disc-shaped specimens of size 6 mm diameter x 2 mm thickness were made, six performulation, and cured at 37 degrees C for 1 hour They were then exposed to desiccating conditions, and the mass measured at regular intervals. All formulations were found to lose water in a diffusion process that equilibrated after approximately 3 weeks. Diffusion coefficients ranged from 2.27 (0.13) x 10(9) with no additive to 1.85 (0.07) x 10(9) m(2)/s with 1.0 mol/dm(3) KCl. For the salts, diffusion coefficients decreased in the order LiCl > NaCl > KCl. There was no statistically significant difference between the diffusion coefficients for 1.0 and 0.5 mol/dm(3) NaCl. For all salts at 1.0 mol/dm(3) and also additive-free cements, equilibrium losses were, with statistical limits, the same, ranging from 6.23 to 6.34%. On the other hand, 0.5 mol/dm(3) NaCl lost significantly more water 7.05%.

Review paper: role of aluminum in glass-ionomer dental cements and its biological effects

The role of aluminum in glass-ionomers and resin-modified glass-ionomers for dentistry is reviewed. Aluminum is included in the glass component of these materials in the form of Al(2)O(3) to confer basicity on the glass and enable the glass to take part in the acid-base setting reactions. Results of studies of these reactions by FTIR and magic-angle spinning (MAS)-NMR spectroscopy are reported and the role of aluminum is discussed in detail. Aluminum has been shown to be present in the glasses in predominantly 4-coordination, as well as 5- and 6-coordination, and during setting a proportion of this is converted to 6-coordinate species within the matrix of the cement. Despite this, mature cements may contain detectable amounts of both 4- and 5-coordinate aluminum. Aluminum has been found to be leached from glass-ionomer cements, with greater amounts being released under acidic conditions. It may be associated with fluoride, with which it is known to complex strongly. Aluminum that enters the body via the gastro-intestinal tract is mainly excreted, and only about 1% ingested aluminum crosses the gut wall. Calculation shows that, if a glass-ionomer filling dissolved completely over 5 years, it would add only an extra 0.5% of the recommended maximum intake of aluminum to an adult patient. This leads to the conclusion that the release of aluminum from either type of glass-ionomer cement in the mouth poses a negligible health hazard.

The use of mineral trioxide aggregate in endodontics - status report

Mineral trioxide aggregate (MTA) is a clinical product comprising a mixture of Portland cement and bismuth oxide which is currently used as a root−filling material in dentistry. It has good biological compatibility, is capable of promoting both osteogenesis and cementogensis, and is finding increasing use in endodontic therapy. It is dimensionally stable, and provides an acceptable and durable seal for endodontically treated teeth. This article reviews the chemistry and applications of MTA, and highlights the fact that very little is currently known about the hydration chemistry, phase evolution and stability of this cement in physiological environments. However, biological effects of MTA have been well documented and are considered in detail. The article concludes that this material is a useful addition to the range of materials available for clinical application in endodontics.

Comparison of properties of traditional and accelerated carbonated solidified/stabilized contaminated soils

The investigation of the long-term performance of solidified/stabilized (S/S) contaminated soils was carried out in a trial site in southeast UK. The soils were exposed to the maximum natural weathering for four years and sampled at various depths in a controlled manner. The chemical properties (e.g., degree of carbonation (DOC), pH, electrical conductivity (EC)) and physical properties (e.g., moisture content (MC), liquid limit (LL), plastic limit (PL), plasticity index (PI)) of the samples untreated and treated with the traditional and accelerated carbonated S/S processes were analyzed. Their variations on the depths of the soils were also studied. The result showed that the broad geotechnical properties of the soils, manifested in their PIs, were related to the concentration of the water soluble ions and in particular the free calcium ions. The samples treated with the accelerated carbonation technology (ACT), and the untreated samples contained limited number of free calcium ions in solutions and consequently interacted with waters in a similar way. Compared with the traditional cement-based S/S technology, e.g., treatment with ordinary portland cement (OPC) or EnvirOceM, ACT caused the increase of the PI of the treated soil and made it more stable during long-term weathering. The PI values for the four soils ascended according to the order: the EnvirOceM soil, the OPC soil, the ACT soil, and the untreated soil while their pH and EC values descended according to the same order.