Paula Carey

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.

Investigation of accelerated carbonation for the stabilisation of MSW incinerator ashes and the sequestration of CO2

Accelerated carbonation has been used for the treatment of contaminated soils and hazardous wastes, giving reaction products that can cause rapid hardening and the production of granulated or monolithic materials. This technology provides a route to sustainable waste management and it generates a viable remedy to the problems of a decreasing number of landfill sites in the UK, global warming (due to greenhouse gas emissions) and the depletion of natural aggregate resources, such as sand and gravel. The application of accelerated carbonation (termed Accelerated Carbonation Technology or ACT) to sequester CO2 in fresh ashes from municipal solid waste (MSW) incinerator/combined heat and power plants is presented. The purpose of this paper is to evaluate the influence of fundamental parameters affecting the diffusivity and reactivity of CO2 (i.e. particle size, the reaction time and the water content) on the extent and quality of carbonation. In addition, the major physical and chemical changes in air pollution control (APC) residues and bottom ashes (BA) after carbonation are evaluated, as are the optimum reaction conditions, and the physical and chemical changes induced by accelerated carbonation are presented and discussed.

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.

Solidification of stainless steel slag by accelerated carbonation

Abstract On exposure to carbon dioxide (CO2) at a pressure of 3 bars, compacts formed from pressed ground slag, and 12.5 weight percent water, were found to react with approximately 18% of their own weight of CO2. The reaction product formed was calcium carbonate causing the slag to self‐cement. Unconfined compressive strengths of 9MPa were recorded in carbonated compacts whereas strengths of <1 MPa were recorded in non‐carbonated slag compacts. As molten stainless steel slag containing dicalcium silicate (C2S) cools it can undergo several phase transitions. The final transformation from the p‐polymorph to γ‐C2S is accompanied by a volume change that causes the slag to self‐pulverise or ‘dust’. As a consequence of this the fine grained portion of the slag contains more of this phase whilst the coarser particles of the slag contain more of the calcium magnesium silicates that contribute the bulk of the waste. The fine fraction (<125μm) of the slag when ground is found to react to the same extent as the ground bulk slag and produces compacts with equivalent strength. A coarser fraction (4–8mm) when ground to a similar grading does not react as extensively and produces a weaker product. Additions of ordinary Portland cement (OPC) at 5 and 10 percent by weight did not alter the degree of reaction during carbonation of the bulk slag or ground fine fraction, however the strength of the 4–8mm fraction was increased by this change.

Production of lightweight aggregate from industrial waste and carbon dioxide

The concomitant recycling of waste and carbon dioxide emissions is the subject of developing technology designed to close the industrial process loop and facilitate the bulk-re-use of waste in, for example, construction. The present work discusses a treatment step that employs accelerated carbonation to convert gaseous carbon dioxide into solid calcium carbonate through a reaction with industrial thermal residues. Treatment by accelerated carbonation enabled a synthetic aggregate to be made from thermal residues and waste quarry fines. The aggregates produced had a bulk density below 1000 kg/m(3) and a high water absorption capacity. Aggregate crushing strengths were between 30% and 90% stronger than the proprietary lightweight expanded clay aggregate available in the UK. Cast concrete blocks containing the carbonated aggregate achieve compressive strengths of 24 MPa, making them suitable for use with concrete exposed to non-aggressive service environments. The energy intensive firing and sintering processes traditionally required to produce lightweight aggregates can now be augmented by a cold-bonding, low energy method that contributes to the reduction of green house gases to the atmosphere.

Examination of the adsorption of ethylene oxide–propylene oxide triblock copolymers to soil

The adsorption of 5 surfactants (P103, P105, F108, F127 and L92) to a sandy soil has been investigated. The surfactants are ABA block copolymers in which the A blocks are synthesised from ethylene oxide and the B block from propylene oxide. CMC values, for the block copolymers, as well as surfactant sorption to soil were measured by surface tension techniques. The adsorption of all five compounds can be described by the Freundlich adsorption isotherm. Adsorption, in each case, is related to the critical micelle concentration of the surfactant and the extent of adsorption appears to be linked also to the fraction of soil organic matter.

Investigation of 4-year-old stabilised/solidified and accelerated carbonated contaminated soil.

The investigation of the pilot-scale application of two different stabilisation/solidification (S/S) techniques was carried out at a former fireworks and low explosives manufacturing site in SE England. Cores and granular samples were recovered from uncovered accelerated carbonated (ACT) and cement-treated soils (S/S) after 4 years to evaluate field-performance with time. Samples were prepared for microstructural examination and leaching testing. The results indicated that the cement-treated soil was progressively carbonated over time, whereas the mineralogy of the carbonated soil remained essentially unchanged. Distinct microstructures were developed in the two soils. Although Pb, Zn and Cu leached less from the carbonated soil, these metals were adequately immobilised by both treatments. Geochemical modeling of pH-dependent leaching data suggested that the retention of trace metals resulted from different immobilisation mechanisms operating in the two soils examined.

Long-term performance of aged waste forms treated by stabilization/solidification

Current regulatory testing of stabilized/solidified (S/S) soils is based on short-term performance tests and is insufficient to determine their long-term stability or expected service life. In view of this, and the significant lack of data on long-term field performance in the literature, S/S material has been extracted from full-scale remedial operations and examined using a variety of analytical techniques to evaluate field performance. The results, including those from X-ray analytical techniques, optical and electron microscopy and leaching tests are presented and discussed. The microstructure of retrieved samples was found to be analogous to other cement-based materials, but varied according to the soil type, the contaminants present, the treatment applied and the field exposure conditions. Summary of the key microstructural features in the USA and UK is presented in this work. The work has shown that during 16 years of service the S/S wastes investigated performed satisfactorily.

Leaching of Mercury from Carbonated and Non-Carbonated Cement-Solidified Dredged Sediments

This study investigated traditional cement-based and non-conventional (using accelerated carbonation) solidification/stabilization to treat 2 dredged sediments contaminated with mercury from two different locations in UK. Canal and estuarine-derived sediments were mixed with blended binders and powdered activated carbon. Fresh mixtures of sediment and cement were exposed to gaseous carbon dioxide and were allowed to carbonate for fixed time periods, after which they were cured for 28 days. Following curing, samples were leach tested to evaluate the fixation of mercury in the treated products. The results obtained indicated that both conventional and accelerated carbonated treatments were capable of reducing the concentration of mercury in the eluates to acceptable limits.

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.