Effect of organics on selenite uptake by cementitious materials

The behaviour of three organic ligands in suspensions of fresh and degraded hydrated ordinary Portland cement pastes (HCP) has been investigated. EDTA arises as a decontamination product whilst ISA (isosaccharinic acid) is a main degradation product of cellulose. GLU (gluconic acid) is used as a retarding organic admixture in concrete. The affinity of EDTA, ISA and GLU with HCP increases with the degradation state. At long contact times, ISA and GLU desorbed from HCP, perhaps as a result of carbonation. Their influence on the uptake of selenium (as SeO3(2-)) on HCP has been studied as a function of time, addition order and HCP degradation state. The sorption study of Se(IV) also shows a positive effect of the HCP degradation with R(d)=120 mLg(-1) for fresh HCP and 1000 mLg(-1) for degraded HCP. The addition order of Se(IV) and EDTA or ISA is important as pre-equilibration of HCP with either EDTA or ISA drastically decreases the uptake of Se(IV) to 10-30 mLg(-1). Mixing of cement with GLU seems to reduce the strong competitive effect of other organic compounds on Se(IV) sorption.     

Use of waste brick as a partial replacement of cement in mortar

The aim of this study is to investigate the use of waste brick as a partial replacement for cement in the production of cement mortar. Clinker was replaced by waste brick in different proportions (0%, 5%, 10%, 15% and 20%) by weight for cement. The physico-chemical properties of cement at anhydrous state and the hydrated state, thus the mechanical strengths (flexural and compressive strengths after 7, 28 and 90 days) for the mortar were studied. The microstructure of the mortar was investigated using scanning electron microscopy (SEM), the mineralogical composition (mineral phases) of the artificial pozzolan was investigated by the X-ray diffraction (XRD) and the particle size distributions was obtained from laser granulometry (LG) of cements powders used in this study. The results obtained show that the addition of artificial pozzolan improves the grinding time and setting times of the cement, thus the mechanical characteristics of mortar. A substitution of cement by 10% of waste brick increased mechanical strengths of mortar. The results of the investigation confirmed the potential use of this waste material to produce pozzolanic cement.     

Evolution of iron speciation during hydration of C4AF

It is now well accepted and demonstrated that calcium silicate, calcium aluminate and calcium sulfo aluminate (ettringite, AFm) phases exhibit a good capability to fix metals and metalloids. Unfortunately the role of minor phases and especially calcium-ferric aluminate phase, shorthand C4AF is not well defined. In other systems like in soils or sediments iron phases play a key role in the fixation of pollutant. In cement sorption isotherms, indicated that various metals can be retained by the C4AF hydrated products. Therefore the capabilities of those phase to retain heavy metal should not be neglected. Previous investigations have shown that the minerals formed during the hydration of C4AF are similar to those formed from C3A (pure tri-calcium aluminate) under comparable conditions. Nevertheless no investigation was conducted at the molecular level and there is still a controversy whether Fe substitutes for Al in the hydrated minerals in whole or in part, or if it forms FeOOH clusters scattered throughout the matrix. In this context we have conducted XAS experiments using synchrotron radiation. It was found that the hydration of C4AF forms C3AH6 (hydrogarnet) in which Fe randomly substitutes for Al as well as an amorphous FeOOH phase. Intermediate products like AFm (i.e., an ill organized lamellar phase) are also formed but rapidly evolve to C3AH6; iron does not seem to be incorporated in the AFm structure.     

Use of glazed ceramic waste as additive in mortar and the mathematical modelling of its strength

This study investigated the reusability of waste material from the tile manufacturing industry as an alternative material to natural pozzolan trass. Yield strength values of mortar made from Portland cement (CEM 142.5), were measured by adding glazed ceramic waste and trass at various weight ratios (5 to 40%). The test results proved that the strength values at 2, 7, and 28 days gave good results for concentrations of waste materials less than 5-10% in the cement. A decrease in strength was observed at higher concentrations. Mathematical modelling results showed a logarithmic correlation between the mortar strength and weight fraction of cement.     

Matt waste from glass separated collection: an eco-sustainable addition for new building materials

Matt waste (MW), a by-product of purification processes of cullet derived from separated glass waste collection, has been studied as filler for self-compacting concrete and as an addition for newly blended cement. Properties of self-compacting concrete compared to reference samples are reported. They include characteristics at the fresh and hardened states, and the compressive strength and porosity of mortar samples that were formulated with increasing amounts of MW to be used as cement replacement (up to 50wt.%). The effects of matt waste are discussed with respect to the mechanical and microstructural characteristics of the resulting new materials.     

Chemical-mineralogical characterization of C&D waste recycled aggregates from São Paulo, Brazil

This study presents a methodology for the characterization of construction and demolition (C&;D) waste recycled aggregates based on a combination of analytical techniques (X-ray fluorescence (XRF), soluble ions, semi-quantitative X-ray diffraction (XRD), thermogravimetric analysis (TGA-DTG) and hydrochloric acid (HCl) selective dissolution). These combined analytical techniques allow for the estimation of the amount of cement paste, its most important hydrated and carbonated phases, as well as the amount of clay and micas. Details of the methodology are presented here and the results of three representative C&;D samples taken from the São Paulo region in Brazil are discussed. Chemical compositions of mixed C&;D aggregate samples have mostly been influenced by particle size rather than the visual classification of C&;D into red or grey and geographical origin. The amount of measured soluble salts in C&;D aggregates (0.15–25.4 mm) is lower than the usual limits for mortar and concrete production. The content of porous cement paste in the C&;D aggregates is around 19.3% (w/w). However, this content is significantly lower than the 43% detected for the C&;D powders (<0.15 mm). The clay content of the powders was also high, potentially resulting from soil intermixed with the C&;D waste, as well as poorly burnt red ceramic. Since only about 50% of the measured CaO is combined with CO₂, the powders have potential use as raw materials for the cement industry.     

Abstraction of mechanistic sorption model results for performance assessment calculations at Yucca Mountain,Nevada

Sorption onto minerals in the geologic setting may help to mitigate potential radionuclide transport from the proposed high-level radioactive waste repository at Yucca Mountain (YM), Nevada. An approach is developed for including aspects of more mechanistic sorption models into current probabilistic performance assessment (PA) calculations. Data on water chemistry from the vicinity of YM are screened and used to calculate the ranges in parameters that could exert control on radionuclide sorption behavior. Using a diffuse-layer surface complexation model, sorption parameters for Np(V) and U(VI) are calculated based on the chemistry of each water sample. Model results suggest that lognormal probability distribution functions (PDFs) of sorption parameters are appropriate for most of the samples, but the calculated range is almost five orders of magnitude for Np(V) sorption and nine orders of magnitude for U(VI) sorption. Calculated sorption parameters may also vary at a single sample location by almost a factor of 10 over time periods of the order of days to years due to changes in chemistry, although sampling and analytical methodologies may introduce artifacts that add uncertainty to the evaluation of these fluctuations. Finally, correlation coefficients between the calculated Np(V) and U(VI) sorption parameters can be included as input into PA sampling routines, so that the value selected for one radionuclide sorption parameter is conditioned by its statistical relationship to the others. The approaches outlined here can be adapted readily to current PA efforts, using site-specific information to provide geochemical constraints on PDFs for radionuclide transport parameters.     

Solid-liquid distribution of selected concrete admixtures in hardened cement pastes

The distribution between hardened cement paste and cement pore water of selected concrete admixtures (BZMs), i.e., sulfonated naphthalene-formaldehyde condensate (NS), lignosulfonate (LS) and a gluconate-containing plasticiser used at the Paul Scherrer Institute for waste conditioning, was measured. Sorption data were fitted to a single-site Langmuir isotherm with affinity constants K=(19+/-4)dm(3)g(-1) for NS, K=(2.1+/-0.6) dm(3)g(-1) for LS and sorption capacities q=(81+/-16)g kg(-1) for NS, q=(43+/-8)g kg(-1) for LS. In the case of gluconate, a two-site Langmuir sorption model was necessary to fit the data satisfactorily. Sorption parameters for gluconate were K(1)=(2+/-1)x10(6)dm(3)mol(-1) and q(1)=(0.04+/-0.02)mol kg(-1) for the stronger binding site and K(2)=(2.6+/-1.1)x10(3)dm(3)mol(-1) and q(2)=(0.7+/-0.3)mol kg(-1) for the weaker binding site. Desorption of these BZMs from cement pastes and pore water in cement specimens prepared in the presence of the BZMs were then used to test the model. It was found that only minor parts of NS and LS could be mobilised as long as the cement composition was intact, whereas the sorption of gluconate was found to be reversible. The Langmuir model makes valuable predictions in the qualitative sense in that the pore water concentration of the BZMs is reduced by several orders of magnitude as compared to the initial concentrations. In view of the necessity for conservative predictions used in the safety analysis for disposal of radioactive waste, however, the predictions are unsatisfactory in that the measured pore water concentrations of NS and LS were considerably larger than the predicted values. This conclusion does not apply for gluconate, because its concentration in cement pore water was below the detection limit of approximately 50 nM.     

Influence of combustion temperature on the performance of sewage sludge ash as a supplementary cementitious material

The potential for using sewage sludge ash (SSA) as a supplementary cementitious material (SCM) has been investigated. Controlled combustion of sewage sludge collected in Croatia from two wastewater treatment plants produced SSA with different characteristics. These were used to substitute for cement in mortar samples. The chemical composition and physical properties of SSA depend on wastewater composition, the sludge treatment process and the combustion temperature. These factors influence the suitability of SSA to be used as a SCM. For three different combustion temperatures (800, 900 and 1000 °C), it was concluded that properties of fresh mortar were not affected while in the hardened state, the most favorable combustion temperature is 900 °C regarding mechanical properties. Regardless of combustion temperature, for all types of SSA used in mortars as cement replacement (up to 30%), the average decrease in both compressive and flexural strength values was less than 8% for every 10% of added SSA. The results presented indicate that using up to 20% replacement of cement by SSA produces mortars that meet the specific technical requirements analyzed in this work.     

Influences of chemical activators on incinerator bottom ash

This research has applied different chemical activators to mechanically and thermally treated fine fraction (<14 mm) of incinerator bottom ash (IBA), in order to investigate the influences of chemical activators on this new pozzolanic material. IBA has been milled and thermally treated at 800 degrees C (TIBA). The TIBA produced was blended with Ca(OH)(2) and evaluated for setting time, reactivity and compressive strength after the addition of 0.0565 mole of Na(2)SO(4), K(2)SO(4), Na(2)CO(3), K(2)CO(3), NaOH, KOH and CaCl(2) into 100g of binder (TIBA+Ca(OH)(2)). The microstructures of activated IBA and hydrated samples have been characterized by X-ray diffraction (XRD) and thermogravimetry (TG) analysis. Thermal treatment is found to produce gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)) phases. The thermally treated IBA samples are significantly more reactive than the milled IBA. The addition of Na(2)CO(3) can increase the compressive strength and calcium hydroxide consumption at 28-day curing ages. However, the addition of Na(2)SO(4), K(2)SO(4), K(2)CO(3), NaOH and KOH reduces the strength and hydration reaction. Moreover, these chemicals produce more porous samples due to increased generation of hydrogen gas. The addition of CaCl(2) has a negative effect on the hydration of TIBA samples. Calcium aluminium oxide carbonate sulphide hydrate (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33)(H(2)O)(11)) is the main hydration product in the samples with activated IBA, except for the sample containing CaCl(2).     

An investigation on the use of shredded waste PET bottles as aggregate in lightweight concrete

In this work, the utilization of shredded waste Poly-ethylene Terephthalate (PET) bottle granules as a lightweight aggregate in mortar was investigated. Investigation was carried out on two groups of mortar samples, one made with only PET aggregates and, second made with PET and sand aggregates together. Additionally, blast-furnace slag was also used as the replacement of cement on mass basis at the replacement ratio of 50% to reduce the amount of cement used and provide savings. The water–binder (w/b) ratio and PET–binder (PET/b) ratio used in the mixtures were 0.45 and 0.50, respectively. The size of shredded PET granules used in the preparation of mortar mixtures were between 0 and 4 mm. The results of the laboratory study and testing carried out showed that mortar containing only PET aggregate, mortar containing PET and sand aggregate, and mortars modified with slag as cement replacement can be drop into structural lightweight concrete category in terms of unit weight and strength properties. Therefore, it was concluded that there is a potential for the use of shredded waste PET granules as aggregate in the production of structural lightweight concrete. The use of shredded waste PET granules due to its low unit weight reduces the unit weight of concrete which results in a reduction in the death weight of a structural concrete member of a building. Reduction in the death weight of a building will help to reduce the seismic risk of the building since the earthquake forces linearly dependant on the dead-weight. Furthermore, it was also concluded that the use of industrial wastes such as PET granules and blast-furnace slag in concrete provides some advantages, i.e., reduction in the use of natural resources, disposal of wastes, prevention of environmental pollution, and energy saving.     

Modelling of long-term dynamic leaching tests applied to solidified/stabilised waste

The paper aims at simulating the closed-system dynamic leaching of a cement-based monolith containing lead with the numerical reactive transport code HYTEC in a 3D-cylindrical geometry. The model considers, simultaneously, the chemical evolution of pore water, the progression of mineralogical alteration fronts, and the concomitant release of elements from the S/S waste. In good agreement with the experiment, element releases were found to be mainly controlled by either diffusion (Na, K, and, to a lesser extent, Cl), by surface dissolution (Ca, Si) or by a mixed evolution (Pb, SO4). All of the calculated mineralogical transformations take place in a thin layer beyond the monolith surface. Consequently, modelling of Ca, Si and SO4 releases was quite sensitive to the node size of the simulation grid and was improved by taking into account the increase of porosity and effective diffusion coefficient due to mineral dissolution in the leached layer. In agreement with experimental results, the deepest front corresponds under closed-system conditions to portlandite dissolution and calcium silicate hydrates CSH 1.8 transformation into CSH of lower Ca/Si ratio. A second, distinct and intermediate, front is made by ettringite dissolution. The network of CSH is globally preserved in the leached layer, complete dissolution occurring over a very small thickness only. Finally, hydrotalcite precipitation in the leached layer is expected by modelling due to pH drop.     

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.     

Effects of composing on sorption capacity of bagasse-based chars

A fresh bagasse sample (0-month) and two composted bagasse and pig manure mixed samples (1-month and 6-month) were used to produce carbon chars. Sample pyrolysis showed greater carbon char yields were obtained from the compost samples than from the bagasse sample. Fourier transform infrared spectra suggested that the chemical structures of the bagasse sample and the two compost samples were quite different, but that the three carbon chars obtained from those precursors were similar. Among the three pyrolyzed chars, the 0-month bagasse char displayed the largest sorption capacity of 3333 mg kg^?1 for the hydrophilic pollutant phenol, presumably resulting from its greater carbon content and O/C ratio. However, the sorption capacities for the hydrophobic pollutant naphthalene of the tow compost chars (3-month, 2001 mg kg^?1; 6-month, 1667 mg kg^?1) were greater than that of the 0-month bagasse char (1428 mg kg^?1). The results indicate that the compost chars had a greater preferential affinity for naphthalene than that in the bagasse char, suggesting that the compost chars possessed greater hydrophobicity.     

固定化海带生物吸附剂的制备及其吸附Ni~(2+)的动力学特性

以海藻酸钠、明胶和海带粉为原料制备了固定化海带生物吸附剂。固定化海带生物吸附剂对Ni2+的吸附过程可分为3个阶段:快速吸附阶段、缓慢吸附阶段和吸附平衡阶段。动力学过程可用Lagergren准二级反应动力学方程描述,限速步骤为化学吸附。随Ni2+初始质量浓度的增加,固定化海带生物吸附剂的Ni2+吸附量逐渐增大,Ni2+去除率逐渐降低。吸附过程符合Langmuir和Freundlich吸附等温方程,说明该吸附体系既有物理吸附又有化学吸附,从吸附状态看属于多层吸附,由Langmuir吸附等温方程得出固定化海带生物吸附剂对Ni2+的最大吸附量为39.43mg/g,说明固定化海带生物吸附剂对Ni2+有较好的吸附性能。     

In situ nitrogen removal from leachate by bioreactor landfill with limited aeration

The feasibility of simultaneous nitrification and denitrification in a bioreactor landfill with limited aeration was assessed. Three column reactors, simulating bioreactor landfill operations under anaerobic condition (as reference), intermittent forced aeration and enhanced natural aeration were hence established, where aerated columns passed through two phases, i.e., fresh landfill and well-decomposed landfill. The experimental results show that limited aeration decreased nitrogen loadings of leachate distinctly in the fresh landfill. In the well-decomposed landfill, the NH(4)(+)-N of the input leachate could be nitrified completely in the aerated landfill columns. The nitrifying loadings of the column cross section reached 7.9 g N/m(2)d and 16.9 g N/m(2)d in the simulated landfill columns of intermittent forced aeration and enhanced natural aeration, respectively. The denitrification was influenced by oxygen distribution in the landfill column. Intermittent existence of oxygen in the landfill with the intermittent forced aeration was favorable to denitrify the NO(2)(-)-N and NO(3)(-)-N, indicated by the high denitrification efficiency (>99%) under the condition of BOD(5)/TN of more than 5.4 in leachate; locally persistent existence of oxygen in the landfill with enhanced natural aeration could limit the denitrification, indicated by relatively low denitrification efficiency of about 75% even when the BOD(5)/TN in leachate had an average of 7.1.     

Production of cement clinkers from municipal solid waste incineration (MSWI) fly ash

This communication reports the laboratory scale study on the production of cement clinkers from two types of municipal solid waste incineration fly ash (MSW ash) samples. XRD technique was used to monitor the phase formation during the burning of the raw mixes. The amount of trace elements volatilized during clinkerization and hydration, as well as leaching behaviours of the clinkers obtained from optimum compositions, were also evaluated. From the results it is observed that all of the major components of ordinary Portland cement (OPC) clinkers are present in the produced clinkers. Results also show the volatilization of considerable amounts of Na, K, Pb, Zn and Cd during the production of clinkers. However, major parts of the toxic elements remaining in the clinkers appear to be immobilized in the clinkers phases. Hydration studies of the clinkers obtained from optimum compositions show that the clinkers prepared from raw MSW ash are more reactive than the washed MSW ash based clinkers. TG/DTA analyses of the hydrated pastes show the formation of hydration products, which are generally found in OPC and OPC derived cements. The initial study, therefore, shows that more than 44% of MSW ash with the addition of very small amounts of silica and iron oxide can be used to produce cement clinkers. The amount of CaCO3 necessary to produce clinkers (approximately 50%) is also smaller than the same required for the conventional process (more than 70%).     

Crystal-chemistry of alteration products of vitrified wastes: implications on the retention of polluting elements

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO(4)*nH(2)O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes the altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.     

Geotechnical properties of municipal solid waste at different phases of biodegradation

This paper presents the results of laboratory investigation conducted to determine the variation of geotechnical properties of synthetic municipal solid waste (MSW) at different phases of degradation. Synthetic MSW samples were prepared based on the composition of MSW generated in the United States and were degraded in bioreactors with leachate recirculation. Degradation of the synthetic MSW was quantified based on the gas composition and organic content, and the samples exhumed from the bioreactor cells at different phases of degradation were tested for the geotechnical properties. Hydraulic conductivity, compressibility and shear strength of initial and degraded synthetic MSW were all determined at constant initial moisture content of 50% on wet weight basis. Hydraulic conductivity of synthetic MSW was reduced by two orders of magnitude due to degradation. Compression ratio was reduced from 0.34 for initial fresh waste to 0.15 for the mostly degraded waste. Direct shear tests showed that the fresh and degraded synthetic MSW exhibited continuous strength gain with increase in horizontal deformation, with the cohesion increased from 1 kPa for fresh MSW to 16–40 kPa for degraded MSW and the friction angle decreased from 35° for fresh MSW to 28° for degraded MSW. During the triaxial tests under CU condition, the total strength parameters, cohesion and friction angle, were found to vary from 21 to 57 kPa and 1° to 9°, respectively, while the effective strength parameters, cohesion and friction angle varied from 18 to 56 kPa and from 1° to 11°, respectively. Similar to direct shear test results, as the waste degrades an increase in cohesion and slight decrease in friction angle was observed. Decreased friction angle and increased cohesion with increased degradation is believed to be due to the highly cohesive nature of the synthetic MSW. Variation of synthetic MSW properties from this study also suggests that significant changes in geotechnical properties of MSW can occur due to enhanced degradation induced by leachate recirculation.