Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

Leaching behavior of some demolition wastes

Demolition wastes may be used in different civil engineering applications as road constructions, concrete, and embankments or landfill. Regardless its application, leaching tests of the waste should be carried out to assess concentrations of pollutants. Concrete, brick and mixture of concrete, bricks, tiles and ceramics wastes were subject to percolation test—CEN/TS 14405, and batch test—SR EN 12457. The leachates were analyzed with respect to concentration of inorganic elements—arsenic, barium, cadmium, chromium, copper, mercury, molybdenum, nickel, lead, selenium, zinc, fluoride, chloride and sulfate, and organic compounds (phenol index). The concentrations of elements in leachates were compared with the limit values of European regulation for the acceptance of inert wastes at landfills. Generally, the releases of inorganic species in leachates were below limits values. Some waste leachates obtained by percolation and batch test had high values for phenol index.     

Reduction of natural resource consumption in cement production in Japan by waste utilization

According to Japanese government policy, the input of natural resources should be minimized and input resources should be utilized to the greatest extent possible so that, eventually, minimum waste is generated. The cement industry of Japan has worked hard to maximize waste utilization. Focusing on the cumulative amounts of the elements needed for clinker and gross calorific values, this study estimated the extent to which waste utilization has directly or indirectly reduced natural resource consumption and greenhouse gas emissions associated with cement production at 32 factories in Japan and clarified the effect of waste utilization in the cement industry on the resource productivity of Japan based on information for fiscal year 2008. Had no wastes been utilized, the cement industry consumption of limestone would have been 18% higher; of clay, 2,899% higher; and of energy, 22% higher. The utilization of wastes in the mixing and burning process of cement production directly reduced greenhouse gas emissions (12% emitted gas reduction) by a larger amount than the indirect reduction achieved by their utilization during the admixing process (10% reduction). Waste utilization for cement production contributed to an increase in resource productivity of about 8,000 Japanese Yen/ton.     

Enrichment of elements in industrial waste incineration bottom ashes obtained from three different types of incinerators,as studied by ICP-AES and ICP-MS

The elemental composition of the industrial waste incineration bottom ash (IWIBA) samples collected from three different types of incinerator with different kinds of wastes were compared. The major-to-ultratrace elements in the IWIBA samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from milligrams per gram to submicrograms per gram could be determined with relative standard deviations of less than 5%. The IWIBA sample from petrochemical wastes contained lower concentrations of the elements, because fewer mineral constituents were contained in the input waste materials. On the contrary, the elemental concentrations in the IWIBA sample from industrial solid wastes provided the highest values for most elements, while the elemental compositions of the IWIBA sample from food wastes were similar to those of municipal solid waste incineration bottom ash. In addition, it was found from the analytical results that the levels of various heavy metals such as Cr, Mn, Fe, Ni, Cu, As, Zr, Mo, Sb, Ba, and Pb were higher in the IWIBA samples than in municipal solid waste incineration bottom ash. The enrichment factors of the elements in the IWIBA samples were estimated from the analytical results to compare the elemental distributions in incineration bottom ashes in relation to their mining influence factors, which are the indices for human use of the elements.     

Trace elements in the leachate of automobile-scrap shredder waste

Leachate from composite samples of automobile-scrap shredder waste was analyzed for trace elements by inductively coupled plasma atomic emission spectrometry, according to the USEPA Toxicity Characteristic Leaching Procedure for solid waste (TCLP). Analytical results confirmed the existence of several environmentally important elements such as barium, cadmium, copper and lead. However, the concentrations of these elements were below the USEPA regulatory limits for the leachate of solid waste. It was also found that representative average values for trace elements, as well as their variability in the leachate of such heterogeneous solid waste, can be arrived at by analyzing composite samples rather than single samples, if a stratified sample selection and composition plan were implemented. Effect of extraction fluids used in the TCLP method was also investigated. The results indicated that the more acidic extraction fluid can leach more of the elements from the shredder waste, regardless of the selection criterion specified in the method.     

Mercury flows in a zinc smelting facility in South Korea

To prepare for the international mercury convention, the characteristics of mercury emissions from a zinc smelting facility in South Korea have been reviewed and a material flow analysis (MFA) has been conducted in this research. As inputs into the mercury MFA study, zinc ores and sulfuric acid were examined, whereas wastewater sludge, effluence water, spent catalyst, and emissions from the casting and roasting processes were examined as outputs. Mercury concentrations extracted from end products like zinc ingots, cadmium ingots, and sulfuric acid were then analyzed. Our results showed that the wastewater sludge discharged from the zinc smelting process had a relatively higher concentration of mercury, indicating that the concentration of mercury was further enriched in the wastewater sludge. The wastes discharged through the zinc smelting process should be thoroughly controlled, as results of the MFA showed that approximately 89 % of the mercury contained in the original input was later found in the waste. According to this study, the higher the concentration of mercury within zinc ores at the input stage, the higher is the mercury concentration found in the wastewater sludge at the output stage.     

Heavy metal leaching from hydroxide, sulphide and silicate stabilised/solidified wastes

A synthetic, mixed-metal solution has been stabilised by treatment with sodium hydroxide, sodium sulphide, and sodium silicate, respectively. The three stabilised filter cakes have subsequently been solidified using additions of ordinary Portland cement and pulverised fuel ash (PFA) which are typically used in UK solidification operations. Both the stabilised filter cakes and the solidified wastes have been subjected to an equilibrium extraction test, a modified TCLP test, and a series of single-extraction, batch leach tests using an increasingly acidic leachant. Metal release was found to be primarily dependent on the pH of the leachate. Under mildly acidic conditions, the percentages leached from the stabilised and the stabilised/solidified wastes were comparable for most metals. A high-volume fraction of these solidified wastes is occupied by the stabilised filter cake. When they are broken up and tested in single-extraction leach tests, the primary effect of the cementitious additives is to increase the pH of the leachate so that most heavy metals remain insoluble. When tested under acidic leachate conditions, copper, lead, and mercury were found to be particularly well retained within sodium sulphide stabilised wastes. Under similar test conditions, cadmium was leached at very low levels from the sodium silicate stabilised waste.     

Online elemental analysis of process gases with ICP-OES: A case study on waste wood combustion

A mobile sampling and measurement system for the analysis of gaseous and liquid samples in the field was developed. An inductively coupled plasma optical emission spectrometer (ICP-OES), which is built into a van, was used as detector. The analytical system was calibrated with liquid and/or gaseous standards. It was shown that identical mass flows of either gaseous or liquid standards resulted in identical ICP-OES signal intensities. In a field measurement campaign trace and minor elements in the raw flue gas of a waste wood combustor were monitored. Sampling was performed with a highly transport efficient liquid quench system, which allowed to observe temporal variations in the elemental process gas composition. After a change in feedstock an immediate change of the element concentrations in the flue gas was detected. A comparison of the average element concentrations during the combustion of the two feedstocks showed a high reproducibility for matrix elements that are expected to be present in similar concentrations. On the other hand elements that showed strong differences in their concentration in the feedstock were also represented by a higher concentration in the flue gas. Following the temporal variations of different elements revealed strong correlations between a number of elements, such as chlorine with sodium, potassium and zinc, as well as arsenic with lead, and calcium with strontium.     

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.     

Optimization of cement-based stabilization/solidification of organic-containing industrial wastes using organophilic clays

The treatment of organically contaminated industrial wastes by cement-based stabilization/solidification has, in the past, been restricted by the detrimental effect of organic compounds on cement hydration. This work investigates the use of organophilic clays as adsorbents for the organic components of industrial wastes prior to conventional cement-based solidification. Three industrial wastes containing between 2–12% organic carbon and trace heavy metal contamination were treated with a quaternary ammonium salt exchanged clay. The organic component of all three wastes was well adsorbed by the clay. Solidification of the waste/clay mixes produced a monolithic mass with adequate strength and very low leaching of either the organic compounds or the metals. This study has shown that organophilic clays can act as successful adsorbents for the organic contaminants of industrial wastes and enable them to be treated by cement-based solidification.     

Use of recycled plastic in concrete: a review

Numerous waste materials are generated from manufacturing processes, service industries and municipal solid wastes. The increasing awareness about the environment has tremendously contributed to the concerns related with disposal of the generated wastes. Solid waste management is one of the major environmental concerns in the world. With the scarcity of space for landfilling and due to its ever increasing cost, waste utilization has become an attractive alternative to disposal. Research is being carried out on the utilization of waste products in concrete. Such waste products include discarded tires, plastic, glass, steel, burnt foundry sand, and coal combustion by-products (CCBs). Each of these waste products has provided a specific effect on the properties of fresh and hardened concrete. The use of waste products in concrete not only makes it economical, but also helps in reducing disposal problems. Reuse of bulky wastes is considered the best environmental alternative for solving the problem of disposal. One such waste is plastic, which could be used in various applications. However, efforts have also been made to explore its use in concrete/asphalt concrete. The development of new construction materials using recycled plastics is important to both the construction and the plastic recycling industries. This paper presents a detailed review about waste and recycled plastics, waste management options, and research published on the effect of recycled plastic on the fresh and hardened properties of concrete. The effect of recycled and waste plastic on bulk density, air content, workability, compressive strength, splitting tensile strength, modulus of elasticity, impact resistance, permeability, and abrasion resistance is discussed in this paper.     

Calcium phosphate stabilization of fly ash with chloride extraction

Municipal solid waste incinerator by products include fly ash and air pollution control residues. In order to transform these incinerator wastes into reusable mineral species, soluble alkali chlorides must be separated and toxic trace elements must be stabilized in insoluble form. We show that alkali chlorides can be extracted efficiently in an aqueous extraction step combining a calcium phosphate gel precipitation. In such a process, sodium and potassium chlorides are obtained free from calcium salts, and the trace metal ions are immobilized in the calcium phosphate matrix. Moderate calcination of the chemically treated fly ash leads to the formation of cristalline hydroxylapatite. Fly ash spiked with copper ions and treated by this process shows improved stability of metal ions. Leaching tests with water or EDTA reveal a significant drop in metal ion dissolution. Hydroxylapatite may trap toxic metals and also prevent their evaporation during thermal treatments. Incinerator fly ash together with air pollution control residues, treated by the combined chloride extraction and hydroxylapatite formation process may be considered safe to use as a mineral filler in value added products such as road base or cement blocks.     

Characterization of char derived from various types of solid wastes from the standpoint of fuel recovery and pretreatment before landfilling

Carbonization is a kind of pyrolysis process to produce char from organic materials under an inert atmosphere. In this work, chars derived from various solid wastes were characterized from the standpoint of fuel recovery and pretreatment of waste before landfilling. Sixteen kinds of municipal and industrial solid wastes such as residential combustible wastes, non-combustible wastes, bulky wastes, construction and demolition wastes, auto shredder residue, and sludges were carbonized at 500 degrees C for 1h under nitrogen atmosphere. In order to evaluate the quality of char as fuel, proximate analysis and heating value were examined. The composition of raw waste had a significant influence on the quality of produced char. The higher the ratio of woody biomass in waste, the higher heating value of char produced. Moreover, an equation to estimate heating value of char was developed by using the weight fraction of fixed carbon and volatile matter in char. De-ashing and chlorine removal were performed to improve the quality of char. The pulverization and sieving method seems to be effective for separation of incombustibles such as metal rather than ash. Most char met a 0.5 wt% chlorine criterion for utilization as fuel in a shaft blast furnace after it was subjected to repeated water-washing. Carbonization could remove a considerable amount of organic matter from raw waste. In addition, the leaching of heavy metals such as chrome, cadmium, and lead appears to be significantly suppressed by carbonization regardless of the type of raw waste. From these results, carbonization could be considered as a pretreatment method for waste before landfilling, as well as for fuel recovery.     

Leachability of heavy metals from copper blasting grit waste

This investigation presents the results of leaching tests, using the multiple-batch procedure, on cadmium, zinc, copper, lead, and chromium from copper blasting grit waste generated from a shipbuilding and repair company in Bahrain. The leaching test results have demonstrated that the metals tested were generally released in low concentrations except for copper and zinc. Metal leachability appeared to be dependent upon the pH and composition of the leaching medium.     

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.     

Utilization of bottom ash from the incineration of separated wastes as a cement substitute.

Waste incineration is still an essential technology in the concept of integrated waste management. Most of the combustion residues are incinerator bottom ash. It has been discovered that incinerator bottom ash from the incineration of separated waste in the primary chamber of the modular two-stage incinerator mainly consists of metal oxides, especially SiO2 and CaO, in proportions that are quite similar to those in cement and so the feasibility of its application as a substitute for cement in concrete was investigated. It was found that after 28 days, the flexural and compressive strengths of the binder using bottom ash were practically comparable with those of a pure cement mixture. The results show that it is reasonable to use a binder containing incinerator bottom ash for applications in which an early-stage lower strength of concrete element is acceptable.     

Utilization of industrial by-products for the production of controlled low strength materials (CLSM)

Industrial by-products were used for the production of controlled low-strength material (CLSM). CLSM, also known as 'flowable fill' is used as a replacement of compacted soil in cases where the application of the latter is difficult or impossible. The low mechanical requirements (compared with structural concrete) enable the use of industrial by-products for the production of CLSM. In this study cement kiln dust, asphalt dust, coal fly ash, coal bottom ash and quarry waste were tested for the possibility of producing CLSM with large proportions of those wastes. The results showed that in most cases, CLSM with good properties could be made with significant amounts of dust (25-50%w), especially when the dust has some cementing or pozzolanic potential as do fly ash and cement kiln dust.     

Influence of composition variations on the initial alteration rate of vitrified domestic waste incineration fly-ash

Vitrification as a waste stabilization technology has often been considered applicable only to high-level radioactive waste for which, with the use of suitable additives, it yields a vitreous material with excellent chemical durability. It has become apparent in recent years that some waste forms-notably domestic waste incineration fly-ash purification residues--contain most of the ingredients of a vitrified material, although their composition variations are difficult to control. It is thus important to ensure not only that the materials are suitable for vitrification, but also that the resulting product exhibits acceptable long-term behavior under all circumstances. An initial study showed that, allowing for the compensation changes inherent in the melting process builtby EDF**, the residue collected by a single fly-ash dust separation defines a composition range within which the suitability of the vitrified material can be verified. "Vitrified material" refers to a melted material that contains no unmelted inclusions after cooling, but that may contain a variable fraction of crystallized phases. Five composition parameters were identified for the long-term behavior assessment: the concentrations of the three major elements (silicon, aluminum and calcium), the total alkali metal (sodium and potassium) concentration, and the sum of the concentrations of two toxic elements (zinc and lead). The other elements were assumed constant at molar ratios representative of industrial wastes. The experimentation plan methodology applied to the composition range identified fourteen materials suilable for developing and validating first-order models of the material components. The fly-ash composition had a very significant effect on the degree and kinetics and crystallization in the vitrified material within the experimental composition range; the cooling rate was the determining factor for some of the fourteen materials studied. Two crystailine phases predominated: spinels rich in chromium, zinc, aluminum, magnesium and iron formed quickly on cooling, and accounted for about 2 vol% of the final material. Gehelenite (Ca2Al2SiO7) crystallized massively in some vitrified materials, accounting for more than half the final product and giving it a rock-like appearance. The effect of composition alone must therefore be distinguished from the effect of crystallization on the leaching behavior. Soxhlet tests were conducted for 14 days according to a protocol based on that of the French AFNOR draft standard NF-M 60313 to determine the maximum alteration rate in pure water at 100 degrees C. The measured rate ranged from 4 to 40 gm(-2) day(-1), illustrating the crucial role of the silicon concentration: within the test composition range, a low silicon content (< 30 wt%) tended to result in a significantly higher initial rate. However, the initial rate alone is not sufficient to assess the chemical durability of the material. Further tests will be carried out at 25 degrees C under conditions approximating those of a proposed disposal site to highlight the role of the alteration layer and the effect of rising concentrations in solution on the decreasing alteration rate.     

Use of Pb blast furnace slag as a partial substitute for fine aggregate in cement mortar

The technical properties of cement mortars containing natural fine aggregate that is replaced by lead blast furnace slag at 25 and 35% level were assessed at fixed water-to-cement (W/C) ratio and at fixed flow table value. The leachabilities of some toxic elements from the cement mortars were also assessed to test the environmental suitability of the slag for use in preparation of cement mortar. At fixed W/C ratio, the strength of the mortar decreased with increase of the slag content. On the other hand, at fixed consistency, strength increased with increasing slag content in the mortar composition. The concentrations of some toxic elements in the leachates collected from the mortars containing slag were slightly higher than for the control mortar, but the concentrations in the leachates remained within the regulatory limits for recycling in construction applications. For most elements, leaching from a mortar containing 35% of slag was similar to that from a mortar containing 25% of slag. Therefore, 35% of natural sand can be beneficially replaced with Pb slag to produce cement mortar without affecting the mechanical and leaching properties studied in this work.     

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.