Leaching of inorganic contaminants from cement-based waste materials as a result of carbonation during intermittent wetting

Characterization of the leaching behavior of wastes is a crucial step in the environmental assessment for reuse or disposal scenarios. The release of inorganic contaminants from waste materials is typically evaluated by tank leaching of continuously water-saturated material. However, materials, in many field or management scenarios, experience cyclic wetting and drying under varied environmental conditions (i.e. variable relative humidity, atmospheric CO2 or CO2 from biologic activities). During periods of storage in an unsaturated environment, many processes may occur that can influence the release potential and release rate of inorganic constituents. The research presented here was carried out to examine how the phenomena of carbonation during drying influence the release of inorganic contaminants from Portland cement-based materials during cyclic wetting and storage. Batch equilibrium leaching tests were used to determine constituent solubility as a function of pH. Dynamic leaching tests on monolithic material were carried out to determine the rate of constituent release as a function of leaching time and intermittent storage conditions. This paper presents the results observed for three typical waste constituents, arsenic, cadmium and lead.     

Criteria selection for landfills: do we need a limitation on inorganic total content?

The chemistry of the landfill environment is complex and dissolution rates may be higher than in natural systems. As will be shown in this paper, there are often great uncertainties in terms of leaching kinetics and long-term emissions of landfills in general. Leaching tests used in the laboratory may reflect a leaching behaviour not consistent with real landfill scenarios. Geochemical calculations for model systems provide an impression of the possible long-term behaviour of buffered, inorganic landfills. For a buffered carbonate-containing system (this system may be a mono-landfill of slag and/or ash after a few decades and/or centuries), maximums for the solubility of the elements Zn, Cd, Pb and Cu can be calculated while taking into account the presence of gypsum, the complexation in water ("speciation") and other factors influencing solubility. We have made these calculations using the recent version of the geochemical code PHREEQC-2. Finally, we conclude that under most circumstances the total elemental content, or the so-called "total availability," is a valuable assessment tool when combined with other criteria, such as leachable amounts and leachate test results. Exceptions may be carbonate-buffered monofill scenarios (e.g. monofill or quasi-monofill of MSWI residues), where setting limits on some elemental contents (Cu, Zn, Fe and Mn) does not seem to be very useful.     

Environmental impact of ferrochrome slag in road construction

Vargon Alloys in Western Sweden is one of the largest producers of ferrochrome slag in Europe. Ferrochrome slag is a by-product from the production of ferrochrome, an essential component in stainless steel. Extensive tests have been carried out on the physical properties of the ferrochrome slag from Vargon Alloys and it was found to be highly suitable as road construction material. The composition and leaching tests of the ferrochrome slag show that the chromium content is high, 1-3%, although leaching under normal conditions is very low. With the exception of potassium (K), which had a potential leaching capacity (availability test) of around 16%, the leaching of chromium, nickel, zinc and other elements was just a few per cent. However, all these tests were conducted in the laboratory. What happens out in the field, under the influence of acid rain and biological activity, and how does this compare with the laboratory results? To answer this question an investigation was carried out to study the environmental impact of ferrochrome slag in roads that were built in 1994. The investigation includes soil sampling (total content and leachable amounts of metals) and groundwater analysis (filtered and non-filtered samples). In addition, a new method involving the bio-uptake of chromium and other metals by the roots of the dandelion (Taraxacum officinale) was tested. The results show that there was a low migration of particles from the slag to the underlying soil and that the leaching into the groundwater was also low for all the elements analysed. However, there seemed to be a significant uptake of Cr by plants growing with their roots in the slag. An investigation of plant uptake was an important complement to laboratory leaching tests on alternative materials.     

Products of steel slags an opportunity to save natural resources

In Germany, and in the most industrial countries, the use of blast furnace and steel slags as an aggregate for civil engineering, for metallurgical use and as fertiliser has a very long tradition. Since the introduction of the basic oxygen steel making furnace (BOF) process and the electric arc furnace (EAF) process the German steel industry started extensive research on the development of fields of application for BOF and EAF slags. These investigations have been mainly performed by Forschungsgemeinschaft Eisenhüttenschlacken e. V. (FEhS), the Research Association for blast furnace and steel slags. Today steel slags are well characterised and long-term experienced materials mainly used as aggregates for road construction (e.g. asphaltic or unbound layers), as armour-stones for hydraulic engineering constructions (e.g. stabilisation of shores), and as fertiliser for agriculture purposes. These multifarious fields of application could only be achieved because the steelworks influence the quality of slags by a careful selection of raw materials and a suitable process route. Furthermore, subsequent procedures like a treatment of the liquid slag, an appropriate heat treatment and a suitable processing have been developed to ensure that the quality of steel slags is always adequate for the end use. Depending on the respective field of application, the suitability of steel slags has to be proven by determining the technical properties, as well as the environmental compatibility. For this reason test methods have been developed to evaluate the technical properties especially the volume stability and the environmental behaviour. To evaluate the volume stability a suitable test (steam test) has been developed and the results from laboratory tests were compared with the behaviour of steel slags under practical conditions, e.g. in a road. To determine the environmental behaviour leaching tests have been developed. In the meanwhile most of these test methods are drafted or already accepted as a CEN standard and are used for a continuous quality control. Usually the suitability of steel slags is stated by fulfilling the requirements of national and/or international standards and regulations. Based on these standards and regulations in Germany in 1998 about 97% of the produced steel slags have been used as aggregates for road construction (e.g. as surface layer, road base and sub base for high trafficked roads), ways, earthworks, and armourstones for hydraulic structures. Consistent to the successful long-term experience not only products of steel slags but also products of blast furnace slags have been eliminated from the European Waste Catalogue and the European Shipment of Waste Regulation of the European Community, as well as from the lists of OECD for transfrontier movements by the decision of the OECD-Council from 21 September, 1995.     

Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

Kinetics of steel slag leaching: Batch tests and modeling

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can be used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.     

The influence of pH on the leaching behaviour of inorganic components from municipal solid waste APC residues

The influence of pH on the leaching behaviour of air pollution control (APC) residues produced in municipal solid waste incineration (MSWI) is addressed in this study. The residue is considered hazardous waste, and in accordance with their chemical properties, the leaching of contaminants into the environment is the main concern. Several leaching tests can be used for research studies or regulatory purposes, where a wide variety of conditions may be tested. Our work deals mainly with the leaching behaviour of toxic heavy metals (Pb, Cd, Zn, Cr, Ni, Cu) and inorganics associated with soluble salts (Na, K, Ca, Cl). The main goal is to obtain an overview of the leachability of APC residues produced in a Portuguese MSWI process. Among the different variables that may have influence on the leaching behaviour, pH of the leachant solution is the most important one, and was evaluated through pH static tests. The acid neutralization capacity (ANC) of the residue was also determined, which is in the range of 6.2–6.8 meq g^?1 (for pH = 7) and 10.1–11.6 meq g^?1 (for pH = 4). The analysis of the leaching behaviour is particularly important when the leaching is solubility controlled. The amphoteric behaviour of some elements was observed, namely for Pb and Zn, which is characterized through high solubilization at low and high pH and moderate or low solubility at neutral or moderate high pH. The solubility curves for Pb, Cd, Zn, Cr, Ni and Cu as a function of pH were obtained, which are very useful for predicting the leaching behaviour in different scenarios. The solubility of K and Na reveals to be nearly independent of the solution pH and the released amount is mainly availability-controlled. Moreover, the pH static test showed that Cl^? is the most pH-independent species. The APC residue turns out to be a hazardous waste because of the high leaching of lead and chloride. On the other hand, leaching of elements like cadmium, nickel and copper is limited by the high pH of the residue, and as long as the waste keeps its ANC, the risk of mobilization of these elements is low.     

Characteristics of element distributions in an MSW ash melting treatment system

Thermal treatment of municipal solid waste (MSW) has become a common practice in waste volume reduction and resource recovery. For the utilization of molten slag for construction materials and metal recovery, it is important to understand the behavior of heavy metals in the melting process. In this study, the correlation between the contents of elements in feed materials and MSW molten slag and their distributions in the ash melting process, including metal residues, are investigated. The hazardous metal contents in the molten slag were significantly related to the contents of metals in the feed materials. Therefore, the separation of products containing these metals in waste materials could be an effective means of producing environmentally safe molten slag with a low hazardous metals content. The distribution ratios of elements in the ash melting process were also determined. The elements Zn and Pb were found to have a distribution ratio of over 60% in fly ash from the melting furnace and the contents of these metals were also high; therefore, Zn and Pb could be potential target metals for recycling from fly ash from the melting furnace. Meanwhile, Cu, Ni, Mo, Sn, and Sb were found to have distribution ratios of over 60% in the metal residue. Therefore, metal residue could be a good resource for these metals, as the contents of Cu, Ni, Mo, Sn, and Sb in metal residue are higher than those in other output materials.     

Comparison of leaching tests to determine and quantify the release of inorganic contaminants in demolition waste

The changes in waste management policy caused by the massive generation of waste materials (e.g. construction and demolition waste material, municipal waste incineration products) has led to an increase in the reuse and recycling of waste materials. For environmental risk assessment, test procedures are necessary to examine waste materials before they can be reused. In this article, results of column and lysimeter leaching tests having been applied to inorganic compounds in a reference demolition waste material are presented. The results show a good agreement between the leaching behaviour determined with the lysimeter unit and the column units used in the laboratory. In view of less time and system requirements compared to lysimeter systems, laboratory column units can be considered as a practicable instrument to assess the time-dependent release of inorganic compounds under conditions similar to those encountered in a natural environment. The high concentrations of elements in the seepage water at the initial stage of elution are reflected by the laboratory column leaching tests. In particular, authorities or laboratories might benefit and have an easy-to-use, but nevertheless reliable, method to serve as a basis for decision-making.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液，考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr，Zn，Cu，Pb，Ni，As，Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中，醋酸缓冲溶液法的重金属浸出种类最多，且浸出量最大;Cd和Cr对环境具有较高的潜在危害性，Cu次之，Zn，Pb，Ni，As主要以残渣态形式存在，对环境的直接危害性较低。     

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.     

Life-cycle impacts of the use of industrial by-products in road and earth construction

A two-stage study "Life cycle analysis of road construction and earthworks" was part of a more extensive Finnish research project "Assessment of the applicability of secondary products in earthworks". In the first stage of this work a life-cycle impact assessment procedure for the comparison and evaluation of alternative road and earth constructions was developed. Additionally, a database containing the environmental burdens of the most significant construction materials and unit operations was constructed. In order to evaluate the applicability of the procedure, the use of coal ash, crushed concrete waste and granulated blast-furnace slag in road construction was evaluated in case studies. The use of these secondary products was also compared with the use of natural materials in corresponding applications. The aim of the second stage was to transfer the assembled data for utilisation as a practical model by creating an inventory analysis program to calculate and compare the life cycle impacts of the most common road constructions and foundation engineering methods. The data obtained in the first stage was also augmented to the extent necessary for this purpose. The results of case studies indicate that the production and transport of the materials used in road constructions produce the most significant environmental burdens. Production of the bitumen and cement, crushing of materials and transport of materials are the most energy consuming single life-cycle stages of the construction. A large part of the emissions to atmosphere originates from energy production. In the expert assessment, consumption of natural materials and leaching behaviour were also regarded as being of great significance.     

Physicochemical properties of slags produced at various amounts of iron addition in lead smelting

In the process of lead production from lead-bearing materials generated in copper metallurgy, a large amount of hazardous waste in the form of slag is produced. To assess the effect of the slag on the environment, its physicochemical properties were determined. In this study, the following methods were used: wavelength dispersive X-ray fluorescence (WD XRF), X-ray diffraction (XRD), and Bunte-Baum-Reerink method to determine softening and melting points, as well as viscosity examination and leaching tests. The measurements were performed on the slag produced with two different amounts of iron addition to the lead smelting process. The resulting slags, an oxide rich phase slag and a sulfide rich phase slag have different compositions and physicochemical properties. It was found that the increase in iron addition causes an increase in the softening melting point of the oxide rich phase slag by about 100 °C, and a twofold increase in the viscosity of both slag phases. The increase in iron addition also results in the decrease in As leachability and increase in Zn, Fe, and Cu leachability from the slags. Slag produced with increased iron addition has a greater impact on the environment.

     

Percolation and batch leaching tests to assess release of inorganic pollutants from municipal solid waste incinerator residues

In this study, percolation and batch leaching tests were considered in order to characterize the behaviour of air pollution control (APC) residues produced in a municipal solid waste incinerator (MSWI) as a function of the liquid to solid ratio (L/S). This waste is hazardous, and taking into account their physical and chemical properties, leaching of contaminants into the environment is the main concern. In our work the leaching behaviour of toxic heavy metals (Pb, Zn, Cr, Ni and Cu) and inorganics associated with soluble salts (Na, K, Ca and Cl) was addressed. Although pH of the leaching solution is the most important variable, L/S may also play an important role in leaching processes. In our work, results from column and batch tests were compared in terms of concentration (mg/L) and releasing (mg/kg). The APC residues revealed to be hazardous according to both tests, and both Pb and Cl⁻ far exceeded the regulatory thresholds. The material exhibits high solubility, and when the liquid to solid ratio was high, more than 50% can be solubilised. The patterns of release may be in some cases availability or solubility controlled, and the former was easier to identify. When the results from column and batch experiments were compared by representing the cumulative released amounts (in mg/kg) as a function of L/S, both curves match for Zn, Ni, Cu, K, Na, Cl and Ca, but for Cr and Pb a significant difference was observed. In fact, the column experiments revealed that under percolation conditions it should be expected slow releasing of Pb along time. From this study, it can be concluded that the released amounts obtained in batch experiments for a certain L/S should be considered as the worst case for medium term. Some simple models proposed on the literature and based on local equilibrium assumption showed good fitting to experimental data for soluble species (non-reactive solutes).     

Road soil retention of Pb leached from MSWI bottom ash

Municipal solid waste incinerator (MSWI) bottom ash may be used as a road construction material; it potentially contains however a sizable quantity of heavy metals, which under the effect of rainfall infiltration through the road structure can be leached out from the material and infiltrate into the underlying soil. An eco-compatibility assessment of MSWI bottom ash reuse in road construction applications necessitates examining the solubility and retention of heavy metals in road soils. This study is dedicated to Pb transfer, sorption and desorption (NEN 7341 standard test) within various soils. These experiments yield results relative to the interaction between road soils and an MSWI bottom ash leachate representative of a "fresh" product, with a high leaching potential. For the soils investigated, the sorption of lead varies between 90% and 99%. For an extraction at pH 7, Pb release is very low (<2%) for all soils, while at pH 4 leaching varies between 4% and 47%. This work shows that Pb may be fixed by some types of road soil in mostly stable forms.     

Vitrification for reclaiming spent alkaline batteries

The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification. Specimens were vitrified using an electrical heating furnace at 1400 °C and the output products included slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn, and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline batteries.     

脱硫用电石渣的重金属浸出特性及其对环境的影响

针对电厂用脱硫剂电石渣,分析了其基本组成及重金属浸出特性,为电厂脱硫设施的参数设计和环境影响评价提供依据和参考。研究结果表明,脱硫用电石渣主要成分为Ca（OH）2,含量在40%～50%之间;在8种重金属的含量中,只有Cd的含量超出土壤质量三级标准的要求,基本不会对土壤造成污染。浸出毒性试验表明,电石渣及其脱硫产物属于非危险废物,其各种重金属的浸出浓度主要受其本身重金属含量和最终pH的影响,这种影响在Pb、Cu和Cd上表现得较为突出,酸性环境下更有利于他们的浸出;碱性环境下有利于Pb和Ni的浸出。     

Leaching from solid waste incineration ashes used in cement-treated base layers for pavements

Waste incineration bottom ash and treated flue gas cleaning products mixed with 2.5% of cement (50 kg/m3) were tested in the laboratory in terms of compressive strength and tank leaching tests over a 64-day period. Although the material displayed lower mechanical strength than a reference concrete, the strength still was sufficient for use as a base layer for roads. The metal content in the incineration-residue-based specimens was up to 100 times higher than in the reference concrete, suggesting that the mixed waste incineration residue should be used only for dedicated purposes. The leaching of Cl and Na was increased by a factor of 20-100 from the incineration-residue-based specimens as compared to the reference, while the leaching of K, Ca and SO4 was increased by a factor of 2-10. The leaching of heavy metals was also higher from the incineration-residue-based specimens than from the reference with respect to Cu (50 times), Cd, Pb and Zn (5 times), but not with respect to Cr and Ni. The leaching curves did only allow for a closer evaluation of the leaching process in a few cases. The physical retention of the constituents seemed to be the same in the reference as in the incineration-residue-based specimens. Heavy metal leaching was limited by enhanced chemical retention in the incineration-residue-specimens as compared to the reference. Since no quality criteria in terms of leaching from a monolithic material are currently available, the leaching issue must be evaluated case by case.     

Geochemical anomalies from bottom ash in a road construction--comparison of the leaching potential between an ash road and the surroundings

A study was performed between June 2001 and December 2004 with the primary objective of assessing long-term leaching from municipal solid waste incineration bottom ash in a test road construction in relation to a reference road made up of conventional materials and the natural geochemical conditions in the surroundings. The metal leaching from the test road and the reference road was compared with the natural weathering in the regional surroundings for three time scales: 16, 80 and 1000 years. The results show that Cu and Zn cause a geochemical anomaly from the test road compared with the surroundings. The leaching of Cu from the test road is initially high but will decline with time and will in the long term be exceeded by natural weathering. Zn on the other hand has low initial leaching, which will increase with time and will in the long term exceed that of the test road and the surroundings by a factor of 100-300. For the other metals studied, Al, Na, K and Mg, there is only very limited leaching over time and the potential accumulation will not exceed the background values in a 1000 years.     

Behaviour of Cd,Cr, Mn,Ni, Pb,and Zn in sewage sludge incineration by fluidised bed furnace

Cd, Cr, Mn, Ni, Pb, and Zn behaviour during sewage sludge incineration was investigated in seven pilot tests using a circulating fluidised bed furnace. Dewatered sludge at a solids concentration of 15-18% was fed to the furnace either alone (two tests) or spiked with chlorinated organic compounds (five tests). The behaviour of metals in the fluidised bed furnace was studied by comparing metal concentrations in the two main ash streams: ash separated from the cyclone immediately following the fluidised bed furnace, and fly ash recovered in the final bag filter. A metal enrichment factor was defined as the ratio of metal concentration between filter ash and cyclone ash. Only Cd and Pb showed any significant enrichment. Their enrichment factors were mainly affected by chlorine concentration in the feed sludge. To check whether simple equilibrium models may explain and predict metal behaviour, experimental data were compared with percentage of the metal vaporisation in the combustion chamber predicted using a thermodynamic model. Discrepancies between model predictions and experimental results are accounted for by considering that kinetics may be a limiting factor in the formation of metal chloride gaseous species. Due to the very short sludge residence time in the fluidised bed furnace, the gaseous compounds have little chance to evolve completely.