Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

Immobilization of copper flotation waste using red mud and clinoptilolite

The flash smelting process has been used in the copper industry for a number of years and has replaced most of the reverberatory applications, known as conventional copper smelting processes. Copper smelters produce large amounts of copper slag or copper flotation waste and the dumping of these quantities of copper slag causes economic, environmental and space problems. The aim of this study was to perform a laboratory investigation to assess the feasibility of immobilizing the heavy metals contained in copper flotation waste. For this purpose, samples of copper flotation waste were immobilized with relatively small proportions of red mud and large proportions of clinoptilolite. The results of laboratory leaching demonstrate that addition of red mud and clinoptilolite to the copper flotation waste drastically reduced the heavy metal content in the effluent and the red mud performed better than clinoptilolite. This study also compared the leaching behaviour of metals in copper flotation waste by short-time extraction tests such as the toxicity characteristic leaching procedure (TCLP), deionized water (DI) and field leach test (FLT). The results of leach tests showed that the results of the FLT and DI methods were close and generally lower than those of the TCLP methods.     

Factors affecting TCLP lead leachability from computer CPUs

The factors impacting lead leachability from computer central processing units (CPUs) during the toxicity characteristic leaching procedure (TCLP) were investigated. Several CPUs were disassembled and their component materials were decreased in size to meet the requirements of the TCLP. The impact of CPU composition was examined by leaching different combinations of the CPU components. The ferrous metal content of the mixture greatly impacted lead leaching. TCLP lead concentrations of CPUs predicted by leaching the lead-bearing printed wire boards alone were much greater than those measured when the ferrous metal of the CPU was included in the mixture. The leaching of iron and zinc from the galvanized steel components of the CPU created electrochemical conditions where lead was less soluble. Additional size reduction beyond that required by the TCLP did not result in additional lead leaching. As the volume of head space above the leaching solution increased, the concentration of lead measured increased as well.     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.     

Long-term leaching test of incinerator bottom ash: evaluation of Cu partition

Two types of leaching tests were performed on the bottom ash from municipal solid waste incinerators. A short-term batch test specified by the America Nuclear Society (ANS) and long-term column tests with acetic acid (pH 5.2) as leaching solution were used to evaluate copper leachability. The Cu leaching after the 5-d ANS test is about 1% of the original Cu content of 5300 mg/kg. Upon addition of a stabilizing agent, the Cu leaching quantity is reduced; the extent of reduction depends on the type of chemical used (phosphate, carbonate and sulfide). The 1.6% Na(2)S addition showed negligible Cu leaching, and Na(2)S was, therefore, used in subsequent column tests. The 30-d column test indicates a steady increase of Cu leaching amount with time and reaches about 1.5% of the original Cu content after 30 d. A 180-d column test further increased the Cu leaching to about 5.1% of the original Cu content, whereas no appreciable Cu leaching was found with the addition of 1.6% Na(2)S. A sequential extraction was conducted on the raw ash, ash with the addition of Na(2)S and the residue ash after 30 d of operation to characterize Cu affinity for different solid fractions. The data were used to evaluate the fate of Cu through these interactions.     

Solidification and recycling of incinerator bottom ash through the addition of colloidal silica (SiO2) solution

The possibility of using incinerator bottom ash as a substitute for natural aggregates was investigated. Rough, porous surface of bottom ash, which diminishes the strength of solidified products, was improved by colloidal silica solution. As a result, a significant increase of mechanical strength was accomplished by a slight amount of silica (<1 wt% to total). Moreover, pozzolanic reaction was induced in initial cement hydration due to the nano-particle size of about 20 nm in colloidal silica solution. Cylindrical specimens and bricks were prepared from bottom ash added to a colloidal silica (SiO2) solution and cement, and then their compressive strengths were evaluated. Cylindrical specimens showed an increase of approximately 60% in compressive strength when colloidal solution containing 4 wt% silica particles was sprayed onto the bottom ash. The strength of bricks containing colloidal silica was in excess of 20 MPa, which meets the requirement of construction materials. Results of leaching tests based on Toxicity Characteristic Leaching Procedure (TCLP) proved that the solidified bottom ash possessed good chemical stability.     

Use of flue gas desulphurisation (FGD) waste and rejected fly ash in waste stabilization/solidification systems

Stabilization/solidification (S/S) processes have been used as the final treatment step for hazardous wastes prior to land disposal. Fly ash is a by-product of coal-fired power generation; a significant proportion of this material is low-grade, reject material (rFA) that is unsuitable as a cement replacement due to its high carbon content and large particle size (>45 microm). Flue gas desulphurization (FGD) sludge is a by-product from the air pollution control systems used in coal-fired power plants. The objective of this work was to investigate the performance of S/S waste binder systems containing these two waste materials (rFA and FGD). Strength tests show that cement-based waste forms with rFA and FGD replacement were suitable for disposal in landfills. The addition of an appropriate quantity of Ca(OH)2 and FGD reduces the deleterious effect of heavy metals on strength development. Results of TCLP testing and the progressive TCLP test show that cement-rFA-Ca(OH)2 systems with a range of FGD additions can form an effective S/S binder. The Leachability Index indicates that cement-based waste forms with rFA replacement were effective in reducing the mobility of heavy metals.     

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).     

CuMn/ZrAlTi-堇青石蜂窝陶瓷催化氧化法处理含酚废水

选取球状堇青石蜂窝陶瓷作为催化剂基体,制备了CuMn/ZrAlTi-堇青石蜂窝陶瓷催化剂,采用XRD、X射线光电子能谱(XPS)、比表面积测定(BET)等分析方法对其进行了表征,测定了其催化湿式氧化含酚废水的活性及催化剂抗压强度、脱落率、Cu2+溶出浓度等性能指标.实验结果表明:CuMn/ZrAlTi-堇青石蜂窝陶瓷催化剂在反应温度220℃、压力5 MPa、搅拌速率为600 r/min时,催化湿式氧化反应300 min,COD去除率可达94.6％;球状CuMn/ZrAlTi-堇青石蜂窝陶瓷催化剂具有强度高、易装填、易更换、脱落率低等特点,Cu2+溶出浓度低于国家排放标准,适合工业化处理含酚废水.     

Leaching toxicity and heavy metal bioavailability of medical waste incineration fly ash

The aim of this study was to provide a comprehensive risk assessment for medical waste incineration fly ash from another aspect through various leaching methods. The differences and connections between leaching concentrations achieved via the toxicity characteristic leaching procedure (TCLP), the physiologically based extraction test (PBET) and the sequential extraction procedure were also described. Heavy metal contents of the used medical waste incineration fly ash were 1.7–31 times higher than that from Japan, indicating poor medical waste management in China. The fly ash leaching concentration in the TCLP test exceeded the regulation value and can be characterized as hazardous waste under current regulations. However, the PBET concentrations were only 1/10 of the TCLP value or even lower, and the calculated ingested contents of all heavy metals were lower than tolerable daily intake, demonstrating that TCLP might have overestimated the environment risk to some degree. The leaching metal content of TCLP ranged from exchangeable to residual forms, and the leaching percentage varied from 7.75 to 92.55 %, while the content for PBET was equal to or lower than the exchangeable form.     

Vitrification of electric arc furnace dusts

Electric arc furnace baghouse dust (EAFD), a waste by-product of the steelmaking process, contains the elements that are volatilized from the charge during the melting (Cr, Pb, Zn, Cu and Cd). The results of leaching tests show that the concentration of these elements exceeds the regulatory limits. Consequently, EAFD cannot be disposed of in ordinary landfill sites without stabilization of the heavy metals. In this work, the vitrification of EAFD, from both carbon and stainless steel productions, were studied. The vitrification process was selected as the inertizing process because it permits the immobilization of the hazardous elements in the glass network and represents an environmentally acceptable method for the stabilization of this waste. Classes of various compositions were obtained by mixing EAFD with glass cullet and sand. The EAFD and the glass products were characterized by DTA, TG, X-ray analysis and by the TCLP test. The results show that the stability of the product is influenced by the glass structure, which mainly depends on the Si/O ratio. Secondary crystallization heat-treatment were carried out on some samples. The results highlighted the formation of spinel phases, which reduced the chemical durability in acid media. The possibility to recover Zn from carbon steel production EAFD was investigated and about 60-70% of metal recovery was obtained. The resulting glass show higher chemical stability than glasses obtained without metal recovery.     

Copper leaching of MSWI bottom ash co-disposed with refuse: Effect of short-term accelerated weathering

Co-disposal of refuse with municipal solid waste incinerator (MSWI) bottom ash (IBA) either multi-layered as landfill cover or mixed with refuse could pose additional risk to the environment because of enhanced leaching of heavy metals, especially Cu. This study applied short-term accelerated weathering to IBA, and monitored the mineralogical and chemical properties of IBA during the weathering process. Cu extractability of the weathered IBA was then evaluated using standard leaching protocols (i.e. SPLP and TCLP) and co-disposal leaching procedure. The results showed that weathering had little or no beneficial effect on Cu leaching in SPLP and TCLP, which can be explained by the adsorption and complexation of Cu with DOM. However, the Cu leaching of weathered IBA was reduced significantly when situated in fresh simulated landfill leachate. This was attributed to weakening Cu complexation with fulvic acid or hydrophilic fractions and/or intensifying Cu absorption to neoformed hydr(oxide) minerals in weathered IBA. The amount of total leaching Cu and Cu in free or labile complex fraction (the fraction with the highest mobility and bio-toxicity) of the 408-h weathered IBA were remarkably decreased by 86.3% and 97.6% in the 15-day co-disposal leaching test. Accelerated weathering of IBA may be an effective pretreatment method to decrease Cu leaching prior to its co-disposal with refuse.     

Treatment of organic-contaminated industrial wastes using cement-based stabilization/solidification—I. Microstructural analysis of cement-organic interactions

The major deficiencies in cement-based stabilization/solidification (S/S) processes are their inability to treat inorganic wastes contaminated with organic material or organic wastes. In general, organic compounds are poorly retained in a cement matrix and frequently have a detrimental, poorly understood, effect upon cement hydration and strength development. These interactions need to be understood as fully as possible, however, if S/S processes are to be developed in ways which will assure the long-term integrity of the resultant products.The work presented in this paper investigates some fundamental aspects of the interactions of two organic compounds, 3-chlorophenol and chloronaphthalene, with a cement matrix. Phenolic compounds have previously been shown to have a detrimental effect upon the macrostructural properties of ordinary Portland cement (OPC), for example, the strength, setting rate and leachability (Montgomery et al. 1988). Microstructural studies in this work have shown that 3-chlorophenol inhibits the hydration of tricalcium silicate (C₃S in cement chemists' notation), with up to 90% of the C₃S remaining after 28 days for highly dosed 3-chlorophenol/OPC samples. The formation of ettringite was found to be increased by the presence of 3-chlorophenol and its conversion to monosulphate inhibited. Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analysis of the samples showed that 3-chlorophenol crystallized in the cement matrix to form discrete crystals containing calcium and phenol. In contrast, chloronaphthalene had no observable effect on hydration reactions. In a subsequent paper, detailed studies will be presented showing how these deleterious effects can be minimized by the use of organophilic clays as a pre-solidification adsorbent.     

Effects of cement on redistribution of trace metals and dissolution of organics in sewage sludge and its inorganic waste-amended products

The suitability of using cement-stabilized sludge products as artificial soils in earth works was evaluated. The sludge products investigated were cemented sludge, cement-treated clay-amended sludge (SS+MC), and cement-treated copper slag-amended sludge (SS+CS). The leachability of lead (Pb), zinc (Zn), copper (Cu), and chromium (Cr) were assessed using the sequential extraction technique, toxicity characteristic leaching procedure (TCLP), NEN 7341 availability test, and column leaching test. The results indicated that Zn leachability was reduced in all the cement-stabilized sludge products. In contrast, Cu was transferred from the organic fraction to the readily leachable phases in the cement-stabilized sludge products and therefore exhibited increased leachability. The increased Cu leachability could be attributed to dissolution of humic substances in the sludge as a result of elevated pH. Good correlation between dissolved organic carbon (DOC) and heavy metal leaching from the cement-stabilized sludge products was observed in the column leaching experiment. Even with a cement percentage as small as 12.5%, calcium silicate hydrate (C-S-H) was formed in the SS+MC and SS+CS products. Inclusion of the marine clay in the SS+MC products could reduce the leaching potentials of Zn, and this was the great advantage of the marine clay over the copper slag for sludge amendment.     

Leaching of wood ash products aimed for spreading in forest floors--influence of method and L/S ratio

Use of biofuels in the form of logging residues is increasing in the European countries. This intensive forestry, where entire trees are removed from the felling sites, may contribute to a negative nutrient balance in the forest soil. Recycling of ash from the combustion of clean wood fuel, sometimes in combination with limestone or additives/binders, back into the forest soil could maintain the soil nutrient reservoir intact. Before spreading ash, it is important to determine its contents and, particularly, its decomposition pattern using reliable laboratory leaching tests. In this study, mineralogy and the leaching of Na, Ca, K, Mg, Mn, Al, Cu, Fe, P, and Zn from wood ash pellets and granules, produced both from green liquor sludge and fly ash, are examined by XRD and by subjecting these substances to three different laboratory leaching tests: upflow percolation (CEN/TS 14405), batch leaching (SS-EN12457), and a new Swedish leaching test using a magnetic stirrer. Mineral phases such as quartz, ettringite, calcite, gehlenite, and aphtitalite were identified in the ash granules and in the ash/green liquor sludge granules, by means of XRD. Six additional minerals were detected in the granules of ash only, and another six in the ash/green liquor sludge granules. At L/S 2, the batch leaching test resulted in the highest amounts of elements leached and the upflow percolation test the lowest. At L/S 10, both the batch leaching test and the upflow percolation test resulted in high amounts of elements leached. The batch leaching test at L/S 10 complies quite well with the percolation test and could be suitable for ash/green liquor sludge granule evaluation in daily practice. The magnetic stirrer test seems to underestimate the release potential of elements from granules. The batch test is simple to perform, and has the ability to dissolve 70-80% of the elements with the highest mobility from the materials under study.     

草酸钴废料协同浸出水钴矿中的钴和铜

利用草酸钴废料协同浸出水钴矿中的钴和铜，考察了工艺条件对浸出率的影响，并推荐了一种二段浸出及后续生产草酸钴的工艺流程。实验结果表明，在草酸钴废料与水钴矿的质量比为20%、反应时间为120 min、反应温度为85 ℃、初始H2SO4浓度为1.00 mol/L、液固比为4 mL/g的最佳工艺条件下，钴和铜的浸出率分别达到98.82%和96.24%。该工艺应用于水钴矿的还原浸出，在回收利用草酸钴废料的同时，降低了还原剂的消耗，且对浸出液后续处理工艺无影响。     

Metal toxicity assessment of mobile phone parts using Milli Q water

Environmentally safe disposal of end-of-life (EoL) or discarded mobile phone is a serious problem on account of their ever increasing number and toxic metals contents. In the present work, metal toxicity of mobile phone plastics, printed wire boards (PWBs) and batteries were assessed through dynamic batch leaching using Milli Q (MQ) water. Phone plastics failed Toxicity Characterization Leaching Procedure (TCLP) and Waste Extraction Test (WET) for Pb as the cumulative amount of Pb leached from plastics (5.33 mg/l) exceeded the regulatory limits (5.0 mg/l) used in characterizing a waste as hazardous. Similarly, the average cumulative amount (21.83 mg/l) of Ni leached from PWBs exceeded the regulatory limit of 20 mg/l and thus PWBs failed WET. Metals leached from batteries in small amounts (Cr: 0.40 mg/l and Ni: 0.15 mg/l). The presence of Fe in the batteries and its precipitation as oxides/hydroxides in the leaching solution hindered the leaching of other metals in MQ water. Both plastics and PWBs should be treated as hazardous waste and should not be disposed in open landfills. Further, MQ water leaching could provide good simulation of metals leaching from the mobile phones disposed at landfill sites.     

氧化改性活性炭催化脱除NO的性能

将活性炭（AC）应用于烟气脱硝中，其自身损耗和脱硝效率是关注焦点。采用不同氧化剂（KMnO4、HNO3、（NH4）2S2O8和H2O2）对AC进行氧化改性，对所得催化剂进行了TG、FTIR、H2-TPR和XPS表征，并对其脱NO活性进行了评价。对AC进行浸渍回流处理，可使AC表面含氧官能团增加，尤其是羧基和羰基等酸性含氧官能团。TG分析结果表明：在没有O2存在时，催化剂表面的O会与NO发生反应，导致催化剂自身损耗；在O2存在时，NO主要与O2中的O反应，因而在一定温度范围内不会发生催化剂自身损耗；同时AC表面的含氧官能团能加速NO的化学吸附活化，从而提高催化剂的脱NO活性。KMnO4改性的AC在180 ℃具有高催化活性，这归因于催化剂表面丰富的含氧官能团以及高价态Mn的存在。     

Treatment of exhaust fluorescent lamps to recover yttrium: experimental and process analyses

The paper deals with recovery of yttrium from fluorescent powder coming from dismantling of spent fluorescent tubes. Metals are leached by using different acids (nitric, hydrochloric and sulphuric) and ammonia in different leaching tests. These tests show that ammonia is not suitable to recover yttrium, whereas HNO(3) produces toxic vapours. A full factorial design is carried out with HCl and H(2)SO(4) to evaluate the influence of operating factors. HCl and H(2)SO(4) leaching systems give similar results in terms of yttrium extraction yield, but the last one allows to reduce calcium extraction with subsequent advantage during recovery of yttrium compounds in the downstream. The greatest extraction of yttrium is obtained by 20% w/v S/L ratio, 4N H(2)SO(4) concentration and 90°C. Yttrium and calcium yields are nearly 85% and 5%, respectively. The analysis of variance shows that acid concentration alone and interaction between acid and pulp density have a significant positive effect on yttrium solubilization for both HCl and H(2)SO(4) medium. Two models are empirically developed to estimate yttrium and calcium concentration during leaching. Precipitation tests demonstrate that at least the stoichiometric amount of oxalic acid is necessary to recover yttrium efficiently and a pure yttrium oxalate n-hydrate can be produced (99% grade). The process is economically feasible if other components of the fluorescent lamps (glass, ferrous and non-ferrous scraps) are recovered after the equipment dismantling and valorized, besides the cost that is usually paid to recycling companies for collection, treatment or final disposal of such fluorescent powders.     

甘氨酸母液脱色废活性炭的微波-Fenton试剂氧化法再生

采用微波-Fenton试剂氧化法对甘氨酸母液脱色过程中产生的废活性炭进行再生,考察了废活性炭再生率的影响因素,并用SEM对再生活性炭进行了表征.实验结果表明,在Fenton试剂中n(H2O2)∶n(Fe2+)为24∶1、H2O2的浓度为25 mmol/L、溶液pH为3、反应温度为55℃、反应时间为18 min、微波功率为600 W时,废活性炭的再生率可达到75.80％.