Fate of heavy metals during municipal solid waste incineration in Shanghai

The transfer behavior of heavy metals during municipal solid waste (MSW) incineration was investigated based on 2-year field measurements in two large-scale incinerators in Shanghai. Great temporal and spatial diversification was observed. Most of Hg and Cd were evaporated and then removed by air pollution control (APC) system through condensation and adsorption processes, thus being enriched in the fine APC residues particles. Cr, Cu, and Ni were transferred into the APC residues mainly by entrainment, and distributed uniformly in the two residues flows, as well as in the ash particles with different sizes. Pb and Zn in the APC residues were from both entrainment and evaporation, resulting in the higher concentrations (two to four times) compared with the bottom ash. Arsenic was transported into the flue gas mainly by evaporation, however, its transfer coefficient was lower. Though the heavy metals contents in the APC residues were higher than that in bottom ash, more than 80% of As, Cr, Cu, and Ni, 74-94% of Zn, as well as 46-79% of Pb remained in the bottom ash, due to its high mass ratio (85-93%) in the residues. While 47-73% of Cd and 60-100% of Hg were transferred into the APC residues, respectively.     

垃圾填埋场的地震响应特性分析

采用二维等效线性有限元程序对典型山谷型填埋场进行非线性动力分析。综合考虑了地基刚度、动荷周期、幅值及填埋体的刚度对填埋场顶部加速度响应特性的影响,从地基基本周期 、地震卓越周期 和填埋场的基本周期 三者相互关系的角度得出了填埋场地震响应的普适性规律：各种影响因素都是通过改变这三个周期的相对大小关系来改变填埋场的响应情况。当 ＝ ＝ 时,填埋场顶部的响应达到最大;如果 ＝ 或者 ＝ ,则填埋场的动力响应值中等;三个周期相差甚远时,填埋场的响应值最小。通常情况下 较大, 较小,对于压得很密实或者填埋时间长久的填埋场,剪切波速增加使 减小;地震幅值的增加,由于材料的非线性使得 和 增加,从而容易使周期接近,而激发较大响应。该结果对填埋场抗震设计有指导意义。     

Characteristics of heavy metals on particles with different sizes from municipal solid waste incineration

Information on the concentration and size distribution of particles in the flue gas streams is essential for selecting and designing particle removal systems. Two municipal solid waste incinerators (MWIs) were selected for conducting flue gas sampling to determine the particulate distribution and heavy metals concentration on particles with different sizes by US EPA Method 5 sampling train and a cascade impactor. In addition, the characteristics of heavy metals contained on particles were investigated via isokinetic sampling of flue gas stream of air pollution control devices (APCDs). The experimental results indicated that average particulate matter (PM) concentrations at APCDs inlet were 2288.2+/-825.9 and 3069.2+/-810. 0mg/Nm(3), while the concentrations of PM at stack were 1.51+/-0.20 and 14.81+/-4.52mg/Nm(3) in MWI-A and MWI-B, respectively. The differential mass size distribution of PM and differential elemental size distribution of Zn, Pb, and Cu in front of APCDs were of bimodal forms. Results indicate that Zn>Pb>Cu in order of mass concentration in each stage. The fine particles represent approximately 70% and the coarse particles account for the rest 30% of total particulate matters collected on eight stages for both incinerators. Zn, Pb and Cu on fine particles account for approximately 80% and those on the coarse particles are less than 20% of the total heavy metals collected on eight stages of the cascade impactor for both incinerators.     

Effects of water-washing pretreatment on bioleaching of heavy metals from municipal solid waste incinerator fly ash

Previous studies demonstrated that the bioleaching of municipal solid waste incinerator fly ash by Aspergillus niger was an efficient "green technology" for heavy metals removal, however, it demanded a long operational period. In this study, water-washing was used as a fly ash pretreatment before the bioleaching process (one-step and two-step). This pretreatment extracted 50.6% of K, 41.1% of Na, 5.2% of Ca and 1% of Cr from the fly ash. Due to the dissolution of alkali chlorides which hold particles together, fly ash particles were smashed into smaller granules by the hydraulic flushing action caused by vibration. After the pretreatment, the lag phase and bioleaching period were reduced by 45 and 30%, respectively, in one-step bioleaching of 1% (w/v) fly ash. Meanwhile, the metals extraction yield both in one-step and two-step bioleaching was increased markedly, e.g. in two-step bioleaching, 96% Cd, 91% Mn, 73% Pb, 68% Zn, 35% Cr and 30% Fe was extracted from 1% water-washed fly ash, respectively. The reduction of the bioleaching period and improvement of metals extraction yield will likely allow the practical application of the bioleaching technology for heavy metals removal from fly ash.     

Stabilization of heavy metals in municipal solid waste incineration ash using mixed ferrous/ferric sulfate solution

The purpose of this study is to test the effectiveness of mixing FeSO4 and Fe2(SO4)(3) solutions with municipal solid waste incineration (MSWI) ash at room temperature to prevent heavy metals in treated ash from being dissolved. After conducting toxicity characteristic leaching procedure (TCLP) tests nine times, the accumulation of extracted lead from treated scrubber ash was lower than regulated limits by the sixth test. X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive spectrometer (SEM/EDS) studies of the ash revealed that the mixed solution reacted with the scrubber ash to form Ca4Fe9O17, which coated the surface of ash particles.     

Extraction of heavy metals from municipal solid waste incinerator (MSWI) bottom ash with organic solutions

Municipal solid waste incinerator (MSWI) bottom ash often cannot be recycled as construction material in Flanders, because leaching of Cu exceeds the limit value of 0.5mg/kg. Leaching of other components such as Mo and Sb is critical as well, but limit values for these elements are to date only informal. A treatment technique was investigated to lower pollutant leaching: extraction with solutions of organic complexants to remove Cu. Six different solutions were used, of which washing with citric acid and ammonium citrate decreases Cu leaching to below the limit value. Extraction was then performed with different concentrations of ammonium citrate. Subsequent washing of the extracted material with distilled water appears to be vital to remove all residual ammonium citrate. Extraction with a 0.2M solution of ammonium citrate followed by three washing steps decreases metal leaching to below the limit values.     

Competitive sorption and desorption of heavy metals by individual soil components

Knowledge of sorption and desorption of heavy metals by individual soil components should be useful for modelling the behaviour of soils of arbitrary composition when contaminated by heavy metals, and for designing amendments increasing the fixation of heavy metals by soils polluted by these species. In this study the competitive sorption and desorption of Cd, Cr, Cu, Ni, Pb and Zn by humified organic matter, Fe and Mn oxides, kaolinite, vermiculite and mica were investigated. Due to the homogeneity of the sorbents, between-metal competition for binding sites led to their preferences for one or another metal being much more manifest than in the case of whole soils. On the basis of k(d100) values (distribution coefficients calculated in sorption-desorption experiments in which the initial sorption solution contained 100mgL(-1) of each metal), kaolinite and mica preferentially sorbed and retained chromium; vermiculite, copper and zinc; HOM, Fe oxide and Mn oxide, lead (HOM and Mn oxide also sorbed and retained considerable amounts of copper). Mica only retained sorbed chromium, Fe oxide sorbed cadmium and lead, and kaolinite did not retain sorbed copper. The sorbents retaining the greatest proportions of sorbed metals were vermiculite and Mn oxide, but the ratios of k(d100) values for retention and sorption suggest that cations were least reversibly bound by Mn oxide, and most reversibly by vermiculite.     

Surface modification of macroporous glycidyl methacrylate based copolymers for selective sorption of heavy metals

Two samples of macroporous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), poly(GMA-co-EGDMA), were synthesized by suspension copolymerization and modified with amines. Initial poly(GMA-co-EGDMA), and the samples modified with ethylene diamine [poly(GMA-co-EGDMA)-en], diethylene triamine [poly(GMA-co-EGDMA)-deta] and triethylene tetramine [poly(GMA-co-EGDMA)-teta], were characterized by mercury porosimetry, FTIR spectroscopy and elemental analysis. The most pronounced increase of specific surface area (75%) was observed for poly(GMA-co-EGDMA)-teta sample with smaller particles (D < 150 μm). The Cu(II) sorption was rapid, depending on porosity of amino-functionalized samples and ligand type. For poly(GMA-co-EGDMA)-deta and poly(GMA-co-EGDMA)-teta sorption half time required to reach 50% of total sorption capacity, t _1/2, were around 3 min. Sorption capacities for Cu(II), Co(II), Cd(II) and Ni(II) as well as for Cr(VI), Co(II), Cd(II) and Ni(II) ions were determined under competitive conditions as a function of pH, ligand type and porosity at room temperature. The results indicate selectivity of poly(GMA-co-EGDMA)-deta for Cu(II) over Cd(II) of 3:1 and for Cu(II) over Ni(II) and Co(II) of 6:1. The decrease in particle size of poly(GMA-co-EGDMA)-teta caused the increase of sorption capacities for all metal ions. At pH 1.8 the selectivity of poly(GMA-co-EGDMA)-teta with smaller particles for Cr(VI) over Ni(II), Co(II) and Cd(II) ions was 8.5:1.     

Electrodialytic removal of heavy metals from municipal solid waste incineration fly ash using ammonium citrate as assisting agent

Electrodialytic remediation, an electrochemically assisted separation method, has previously shown potential for removal of heavy metals from municipal solid waste incineration (MSWI) fly ashes. In this work electrodialytic remediation of MSWI fly ash using ammonium citrate as assisting agent was studied, and the results were compared with traditional batch extraction experiments. The application of electric current was found to increase the heavy metal release significantly compared to batch extraction experiments at comparable conditions (same liquid-to-solid ratio, same assisting agent, and same extraction time). Up to 86% Cd, 20% Pb, 62% Zn, 81% Cu and 44% Cr was removed from 75 g of MSWI fly ash in electrodialytic remediation experiments using ammonium citrate as assisting agent. The time range for the experiments varied between 5 and 70 days.     

Characterization of carbonated tricalcium silicate and its sorption capacity for heavy metals: a micron-scale composite adsorbent of active silicate gel and calcite

Adsorption-based processes are widely used in the treatment of dilute metal-bearing wastewaters. The development of versatile, low-cost adsorbents is the subject of continuing interest. This paper examines the preparation, characterization and performance of a micro-scale composite adsorbent composed of silica gel (15.9 w/w%), calcium silicate hydrate gel (8.2 w/w%) and calcite (75.9 w/w%), produced by the accelerated carbonation of tricalcium silicate (C(3)S, Ca(3)SiO(5)). The Ca/Si ratio of calcium silicate hydrate gel (C-S-H) was determined at 0.12 (DTA/TG), 0.17 ((29)Si solid-state MAS/NMR) and 0.18 (SEM/EDS). The metals-retention capacity for selected Cu(II), Pb(II), Zn(II) and Cr(III) was determined by batch and column sorption experiments utilizing nitrate solutions. The effects of metal ion concentration, pH and contact time on binding ability was investigated by kinetic and equilibrium adsorption isotherm studies. The adsorption capacity for Pb(II), Cr(III), Zn(II) and Cu(II) was found to be 94.4 mg/g, 83.0 mg/g, 52.1 mg/g and 31.4 mg/g, respectively. It is concluded that the composite adsorbent has considerable potential for the treatment of industrial wastewater containing heavy metals.     

Partitioning characteristics of targeted heavy metals in IZAYDAS hazardous waste incinerator

Partitioning of eight targeted heavy metals (Cr, Mn, Cu, Pb, Sn, Co, Ni and Zn) was carried out during five trial burns in Izmit hazardous and clinical waste incinerator (IZAYDAS). Metal contents of the original wastes and their concentration in the bottom ash (BA), fly ash (FA), filter cake (FC) and flue gas were determined. Partitioning behavior of metals during the two-stage incineration was evaluated with respect to physico-chemical properties of feed waste and metals, and the operational conditions. Results suggest that combustion temperatures and retention times are the dominant parameters determining the volatility of metals in the first combustion chamber. Targeted metals were generally partitioned in the rank of bottom ash, filter cake, fly ash and flue gas. High filter cake/fly ash ratios showed that high temperatures in the second stage increase both the formation of gaseous metallic compounds and the enrichment of metals in fine particles. Since ESP could not be effective in removing fine particles and volatilized metallic compounds, the necessity of an additional system that would remove heavy metals efficiently was emphasized for the modern incinerators.     

Adsorption of heavy metals from wastewater with waste activated sludge

Abstract

The purpose of this study is the investigation of the adsorption of heavy metals from wastewater with waste activated sludge (WAS) so as to increase the operational flexibility of activated sludge processes for the shock loading problems of heavy metals. By contacting the raw wastewater with WAS, before it entered the activated sludge process unit, some heavy metals in the wastewater were removed, and the pH value of the acidic wastewater rose. Five metals, Cu, Zn, Ni, Cd and Pb, were studied, some factors which affected this biosorption phenomena were investigated, and expressions of the adsorption isotherms were discussed. A semi‐empirical mass transfer‐adsorption model was developed to describe the kinetic experimental data.     

原子吸收光谱法测定红树林中的重金属

本文采用原子吸收光谱法测定白骨壤(Avicenia marina),秋茄树(Kandelia candel)两种红树林中的铜、锌、铅、镉四种重金属含量。回收率在98.3%～104%之间,相对标准偏差在1.57%～3.92%之间,该方法快速、灵敏、准确.     

Influence of clinoptilolite rock on chemical speciation of selected heavy metals in sewage sludge

The chemical speciation of Cd, Cu, Pb, Cr and Ni in Torun municipal sewage sludge is investigated with addition of a natural sorbent (clinoptilolite rock). The total contents of the heavy metals in the sludge are substantially lower than the corresponding limits established by European or Polish legislation excepting nickel only. But the metals concentrations excepting lead exceed significantly the natural background (average contents in soils and in the Earth's crust) in dozens. Application of the sequential chemical extraction indicated that the metals in the sewage sludge are bound mainly (over 50%) in the residual fraction. The metals form the following order by parts of the mobile form: Ni> Cd> Cr> Cu> Pb. Addition of the clinoptilolite to the sludge leads to the metals contents fall in all four fractions of the sequential procedure. Concentrations of mobile forms of cadmium, chromium, copper and nickel decrease by 87, 64, 35 and 24%, respectively, as a result of addition of 9.09% of the clinoptilolite. The total decreases of the metals amount after 9.09% clinoptilolite addition to the sludge are around 11, 15, 25, 41 and 51% for copper, nickel, chromium, cadmium and lead, respectively.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Efficiency of a zeolitized pumice waste as a low-cost heavy metals adsorbent

The unextracted residue obtained after a countercurrent two-step extractive process of silica from pumice lapillus, at 100 degrees C and room pressure, has been found mainly crystallized to the pseudo-cubic form typical of zeolite P. This residue could be active as a low-cost agent for the removal of heavy metals from wastewater. In this paper the removal capacity of six metallic cations (i.e. Cu(2+), Ni(2+), Zn(2+), Cd(2+), Pb(2+) and Cr(3+)) was studied in a stirred batch reactor. Results obtained showed that the removal of metal ions (100-500mgg(-1)) from wastewater is achieved in a short time and the concentration lowered under the legal limits. The adsorption mechanism mainly involves an ionic exchange between sodium ions from the solid phase and heavy metals in solution. However, if wastewater was accompanied by free acidity, it first should be neutralized to pH 4-5 to prevent zeolite destruction.     

The influence of dissolved organic carbon on sorption of heavy metals on urea-treated pine bark

A previous study showed considerably higher metal adsorption by urea-treated pine bark (UTB) compared to non-treated bark (NTB) at metal adsorption from their individual relatively concentrated solutions. Comparison of the sorption characteristics of the two pine barks at low but environmentally relevant metal concentrations, and investigation of the influence of pH and dissolved organic carbon (DOC) on the sorption process are the aims of the present study. Sorption of Cu²⁺, Ni²⁺, Zn²⁺ and Pb²⁺ on pine bark of the species Pinus sylvestris was measured in multi-metal solutions in the presence and absence of DOC. In the absence of DOC, UTB gave lower residual metal concentrations (2–7 μg/l for copper, 1–5 μg/l for nickel, <0.05 μg/l for zinc and lead) in the range of initial concentrations up to 0.7 mg/l, compared to NTB (6–15 μg/l for copper, 2–24 μg/l for nickel, 2–9 μg/l for zinc, 2–3 μg/l for lead). In the presence of DOC, sorption of Zn, Ni and Pb decreased by up to 75% depending on the DOC concentration. Metal sorption on UTB is less sensitive to pH and more adsorbed metal ions are retained compared to NTB. The potential use of urea-treated bark for treatment of waste water containing DOC and low concentrations of metals is discussed.     

Sequential extraction for evaluating the leaching behavior of selected elements in municipal solid waste incineration fly ash

A sequential extraction method has been applied for the determination of binding forms of trace elements in the municipal solid waste incineration (MSWI) fly ash and evaluating their leaching behavior in view of their potential environmental impact. The elemental determinations in the different leachates are performed by ICP-AES and ICP-MS, respectively. The morphology and mineralogical phases after extraction step were performed by scanning electron microscopy (SEM). Total of 20 elements in the samples are investigated. A reference material of city waste incineration fly ash (BCR No. 176) is also tested to examine the applicability as well as accuracy of the proposed method. The sum of most elements present in the individual fractions shows a good agreement with the total elemental concentrations. The extraction efficiencies are generally higher than 80% except for that of Cr and V. The extractable data of most elements give information about the binding forms of various elements in both incineration fly ashes. It was found that the elements such as Ca, K, Na, Pb, Zn, Cd, Cu and Sr have exhibited a remarkable mobility in fly ash. More than half of them would be dissolved or exchanged under a mild leaching condition. The toxic elements such as Pb, Cd, Zn and Cu have a great potential to be released into the environment under normal conditions.     

Influence of supercritical water treatment on heavy metals in medical waste incinerator fly ash

In this work, medical waste (MW) incinerator fly ashes from different types of incinerators were subjected to supercritical water (SCW) and SCW + H₂O₂ (SCWH) treatments. Sequential extraction experiments showed that, after SCW treatment, heavy metals in exchangeable and carbonate forms in the ashes could be transferred into other relatively stable forms, e.g., Ba and Cr into residual fraction, Cu and Pb into organic matter fraction. SCWH treatment could stabilize heavy metals in Fe–Mn oxides and residual fractions. However, the behavior of As was quite different from heavy metals, which could be leached out from residue fraction after SCW and SWCH treatments. The leached As tended to absorb onto Fe–Mn oxides and organic matters under near neutral environment, but it could react with Ca²⁺ at lower pH, increasing the mobility of this element. Therefore, it is necessary to neutralize acidic ash to near neutral condition before subjecting it to SCW and SCWH treatments so as to effectively stabilize hazardous elements in the ash. Consequently, it is believed that SCWH treatment is an effective alternative for hazardous elements detoxification in MW fly ash.     

Extraction of metals from municipal solid waste incinerator fly ash by hydrothermal process

This work examined the extraction properties of metallic elements from municipal incinerator fly ash under hydrothermal conditions. The ash was firstly pre-washed by distilled water, then subjected to hydrothermal treatments. The pre-washing process was effective for Na, K, Ca extraction with extraction percentages of 67%, 76% and 48%, respectively. The optimum contact time was 30 min for the pre-washing process. Five types of acids were tested for the extraction experiments and hydrochloric acid was found to be most effective for metal extraction from the ash. Compared to room condition, hydrothermal treatment accelerated the dissolution of the ash, thus promoted the reaction of acid with hazardous metals such as Cr, Cd, Pb, and furthermore, the consumption speed of acid was slowed down under hydrothermal condition. The acid simultaneously reacted with all the metal in the ash under hydrothermal condition but preferentially reacted with Ca at room condition. The optimum hydrothermal treatment temperature, time and liquid/solid ratio were 150 degrees C, 5h and 10:1 (ml:g), respectively.