Extraction of heavy metals from MSW incinerator fly ash using saponins

An extraction process with saponins was evaluated for removing heavy metals from MSW (municipal solid waste) incinerator fly ashes. Two different fly ashes, A and B, were treated on a laboratory scale with three triterpene-glycoside type of saponins, M, Q, and T, in the pH range 4-9. The results were compared with those of the HCI and EDTA treatment. The treatment with saponins extracted 20-45% of Cr from the fly ashes. Saponins were also effective in extracting Cu from fly ash A attaining 50-60% extraction. Saponin T extracted 100% of Pb from fly ash A at pH around 4. The extraction of Zn with the saponin treatment was similar to that of the HCl treatment. Further, Cr, Cu, Pb, and Zn were fractionated by sequential extraction to investigate the effect of saponins on each fraction. Extraction behavior of other elements during the saponin treatment was also studied. The leaching test on the residues received after the saponin treatment showed that the fly ashes were successfully detoxified to meet the landfilling guideline.     

水泥对垃圾焚烧飞灰中重金属的固化研究

采用水泥固化法处理垃圾焚烧飞灰,研究了飞灰与水泥质量比、养护时间、添加剂和化学预处理对垃圾焚烧飞灰固化块中重金属Zn、Pb、Cu、Cd、Cr浸出的影响.结果表明,当飞灰与水泥质量比为3:4,养护时间为11d的条件下,以砂浆塑化剂为添加剂,固化块Pb、Cu、Cd和Cr的浸出浓度分别降低了72.4％、70.6％、60.0％...     

有机螯合剂与磷酸盐联合稳定垃圾焚烧飞灰中重金属的作用机理

为探讨二硫代氨基甲酸型有机螯合剂(FACAR)和重过磷酸钙(TSP)对垃圾焚烧飞灰中重金属Pb、Cd、Ni的稳定作用机制,对稳定前后的飞灰采用BCR连续提取法、X射线衍射(XRD)分析以及扫描电镜-能谱(SEM-EDS)联用等分析方法进行了表征。结果表明：投加质量分数5%的FACAR能有效稳定飞灰中Pb、Cd和Ni,其浸出浓度低于《生活垃圾填埋场污染控制标准》(GB 16889-2008)规定的浸出浓度限值;采用3% FACAR和3% TSP复配药剂处理,可使飞灰达到GB 16889-2008进场要求;经复合药剂稳定处理后的飞灰颗粒表面孔隙度明显降低,飞灰中Pb、Cd和Ni的形态均由不稳定态向稳定态转化。该复合稳定剂的稳定机制主要为螯合、共沉淀和吸附联合作用机制,其中,有机螯合剂中含硫官能团是影响重金属稳定的主要因素,且重金属具有优先与含硫官能团结合的特性。     

油页岩循环流化床锅炉底渣和飞灰中重金属元素浸出毒性研究

为了研究我国桦甸油页岩65 t/h循环流化床锅炉的底渣和飞灰中重金属元素Cr、Cu、Pb和Zn的赋存状态及不同酸度条件下的浸出特性,分别进行了逐级提取实验和分批浸出的淋滤实验。逐级提取实验结果表明,这4种元素在底渣和飞灰中具有基本相当的赋存状态。硫化物结合态和稳定的残渣态是各元素的主要赋存状态,元素的潜在浸出能力大小表现为:PbCrCuZn,飞灰中各元素的潜在浸出能力大于底渣中的。浸出实验结果表明,元素的赋存状态决定了其浸提能力,浸提液的pH值对各元素浸出能力的影响不尽相同,各元素的浸出能力随浸提时间的延长都会趋于平衡,Cr和Pb的浸出浓度都高于地表水和饮用水的国家标准。     

火电灰渣场自然恢复下灰渣养分及重金属含量研究

对自然恢复下4类不同年代样地的灰渣养分含量及重金属含量进行研究,通过对比分析发现,有机质、全氮、全钾、全磷含量随着自然恢复时间的增加呈现递增的趋势,全磷含量在各恢复阶段与对照样地之间并不存在显著差异(P0.05)。pH随着恢复时间的增加呈现递减的趋势。对灰渣综合质量指数进行研究发现,自然恢复长期、中期、短期与自然恢复初期对比均有显著提高(P0.05),且随着自然恢复时间的增加灰渣综合质量指数逐渐提高。对灰渣场锌、铅、铜3种重金属研究后发现,在自然恢复下随着时间的增加,灰渣中重金属含量均呈现递减的趋势。     

SGA对垃圾焚烧飞灰中重金属的固化性能研究简

根据EPA 1311、HJ/T 299-2007、HJ/T 300-2007和HJ 557-2009等国内外不同标准,研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性,探讨了六硫代胍基甲酸（sixthio guanidine acid,SGA）、二甲基二硫代氨基甲酸盐（sodium dimethyl dithio carbamate,SDD）和Ca（OH）₂浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明,随着浸提液pH的降低,该厂焚烧飞灰中大部分金属元素的浸出量增大,焚烧飞灰浸出液中的Cd、Ni、Pb和Zn浓度分别超过国家危险废物鉴别标准（GB5085.3-2007）规定值的4.75倍、1.47倍、6.72倍和2.20倍,属于危险废弃物,必须进行稳定化处理。当固化剂SGA加入量为0.1 mol/kg时,稳定化后的重金属浸出浓度已经低于危险废物鉴别标准,且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）₂;当固化剂SGA、SDD和Ca（OH）₂加入量为0.5 mol/kg时,稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB 5085.3-2007）中的规定值。与SDD和Ca（OH）₂相比,SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

螯合剂与水泥协同稳定垃圾焚烧飞灰中的重金属

开展了水泥和螯合剂协同处置全烧垃圾循环流化床炉飞灰的研究,并对经济性进行了分析.实验结果表明,当水泥添加比例为30%时,重金属的浸出毒性均低于生活垃圾填埋污染物控制标准的规定.有机硫螯合剂TMT(三巯基均三嗪三钠盐类)对Cu、Pb、Cd的稳定效果最好,有机硫螯合剂DTCR(二硫代氨基甲酸盐衍生物)以Cu、Pb最佳,同等有效添加量时TMT的稳定效果优于DTCR,完全达标时二者所需的添加量分别为2%和3%.水泥和螯合剂协同处置时,满足生活垃圾填埋标准的水泥和螯合剂之间的用量关系并非为线性.螯合剂在实现减容化的同时,存在成本提高的问题,以DTCR为例,在兼顾经济性和增容性时水泥用量可以控制在20%,稳定剂为1.75%.     

SGA对垃圾焚烧飞灰中重金属的固化性能研究

根据EPA1311、HJ／T299—2007、HJ／T300—2007和HJ557—2009等国内外不同标准,研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性,探讨了六硫代胍基甲酸（sixthioguanidineacid,SGA）、二甲基二硫代氨基甲酸盐（sodiumdimethyldithiocarbamate,SDD）和Ca（OH）2浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明,随着浸提液pH的降低,该厂焚烧飞灰中大部分金属元素的浸出量增大,焚烧飞灰浸出液中的cd、Ni、Ph和zn浓度分别超过国家危险废物鉴别标准（GB5085．3—2007）规定值的4．75倍、1．47倍、6．72倍和2．20倍,属于危险废弃物,必须进行稳定化处理。当固化剂SGA加入量为0．1mol／kg时,稳定化后的重金属浸出浓度已经低于危险废物鉴别标准,且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）2;当固化剂SGA、SDD和Ca（OH）2加入量为0．5mol／kg时,稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB5085．3-2007）中的规定值。与SDD和Ca（OH）：相比,SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

Immobilization and volume reduction of heavy metals in municipal solid waste fly ash using nano-size calcium and iron-dispersed reagent

This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO₄-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO₄] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals.

Implications: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.     

垃圾焚烧飞灰有毒重金属固化稳定技术研究综述

采用焚烧法处理生活垃圾正呈快速增长的趋势,焚烧过程产生的飞灰中所含有的大量有毒重金属对自然环境和人类生存都造成极大影响。阐述了目前常用的几种固化稳定垃圾焚烧飞灰有毒重金属的方法,综合分析了其固化特点和优缺点,并初步探索了一种低能耗环境下实现高温熔融处置技术的有效途径,从而为垃圾焚烧飞灰高温固化稳定有毒重金属的实施提供一定的理论基础和技术支持。     

Genotoxic assessment and optimization of pressmud with the help of exotic earthworm Eisenia fetida

Genotoxicity of pressmud (PM) to Allium cepa was investigated to assess its toxic potential and to elucidate the effect of vermicomposting to reduce its toxicity. The PM produced as a waste by product of the sugar cane industry was mixed with cow dung (CD) at different ratios of 0:100 (V₀), 25:75 (V₂₅), 50:50 (V₅₀), 75:25 (V₇₅) and 100:0 (V₁₀₀) (PM:CD) on a dry weight basis for vermicomposting with Eisenia fetida. Different concentrations of 100 % PM sludge extract (10 %, 20 %, 40 %, 60 %, 80 % and 100 %) and negative control (distilled water) and positive control (maleic hydrazide) were analyzed with A. cepa assay to evaluate frequency of chromosomal aberrations before and after vermicomposting. Percent aberration was greatest (30.8 %) after exposure to 100 % PM extract after 6 h but was reduced to 20.3 % after vermicomposting. Exposure to the extract induced c-mitosis, delayed anaphase, laggards, stickiness and vagrant aberrations. Microscopic examination of root meristem exposed to PM sludge extract showed significant inhibition of mitotic index. Also, the mitotic index decreased with increase in concentration of PM sludge extract. After vermicomposting the mitotic index was increased. However, increasing percentages of PM significantly affected the growth and fecundity of the worms and maximum population size was reached in the 25:75 (PM:CD) feed mixture. Nitrogen, phosphorus, sodium, electrical conductivity (EC) and pH increased from initial feed mixture to the final products (i.e., vermicompost), while organic carbon, C/N ratio and potassium declined in all products of vermicomposting. Scanning electron microscopy (SEM) was recorded to identify the changes in texture with numerous surface irregularities and high porosity that proves to be good vermicompost manure. It could be concluded that vermicomposting could be an important tool to reduce the toxicity of PM as evidenced by the results of genotoxicity.     

粉煤灰免烧陶粒制备及其重金属废水净化性能

摘要重金属废水对环境的污染已经引起科研人员的广泛关注。以粉煤灰和水泥为原料、添加活性成分FeS,制备一种免烧陶粒用于含重金属Cu2＋、Zn2＋、Pb2＋的废水处理。探讨了物料配比及蒸养时间对陶粒筒压强度及其比表面积的影响;研究了固液比、接触时间、pH、温度及初始溶液浓度等因素对Cu2＋、Zn2＋、Pb2＋离子净化效果的影响规律,并对实验结果进行了等温线拟合。XRD分析显示,免烧陶粒中存在Ca（OH）2、C—D—H、FeS等矿物相,对重金属离子具有非常好的固定化作用。该免烧陶粒对重金属离子具有很好的去除效果,具备较好的应用前景。     

养护条件对二次铝灰-垃圾飞灰基地聚物中重金属稳固化的影响

以添加SiO2粉末后的二次铝灰和垃圾焚烧飞灰为原料,经过碱激发制备地聚物固化体。将制备好的地聚物固化体样品分别放在30、35、40、45和50 ℃,相对湿度为80%的恒温恒湿培养箱内养护,探究不同养护条件对固化体中重金属浸出特性的影响,并考察生活垃圾焚烧飞灰处理前后重金属化学形态、晶体结构和微观形貌的改变。结果表明：重金属Cr的相对浸出率在30～45 ℃下降明显,45～50 ℃内趋于平缓;而Cd和Pb的相对浸出率在30～40 ℃略微上升,40～50 ℃呈下降趋势,并且Pb的相对浸出率在40～45 ℃下降明显;Zn的相对浸出率随着养护温度的升高缓慢下降。重金属Cr、Cd、Zn和Pb的相对浸出率在前10 d内下降较大,10～14 d下降缓慢。当养护温度为50 ℃时,地聚物中重金属Cr、Cd、Zn和Pb的浸出浓度分别降到0.172、0.072、0.218和3.803 mg·L-1,满足《生活垃圾填埋场控制标准》（GB 16889-2008）的浸出要求。     

水泥、粉煤灰及DTCR固化/稳定化重金属污染底泥

采用水泥、粉煤灰及有机硫稳定剂DTCR固化/稳定化处理重金属污染的底泥,考察固化体的抗压强度及重金属浸出毒性,确定了底泥固化/稳定化的最佳工艺条件。结果表明:仅用水泥固化/稳定化重金属污染底泥,固化体抗压强度随水泥用量的增加而上升,重金属浸出浓度则下降,当水泥∶干底泥质量比为0.6∶1.0时,固化体7 d抗压强度能达到0.99 MPa的标准值;进一步研究发现,水泥∶粉煤灰∶干底泥质量比为0.54∶0.06∶1.0时,重金属浸出浓度有所上升,但7 d及28 d抗压强度仍能分别达到1.2 MPa和2.8 MPa;加入DTCR后,当水泥∶粉煤灰∶DTCR∶干底泥质量比为0.54∶0.06∶0.012∶1.0时,固化体7 d及28 d抗压强度分别为1.1 MPa和2.1 MPa,醋酸缓冲溶液法浸出的Cd、Pb、Zn和Cu浓度分别为0.102、0.189、0.180和0.032 mg/L。     

Effects of metals on life cycle parameters of the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils

Two control and eight field-contaminated, metal-polluted soils were inoculated with Eisenia fetida (Savigny, 1826). Three, 7, 14, 21, 28 and 42 days after inoculation, earthworm survival, body weight, cocoon production and hatching rate were measured. Seventeen metals were analysed in E. fetida tissue, bulk soil and soil solution. Soil organic carbon content, texture, pH and cation exchange capacity were also measured. Cocoon production and hatching rate were more sensitive to adverse conditions than survival or weight change. Soil properties other than metal concentration impacted toxicity. The most toxic soils were organic-poor (1-10 g C kg(-1)), sandy soils (c. 74% sand), with intermediate metal concentrations (e.g. 7150-13,100 mg Pb kg(-1), 2970-53,400 mg Zn kg(-1)). Significant relationships between soil properties and the life cycle parameters were determined. The best coefficients of correlation were generally found for texture, pH, Ag, Cd, Mg, Pb, Tl, and Zn both singularly and in multivariate regressions. Studies that use metal-amended artificial soils are not useful to predict toxicity of field multi-contaminated soils.     

Arrested municipal solid waste incinerator fly ash as a source of heavy metals to the UK environment

Arrested fly ash samples from most currently operating municipal solid waste (MSW) incinerators in the UK have been analysed for a range of elements. Some of the more important heavy metals ranged in concentration as follows: Cd, 21-4646 (median = 271) mg kg(-1); Cu, 296-1307 (642) mg kg(-1); Cr, 44-1328 (574) mg kg(-1); Ni, 45-2204 (74) mg kg(-1); Pb, 447-9704 (4337) mg kg(-1); and Zn, 2285-13,500 (9232) mg kg(-1). These concentrations represent considerable enrichments relative to median UK soil concentrations. Enrichment ratios (defined as median fly ash: median UK soil) were as follows: Mn 1.6; Co 2.6; Ni 3.3; Ba 11; Sr 11; Cr 15; Cu 35; Pb 108; Zn 113; Cd 387. It is estimated that MSW incinerator ash contributes c. 15 t Cd and 241 t Pb to UK landfill sites per annum. These figures compare with previous studies by Hutton & Symon (Hutton, M. & Symon, C. (1986). The quantities of cadmium, lead, mercury and arsenic entering the UK environment from human activities. Sci. Total Environ., 57, 129-50.) which estimated that annual inputs to UK landfills from coal fly ash are c. 60 t Cd and 1270 t Pb. However, it is argued that metals associated with MSW ashes are potentially of greater environmental significance than in coal ashes, because they are much more available and present at much higher concentrations.     

Immobilization of heavy metals in polluted soils by the addition of zeolitic material synthesized from coal fly ash

The use of zeolitic material synthesized from coal fly ash for the immobilization of pollutants in contaminated soils was investigated in experimental plots in the Guadiamar Valley (SW Spain). This area was affected by a pyrite slurry spill in April 1998. Although reclamation activities were completed in a few months, residual pyrite slurry mixed with soil accounted for relatively high leachable levels of trace elements such as Zn, Pb, As, Cu, Sb, Co, Tl and Cd. Phytoremediation strategies were adopted for the final recovery of the polluted soils. The immobilization of metals had previously been undertaken to avoid leaching processes and the consequent groundwater pollution. To this end, 1100 kg of high NaP1 (Na6[(AlO2)6(SiO2)10] .15H2O) zeolitic material was synthesized using fly ash from the Teruel power plant (NE Spain), in a 10 m3 reactor. This zeolitic material was manually applied using different doses (10000-25000 kg per hectare), into the 25 cm topsoil. Another plot (control) was maintained without zeolite. Sampling was carried out 1 and 2 years after the zeolite addition. The results show that the zeolitic material considerably decreases the leaching of Cd, Co, Cu, Ni, and Zn. The sorption of metals in soil clay minerals (illite) proved to be the main cause contributing to the immobilization of these pollutants. This sorption could be a consequence of the rise in pH from 3.3 to 7.6 owing to the alkalinity of the zeolitic material added (caused by traces of free lime in the fly ash, or residual NaOH from synthesis).     

酸洗-电沉积联用技术回收垃圾焚烧飞灰中的重金属

垃圾焚烧飞灰中的重金属浸出能力强、毒性大,属于危险废物,若处置不当将会对环境造成严重污染。采用酸洗-电沉积联用技术,考察硝酸浓度、液固比和酸洗时间对重金属去除率的影响,研究电沉积电压和时间对酸洗废液中重金属回收率的影响,同时评估处理后飞灰的浸出毒性。结果表明,在浓度为2 mol·L⁻¹、液固比为25的硝酸中浸渍洗涤60 min条件下,酸洗能成功去除飞灰中95.26%的Zn、83.06%的Pb、72.62%的Cu和97.85%的Cd;在电压为14 V,电沉积4 h的条件下可回收酸洗废液中95.80%的Zn、99.04%的Pb、79.95%的Cu和90.37%的Cd。对Zn、Pb、Cu、Cd的连续提取和浸出毒性测试表明,处理后飞灰易浸出组分占比降低,残余态物质占比提高,重金属浸出质量浓度符合《生活垃圾填埋场污染控制标准》(GB 16889-2008)要求,可直接进行填埋或作为非危废固体进行资源化利用。本研究结果可为飞灰中重金属脱除和回收利用提供参考。     

Molecular and ultrastructural insights into the earthworm Eisenia fetida of the assessment of ecotoxicity during colistin exposure

Colistin is a peptide antibiotic widely used as a feed additive in animal farming, especially in poultry and swine production, for treatment and prevention of gram-negative bacterial infections, as well as for growth promotion use. When orally ingested, colistin is poorly absorbed and is eliminated almost unaltered by the enteric canal into the environment. Thus, risk of environmental toxicity cannot be ignored. In the present study, we examined the effects of colistin on Heath Shock Protein (HSP) 70, metallothionein (MT) gene expressions, and the ultrastructure of intestinal cells, following treatment of the soil indicator earthworm Eisenia fetida with 10, 20, and 100 mg/kg colistin for 7, 14, and 21 days. The results showed that, compared with the control, the expressions of HSP70 and MT genes changed significantly. Colistin caused up-regulations of HSP70’s expression while inhibited the expression of MT gene. In addition, most mitochondria and endoplasmic reticulum were damaged in the group treated with high concentration. The investigation of gene expressions of HSP70 and MT, as well as pathological alterations in the intestinal cells, may provide important information in terms of ecotoxicity of colistin and can be used as early warning system.     

Accumulation,speciation and localization of silver nanoparticles in the earthworm Eisenia fetida

Environmental Science and Pollution Research - The use of silver nanoparticles (AgNPs) in agriculture and many consumer products has led to a significant release of Ag in the environment. Although...