废物水泥窑共处置产品中重金属释放模型研究——混凝土路面场景

通过模拟煅烧试验制取水泥熟料,并制得混凝土样品。在混凝土路面场景分析的基础上,参照欧盟固体中无机组分有效量测试方法(EA NEN7371),以pH=3.2的HNO3/H2SO4溶液(质量比为1∶2)为浸取液,在液固比为20 L/kg条件下,对混凝土样品进行模拟浸出实验;参照欧盟块状材料中无机组分的扩散实验方法(EA NEN7375)测定混凝土样品中重金属的有效释放量。模拟浸出实验结果表明,Cr、Ni和Cd在浸出过程中扩散控制是其释放的主要因素。在此基础上建立了重金属在混凝土路面中的释放模型。实验室实测累积释放量(实测值)与模型预测累积释放量(预测值)的拟合检验结果表明,实测值与预测值之间差异不显著,释放模型能较好地预测混凝土路面中重金属的长期累积释放量。     

间歇浸取对废物水泥窑共处置产品中Cr和As释放的影响

研究间歇浸取条件下废物水泥窑共处置产品中重金属Cr、As的释放,对水泥产品在实际应用中的环境安全性评价有重要意义.通过模拟煅烧实验制取含Cr和As的水泥熟料,并制取混凝土样品,采用pH影响实验和扩散浸出实验,研究了混凝土中Cr和As的溶解特性及其间歇浸取对混凝土中Cr和As释放的影响.结果表明,浸取方式对浸取液pH有较...     

干湿交替中碳酸化对废物水泥窑共处置产品中重金属浸出的影响

通过比较连续浸出、碳酸化保存间歇浸出和密封保存间歇浸出3种浸出条件下,废物水泥窑共处置产品--混凝土中Cr、Ni、As、Cd和Pb的浸出量,研究了干湿交替的环境中碳酸化对混凝土中重金属浸出的影响.结果表明,不同的漫出条件对混凝土中重金属的浸出产生了一定的影响.间歇浸出过程降低了重金属在混凝土固相与孔隙水(液相)中的浓度...     

镍渣的重金属浸出特性

在分析镍渣的矿物相组成和重金属元素含量的基础上,鉴定了镍渣样品的浸出毒性,并考察了pH、液固比和浸出时间等条件对镍渣样中铬、铅、铜和锌等重金属浸出特性的影响。结果表明,镍渣中的重金属总量约为渣样的0.9%,且铬、铜和锌的含量较高,需进行安全管理。实验所用镍渣样品为第Ⅰ类一般工业固体废物。在强酸条件下镍渣中重金属浸出浓度较大,pH3后浸出浓度显著降低;液固比40 L/kg时,镍渣中重金属不断溶出,液固比40 L/kg后,浸出达到饱和,浸出浓度趋于平衡;随着浸出时间的增加,重金属离子的浸出浓度先增加后减少,但由于各重金属性质不同,各重金属达到最大浸出浓度的时间不同。     

pH值对烧结砖中重金属释放的影响

采用酸消解实验和NEN 7371浸出实验研究了烧结砖中重金属总量和有效释放量,采用pH-dependence实验研究pH对破碎烧结砖样品中重金属(Cr、Ni、As、Cd和Pb)浸出特性的影响,以及烧结砖样品的酸碱缓冲容量。结果表明,烧结砖中重金属的有效释放量低于总量,释放率从大到小依次为CdAsPbNiCr;烧结砖的酸缓冲容量较小,浸出液pH从7.03降到3.64,消耗了29.33 mmol/kg硝酸,碱缓冲容量较大,pH从7.03升到12.40,共消耗256 mmol/kg氢氧化钠溶液,因此在使用烧结砖的过程中要特别注意环境pH;浸提液的酸碱性是影响烧结砖中重金属浸出的重要参数,在实验研究的pH范围内,不同重金属的浸出规律不同。Cr和As的释放受pH影响较小,而Ni和Cd的浸出量随pH的增大而降低,Pb的浸出量在强酸和强碱条件下均较大,当pH在5.59~9.86的范围内浸出量很低。     

基于重金属提取的垃圾焚烧飞灰无害化处理

采用加酸浸出工艺对垃圾焚烧飞灰进行无害化处理。研究证明盐酸能有效分离飞灰中重金属,重金属浸出率与盐酸浓度及液固比有关;重金属在实验的盐酸浓度和液固比下都能达到高浸出率,但液固比越低,浸出液中重金属的浓度就越高,越有利于重金属的回收。当盐酸浓度为5 mol·L~(-1)、液固比为2(mL:g)时,Pb、Cd和Zn浸出率均达到95%以上,而Cu的浸出率也达到81.38%,Pb、Cd、Zn和Cu的浓度分别为468.10、78.12、2 268.80和347.78 mg·L~(-1)。残灰采用加盐水洗工艺后,浸出毒性超标的重金属Pb和Cd浸出毒性低于GB 16889-2008标准限值,符合填埋要求。     

重金属污染土壤的草酸和EDTA混合淋洗研究

采用不同浓度的草酸(oxalic acid,OX)和乙二胺四乙酸(EDTA)混合的淋洗方法研究重金属污染土壤的最佳混合淋洗方式,探讨了液固比、淋洗时间及pH对淋洗效果的影响,并分析了0.2 mol/L OX+0.2 mol/L EDTA处理前后土壤中重金属形态的变化。结果表明,采用0.2 mol/L OX+0.2 mol/L EDTA混合的淋洗法可同时去除多种重金属,且对Cu、Zn、Ni和Cr的去除率明显高于单用OX和EDTA,去除率分别为Cu 41.29%、Zn 84.73%、Ni 54.2%和Cr 66.01%。0.2mol/L OX+0.2 mol/L EDTA在液固比为5∶1、淋洗时间为4 h、pH为6时可分别达到最佳淋洗效果,且分别为Cu 62.59%、Zn 93.48%、Ni 55.95%和Cr 71.57%;Cu 50.47%、Zn 86.67%、Ni 61.53%和Cr 72.68%;Cu 44.40%、Zn 81.82%、Ni68.76%和Cr 74.93%。形态分析结果表明,0.2 mol/L OX+0.2 mol/L EDTA能较好地改变土壤中重金属形态的分布。     

淋洗对污染土壤重金属形态分布及生物可利用性影响研究

淋洗是一种快速高效的土壤重金属修复技术,淋洗条件的选择对不同土地利用类型的重金属污染修复具有重要意义。以Ni、Cu、Cd复合污染土壤为研究对象,在不同淋洗条件(液固比和pH)下考察6种淋洗剂(去离子水、模拟酸雨、柠檬酸、草酸、乙二胺四乙酸二钠(Na2EDTA)和氨三乙酸(NTA))对Ni、Cu、Cd的淋洗效果、形态分布及生物可利用性影响。结果表明:(1)当液固比5∶1mL/g时,柠檬酸、Na2EDTA、NTA表现出良好的淋洗效果,对建设用地土壤Ni、Cu、Cd的去除率分别达到84.53%、92.30%、56.00%以上。(2)淋洗后土壤中可交换态、可还原态Ni、Cu、Cd浓度均明显降低。(3)总体上,淋洗使残余指数升高、迁移系数降低,重金属离子在液固比20∶1 mL/g时生物可利用性最低。(4)根据实际污染土壤效果,pH 5.2的柠檬酸或pH 7.5的Na2EDTA在液固比20∶1mL/g时可降低农业土壤的风险;建设用地土壤使用液固比5∶1mL/g、pH 7.5的Na2EDTA或pH 7.5的NTA对3种重金属的去除率达80.43%以上。     

铅冶炼水淬渣中金属源释放特征及影响因素

固废中金属源释放机理和特征研究对于环境管理和环境风险防控具有重要意义。采用连续浸出和渗流释放方法，分析了铅冶炼水淬渣中金属元素在不同pH、液固比以及溶解性有机质(DOM)条件下的释放特征。结果表明，铅冶炼水淬渣中含有Cr、Co、Cd、Ni、Mo、Zn等重金属，Al、Li含量也较高。液固比影响金属释放率，总体上液固比越大释放率越大。金属种类和释放率受pH影响显著，在pH=4.5时有Cd、Zn、Mo和Ni溶出；而在pH=7.0时只有Mo溶出，累积释放率也低于pH=4.5时。在相同pH下DOM促进了Mo释放。在实际场景中，应加强含金属类固废全生命周期的风险管控。     

三峡库区垃圾渗滤液-城镇污水合并处理时的重金属含量研究

应用微波消解-电感耦合等离子体发射光谱法（ICP-OES）测定三峡库区垃圾渗滤液、渗滤液城镇污水合并处理厂进、出水以及剩余污泥中重金属元素的浓度。结果表明，合并处理后，除5个污水厂出水Ni超标（浓度为59.79～104.30 μg/L）外，其余重金属元素均低于GB 18918-2002污水排放标准；剩余污泥中的总重金属含量在15.31～27.73 g/kg之间，各元素含量均远低于污泥农用标准。因此，在目前各合并处理厂的运行条件下，控制渗滤液与城镇污水比例在1∶2 700～1∶50（V/V）范围内，渗滤液汇入生活污水进行合并处理是解决渗滤液重金属污染的有效方式。     

生物沥浸法去除猪粪中重金属的研究

探讨以猪粪为培养介质，驯化和加富培养获得硫细菌混合菌液，并研究其对猪粪中重金属的生物沥浸效果。结果表明：猪粪可以在18 d内完成驯化，经3轮富集培养的猪粪粪液可作为硫细菌接种菌液。采用此菌液对猪粪粪液接种并投加硫粉，经过9 d的生物沥浸，Cu、Zn和Cd的沥出率分别达到93.0%、90.1%和67.8%。     

巯基化改性膨润土对重金属的吸附性能

以钙基膨润土为基本材料,制备了巯基化改性膨润土,并对比研究了此材料与其他17种改性膨润土和原材料对重金属的吸附性能.结果表明,巯基化膨润土对镉的吸附能力显著优于其他材料,在本实验条件下,其对镉的吸附率高于其他材料30％以上,对镉的吸附量可达52.1 mg/g.巯基化膨润土对铅的吸附能力在重金属竞争吸附条件下优于其他材料,而其对镍的吸附能力在所有材料中处于中等水平;另外,巯基化膨润土对3种重金属的吸附受重金属竞争吸附影响较小.因此,在所研究的材料中,巯基化膨润土材料是一种最理想的重金属吸附材料.     

Salinity increases mobility of heavy metals in soils

The effect of salinity induced by CaCl₂, MgCl₂, NaCl and Na₂SO₄ on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl₂ and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl₂ was applied, Cd and Cu were mobilized the most. Finally, an increase of Na₂SO₄ also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl₂ and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca²⁺ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg²⁺. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca²⁺ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.     

Earthworm contamination by PCBs and heavy metals

A comparison is made of soil and earthworm contamination by PCBs and heavy metals between a nature reserve and two sites conditioned by the addition of sewage sludge and compost.The tissues and gut content of the earthworms shows a higher PCB concentration than that of the surrounding soil and also a difference in the fingerprint of some single PCB compounds.Earthworms display a selective accumulation of cadmium and zinc in their tissues and gut content.     

Road traffic emission factors for heavy metals

Quantifying the emissions and concentrations of heavy metals in urban air is a prerequisite for assessing their health effects. In this paper a combination of measurements and modelling is used to assess the contribution from road traffic emissions. Concentrations of particulate heavy metals in air were measured simultaneously during 1 year at a densely trafficked street and at an urban background site in Stockholm, Sweden. Annual mean concentrations of cadmium were 50 times lower than the EU directive and for nickel and arsenic concentrations were 10 and six times lower, respectively. More than a factor of two higher concentrations was in general observed at the street in comparison to roof levels indicating the strong influence from local road traffic emissions. The only compound with a significantly decreasing trend in the urban background was Pb with 9.1 ng m^?3 in 1995/96 compared to 3.4 ng m^?3 2003/04. This is likely due to decreased emissions from wear of brake linings and reduced emissions due to oil and coal combustion in central Europe.Total road traffic emission factors for heavy metals were estimated using parallel measurements of NOx concentrations and knowledge of NOx emission factors. In general, the emission factors for the street were higher than reported in road tunnel measurements. This could partly be due to different driving conditions, since especially for metals which are mainly emitted from brake wear, more stop and go driving in the street compared to in road tunnels is likely to increase emissions. Total emissions were compared with exhaust emissions, obtained from the COPERT model and brake wear emissions based on an earlier study in Stockholm. For Cu, Ni and Zn the sum of brake wear and exhaust emissions agreed very well with estimated total emission factors in this study. More than 90% of the road traffic emissions of Cu were due to brake wear. For Ni more than 80% is estimated to be due to exhaust emissions and for Zn around 40% of road traffic emissions are estimated to be due to exhaust emissions. Pb is also mainly due to exhaust emissions (90%); a fuel Pb content of only 0.5 mg L^?1 would give similar emission factor as that based on the concentration increment at the street. This is the first study using simultaneous measurements of heavy metals at street and roof enabling calculations of emission factors using a tracer technique.     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

微生物沥浸法去除底泥中的重金属

以硫酸亚铁盐为底物,培养以氧化亚铁硫杆菌为主要菌种的土著沥滤微生物,采用批式方法对湘江长沙段底泥进行微生物沥浸实验。实验结果表明,底物投加量与底泥固体浓度比(Sd/Sc)为1.5时已能满足底泥的微生物沥浸要求,进一步研究发现底泥固体浓度为13%、底物投加量为19.5 g/L、沥浸时间为6 d时,底泥中超标重金属Cd、Zn和Cu的去除率可分别达到83.1%、75.3%和61.2%;沥浸后底泥中大部分重金属以残渣态存在,且含量低于农用污泥中污染物控制标准,其中硫化物有机结合态Cu浸出较Zn、Cd需更低的pH,且Cu以间接机理浸出为主;以Fe2+为底物的沥浸体系中,黄铁矾的重吸附或共沉淀是沥浸实验后期重金属浸出率下降的原因之一。     

ES稳定重金属污染底泥效果

就新型有机重金属稳定剂ES和常用稳定剂氧化钙、硫化钠、硫酸亚铁、磷酸氢二钠、壳聚糖对Cu、As、Cd、Hg单一重金属模拟底泥的稳定化效果进行了对比实验研究。结果表明,氧化钙对几种重金属均有一定稳定效果,但用量大,成本高;硫化钠也对4种重金属有一定效果,对Hg、Cu效果较佳,As、Cd效果一般;磷酸氢二钠则对Hg、As基本无稳定效果;硫酸亚铁虽对As有较高的稳定化率,对于其余3种重金属则基本无效;壳聚糖则对As有明显反作用。根据稳定模拟底泥实验结果对新型有机重金属稳定剂-ES的稳定现场原状污染底泥的工程应用和机理进行了研究。结果表明,投加量为5%,pH为8,液固比为1.2∶1时,ES对复合重金属底泥中的重金属稳定化率最高。经ES稳定后各重金属形态残渣态占较大比例,稳定性佳。     

河流重金属污染底泥的稳定化实验研究

以实现河道疏浚底泥中富含的重金属Cu、Zn、Ni的稳定化为目标,选用EDTA、DTCR、Na_2S、Na_2S_2O_3、膨润土、水泥及自主研发的特殊胶凝材料作为稳定剂,对底泥中的重金属进行固化稳定,通过分析稳定后重金属浸出液浓度及赋存形态变化,探讨各药剂稳定效果,并寻求稳定剂的最佳投加量。研究表明,7种稳定剂对3种重金属的综合稳定化效果由好到差依次为:水泥胶凝材料膨润土DTCR硫化钠硫代硫酸钠EDTA;对Cu、Zn、Ni单种重金属而言,稳定效果最好的药剂分别为膨润土、胶凝材料及DTCR,而EDTA则使重金属浸出液浓度升高。除EDTA外,其他药剂对重金属Cu和Zn的稳定效果要明显优于Ni。根据稳定后重金属赋存形态变化结果,EDTA可使重金属可交换态比例升高,而膨润土对重金属4种形态分布基本无影响,其他药剂使重金属可交换态比例降低。