Changes of Cu, Zn, and Cd speciation in sewage sludge during composting

The potential toxicity risks from heavy metals depend on their chemical speciation. The four stages of the Tessier sequential extraction method were employed to investigate changes in heavy metal speciation （Cu, Zn, and Cd） of sewage sludge during forced aeration composting, and then to identify whether the composting process would reduce or enhance their toxicities. Throughout the composting process, the exchangeable, carbonate-bound, Fe-Mn oxide-bound, and organic matter-bound fractions of Cu were converted to the residual Cu fraction. The organic matter-bound Cu fraction greatly contributed to this transformation. Residual Zn fraction was transformed to the Fe-Mn oxide-bound and organic matter-bound fractions after composting. The residual Zn fraction was a major contributor to the organic matter-bound Zn fraction. The availability of Cu and Zn was reduced by composting such that the risk of heavy metal toxicity decreased with prolonged treatment times. Additionally, attention should be paid to the increased availability of Cd in sewage sludge after composting treatment.     

污泥对樟子松生物量及其重金属积累和土壤重金属有效性的影响

采用盆栽试验研究了不同剂量污泥(体积分数,即污泥体积占污泥和沙土总体积的百分比,分别为:0、20%、33.3%、50%和100%)施用于风沙土条件下,污泥剂量对樟子松幼苗生物量及其对重金属的累积和土壤中重金属有效性的影响.结果表明,在养分含量低的风沙土中,施用污泥能够显著提高樟子松幼苗生物量,最适剂量为50%;污泥剂量的增加可促进樟子松植株对重金属的吸收和累积,在最适剂量(50%)条件下,樟子松植株中Cu、Cd、Pb、Zn的累积量分别是对照(不施污泥)的18.0、8.9、17.1、11.5倍;樟子松植株重金属吸收速率顺序为:ZnCuPbCd,而迁移系数顺序为:ZnCdCuPb;土壤中有效态重金属含量随污泥剂量的增加而增加,而植株收获后土壤中有效态重金属下降幅度均小于对照.     

氨络合法电化学捕集去除城市污泥中重金属的研究

采用自行设计的电动污泥处理装置,以城市污水厂污泥作为试验对象,设置氨水添加比分别为0、0.08、0.10、0.12 (V:V,氨水/试样污泥),在恒定直流电压下运行120h,研究氨络合效应与直接利用阳极产酸对污泥中重金属捕集去除效果的影响.结果表明,阳极酸化对污泥中重金属有一定的溶出去除作用;氨水的添加对电动处理过程中污泥pH值的降低与电流密度的提高没有阻碍,但能够有效提高污泥中重金属的捕集去除率;当氨水添加比为0.12时,污泥中Zn和Cu的捕集去除效果最佳,分别达91.62%和71.49%.氨水添加比为0.08时,Pb的捕集去除率最佳,达47.85%.氨水的添加对污泥中重金属的形态和迁移性有明显影响,主要表现为稳定形态如残渣态、有机结合态的减少及可交换形态的增加.     

污泥干化使重金属形态变向稳定的原因分析

在模拟条件下对不同类型污泥进行连续干化,研究了不同干化温度下污泥重金属存在形态的分布特征.同时,通过测定污泥含水率、密度、温度和电导率等物性参数,分析了污泥干化过程重金属形态向稳定态转变的原因.结果表明,污泥中重金属存在形态的分布特征因污泥类型及来源不同而具有明显的差异;污泥干化过程可以使酸溶态、可还原态和可氧化态重金属向残渣态重金属转变;干化过程中污泥物性的改变和部分有机质和硫化物的分解是引起污泥重金属存在形态发生变化的主要原因.研究结果对于深入了解污泥中重金属的环境地球化学行为具有重要的理论意义,同时还可为污泥无害化、减量化和资源化的最终处理提供科学依据.     

北京地区不同城镇污水处理厂堆肥污泥的营养含量和重金属污染

研究了北京地区不同城镇污水处理厂堆肥污泥(以A、B型表示)的营养含量变化和重金属污染状况.结果表明,A、B型堆肥污泥的p H、营养成分、微量元素和重金属含量因污泥来源和年份而异.其中,A型堆肥污泥不同年份的有机质平均值为203 338.0 mg·kg-1,达到了《城镇污水处理厂污泥处置-农用泥质》(CJ/T 309-2009)和《城镇污水处理厂污泥处置-土地改良用泥质》(GB/T 24600-2009)中的标准要求,但未达到《城镇污水处理厂污泥处置-园林绿化用泥质》(GB/T 23486-2009)中的标准;而B型堆肥污泥不同年份的有机质平均值为298 531.5 mg·kg-1,A、B型堆肥污泥不同年份的p H平均值分别为7.1和7.2以及氮磷钾总养分(N+P2O5+K2O)平均值分别为41 111.7 mg·kg-1和65 901.5 mg·kg-1,均达到以上各城镇污水处理厂污泥处置类型的标准限值要求.除了Hg、Ni含量存在超标现象外,A、B型堆肥污泥中的重金属含量均低于我国最为严格的《城镇污水处理厂污泥处置-农用泥质》中A级污泥的标准限值.总体而言,北京地区不同城镇污水处理厂堆肥污泥在今后的农用、土地改良以及园林绿化处置中,存在潜在的Hg、Ni环境污染状况,须优先关注.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Effect of manganese oxide-modified biochar addition on methane production and heavy metal speciation during the anaerobic digestion of sewage sludge

Low organic matter content and high heavy metal levels severely inhibit the anaerobic digestion (AD) of sewage sludge. In this study, the effect of added manganese oxide-modified biochar composite (MBC) on methane production and heavy metal fractionation during sewage sludge AD was examined. The MBC could increase the buffering capacity, enhance the methane production and degradation of intermediate acids, buffer the pH of the culture, and stabilize the sewage sludge AD process. The application of MBC positively impacted methane production and the cumulative methane yield increased up to 121.97%, as compared with the control. The MBC addition can improve metal stabilization in the digestate. An optimum MBC dose of 2.36?g was recommended, which would produce up to 121.1?L/kg volatile solids of methane. After the AD process, even though most of the metals accumulated in the residual solids, they could be transformation from the bio-available fractions to a more stable fraction. The total organic- and sulfide-bound and residual fraction content at a 3?g dose of MBC that is 0.12?g/g dry matter were 51.06% and 35.11% higher than the control, respectively. The results indicated that the application of MBC could improve the performance of AD and promote stabilization of heavy metals in sewage sludge post the AD process.     

广州城市污泥中重金属形态特征及其生态风险评价

分析了广州市4个不同来源的城市污水处理污泥中重金属含量,考察了污泥样品中重金属形态分布和生物可利用性,并分别利用风险评价指数(RAC)和固废重金属毒性浸出方法评价了污泥中重金属生态危害风险和浸出毒性风险.结果表明,污泥样品中Cu、Cr、Pb和Zn含量较高,不同来源污水处理污泥中重金属含量差别较大.污泥样品中重金属绝大部分以非稳定态存在,酸性污泥中可迁移的酸溶态重金属比例较高.由单一萃取结果,1 mol·L-1NaOAc溶液(pH 5.0)和0.02 mol·L-1EDTA+0.5 mol·L-1NH4OAc溶液(pH 4.6)分别对酸性和碱性污泥中生物可利用态重金属具有较好的萃取能力.污泥酸性越强,其中生物可利用态重金属比例越大.污泥中重金属的迁移能力使其处于高生态危害风险程度;重金属的生物可利用性使酸性污泥大多处于极高危害风险程度,而使碱性污泥大多处于中等危害风险水平.除城市污水处理污泥外,污泥样品中重金属具有高的浸出毒性风险,萃取重金属生物可利用态后,污泥仍具有高浸出毒性风险,但由于浸出毒性风险降低使部分污泥可进行填埋处置.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land.A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi.The loamy soil was mixed with 0%,20%,40%,60% and 80%(by weight)of digested sewage sludge(SS)and composted sludge (SC).The additions of the both sludges caused a significant raise in all fractions,resulting in that exchangeable(EXCH)and organic matter(OM) became predominance for Zn and organic bound Cu occupied the largest portion.There was more available amount for Zn and Cu in SS treatments than SC treatments.During the pot experiment,the concentration of Zn in EXCH,carbonate(CAR)and OM and Cu in EXCH and OM fractions decreased in all treatments,so their bioavailability reduced.Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi.The two sludges increased tissue contents of Zn and Cu especially in the SS treatments.Zn in pakchoi was not only in relationship toΔEXCH andΔCAR forms but also inΔOM forms in the sludge-soil mixtures.Tissue content of Cu in pakchoi grown on SC-soils could not be predicted byΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time,which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

The influence of sewage sludge properties on sludge-borne metal availability

With the advent of more stringent controls on wastewater treatment, sewage sludge production in Europe and many parts of the world is increasing. With this increase comes the problem of sludge disposal, and recycling to land arguably offers an economically and environmentally sustainable option. However, a major limitation of sewage sludge reuse is the potential release of heavy metals from the sludge and heavy metal accumulation to toxic levels in topsoils. The properties of the sludge play a crucial role in determining the initial release and subsequent availability of heavy metals in amended soils. Bioavailable forms of heavy metals in recently amended soils are most likely to be those that are bioavailable in the sewage sludge. In this paper, published research on the importance of sewage sludge characteristics on metal release and bioavailability will be reviewed and contrasted with original research. A selection of sludges from around Australia has been collected for this purpose. Through the use of incubation studies, isotope dilution techniques, ion-selective electrode measurements and ¹³C-NMR spectroscopy, the importance of a range of sludge properties on heavy metal behaviour in sludges and sludge-amended soils is addressed.     

大庆市城市污泥土地利用与环境影响研究

统计了大庆市生活污水处理厂污泥泥质重金属含量和本地区土壤环境重金属现状监测值,结果表明:大庆地区土壤属于天然低背景,污泥中重金属含量符合《城镇污水处理厂污泥处置农用泥质》(CJ/T 309-2009)标准的要求.结合本地区土壤的理化性质和污水厂污泥泥质特性,分析堆肥后污泥土地利用前景与环境影响,建议城市污泥处置应遵循源头削减和全过程控制原则,为大庆污泥处理厂的运行和管理提供合理化建议.     

广州城市污泥中重金属的存在特征及其农用生态风险评价

分析了广州7种城市污泥中Zn、Cu、Pb、Cr、Mn、Ni的含量,研究了其中5种污泥中重金属的形态特征,并利用地累积指数（Igeo）和潜在生态危害指数法（RI）对污泥农用过程中重金属的潜在生态风险进行了综合性评价. 结果表明,广州不同来源城市污泥中Cu、Zn、Mn、Ni含量较高,变化幅度较大,而Pb、Cr含量较低. 除一种污泥中Cu超标外,其他重金属基本符合国家农用控制标准（GB18918-2002）,但所有污泥中重金属含量都超过珠江三角洲耕地土壤均值.不同重金属在不同污泥中的形态分布差异较大. 其中,含工业污水污泥中Cu、Cr还原态占很大的比例,Pb、Fe主要以还原态和残渣态存在;生活污水污泥中重金属主要以可氧化态和残渣态存在,酸可交换态中Mn的比例较高,易还原态中Zn的比例较高;5种污泥中Cu、Zn、Mn潜在迁移性最强.Igeo和RI评价结果表明,污泥中Cu、Zn、Mn是潜在的强生态风险元素,污泥在农用过程中具有一定生态风险性. Igeo和RI用于污泥农用过程中重金属的生态风险评价是可行的,与其它评价方法相比较, RI能更好地反映污泥中重金属对生态环境的综合影响.     

皂角苷和柠檬酸联合对污泥中Cu、Pb和Zn的去除及其稳定性特征

以武汉某污水处理厂的污泥为研究对象(S1和S2),通过皂角苷和柠檬酸联合振荡淋洗试验,研究不同体积比(20∶1~1∶20)、固液比(1∶20~1∶80)、淋洗时间(0~2 880 min)、淋洗次数(1~4)对污泥中重金属Cu、Pb和Zn去除的影响.分析淋洗前后各形态重金属的去除特点,并通过计算稳定性指数(I_R值)和移动性指数(MF值)探究重金属稳定性和移动性的变化.结果表明,在体积比(皂角苷∶柠檬酸)为5∶1,固液比为1∶60,淋洗时间1 440 min时,污泥中Cu、Pb和Zn的最高去除率分别可达43.16%(S1)、32.45%(S2)和38.69%(S1).增加淋洗次数对Cu和Pb的去除率有较大幅度提高,而对Zn的影响较小,尤其在2~3次淋洗后差异显著.4次淋洗后Cu、Pb和Zn的最高去除率分别为78.89%(S1)、77.08%(S2)和49.39%(S1).单次淋洗后,除酸溶态和可还原态外,污泥中其余形态的去除率均较低.增加淋洗次数,重金属的各形态去除率逐渐升高,尤其是Pb中的残渣态去除率增长明显.淋洗改变了重金属的稳定性和移动性,4次淋洗后Cu、Pb和Zn的IR值最大增长率分别为43.63%(S1)、39.44%(S2)和32.00%(S1),MF值减少30.19%~79.45%.     

用分级方法评估土壤对重金属的缓冲能力

研究了不同Cd,Zn,Cu和Pb负荷对5种土壤(油黄泥土、棕红壤、红壤、石砂土和紫砂土)中的重金属形态的影响,分析了不同土壤对重金属的缓冲作用及其影响因素.结果表明,未污染土壤中的重金属主要以残余态为主,占土壤重金属总量的51%以上.随着土壤重金属负荷的提高,土壤中交换态重金属的比例增大,残余态比例下降,有效性提高,对重金属的缓冲作用下降.由于Cd,Zn,Cu和Pb本身的特性不同,土壤中各组分与Cd,Zn,Cu和Pb的结合方式及程度不同.当外源重金属进入土壤后,土壤对重金属的缓冲性为:Pb>Cu>Zn Cd,酸性土壤和砂质土壤的缓冲能力较低.当重金属加入量较低时,重金属优先向氧化物结合态和有机质结合态转化;而当加入量较高时,向交换态和碳酸盐结合态转化的比例增加.土壤pH下降可使交换态Cd,Zn,Cu和Pb的比例递增,降低土壤对重金属的缓冲性,增加了重金属对环境影响的风险.      

聚环氧琥珀酸对污泥中铅的萃取研究

以上海市桃浦污水厂污泥为对象,研究了易生物降解的聚环氧琥珀酸(PESA)对污泥中重金属Pb的萃取作用,重点考察了萃取体系的pH值和萃取剂PESA的用量对重金属Pb萃取的影响.研究发现,PESA对污泥中的重金属Pb具有较好的萃取效果,形态分析结果表明,被PESA萃取的锌主要来自水溶态、酸溶态、可还原态和可氧化态4种形态.当萃取体系的pH=4且PESA与污泥中重金属总量的摩尔比为4∶1时,Pb的萃取效率可达73%.实验结果还表明,萃取体系的pH值和PESA用量是影响污泥中Pb萃取的重要因素.随着萃取体系pH值的降低,Pb的萃取效率总体呈现逐渐下降的趋势;随着PESA用量的增加,Pb的萃取效率逐渐提高,且对体系pH值的依赖性减小.     

黄铁矿与硫粉配合提高污泥重金属的淋滤效果

通过接种嗜酸性硫杆菌复合菌株(氧化亚铁硫杆菌与氧化硫硫杆菌)并采用序批式试验,研究了黄铁矿与硫粉2种底物配合使用对污泥中重金属生物淋滤效果的影响.结果表明,2种底物配合可加速污泥中重金属(Zn, Cu)的浸出,显著提高其去除率.经过18d的生物淋滤,在2种底物配合并接种的处理中,Zn和Cu的去除率分别可达89.2%,56.5%;而在单独加黄铁矿并接种的处理中两者的去除率分别为12.0%, 0.9%;单独添加硫粉并接种处理中分别为85.2%,37.6%,进一步验证了生物淋滤技术去除污泥中重金属的可行性.     

硫粉投加量与污泥含固率之比对生物淋滤过程的影响

通过接种污泥硫细菌混合菌液,研究了S粉投加量与污泥含固率之比(SA/TS)对城市污泥中重金属生物淋滤效果的影响.结果表明,增大SA/TS值能显著缩短淋滤时间,提高淋滤效果.当SA/TS为2.5,经过8 d生物淋滤,Cu和Zn的淋滤效果可达到最佳,溶出率分别为66.2%和63.9%.淋滤进行16 d后,Pb的溶出率为30.8%.对于Cu,不论淋滤前后有机态都是较强的结合态.Zn的溶出主要是由于结合能力强的铁锰氧化态在淋滤过程中被大量浸出.Pb经过16 d的淋滤,铁锰氧化态所占比例有所下降而有机态比例上升.加大SA/TS有利于提高S粉的利用率,对N的保存影响不大,但增加了P的流失.     

伊通河沉积物重金属赋存特征的统计分析

分析了长春市伊通河卫星桥(1#),自由大桥(2#)和东大桥(3#)三个采样点不同深度的沉积物样品中Cu,Pb,Zn,Ni,Co,As的含量及赋存形态,并利用多元统计分析方法研究金属间以及不同形态与沉积物性质之间的相互联系,从而深入揭示城市河流沉积物中金属的空间累积规律。结果表明:伊通河1#和2#采样点不同深度的重金属浓度随深度变化幅度不明显,而3#采样点中Pb、Cu和Zn含量随深度变化显著,它们的相对标准偏差分别达到70.3%,48.1%和52.2%。三个采样点中Cu,Pb,Zn显著相关(r=0.914,0.798和0.949),而Ni,Co,As之间呈显著相关关系(r=0.924,0.843和0.812)。说明这2组金属可能分别具有相同的来源和迁移特性。形态分析结果指出,在沉积物中Cu主要与有机质或硫化物相结合,Pb,Zn和Ni主要存在于由铁氧化物结合态和有机/硫化物结合态中,以碳酸盐和锰氧化物形式存在的比例相对较少。统计分析进一步说明,Cu,Pb,Zn与锰氧化物结合方式类似,Pb在有机/硫化物结合态中可能主要与硫化物相结合,而不是有机质。Cu和Zn有机硫化物结合态的含量与有机质的含量密切相关。     

城市污水处理厂污泥重金属污染状况及特征

研究了我国16家城市污水处理厂污泥中重金属(Cu,Cr,Pb,As和Cd)污染状况及特征,并探讨了可行的污泥处置方法. 结果显示:w(Cu),w(Cr),w(Pb),w(As)和w(Cd)(干基)分别为14.48～239.93,7.86～200.00,6.10～121.00,3.15～11.70和0.31～6.16 mg/kg;不同种类的重金属在污泥中的质量分数也不同,w(Cu)和w(Cr)高于w(Pb),w(As)和w(Cd);污泥中重金属质量分数还随污水处理厂的不同而变化,这与污水来源和污水处理工艺有关. 分析表明,除7号污水处理厂污泥中w(Cd)超出我国农用泥质(CJ/T309—2009)A级污泥、园林绿化用泥质(GB/T23486—2009)和土地改良用泥质(CJ/T291—2008)中酸性土壤(pH<6.5)施用标准外,其他污水处理厂的污泥重金属质量分数均低于我国农用泥质(CJ/T309—2009)A级污泥标准以及美国、德国和欧盟农用污泥标准的重金属控制限值. 达标的污泥可将混合填埋、农用、园林绿化、土地改良、制砖和水泥熟料生产作为污泥处置备选方案.      

污泥预植重金属Cu炭化及炭中重金属的稳定性研究

提出一种污泥预植重金属炭化后固定的概念,并以重金属Cu为代表,以CuCl2的形式植入;研究了在不同Cu预植浓度、不同温度下炭化后污泥本身以及额外添加的重金属在炭中的保留率以及稳定特性,同时采用不同的浸出方法,确定与污泥炭最终处置目标相关的最大可预植量.结果表明,在污泥中Cu的预植量为0.5%(质量分数,以Cu元素计)时,经过热解炭化,90%以上的Cu都保留在污泥炭中,其固定效果与温度有关,400℃以上时,炭化温度越高,Cu越容易浸出.在污泥中预植重金属Cu存在最大容量限制,最大可预植量与污泥炭最终处置目标有关,若选择在卫生填埋场进行填埋,则Cu的预植量不宜超过0.5%.本研究提供了一种污泥包裹其他含重金属的废料共炭化实现无害化的新思路,从而达到用污泥治废的效果.