中国城市污泥的重金属含量及其变化趋势

对相关研究结果的系统统计表明，Zn是我国城市污泥中平均含量最高的重金属元素，其次是Cu，再次是Cr，而毒性较大的元素Hg、Cd、As含量往往较低，通常在几个到十几个mg/kg范围内；70％统计样本的As含量在20ms／kg以内，而Cd、Cr、Ca、Hg、Ni、Pb、Zn含量则分别在2．8、250、417、5、75、130、1701ms／kg以内．我国城市污泥中的重金属含量普遍低于英美等发达国家，而且其中的重金属含量呈现逐渐降低的趋势．按照1984年颁布的《农用污泥污染物控制标准》(GB4284-84)，Zn是我国城市污泥中超标问题最突出的重金属，其超标率为55％；但按照2002年新修订的《城镇污水处理厂污染物排放标准(报批稿)》，Zn的超标率仅为9％．一方面，我国的土壤和儿童普遍缺Zn，另一方面，我国现行的农用污泥污染物控制标准对城市污泥中的Zn控制过于严格，而且也不尽合理，急需对其进一步完善，以合理解决城市污泥的处理处置途径，推动城市污泥的资源化和无害化利用．     

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.     

Characteristics of sewage sludge and distribution of heavy metal in plants with amendment of sewage sludge

In order to better understand land application of sewage sludge, the characterization of heavy metals and organic pollutants were investigated in three different sewage sludges in Shanghai City, China. It was found that the total concentrations of Cd in all of sewage sludge and total concentrations of Zn in Jinshan sewage sludge, as well as those ofZn, Cu, and Ni in Taopu sludge are higher than Chinese regulation limit of pollutants for sludge to be used in agriculture. Leachability of rig in all of studied samples and that of Cd in Taopu sewage sludge exceed the limit values of waste solid extraction standard in China legislation. Based on the characteristics for three kinds of sewage sludge, a pot experiment was conducted to investigate the effect of soil amended with Quyang sewage sludge on the accumulation of heavy metalo.by Begonia semperfloreas-hybr; Ophiopogon japonicas （L.F.） Ker-Gaw; Loropetalum chindense-var, rubrum; Dendranthema morifolium; Viola tricolor; A ntirrhinum majas; Buxas radicans Sieb; Viburnum macrocephalum; Osmanthas fragrans Lour; Cinnamomum camphora siebold and Ligustrum lucidum ait. Results showed that 8 species of plant survived in the amended soil, and moreover they flourished as well as those cultivated in the control soil. The heavy metal concentration in plants varied with species, As, Pb, Cd and Cr concentration being the highest in the four herbaceous species studied, particularly in the roots of D. morifolium. These plants, however, did not show accumulator of As, Pb, Cd and Cr. The highest concentration of Ni and Hg was found in the roots ofD. morifolium, followed by the leaves ofB. semperflorens-hybr. Levels of Zn and Cu were much higher in D. morifolium than in the other plant species. D. morifolium accumulated Ni, Hg, Cu and Zn, which may contribute to the decrease of heavy metal contents in the amended soil. Treatment with sewage sludge did not significantly affect the uptake of heavy metals by the L. chindense-var, rubrum, however, it significantly affected the uptake of heavy metals by D. morifolium.     

Toxic metals in sewage sludge-amended soils: has promotion of beneficial use discounted the risks?

Land application of contaminated waste products has been defended as beneficial use by some scientists and regulators, based on the premise that the behavior of any toxins accumulated in soils from this practice is reasonably well understood and will not have detrimental agronomic or environmental impacts into the foreseeable future. In this review, I use the case of toxic metals in sewage sludges applied to agricultural land to illustrate that metal behavior in soils and plant uptake is difficult to generalize because it is strongly dependent on the nature of the metal, sludge, soil properties and crop. Nevertheless, permitted agricultural loadings of toxic metals from sewage sludges are typically regulated using the sole criterion of total metal loading or concentrations in soils. Several critical generalizing assumptions about the behavior of sludge-borne metals in soil-crop systems, built into the US EPA risk assessment for metals, have tended to underestimate risks and are shown not to be well justified by published research. It is argued that, in the absence of a basic understanding of metal behavior in each specific situation, a more precautionary approach to toxic metal additions to soils is warranted.     

城市污泥用于铅锌矿区重金属污染修复的试验研究

选取黔西北矿渣为研究对象,研究了城市污泥改良矿区重金属污染的可行性和存在的问题,同时在借鉴前人利用污泥的经验基础之上,通过盆栽试验,探讨了纯污泥和不同配比的粉煤灰钝化污泥对铅锌冶炼废渣中重金属有效性的影响,以及不同处理的栽培基质对玉米的生长发育、营养状况和植株中重金属累积的影响,并分析了粉煤灰钝化污泥在矿山土地复垦中的应用前景,以为粉煤灰和污泥的土地利用提供一定的依据,达到既能充分利用这些固体废弃物资源又不污染环境的目的。     

皂角苷和柠檬酸联合去除厌氧消化污泥中重金属的研究

以武汉某污水处理厂未厌氧消化与厌氧消化的污泥(分别为S1和S2)为研究对象,通过振荡淋洗实验,研究了皂角苷(质量分数0.1%~2.0%)和柠檬酸(0~1 mol·L~(-1))联合对2种污泥中Ni、Pb、Zn的去除效果,确定皂角苷和柠檬酸联合淋洗的最佳浓度组合,并采用BCR连续提取法分析淋洗前后3种重金属的形态变化.结果表明,皂角苷和柠檬酸联合对污泥中3种重金属均有较好的去除效果,Ni、Pb、Zn的最高总去除率分别为76.02%、59.93%和15.94%.综合分析,1%的皂角苷与0.4 mol·L~(-1)的柠檬酸联合淋洗的去除效果最好,2种污泥中重金属去除率的大小均为未厌氧消化污泥(S1)厌氧消化污泥(S2).与未厌氧消化污泥相比,厌氧消化污泥Ni的残渣态、Pb的可还原态及Zn的可氧化态含量明显增加,而Ni的可还原态含量减少.联合淋洗后S1、S2中约80%的酸溶态和可还原态的Ni、Zn被去除,Pb的可还原态分别去除67.07%和58.06%;且各重金属残渣态所占比例大幅度增加,其中,Pb的增加最为明显,所占比例超过90%.     

污泥中重金属和多环芳烃(PAHs)的存在特性及其相互关系

在深入研究9种不同污水处理厂污泥中重金属存在形态和15种PAHs含量水平的基础上,讨论了污泥中PAHs和重金属含量之间的相互关系.结果表明,生活污水污泥中Zn的含量最高,其次为Cu,而As和Cd含量较低;工业废水污泥中各重金属含量差异较大,制革污泥的Cr含量超过15000 mg·kg-1.污泥中As、Cr、Cu、Pb主要以可氧化态和残渣态存在;Ni和Zn的酸溶态及可还原态的比例较高;Cd在不同污泥中的形态分布变化较大.生活污水和工业废水污泥中∑PAHs的平均含量相差不大,分别为13.74 mg·kg-1和13.95 mg·kg-1.不同污泥中各PAHa呈现4环>3环>2环>5环>6环的分布特征,化石燃料不完全燃烧和石油类污染是污泥中PAHs的主要来源.污泥中低分子量(2环和3环)PAHs与Cd、Ni、Zn等重金属含量存在显著的相关关系,这种相关关系与重金属作用于污泥中的微生物并最终影响微生物对PAHs的降解有关.     

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%.     

Changes of Cu, Zn, and Ni chemical speciation in sewage sludge co-composted with sodium sulfide and lime

A batch composting study was performed to evaluate the feasibility of co-composting sewage sludge with sodium sulfide and lime （SSL） mixture （Na2S/CaO= 1：1）, aiming at reducing the availability of heavy metals in the sludge compost. Sewage sludge with sawdust as a bulking agent was amended with SSL at 3% （w/w, dw）, and composted for 15 d in laboratory batch reactors. The four stages of the Tessier sequential extraction method was employed to investigate changes in heavy metal fractions of Cu, Zn, and Ni in sewage sludge composted with SSL. For all the three metals, the mobile fractions, such as, exchangeable and carbonate bound were mainly transformed into low availability fractions （organic matter and sulfide, Fe-Mn oxides bound and residual forms）, and the addition of SSL enhanced this transformation. Therefore, SSL is a suitable material to co-compost with sewage sludge to reduce the availability of heavy metals. According to the cabbage seed germination test, a SSL amendment of ≤3% （w/w, dw） is recommended to co-compost with sewage sludge.     

污泥资源化利用的途径与分析

城市污泥既是污染物又是一种资源。从土地利用、回收能源和生产建材等几个方面对污泥资源化利用的途径进行了介绍 ,指出了从源头控制污泥中重金属的含量对土地利用的重要性 ,讨论了利用污泥生产水泥的方法。     

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.     

广州市污水污泥中的重金属及其农用探讨

分析了广州市6种污水污泥中重金属(Zn,Cu,Pb,Cr,Mn和Ni)质量分数及其存在形态,并对污泥农业利用过程中施用的最大量进行了估算.结果表明:广州不同来源污水污泥中.(Cu),w(Zn),w(Mn)和,(Ni)较高,变幅较大,而w( Ph )和w( Cr)低.除一种污泥中w(Cu)超标外,其他重金属基本符合国家农用控制标准(G1318918-2002),但所有污泥中重金属质量分数都超过广州市农田土壤平均值.不同重金属以及同一重金属在不同污泥中的形态分布也不同,其中Zn,Mn和Ni的潜在迁移性强,Cu和Cr中的还原态占有很大的比例,污泥中Pb主要以还原态和残渣态存在.根据广州市主要旱地赤红色土壤静态环境容量和动态环境容量计算表明,污泥农用过程中Cu和Zn是主要监控污染元素,不同来源污泥的最大施用量有明显差异.为保证土壤环境的安全,建议将Cu和Zn作为控制城市污水污泥农用过程中最高施用量的计算参考指标.     

固体添加剂对污泥焚烧过程中重金属迁移行为的影响

利用高温固定管式炉研究了4种固体添加剂(CaO、Al2O3、粉煤灰和高岭土)对污泥焚烧过程中6种重金属(Pb、Cd、Cu、Cr、Ni、Zn)在底渣中的迁移行为与固化残留特征的影响.结果表明,污泥焚烧过程中4种固体添加剂(CaO、Al2O3、粉煤灰和高岭土)的加入有利于重金属固定并且残留在焚烧底渣中,并且随着固体添加剂添加比例的增多,重金属的残留率也逐渐增加.焚烧温度对固体添加剂吸附重金属的效果有很大影响,其中重金属自身熔点、沸点及重金属在污泥中的赋存形态是决定其挥发性的一个重要因素.不同固体添加剂对不同重金属迁移的抑制效果有很大差异,从控制重金属挥发角度来看,固体添加剂高岭土和CaO要优于其他固体添加剂.固体添加剂活性中心与重金属化合物分子的相互作用取决于这些活性位的分布及重金属的化学性质.     

东北地区城市污水处理厂污泥中重金属的形态分布及其潜在生态风险评价

分析了东北地区7个城市污水处理厂脱水污泥中Cu、Zn、Cr、Ni、Mn的含量,利用修正的BCR法研究了污泥中重金属的形态分布特征,并使用地累积指数(Igeo)法和内梅罗指数法(PI)评估了污泥在土地利用过程中重金属的潜在生态风险.结果表明,污水厂污泥中Zn含量超过了国家标准(GB4284—1984)限值,且污泥中Cu、Zn和Mn的含量远远超过东北耕地黑土中的背景含量.污泥中Cu和Cr的有机物结合态(即可氧化态)所占比例较大,可迁移形态含量最高的重金属是Zn,Ni广泛分布于可交换态、酸溶态、可还原态、可氧化态和残渣态中,Mn的残渣态在5种形态中所占比例最高.5种金属中迁移性最强的是Zn,其次为Mn,Cr的迁移性最差.内梅罗单项污染指数法和地累积指数法的评价结果表明,Cu、Zn和Mn是污泥土地利用过程中潜在的污染元素.内梅罗综合指数法的评价结果显示,种脱水污泥均对耕地黑土环境存在严重的潜7在生态风险.     

城镇污水处理厂污泥泥质监测及资源化风险评价

在城市固废管理中,污水处理厂污泥科学合理地处置利用问题越来越重要,阐明城镇污水处理厂污泥的污染状况和化学性质,评价城市污泥污染物的生态风险和危害,可以为污泥的资源化利用提供依据.对某市49家城镇污水处理厂污泥泥质（pH、含水率、Cd、Cr、Cu、Zn、Pb、As、Hg、Ni、矿物油、挥发酚、多环芳烃、有机质和氮磷钾）开展监测,分析其重金属和有机污染物状况、污染物含量频数分布以及污泥养分变化特征,并应用内梅罗指数法和Hakanson潜在生态危害指数评估污泥在农用过程中重金属的潜在生态风险和危害.结果表明,在污泥pH总体呈现中性、且高含水率的状况下,重金属含量高低为：Zn > Cu > Cr > Pb > Ni > As > Hg > Cd,其中,Cd、Pb、Hg、Ni和As为重金属来源第一主成分（生活清洁和医疗）的主要载荷因素;在所有样品中,8项重金属频数分布最集中的含量分别为：38.9~1380.0、62.6~182.7、63.6~181.3、0.0~97.8、19.3~68.4、0.8~29.2、0.3~8.7和0.01~0.96 mg·kg^-1;矿物油、挥发酚和多环芳烃含量最集中的频数分布占比分别为：87.0%、87.9%和77.6%;污泥养分含量高于我国平均水平,有机质含量为农家粪肥（猪粪、牛粪和鸡粪）的67.4%、75.9%和92.5%,氮磷钾含量与农家粪肥相差不大.内梅罗指数和Hakanson生态危害指数显示某市城镇污水处理厂污泥存在一定的生态风险;此外,在符合污泥农用标准的44家城镇污水处理厂中,共有4家污水处理厂污泥属于重度污染或强生态危害.综上所述,某市污水处理厂污泥农用存在一定的潜在生态风险,施用前需降低其重金属含量,在污泥符合农用标准的前提下,还需综合生态风险评价,合理选择污泥资源化方式.     

Clay mineralogy affects the efficiency of sewage sludge in reducing lead retention of soils

Recent studies have shown the feasibility of using of sewage sludge for the remediation of heavy metal-contaminated soils. However, there are no researches to check the influence of clay mineralogy on the efficiency of the sewage sludge to remediation of contaminated soils with heavy metals. For this purpose, we use two contrasting soils:Oxisol rich in hematite and gibbsite and Inceptisol rich in kaolinite. Thermal-treated sludge was applied to Pb-contaminated soil samples and incubated for 40 days. The soil samples were submitted to seven sequential extractions: soluble-Pb, exchangeable-Pb,precipitated-Pb, organic matter-Pb, Fe and Mn oxide-Pb, gibbsite and kaolinite-Pb, and residual-Pb. The reduction of soluble Pb forms by thermal sludge application was more pronounced in the Oxisol than in the Inceptisol because of the conversion of soluble-Pb into more stable forms, such as precipitated-Pb and oxides-Pb. For Inceptisol was necessary to apply high rates of thermal sludge to reach a significant reduction in soluble-Pb contents. The addition of humic fractions in the form of thermal sludge increased the concentration of organic matter-Pb. In confined area, the use of sewage sludge to reduce the heavy metals levels in soils must be better considered, mainly in more weathered soils.     

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.     

污泥生物炭在污泥好氧降解中的原位应用

在300,500,700℃下热解获得的污泥生物炭C300、C500和C700,分别添加至污泥中进行好氧降解反应,研究降解过程中污泥性质的变化,及反应前后污泥生物炭重金属含量的变化.结果表明,添加污泥生物炭提高了污泥降解产物的稳定性,降低了污泥中重金属的生物有效性.添加C300的产物稳定性最高、重金属生物有效性最低,相比对照工况,其产物的5日耗氧量降低了27%,Cu、Zn、As和Ni的生物有效性分别降低了24%、15%、26%和19%.反应后C300和C500中水溶性重金属含量没有显著变化,而C700中水溶性Cu、Zn和Ni的含量分别增加了16,94,4mg/kg. C300作为污泥好氧降解添加剂经济可行.     

Heavy metal contamination of soils and crops from auto traffic,sewage sludge,pig manure and chemical fertilizer

The present paper describes heavy metal contamination of soils and crops resulting from auto traffic, sewage sludge, pig manure and chemical fertilizers, in three separate experiments.The first experiment revealed that although the ADDT (average annual daily traffic) value of the Agricultural Area was lower, higher concentrations of Cu, Cd, Zn, Pb and Mn were obtained in soil when compared with the Commercial-Residential Area. Contaminations of trace metals from various source, e.g., chemical fertilizer, animal manure, night soil and pesticides of the nearby agricultural land were suspected.The second experiment compared the effects of adding a commercial fertilizer and digested sludge which contain substantial amounts of various trace metals to a sandy loam for growing Chinese radish. The results indicated that repeated applications of the fertilizer elevated the contents of various trace metals in the roots of Chinese radish. The phenomenon was further aggravated when digested sludge was also incorporated.The third experiment compared the contents of trace metals in the root and leaf tissues of tree seedlings (Acacia confusa) added with a single dose of the trace metalenriched fertilizer, and different portions of pig manure compost. It was revealed that the fertilizer-treated tree seedlings had a higher content of trace metals in the tissues than those amended with manure compost. Although the metal contents of soil increased as more manure compost was added, the contents in plant tissues did not increase correspondingly.     

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.