污泥中重金属的环境活性及生态风险评估

研究了湖南省长沙市、株洲市和常德市10个污水处理厂剩余污泥中As,Cd,Cu,Ni,Pb,Zn的含量和形态特征,并利用潜在生态危害指数法对污泥农用过程中重金属的生态风险进行了综合评价。结果表明,城市污泥中富含有机质及N,P,K等养分,然而,污泥表现为以Cd为主的多金属污染,不能直接农用。污泥中Cd含量为1.43～260mg/kg,以可还原态为主,占全量比例高于28.9%;As,Pb的可还原态,Ni,Zn的酸可溶态和可还原态,Cu可还原态和氧化态所占比例较高,表明污泥中重金属的潜在环境活性较高。风险指数评价结果表明,污泥中Cd和As是潜在的强生态风险元素;以工业废水处理为主的污水处理厂污泥重金属单因子生态风险相对较高,且综合潜在生态风险严重。     

兰州市城市污水处理厂污泥中重金属形态分布特征与潜在生态风险评价

通过现场调查采样及室内分析,研究了兰州市七里河安宁污水处理厂和雁儿湾污水处理厂污泥中重金属的形态分布特征,并对其进行了潜在生态风险评价。结果表明,污泥总体呈高有机质、高全N和有效P、高微量营养元素,且Cu、Zn、Cd、Pb、Ni5种重金属的含量均低于污泥农用控制标准,具有很好的农用价值。污泥中Zn、Cd、Pb主要以有机结合态和残渣态存在,而Cu、Ni可交换态所占比例较高,分别为14.95%和14.41%,不稳定态所占比例分别为41.12%和31.04%,表现出较高的生物活性和可利用性。七里河和雁儿湾污泥中重金属的潜在生态风险属于低度风险;Cd、Cu是污泥中重金属潜在生态风险的主要贡献者,在污泥处理处置时应引起高度重视。     

厌氧消化污泥化学组成及其环境化学性质

本文剖析了厌氧消化污泥主要组成分的特征和污泥的农业利用价值。认为厌氧消化污泥含较多的有机质和N、P等养分，且有机态养分中相当部分容易矿化，因此具有很好的肥料价值。污泥中所含的各种重金属是一般土壤的20～40倍，但基本未超过我国污泥农用污染物控制标准。Cd和Zn，在污泥中主要以水溶态、交换态和松结合有机态存在，活性相对较高。此外，污泥也具明显的生物毒性。     

重庆市城市污泥中的重金属及其农用环境容量

城市污泥农用的环境风险取决于城市污泥中的污染物含量及土壤理化性质。该文分析了重庆市10个城市污水处理厂污泥中的Cu,Zn,Pb和Cd含量及形态,根据土壤环境容量及氮肥施用量计算了重庆主要旱地土壤的最大施用量和年施用量。结果表明,重庆市城市污泥中的Zn、Cu、Pb和Cd含量分别为362.12～725.32mg/kg,69.84～170.22mg/kg,21.25～107.24mg/kg和1.26～4.25mg/kg。污泥中不稳定态Zn、Cu、Pb和Cd的比例分别为42.89%～44.74%,2.69%～9.45%,0.95%～12.06%和61.05%～79.91%。根据土壤重金属的静态容量,计算出重庆主要旱地土壤紫色土和黄壤城市污泥的一次性最高施用量分别为384.62t/hm2和98.90t/hm2。根据土壤重金属动态容量,以15、20、50为年限,计算出的城市污泥的年施用量,紫色土为66.10,60.91和55.71t/(hm2·a),黄壤为30.32,28.99和27.53t/(hm2·a)。根据作物的需氮量计算城市污泥的年施用量为3.04～6.40t/(hm2·a),该施用量低于根据土壤环境的动态容量计算的施用量,按此用量施用城市污泥更安全。     

长江三角洲近岸水域表层沉积物重金属分布特征及其影响因子

采用ICP-MS测定了不同季节长江三角洲沉积物中重金属(Ni,Cu,Cr,Zn,Cd和Pb)含量并探讨了其影响因子。结果表明:(1)长江三角洲沉积物中Pb和Zn占重金属总量比例最高,Hg和Cd占重金属总量比例较小;沉积物重金属含量均以秋季和冬季最高,夏季次之,春季最低。(2)长江三角洲沉积物中Cr,Cu和Ni元素均以残渣态为主,Zn和Cd主要以弱酸提取态为主,Pb较均匀地分布于不同形态中。(3)长江三角洲沉积物中pH值和电导率基本表现为春季夏季秋季冬季,其中秋季和冬季pH值差异不显著(p0.05),二者显著低于春季和夏季(p0.05);沉积物中全碳、全氮、全磷和全钾含量均以秋季和冬季最高,夏季次之,春季最低,其中不同季节全氮和全钾含量差异均显著(p0.05)。(4)Pearson相关性分析可知,长江三角洲沉积物中Cr,Pb,Cd的弱酸浸提与重金属总量之间表现出显著的正相关关系(p0.05),而6种重金属元素的可还原态与重金属残渣态之间没有显著的相关性(p0.05);Cr,Cu,Pb的弱酸浸提与可还原态没有显著的相关性(p0.05),Ni,Zn和Cd的弱酸浸提与可还原态具有显著的相关性(p0.05)。(5)长江三角洲沉积物中6种重金属元素的不同形态均与养分等指标存在显著的正相关性,而pH值和电导率与不同形态重金属呈负相关,全碳含量是控制长江三角洲沉积物重金属元素分布的主要因素。     

长期施用污泥对土壤-萝卜系统重金属积累及土壤养分含量的影响

为了探究不同用量污泥长期施用后对土壤-萝卜系统中重金属及土壤养分含量的影响,采用长期定位试验,研究连续10年单施化肥(CK)以及施用不同用量(4.5、9、13.5、18 t·hm~(-2))污泥对土壤、萝卜叶(地上部)和萝卜(地下部)中重金属(Pb、Cd、Cr、Ni、Cu、Zn)累积情况及土壤pH、有机质及氮磷钾含量的影响。结果表明:连续施用10年后,单施化肥和不同用量污泥处理对萝卜产量影响不大,土壤、萝卜叶和萝卜中的Pb、Cd、Cr、Ni、Cu和Zn含量均随污泥施用量的增加而增加,且中高量和高量污泥处理中重金属的累积量较大,显著或极显著高于对照、低量和中量处理。中量以上污泥处理土壤的Pb、Cr、Ni和Cu超出了土壤环境质量国家标准;除高量污泥处理Pb超标外,其他处理萝卜的各重金属含量均未超过食品安全国家标准。与CK处理相比,长期施用不同用量污泥能提高土壤pH 0.58～0.71个单位,并显著或极显著地提高有机质、全量氮磷以及速效氮磷含量。研究表明,连续10年施用不同用量污泥,土壤和萝卜中Pb、Cd、Cr、Ni、Cu、Zn的含量随污泥用量的增加而增加,其中Pb、Ni、Cr和Cu出现超标现象,萝卜中的重金属含量除高量污泥处理中Pb超标外,其他处理均未超过食品安全国家标准。随着作物产地土壤中污泥施用年限增长或用量增加,食品安全应得到更多的重视。     

长春市城区土壤中Pb、Cu、Zn、Cd及Cr化学形态特征

为弄清长春市城市土壤中Pb、Cu、Zn、Cr及Cd的化学形态分布特征,系统采集了26件城市表层(0~20 cm)土壤样品,采用连续提取法对重金属各化学形态含量进行了测定。结果表明:Pb、Zn、Cu及Cr主要以残渣态存在,其次是铁锰氧化物结合态、腐殖酸结合态和强有机结合态占有次要地位,离子交换态和水溶态所占比例均较低;Cd则主要以碳酸盐结合态存在,同时,水溶态和离子交换态所占比例较高。残渣态Pb和Zn在城区表层土壤中所占比例较近郊土壤中略有下降,但幅度不大,除Cu外,其余各元素易迁移、高生物有效性的水溶态在城区表层土壤中所占比例略有上升。Pearson相关分析结果表明,各元素残渣态与全量均呈极显著正相关,其它各活性态与全量间的相关程度与重金属种类有关。土壤pH值和Fe、Mn含量对重金属的化学形态的影响也与重金属种类有关,而且,同一重金属的不同存在形态受土壤pH值和Fe、Mn含量的影响程度也不同。     

城市污泥与花生壳制活性炭的重金属形态分析及生态风险评价

采用BCR提取法对以污泥和花生壳为原料制备的活性炭进行重金属形态分析,利用原子吸收法测定污泥热解前后Cd、Cr、Cu、Zn、Ni、Pb的不同形态含量。结果表明,污泥中Zn的含量最高,Zn和Cu的含量超过了污泥农用标准。热解可使污泥中的可溶解态和可还原态重金属转化为性质稳定的残渣态重金属,在此基础上,利用重金属潜在生态风险指数法（IR）对污泥活性炭的重金属潜在生态风险进行评价,结果得出花生壳添加量为20%,热解温度为600℃条件下,制备出来的活性炭风险最小。同时证实Cd的潜在生态风险系数较大,在利用时应引起足够的重视。     

我国部分城市污泥化学组成及其农用标准初探

本文分析了我国6个城市的典型污水污泥及其产品的主要化学组成。结果表明,6个城市污泥中都含有丰富的有机质、氮、磷,相对贫钾;但重金属含量超标,不符合我国目前农用污泥标准。本文对我国目前农用污泥标准进行了初步的探讨。     

武汉城市街道灰尘Cd和Pb的季节变化规律及健康风险评价

按季节采集武汉街道灰尘,分析Cd和Pb在夏季和冬季的含量和化学形态。结果发现:武汉市街道灰尘中Cd和Pb的平均含量分别是1.61 mg kg-1、93.3 mg kg-1,分别是湖北省土壤背景值的9.5倍和3.5倍。街道灰尘中Cd含量夏季高于冬季;Pb含量冬季高于夏季。Cd和Pb的化学形态分布特征在同一季节是相似的,且重金属在冬季的化学活动性高于夏季。暴露及健康风险评价结果表明:成人和儿童重金属的非致癌风险顺序均为PbCd,重金属元素对人体不构成非致癌健康威胁;儿童重金属暴露的健康风险高于成人,但非致癌风险控制在安全限内。致癌元素Cd基本不具致癌风险。     

中国五个典型城市污水厂污泥中重金属的形态分布研究

Metal content and bioavailability are often the limiting factors for application of sewage sludge in agricultural fields. Sewage sludge samples were collected from five typical urban wastewater treatment plants in China to investigate their contents and distribution of various chemical fractions of Cu, Zn, Ni, Cr, Pb and Mo by using the BCR （Community Bureau of Reference） sequential extraction procedure. The sludges contained considerable amounts of organic matter （31.8%- 48.0%）, total N （16.3-26.4 g kg^-1） and total P （15.1-23.9 g kg^-1）, indicating high potential agricultural benefits of their practical applications. However, total Zn and Ni contents in the sludge exceeded the values permitted in China＇s control standards for pollutants in sludges from agricultural use （GB 4284-1984）. The residual fraction was the predominant fraction for Mo, Ni and Cr, the oxidizable fraction was the primary fraction for Cu and Pb, and the exchangeable and reducible fractions were principal for Zn. The distribution of different chemical fractions among the sludge samples refiected differences in their physicochemical properties, especially pH. The sludge pH was negatively correlated with the percentages of reducible fraction of Cu and exchangeable fraction of Zn. The sludges from these plants might not be suitable for agricultural applications due to their high contents of Zn, Ni and Cr, as well as high potential of mobility and bioavailability of Zn.     

Cadmium and zinc additions to wisconsin soils by commercial fertilizers and wastewater sludge application

Cadmium and Zn concentrations were determined on 21 commercial fertilizer samples by atomic absorption. The Cd concentration ranged from 1.5 to 9.7 mg kg^?1, the median being 4.3 mg kg^?1. Zinc showed a much wider range. The Cd added to soil by commercial fertilizers may be as much as 2150 kg annually in Wisconsin, compared to a potential of 1700 kg if wastewater sludges from all municipal sewage treatment plants in the state were disposed of on land. However, because of the higher application rates, sludge Cd on a soil concentration basis is a much more concentrated source of Cd than that from phosphate fertilizers.     

Residual heavy metal concentrations in sludge‐amended coastal plain soils ‐ I. Comparison of extractants

Abstract

The purposes for this research were: to examine the long‐term residual effects of farmland applications of municipal sludges from four treatment technologies on the total and extractable Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations in Coastal Plain soils; to investigate the effects of sludge sources and rates on the effectiveness of soil extractants to remove the various metals; and to determine correlation coefficients for soil extractable versus plant accumulation in tobacco. The extractants evaluated were Mehlich 1 and 3, and DTPA‐pH 7.3. Composite Ap horizon soil samples and tobacco leaf samples were obtained in 1984 from research plots at two sites in Maryland that were established in 1972 and 1976, respectively, using sludge materials from three wastewater treatment facilities in the Washington, D.C. metropolitan region. Similar application rates were used at both sites.

A wide range in soil pH values was found among treatments at each site. Significant (p ≤ 0.05) increases were observed in total Zn, Cu, Fe, Pb, Ni, and Cd for all sludge sources with increased rates; however, values for total soil Mn exhibited high variability in all cases. The rankings among the extractants varied for some elements depending on the sludge sources. For Zn, the rankings were Mehlich 1 > Mechlich 3 > DTPA‐pH 7.3 across all sources and rates. For Cu, Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was found for soils amended with Blue Plains digested (BPD) and Piscataway limeddigested (PLD) sludges but Mehlich 1 ≥ DTPA pH 7.3 > Mehlich 3 for Blue Plains limed compost (BPLC) and Annapolis Fe and heat treated (AFH) sludges. Concerning extractable Mn, Mehlich Mehlich 1 > Mechlich 3 > DTPH pH 7.3 was the order for BPLC and AFH sludges but Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was observed for BPD and PLD sludges. The rankings among extractants for Fe (Mehlich 3 > Mehlich 1 > DTPA‐pH7.3), Ni (Mehlich 3 ≥ Mehlich 1 > DTPA‐pH 7.3), Pb (Mehlich 3 > DTPA‐pH 7.3 > Mehlich 1) and Cd (Mehlich 1 > Mehlich 3 > DPTA‐pH7.3) were somewhat similar across all sludge sources. Significant correlation coefficients were obtained for all three extractants for soil extractable vs. plant Zn, Cu, Ni, and Cd at both sites; however, Mehlich 3 was not significant for Mn. Also, neither of the extractants produced significant coefficients for Fe and Pb.     

Leaching of heavy metals from sewage sludge through coastal plain soils

Abstract

Three types of sewage sludge are applied to the surface of soil columns of Coastal Plain soils and leached with distilled water. The Zn concentrations in leachate samples from a Sassafras loamy sand soil loaded with an industrial sludge increased with sludge loading rate. All leachate samples contained very low concentrations of Cd, Cr and Cu. Hazardous amounts of Cd, Cr, Cu and Zn would not be leached to the groundwater when recommended rates of the tested sludges are applied to Coastal Plain soils under most conditions.     

重金属在猪饲料-粪便-土壤-蔬菜中的分布特征研究

本文调查分析了江西省余江县39个大型养猪场的饲料、猪粪、以及长期施用这些猪粪的菜地土壤及蔬菜的Cu、Zn、Pb、Cd含量,并对饲料、猪粪、土壤和蔬菜重金属含量进行了相关分析。结果表明,大猪和小猪饲料Cu含量超标率分别达81.6%和30.8%,Zn含量超标率分别达89.5%和94.9%,而Pb、Cd未超标。猪粪Cu、Zn含量亦严重超标,且饲料和猪粪中Cu、Zn、Pb、Cd含量呈显著正相关关系。土壤总Zn和总Cd含量分别有7.8%和5.2%的样品超过三级标准,污染较为严重。所有蔬菜样品Cu、Zn、Pb含量均未超过我国食品卫生质量标准,空心菜和芋头Cd含量超标。土壤总Cu、Zn、Cd含量与提取态呈显著正相关。     

珠三角滩涂围垦农田土壤和农作物重金属污染

为了研究珠三角滩涂围垦农田土壤和农作物重金属污染状况,采集了广州南沙、中山一带围垦农田农作物及其根际土壤样品,测定重金属的质量分数。结果表明,围垦农田土壤样品中Cu、Ph、Cd、Ni、Cr和Zn含量均大于广东省相应土壤环境背景值,其中Cu（56．06mg·kg^-1）、Pb（48．30mg·kg^-1）、Cd（0．72mg·kg^-1）、Ni（41．15mg·kg^-1）、Cr（115．1mg·kg^-1）和Zn（200．1mg·kg^-1）分别为背景值的3．30、1．34、12．82、2．26、2．28和4．23倍。与《土壤环境质量标准》（GB15618-1995）中Ⅱ级标准（pH〈6．5）比较,土壤样品中Cu、Cd、Ni和Zn的超标率分别为73．7％、88．6％、59．6％和28．9％。以GB15618-1995中Ⅱ级标准为评价标准,采用Nemerow指数法进行评价,土壤重金属平均综合污染指数为1．86,属3级轻污染。与《食品中污染物限量》（GB2762-2005）等相关标准比较,农作物中Cu、Pb、Cd、Ni、Cr和Zn含量的样品超标率分别为0、28．9％、2．6％、48．3％、12．3％和6．1％。由此可见,珠三角滩涂围垦农田土壤和农作物重金属污染问题已经比较突出,土壤污染以Cd为主,而农作物污染则以Ni、Ph、Cr为主。     

Initial results from long-term field studies at three sites on the effects of heavy metal-amended liquid sludges on soil microbial activity

In a long‐term study of the effects on soil fertility and microbial activity of heavy metals contained in sewage sludges, metal‐amended liquid sludges each with elevated Zn, Cu or Cd concentrations were applied over a 3‐year period (1995–1997) to three sites in England. The experiments were sited adjacent to experimental plots receiving metal‐rich sludge cakes enabling comparisons to be made between the effects of heavy metal additions in metal‐amended liquid sludges and sludge cakes. The liquid sludge additions were regarded as ‘worst case’ treatments in terms of likely metal availability, akin to a long‐term situation following sewage sludge additions where organic matter levels had declined and stabilised. The aim was to establish individual Zn (50–425 mg kg^?1), Cu (15–195 mg kg^?1) and Cd (0.3–4.0 mg kg^?1) metal dose–response treatments at each site, but with significantly smaller levels of organic matter addition than the corresponding sludge cake experiments. There were no differences (P > 0.05) in soil respiration rates, biomass carbon concentrations or most probable numbers of clover Rhizobium between the treatments at any of the sites at the end of the liquid sludge application programme. Soil heavy metal extractability differed between the metal‐amended liquid sludge and metal‐rich sludge cake treatments; Zn and Cd extractabilities were higher from the liquid sludge additions, whereas Cu extractability was higher from the sludge cake application. These differences in metal extractability in the treated soil samples reflected the contrasting NH₄NO₃ extractable metal contents of the metal‐amended liquid sludges and sludge cakes that were originally applied.     

Schwermetalle im Boden eines Klärschlamm-Versuchsfeldes

Heavy metals in soil of a sewage sludge experimental field The total amounts of Zn, Cd, Pb, Cu, Cr and Ni were determined in different depths of soils which have obtained sewage sludges in amounts between 180 and 1620 dt dry matter/ha. The elements Zn, Cd. Pb and Cu have been most enriched in the first twenty cm of the soils. The contents of Zn, Cd and Pb in the depth of 40–60 cm also showed a significant increase. The treshold values for Zn and Cd in soils were almost attained respectivly slightly exceeded in the first twenty cm of the soil which has obtained 1440 dt dry matter sewage sludge per ha.     

Sewage sludges in Hawaii: Chemical composition and reactions with soils and plants

Sewage sludges from six wastewater treatment plants in Hawaii were periodically sampled to determine the seasonal variation of their elemental composition. The Sand Island and Honouliuli treatment plants produced primary sludges averaging 1.6% and 2.0% total N, respectively. The Kailua, Kaneohe, Waimanalo, and Waianae treatment plants produced secondary sludges averaging 5.4, 5.1, 6.1, and 3.5% N, respectively. All the sludges tested were virtually devoid of K with concentration ranging from 0.01 to 0.15%, which was less than half of the 0.30% K considered typical for a US sewage sludge. Mean concentrations of Cd, Cu, Fe, Ni, and Zn in the Hawaii sludges were 5.9, 373, 12343, 218, 36.7, and 817 mg kg^?1, respectively, which were within the norms for sludge heavy metals as reported by the US Environmental Protection Agency. Seasonal variations in elemental concentration were small and only statistically significant for Ca and Zn. Sludges from the three treatment plants with highest annual production (Sand Island, Honouliuli, and Kailua) were then mixed at 5, 50, and 250 g kg^?1 with three representative tropical soils (a Mollisol, and Oxisol, and an Ultisol) to study sludge-soil reactions and plant responses. Soil-solution data indicated that chemical properties of a sludge-soil mixture depended not only on the soil, sludge, and its application rate, but also on sludge-soil interactions. At an agricultural rate of 5 g kg^?1 (10 Mg ha^?1), the anaerobically digested Kailua sludge increased corn (Zea mays L.) biomass, whereas the two undigested sludges reduced it. At higher rates, Mn phytotoxicity resulted from sludge applications to the Mollisol and Oxisol, both of which contained reducible Mn nodules. Significant growth reductions would be expected when corn seedlings contained ≥200 mg Mn kg^?1 or ≤0.30 % Ca; and, adequate supplies of Ca and Zn seemed to lessen Mn phytotoxicity.     

Heavy Metals in Water Percolating Through Soil Fertilized with Biodegradable Waste Materials

The influence of manure and composts on the leaching of heavy metals from soil was evaluated in a model lysimeter experiment under controlled conditions. Soil samples were collected from experimental fields, from 0- to 90-cm layers retaining the layout of the soil profile layers, after the second crop rotation cycle with the following plant species: potatoes, spring barley, winter rapeseed, and winter wheat. During the field experiment, 20 t DM/ha of manure, municipal sewage sludge composted with straw (SSCS), composted sewage sludge (SSC), dried granular sewage sludge (DGSS), “Dano” compost made from non-segregated municipal waste (CMMW), and compost made from municipal green waste (CUGW) was applied, i.e., 10 t DM/ha per crop rotation cycle. The concentrations (μg/dm³) of heavy metals in the leachate were as follows: Cd (3.6–11.5)?<?Mn (4.8–15.4)?<?Cu (13.4–35.5)?<?Zn (27.5–48.0)?<?Cr (36.7–96.5)?<?Ni (24.4–165.8)?<?Pb (113.8–187.7). Soil fertilization with organic waste materials did not contaminate the percolating water with manganese or zinc, whereas the concentrations of the other metals increased to the levels characteristic of unsatisfactory water quality and poor water quality classes. The copper and nickel content of percolating water depended on the concentration of those metals introduced into the soil with organic waste materials. The concentrations of Cd in the leachate increased, whereas the concentrations of Cu and Ni decreased with increasing organic C content of organic fertilizers. The widening of the C/N ratio contributed to Mn leaching. The concentrations of Pb, Cr, and Mn in the percolating water were positively correlated with the organic C content of soil.