污泥土地利用对土壤中重金属形态的影响

土地利用是资源化利用城市污水厂污泥的有效途径，随污泥中的营养成分一起进入土壤中的还有其中的重金属元素，它们有可能成为一种环境安全的隐患。本实验所用的土壤为污泥经过无害化及稳定化处理后，与上海潮滩沙土按不同比例(干污泥质量比)混配而成。种植前后分别对沙土、污泥及混配土的重金属含量及形态进行测试。选择几种花卉植物，如菊花(Calendula officinalis）等进行植物种植试验，一个生长季后对植物中的重金属含量及形态进行测试。应用Tessler连续提取法，对污泥中的重金属进入土壤后，土壤中重金属的含量、赋存状态等方面的规律进行研究，发现污泥的土地利用会明显增加土壤中的重金属含量，而且重金属的形态也有明显的变化，可交换态和碳酸盐结合态的重金属含量有明显的增加；如长期使用，则必须采取相应的措施，以消除有害的影响。     

Eco-friendly approach for leaching out heavy metals from sewage sludge

Sewage sludge contains rich organic matter and nutrients essential for the growth of plants but the presence of toxic heavy metals restricts its land application. To overcome this, the study aims an eco-friendly approach for leaching out heavy metals. Sewage sludge from sewage treatment plant, Chennai, India was characterised. The analysis of total heavy metal concentration was done by digesting in nitric acid and different forms were extracted by community bureau of reference sequential method. Heavy metals: As, Cd, Cr, Cr, Ni, Pb and Zn were determined using inductively coupled plasma optical emission spectrometry Perkin Elmer Optima 5300 DV. The experimental set-up for heavy metal leaching was held for five consecutive days at different concentrations of humic acid (0.1%, 0.5% and 1%) at varied pH (5–9). Results revealed that at the end of fifth day at pH 8, 1% humic acid is capable of leaching out 75.5% cadmium, 66.0% nickel, 52.0% lead, 51.2% zinc, 31.2% copper and 8.5% cadmium from sewage sludge. Statistically positive correlation (0.7088) existed between the percentage of heavy metals leached out and the sum of soluble and reducible fractions. Thus, from ecological point of view, humic acid can be used to leach out heavy metals from sewage sludge serving the need in restoration of soil fertility upon land application.     

Synthesis of 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 resin: Applications for the separation and preconcentration of trace metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

A simple, sensitive column solid-phase extraction procedure for separation and preconcentration of Cu(II), Ni(II), Co(II), and Cd(II) in spiked and natural water samples using 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 (XAD-4-DHN) chelating resin prior to their determination by inductively coupled plasma atomic emission spectrometry was discussed. The optimum experimental parameters such as pH, volume of sample and eluent, flow-rates of uptake and stripping, and sorption capacity of the chelating resin, were evaluated. The effect of the electrolytes and the cations on the preconcentration of metal ions was also investigated. The chelating resin could be reused for more than 20 cycles of sorption–desorption without any significant change (<1.0%). Recoveries obtained from this method range from 96 to 102% with R.S.D of 2.50 (n = 4). The detection limits for Cu(II), Ni(II), Co(II), and Cd(II) were found to be 1.9, 0.9, 1.2 µg, and 1.4 µg L^?1, respectively. The proposed method was applied for the determination of Cu(II), Ni(II), Co(II), and Cd(II) in spiked, tap water, and river water samples.     

Current status and developing trends of the contents of heavy metals in sewage sludges in China

It is essential to determine the heavy metal concentrations in sewage sludge to select appropriate disposal methods. We conducted a national survey of heavy metal concentrations of sewage sludge samples from 107 municipal sewage treatment plants located in 48 cities covering the 31 provinces and autonomous regions, as well as Hong Kong, Macao and Taiwan by Xinjiang Production and Construction Corps in 2006, and identified the temporal trends of heavy metal contents in sewage sludge by comparison with surveys conducted in 1994-2001. In 2006, the average concentrations of As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn in sewage sludge were 20.2, 1.97, 93.1, 218.8, 2.13, 48.7, 72.3, and 1058mg.kg-1, respectively. Because of the decreased discharge of heavy metals into industrial wastewater in China and the increasingly stringent regulations governing the content of industrial wastes entering sewers, the average concentrations of Cd, Cr, Cu, Hg, Ni, Pb, and Zn have decreased by 32.3%, 49.7%, 54.9%, 25.0%, 37.2%, 44.8%, and 27.0%, respectively, during the past 12 years. The concentrations of Cd, Cr, Cu, Ni, and Zn in the samples exceeded the heavy metal limits of the Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant in China （GB 18918-2002） by 6.5%, 3.7%, 6.5%, 6.5%, and 11.2%, respectively. From these results, 85 of the 107 municipal sludges analyzed would be considered suitable for land application.     

电感耦合等离子体质谱法分析锰结核中的多种元素含量

本文使用岛津ICPMS-2030电感耦合等离子体质谱仪,采用微波消解法对锰结核样品进行前处理,测定了锰结核样品中32种元素含量.实验结果表明,各元素在1.0-100μg·L-1范围内线性关系良好,相关系数均大于0.9998,检出限低,各元素检出限都在0.00004-0.73 μg·g-1之间.该方法操作简便、快速,测试...     

干法灰化和微波消解-火焰原子吸收法测定铅锌冶炼厂废旧除尘布袋中重金属

采用干法灰化和微波消解两种样品分解方法处理广东省某铅锌冶炼厂布袋试样,用火焰原子吸收光谱法测定样品中Cu、Zn、Pb、Cr、Ni、Cd 6种重金属元素含量.同时用两种前处理方法对国家一级标准物质进行测定,与标准值比对,验证两种方法的准确度和精密度.结果表明,不同的样品分解方法对各重金属元素的测定结果会产生不同程度的影响.微波消解法相对于干法灰化法的准确度高,试剂利用率高,有利于元素的分析.干法灰化和微波消解两种前处理方法的精密度（RSD,n=11）均小于5%.     

可控湿法氧化聚沉工艺对城市污泥中重金属的稳定化影响

采集了长沙市污水厂的剩余污泥（S1）和湿法氧化聚沉工艺处理的深度脱水污泥（S2）,对比分析了处理前后污泥的形貌变化及重金属Zn、Cu、Pb、Cd、Hg和As的形态分布,初步探讨了重金属稳定化机理,对脱水污泥中重金属Zn、Cu、Pb、Cd、Hg和As进行了稳定性评估.结果表明,脱水污泥中重金属的总量均低于我国污泥农用标准中的酸性限值,符合B级污泥泥质要求.处理后,污泥中Zn、Cu、Pb、Cd、Hg和As主要以硫化物有机结合态和残渣态（稳定态）存在,不稳定态在不同程度上向稳定态发生了转变,Cu、Hg的增幅最大,达21.1%.S2中重金属的生物可利用性较S1都有显著的降低,平均降幅达73.1%,S2中重金属的生物可利用性顺序为：Zn〉Pb〉Cu〉Cd〉As〉Hg.污泥经过湿法氧化聚沉工艺处理后,污泥中重金属Zn、Cu、Pb、Cd、Hg和As得到了明显的稳定化,为污泥后续资源化、安全化提供了科学依据.     

吊兰和蝴蝶梅对污泥中重金属的去除效果

采用盆栽土培方法,将剩余污泥与供试土壤按质量比为0∶3,1∶2,2∶1和3∶0配比,吊兰和蝴蝶梅栽培幼苗,定期测定植物的株高、根长、干重、鲜重等生物量和叶绿素与根活力变化,以及植物体内Cu、Zn、Cd、Pb和Cr等的重金属含量变化;测定种植前后植物根系旁污泥中的重金属含量和重金属的EDTA提取含量等结果表明,吊兰对多种重金属具有很好的耐性,受重金属影响不大.吊兰对Cr和Zn的富集效果较好,对Cr的富集系数在某个特定的生长期是大于1,且它对Zn的富集效果较稳定,不易受重金属浓度的影响.由于吊兰具有生物量大、根系发达、生物量增长迅速等优点,其有利于被重金属污染的土壤改良.而蝴蝶梅因为根系不发达和生物量较小等原因,对重金属的耐性不强,生长中易受重金属影响,因此不宜用于修复污染土壤的植物.图9,表5,参7.     

微波消解-原子荧光法测定染毒小鼠体内汞的分布

小鼠经腹腔注射氯化汞(HgCl2)染毒后,采用微波消解-原子荧光法研究汞在小鼠全血、脑、睾丸、脾、肝脏以及肾脏的分布情况.结果表明,方法的检出限为0.002μg.L-1,加标回收率为92.12%—108.46%.该方法操作简便,灵敏度高,检出限低,线性范围宽,可作为生物体内汞含量的测定方法.汞在染毒小鼠血和各脏器中含量随染汞剂量的增加而明显增加,与对照组相比差异有统计学意义(P<0.05);小鼠体内总汞绝大部分蓄积在肾脏内,其次是肝脏,然后是脾、睾丸、脑;全血的总汞含量与肾脏、肝脏、脾、睾丸、脑的总汞含量有相关性.     

Speciation evolutions of target metals （Cd,Pb） influenced by chlorine and sulfur during sewage sludge incineration

In sludge incineration, the thermal behavior of heavy metal is a growing concern. In this work, the combined analysis of metal partitioning behavior between vapor phase and condensed phase, speciation redistribu- tion in condensed phase and the difference of metal species in binding energy was carried out to investigate the possible volatilization-condensation mechanism of heavy metals in high-temperature sludge incineration. It was found that there were two steps in metal volatilization. The initial volatilization of heavy metal originated from their exchangeable （EXC）, carbonate bound （CAR） and iron- manganese bound （FM） fractions, which is primarily composed of simple substance, chlorides, oxides and sulfides. With the increase of chlorine and sulfur in sludge, the inner speciation redistribution of heavy metals occurred in condensed phase, which was an important factor affecting the potential volatility of heavy metals. A partial of metal species with complexed （COM） and residual （RES） fractions gradually decomposed into simple substance or ions, oxides and carbonates, which signifi- cantly strengthened the second volatility. In presence of chlorine, about 46% of Cd with the RES fraction disappeared when the volatility rate of Cd increased by 44.89%. Moreover, about 9% of Pb with COM fraction disappeared when there was an increase of nearly 10% in the volatilization rate. Thus, the second volatilization was mainly controlled by the decomposition of metal species with COM and RES fractions. By virtue of XRD analysis and the binding energy calculation, it was found that metal complex and silicates were inclined to decompose under high temperature due to poor thermo stability as compared with sulfates.     

Analysis of heavy metals in ecstasy tablets by electrochemical methods

Trace amounts of heavy metals have been analysed by electrochemical techniques in ecstasy tablets obtained from different police seizures in Spain. Lead, cadmium, copper and zinc were determined by differential-pulse anodic stripping voltammetry at a hanging mercury drop electrode, whereas nickel and cobalt were determined by adsorptive differential-pulse cathodic stripping voltammetry from their dimethylglyoxime complexes, M(DMG)₂. The performance of the procedure was compared with electrothermal atomic absorption spectrometry. The procedure was applied to the determination of these elements in nine ecstasy samples, finding that Zn is the element present in the highest concentration, ranging from 0.3 to 200?mg?kg^?1, Ni, Cu appear below 15?mg?kg^?1 and Pb below 8?mg?kg^?1, while Cd and Co levels were always lower than 0.51?mg?kg^?1.     

The correlation of total and extractable heavy metals from soil and domestic sewage sludge and their transfer to maize ( Zea mays L.) plants

A study to understand the mobility and transport of heavy metals (HMs) from soil and soil amended with sewage sludge to maize plants was carried out. The total and ethylenediaminetetraaceticacid (EDTA)-extractable HMs in agricultural soil and untreated domestic sewage sludge samples, and the correlation between the total and extractable metals in soil and sewage sludge were carried out. Pot experiments were performed to study the transfer of HMs to maize grains, grown in soil (control) and in soil amended with sewage sludge (test samples). The total and extractable HMs in soil, sewage sludge, and maize grains were analysed by FAAS/ETAAS (flame atomic absorption spectrometer/electrothermal atomic absorption spectrometer) after digestion in microwave oven. Statistically significant correlations were obtained between the total contents of Cu, Cd, As and their respective extractable fractions in soil, while in domestic wastewater sludge (DWS) the better correlation was observed only for Ni and Cd. The edible part of maize plants (grains) from test samples presented high concentration of Zn, Pb, Ni, Cd, Cu, As, and Cr concentrations (80.7–85.6, 3.8–3.95, 2.35–2.5, 0.75–0.82, 3.21–3.29, 0.23–0.27, and 0.22–0.29?mg?kg^?1, respectively). Good correlations were found between metals in exchangeable fractions of both soil and DWS and total metals in control and test samples of maize grains. The transfer factor of all HMs from DWS to maize grains was also determined.     

混酸微波辅助萃取ICP-MS测定不同性质土壤中的重金属元素

比较了硝酸(HNO3)、硝酸-盐酸(HNO3∶HCl=3∶1)、硝酸-盐酸-双氧水(HNO3∶HCl∶H2O2=3∶1∶1)和硝酸-盐酸-高氯酸(HNO3∶HCl∶HCl O4=3∶1∶1)等4种消解液对土壤中铅(Pb)、镉(Cd)、砷(As)、铬(Cr)、镍(Ni)、铜(Cu)和锌(Zn)等7种重金属元素的萃取效率.结果表明,硝酸-盐酸-高氯酸混合液的萃取效果最好,硝酸-盐酸混合液次之.通过对6种土壤标准物质的分析发现,除了Cr之外,其他重金属元素在土壤中的混酸微波可提取态含量与总含量接近.土壤中的Cr有一部分是以铬铁矿的形式存在,在环境中相对较为稳定,采用混酸微波可提取态的Cr来评估其对环境的危害能够获得更加准确的结果.重金属与土壤的结合强弱与成土母质相关,冲积母质的土壤中Pb、Zn和Cu的结合较强,萃取相对较难,Cd、Ni和As与土壤的结合强弱则与成土母质关系不大.采用最优的消解液萃取矿区河流底泥和土壤中的重金属,ICP-MS分析结果表明,底泥中重金属含量较高,应为尾砂冲积而成,矿区周边的土壤也受到不同程度重金属的污染.     

Assessment of heavy metals contamination in soils surrounding a gold mine: comparison of two digestion methods

This study investigated two digestion methods (USEPA 3051: microwave, HNO₃ or Hossner: hot plate, HF–H₂SO₄–HClO₄) for heavy metals analysis in contaminated soil surrounding Mahad AD'Dahab mine, Saudi Arabia. Moreover, contamination metal levels were estimated. The Hossner and USEPA 3051 methods showed, respectively, average total contents of 17.2 and 18.1 mg kg^?1 for Cd, 11.6 and 10.6 mg kg^?1 for Co, 45.7 and 34.7 mg kg^?1 for Cr, 1030 and 1100 mg kg^?1 for Cu, 33,300 and 27,400 mg kg^?1 for Fe, 963 and 872 mg kg^?1 for Mn, 33.2 and 22.8 mg kg^?1 for Ni, 791 and 782 mg kg^?1for Pb, and 6320 and 2870 mg kg^?1 for Zn. A lack of significant differences and a high correlation coefficient (>90%) for Cd, Pb and Cu between the two digestion methods suggest that the total-recoverable method (USEPA 3051) may be equivalent to the total-total digestion method (Hossner) for determining these metals in the studied soil. However, significantly higher concentrations of Cr, Fe, Ni and Zn were found by the Hossner method comapred with the USEPA 3051 method. The soil samples have very or extremely high levels of Zn, Cu, Cd and Pb contamination, indicating very high potential ecological risk.     

Application of ultra-sonication,acid precipitation and membrane filtration for co-recovery of protein and humic acid from sewage sludge

A novel method was applied to co-recover proteins and humic acid from the dewatered sewage sludge for liquid fertilizer and animal feed. The proteins in sewage sludge were first extracted using the processes of ultra-sonication and acid precipitation, and then the humic acid was recovered via membrane filtration. The extraction efficiency was 125.9 mg humic acid?g⁻¹VSS volatile suspended solids (VSS) and 123.9 mg proteins?g⁻¹ VSS at the optimal ultrasonic density of 1.5 W?mL⁻¹. FT-IR spectrum results indicated that the recovered proteins and humic acid showed similar chemical characteristic to the natural proteins and humic acid. The acidic solution (pH 2) could be recycled and used more than 10 times during the co-recovery processes. In addition, the dewatered sludge could be easily biodegraded when the humic acid and proteins are extracted, which was essential for further utilization. These findings are of great significance for recovering valuable nutrient from sewage sludge.     

Assessment of potentially toxic elements in Swiss chard and sediments of Akaki River,Ethiopia

For the determination of 15 potentially toxic elements (V, Cr, Fe, Mn, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sn, Hg, and Pb) in plant and sediment samples of the Akaki River, Ethiopia, inductively coupled plasma–mass spectrometry, inductively coupled plasma–optical emission spectrometry, and a RA-915+ mercury analyzer were applied. Sediment and plant samples were mineralized using a closed-vessel microwave-assisted digestion system. The elemental concentrations varied considerably in plant and sediment samples. The minimum concentration was observed for known toxic elements (As, Hg, and Cd) while the highest concentration was observed for the elements of relatively low toxicity Zn, Mn, and Fe. The concentration of Cr, Fe, Pb, Zn, and As in Swiss chard surpassed the maximum permissible levels at specific sites. At some of the sites, the sediment quality guidelines are surpassed for Cu, Zn, and Pb.     

污泥堆肥利用中AM对稗草生长及Cu、Pb吸收的影响

在滨海盐渍土中分别混加质量分数为0%、20%、40%和60%的污泥堆肥,作为盆栽基质,研究摩西球囊霉（Glomusmosseae）和根内球囊霉（Glomus intraradices）2种AM真菌对稗草（Echinochloa crusgalli）生长及其吸收Cu、Pb的影响,分别以不接种AM真菌的处理为各自的对照。结果显示：添加污泥堆肥处理中稗草接种苗菌根侵染率均显著高于纯盐泽土处理。同时,随着盐渍土中污泥堆肥含量增加稗草生物量上升,其中在含有40%和60%污泥堆肥处理中接种AM真菌稗草的地上及地下部生物量显著高于未接种苗。接种AM真菌显著提高了稗草Cu、Pb富集总量;接种AM真菌显著提高了稗草地下部Cu富集量,却降低了地下部Pb累积量,提高了Pb向地上部的转运,增加了地上部Pb累积量。这些结果表明污泥堆肥中接种AM真菌可以促进稗草的生长和提高对重金属Cu、Pb的富集能力。     

模拟酸雨对街道灰尘重金属淋溶的累积释放特征与释放模型

以泉州市交通繁忙区街道灰尘为研究对象,采用模拟酸雨动态淋溶实验和改进的BCR四步提取法研究街道灰尘中重金属元素在不同酸度(pH=3.5、4.5、5.6)模拟酸雨淋溶下的溶出规律及形态变化.结果表明,街道灰尘中重金属元素的累积释放量均随模拟酸雨pH的降低而增加,当pH值为3.5和4.5时,Cu、Pb、Mn、Ni、V、As和Co的释放过程为快速释放阶段,Cr、Zn和Fe的释放过程分为快速释放和相对平稳释放两个阶段;当pH值为5.6时,除Co、V为快速释放过程外,其余重金属都处于相对慢速的释放过程.动力学方程拟合结果表明,双常数速率方程能更好地描述上述重金属元素的累积释放特征.尘样经模拟酸雨淋溶后,弱酸可溶态中Co、Cu、Mn、Zn、Ni百分含量有所增加,Cr、Fe、Pb百分含量变化不明显;可还原态中Cr、Pb、Cu、Ni百分含量有所增加,Mn、Zn、Co百分含量有所下降;可氧化态中上述各元素的百分含量均有所降低;残渣态中除Ni、Mn百分含量有所下降外,其它元素百分含量变化均不显著.     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Effect of clay minerals on extractability of heavy metals and sewage sludge mineralization in soil

An incubation experiment lasting 111 d was carried out to study the effect of the addition of three clay minerals (Na-bentonite, Ca-bentonite, and zeolite) to soil derived from sewage sludge on water-extractable and exchangeable forms of four heavy metals (Zn, Cd, Cu, and Ni), as well as on soil organic matter mineralization, microbial biomass C and the release of inorganic N. The addition of clay minerals led to a significant decrease in water-extractable and exchangeable forms of heavy metals. The extent of decrease ranged from 14 to 75% for the water-extractable heavy metals and from 12 to 42% for the exchangeable form over the incubation time, as compared with untreated soil. The reduction in extractability of heavy metals was greater due to the addition of Na-bentonite and Ca-bentonite than that due to the addition of zeolite. Addition of clay minerals did not affect any of the following microbiological parameters in the soil: microbial biomass C, organic C (C_org) mineralization, and metabolic quotient (qCO₂), and release of inorganic N during the first 3 weeks of incubation. However, as the incubation period increased, these parameters were significantly increased by the addition of clay minerals, especially by the addition of Na-bentonite and Ca-bentonite. This result is explained by a strong reduction in extractability of heavy metals after the addition of Na-bentonite and Ca-bentonite.