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.     

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.     

Heavy metals in contemporary Chinese sewage sludges

The heavy metal content in sewage sludges from a big Chinese city was investigated. Concentrations of zinc (Zn), lead (Pb), copper (Cu), chromium (Cr), nickel (Ni), cadmium (Cd) and mercury (Hg) in the sludges were 258–4050 mg kg^‐1, bd: 994 mgkg^‐1, 8.3–566 mg kg^‐1, 26.3–370mgkg^‐1 4.2–113 mg kg^‐1 0.9–6.4 mg kg^‐1 and 1.8–12.4 mg kg^‐1 respectively. The concentrations of Zn and Pb in the sewage sludges from the residential areas were higher than those in the mixed ones (from both residential and industrial areas). The concentrations of heavy metals in the flocculently dewatered sewage sludges were higher than those in the sediment of the centrifuged undewatered sewage sludges. After centrifuging, more than 60% of heavy metals remained in the sludge sediment with an exception of Cd. The content of organic matter, total phosphorus (T‐P) and total potassium (T‐K) in these sewage sludges was also measured.     

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。     

Fate of herbicides and nonylphenol in soil–plant–water systems amended with contaminated sewage sludge

We studied the fate of sludge spiked with ¹⁴C-labelled diuron, glyphosate and nonylphenol applied to the soil by the way of contaminated sewage sludge in the soil-plant-water system. Here we show that the mineralization of the chemicals in mixture is reduced by 40–80% by comparison with a direct soil contamination. The persistence of the chemicals in soils is increased in the presence of sludge. We showed also that the chemicals present in the sludge are mobile and partly transferred to soil leachates and plant seedlings. These results allow postulating that these compounds may induce an ecotoxicological impact on the soil ecosystem.     

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.     

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.     

Co-pyrolysis of sludge and kaolin/zeolite in a rotary kiln: Analysis of stabilizing heavy metals

• Adding kaolin/zeolite promotes the formation of stable heavy metals. • The potential ecological risk index of co-pyrolysis biochar is extremely low. • Increasing the pyrolysis temperature reduces the leaching toxicity of heavy metals. • The toxicity of biochar reduces with the increasing content of stable heavy metals. Pyrolysis is a promising technique used for treating of sewage sludge. However, the application of pyrolysis products is limited due to the presence of heavy metals. In this study, sewage sludge mixed with kaolin/zeolite was pyrolyzed in a rotary kiln, aiming to improve the immobilization of heavy metals in pyrolytic carbon. The total concentrations, speciation distributions, leaching toxicities, and potential ecological risk indices of heavy metals in pyrolysis biochar were explored to examine the effects of kaolin/zeolite and pyrolytic temperature on immobilizing heavy metals. Further, mineral composition and surface morphology of biochar were characterized by X-ray diffraction and scanning electron microscopy to reveal the potential mechanism of immobilizing heavy metals. Increasing pyrolysis temperature facilitated the stabilization of heavy metals in pyrolysis biochar. The proportions of stable heavy metals in biochar obtained at 650℃ were 54.50% (Cu), 29.73% (Zn), 79.29% (Cd), 68.17% (Pb) and 86.70% (Cr). Compared to sewage sludge, the potential contamination risk index of pyrolysis biochar obtained at 650℃ was reduced to 17.01, indicating a low ecological risk. The addition of 7% kaolin/zeolite further reduced the risk index of co-pyrolysis biochar prepared at 650℃ to 10.86/15.28. The characterization of biochar revealed that increase in the pyrolysis temperature and incorporation of additives are conducive to the formation of stable heavy metal-inorganics. This study demonstrates that the formation of stable mineral compounds containing heavy metals is the key to stabilizing heavy metals in pyrolysis biochar.     

Heavy metal concentration in soil and woody plants in a quarry

This study determined the concentration of three heavy metals zinc (Zn), lead (Pb), and cadmium (Cd) in soil and in a woody plant species, Milicia excelsa, at Ishiagu quarry, Nigeria. The highest soil concentrations of Zn, Pb, and Cd in soil were obtained at 1?m from the quarry site. In M. excelsa, the highest concentrations of Zn, Pb, and Cd were 3.12–9.1, 3.9–6.01, and 0.51–1.12?mg?kg^?1, respectively. There were significant positive correlations between Cd and Zn (r?=?0.963) and Cd and Pb (r?=?0.974) in plants as well as between Cd and Pb (r?=?9.84) in soil. The level of Cd in soil reflected significant pollution compared to average global concentrations in soils.     

未消化生活污泥中氮磷供应特性及其环境行为

采用土柱模拟试验，比较了生活污泥和化肥在水－旱耕作制下氮磷的肥效及其对地下水的影响。结果表明，污泥氮磷生物有效性在当季虽比等量的化肥略低，但仍有较大的肥效，且较化肥后效显著，有利于后茬作物的稳健生长。种水稻施用污泥或化肥都未发现有氮磷下渗现象；旱作条件下施化肥和污泥会产生较多的硝酸盐，且极易向下层土壤移动，但污泥的影响程度远没有化肥的大。作者认为在供试条件下按作物对养分的需要来施用污泥，不会构成氮磷对地下水污染的威胁。     

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.     

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.     

Sewage sludge ditch for recovering heavy metals can improve crop yield and soil environmental quality

• Indirect use of sludge in ditches alongside plants was tested in field experiments. • The dried and stabilized sludge in ditches was recovered with heavy metals. • Cd, Pb, Cu and Zn in the planted soil were all in a safe range. • The indirect use of sludge increased plant yield, soil N content and C storage. The treatment and disposal of municipal sewage sludge (MSS) is an urgent problem to be resolved in many countries. Safely using the nutrients within MSS to increase crop yield and enhance the fertility of poor soil could contribute to achieving sustainable development. An indirect use of MSS in ditches alongside Pennisetum hybridum plants was studied in field plots for 30 months and the contents of heavy metals and macronutrients were monitored in soil, sludge and plant samples. We found that the yield of P. hybridum was significantly increased by 2.39 to 2.80 times and the treated plants had higher N content compared with no sludge. In addition, the organic matter (OM) and N contents in the planted soil increased significantly compared with the initial soil. The OM content in the planted soil of the MSS treatment was 2.9 to 5.2 times higher than that with no sludge, and N increased by 2.0 to 3.8 times. However, MSS had no significant effect on the N, P and K contents in the soil at the bottom of the MSS ditch, and the content of heavy metals (Cd, Pb, Cu and Zn) were also within the safe range. Moreover, the moisture content and phytotoxicity of MSS after this indirect use were reduced and the heavy metal contents changed little, which is favorable to the further disposal of recovered MSS. Therefore, this indirect use of MSS is beneficial to agricultural production, soil quality and environmental sustainability.     

Characterization of value-added chemicals derived from the thermal hydrolysis and wet oxidation of sewage sludge

• Hydrothermal treatment can greatly improve resource recovery from sewage sludge. • tCOD removal during WO was ~55% compared with ~23% after TH. • TOC solubilization during hydrothermal treatment followed first-order kinetics. • Solids and carbon balance confirmed loss of organics during thermal hydrolysis. • Reaction pathways for thermal hydrolysis and wet oxidation are proposed. We evaluated the effect of hydrothermal pretreatments, i.e., thermal hydrolysis (TH) and wet oxidation (WO) on sewage sludge to promote resource recovery. The hydrothermal processes were performed under mild temperature conditions (140°C–180°C) in a high pressure reactor. The reaction in acidic environment (pH= 3.3) suppressed the formation of the color imparting undesirable Maillard’s compounds. The oxidative conditions resulted in higher volatile suspended solids (VSS) reduction (~90%) and chemical oxygen demand (COD) removal (~55%) whereas TH caused VSS and COD removals of ~65% and ~27%, respectively at a temperature of 180°C. During TH, the concentrations of carbohydrates and proteins in treated sludge were 400–1000 mg/L and 1500–2500 mg/L, respectively. Whereas, WO resulted in solids solubilization followed by oxidative degradation of organics into smaller molecular weight carboxylic acids such as acetic acid (~400–500 mg/L). Based on sludge transformation products generated during the hydrothermal pretreatments, simplified reaction pathways are predicted. Finally, the application of macromolecules (such as proteins), VFAs and nutrients present in the treated sludge are also discussed. The future study should focus on the development of economic recovery methods for various value-added compounds.     

污泥施用对林地土壤基本性质及酶活性的影响

以无锡卢村污水处理厂厌氧消化的脱水污泥为有机肥源,采用土培盆栽试验的方法,研究了不同用量污泥施用后土壤基本性质的变化及对土壤酶活性的影响。试验设计5种处理,污泥施用量和占土质量的比例分别为0（不施污泥的对照处理,CK）,30（3%）,60（6%）,120（12%）和240（24%）g·kg^-1。结果表明,污泥使用提高了土壤中养分元素和有机质的含量;黄棕壤中过氧化氢酶的活性平均比潮土中的高5.2%,随污泥用量的增加潮土中过氧化氢酶活性提高,而黄棕壤中的无明显变化;与对照相比,土壤脲酶活性在两种土壤上分别增加55.6%～122%（黄棕壤）和46.2%～67.5%（潮土）,且与土壤全氮、全磷、水解氮、速效磷和有机质（黄棕壤）和土壤全氮、水解氮和有机质（潮土）呈正相关;结果还显示污泥使用增加了土壤蔗糖酶活性,但不同污泥用量之间无明显差异。     

Distribution of heavy metals in soil and accumulation in plants at an agricultural area of Umudike,Nigeria

This study assessed the distribution of heavy metals in soil and their subsequent accumulation in plants at a site at Umudike, Nigeria, that had been contaminated by agrochemicals. Soil and plant samples were analysed for zinc (Zn), chromium (Cr) and cadmium (Cd). The highest concentrations of Zn (251.50 mg/kg) and Cd (61.33 mg/kg) were obtained at a soil depth of 0–10 cm. The highest concentrations of Zn (16.52 mg/kg), Cd (27.12 mg/kg) and Cr (164.07 mg/kg) were accumulated by Baphia nitida. The levels of Cd, Cr and Zn in soil were 27.97–61.33, 24.97–45.43 and 148.57–251.50 mg/kg, and their concentrations in B. nitida were 16.18–27.13, 97.99–164.07 and 0.10–16.52 mg/kg, respectively. There were significant correlations between Cd and Cr and Cd and Zn in soil, as well as between Cd and Cr in plants. The concentration of Cd in soil reflected a state of pollution relative to Dutch criteria for soil and the FAO/WHO Codex Alimentarius Commission.