PESA对污泥中铬的萃取研究

An environmentally benign biodegradable chelant,polyepoxysuccinic acid(PESA),was used to separate heavy metals from sewage sludge from the Shanghai Taopu Wastewater Treatment Plant,China,based on chemical extraction technology.The extraction of chromium(Cr) from sewage sludge with an aqueous solution of PESA was studied under various conditions.It was found that the extraction of Cr using PESA was more efficient than that using ethylenediaminetetraacetic acid(EDTA) and S,S-ethylenediaminedisuccinic acid(EDDS) under similar conditions.PESA was capable of extracting Cr from the sewage sludge,and the extraction efficiency was obviously dependent on both the pH and the concentration of the chelating reagent.The extraction efficiency decreased gradually with increasing pH,and the dependence on pH decreased as the concentration of PESA increased.The extraction efficiency reached 58% under conditions of pH = 4 and a ratio of PESA to total heavy metals of 10:1.The extraction efficiency was maintained above 40% within the pH range from 1 to 7 at the high ratio of PESA to total heavy metals of 10:1.Comparing the contents of heavy metals in the sewage sludge before and after the extraction,it was found that the extracted Cr came mainly from the reducible and oxidizable fractions.     

污泥加石灰后作为肥料用于玉米生长中施肥研究

The use of sewage sludge on agricultural land provides an alternative for its disposal. Therefore, the aim of the present study was to evaluate the feasibility of using industrial sewage sludge produced in Pakistan, as an agricultural fertilizer. The agricultural soil amended with 250 g kg^-1 sewage sludge with or without lime treatment was used for the growth of the common local grain crop, maize （Zea maize）. The mobility of the trace and toxic metals in the sludge samples was assessed by applying a modified BCR sequential extraction procedure. The single extraction procedure was comprised of the application of a mild extractant （CaCl2） and water, for the estimation of the proportion of easily soluble metal fractions. To check the precision of the analytical results, the concentrations of trace and toxic metals in every step of the sequential extraction procedure were summed up and compared with total metal concentrations. The plant-available metal contents, as indicated by the deionized water and 0.01 mol L^-1 CaCl2 solution extraction fractions and the exchangeable fraction of the sequential extraction, decreased significantly （P 〈 0.05） with lime application because of the reduced metal availability at a higher pH, except in the cases of Cd and Cu, whose mobility was slightly increased. Sludge amendment enhanced the dry weight yield of maize and the increase was more obvious for the soil with lime treatment. Liming the sewage sludge reduced the trace and toxic metal contents in the grain tissues, except Cu and Cd, which were below the permissible limits of these metals. The present experiment demonstrates that liming was an important factor in facilitating the growth of maize in sludge-amended soil.     

污泥污水在棉花上的施用: Ⅰ.对土壤性质的影响

A field experiment with cotton was conducted on a well drained,calcareous,clay loamy Typic Xerochreph to investigate the utility of sewage sludge as a partial substitute for fertilizers and the influence of tis application on the basic soil properties and heavy metal concentrations.The experimental design was completely randomized blocks with five treatments replicated four times each.Sewage sludge came from the treatment plant of the municipality of Volos,Central Greece,with the following characteristics:organic matter content 36.6%,pH(H2O1:5)6.89,CaCO3 53.4g kg^-1,total N 265.g kg^-1,ttal P33.5g kg^-1,and total K 968mg kg^-1 soil.Heavy metal concentrations were Cd 5.24,Pb 442,Ni38,Cu 224,Zn1812,and Mn 260mgkg^-1 dry weight,respectively.The soil was high in potassium(K)and poor in available phosphorus(P).The results showed that sewage sludge application increased cotton yield and K and P concentrations in cotton leaves,Soil pH was reduced in the case of higher sewage sludge rate.Electrical conductivity,organic matter content,totalN,and avaiable P were significantly increased.Total concentrations of Zn,Pb,and Cu were slightly increased.DTPA-extractable Zn,Cu,and Mn were also significantly increased.Available forms of all heavy metals,except Cd,were significantly correlated with organic matter content in a positive way and negatively with soil pH.     

热带土壤上连续9年施入污水污泥后重金属Zn, Cd和Pb的分离研究

A long-term field experiment was carried out in the experiment farm of the Sao Paulo State University, Brazil, to evaluate the phytoavailability of Zn, Cd and Pb in a Typic Eutrorthox soil treated with sewage sludge for nine consecutive years, using the sequential extraction and organic matter fractionation methods. During 2005-2006, maize (Zea mays L.) was used as test plants and the experimental design was in randomized complete blocks with four treatments and five replicates. The treatments consisted of four sewage sludge rates (in a dry basis) : 0.0 (control, with mineral fertilization), 45.0, 90.0 and 127.5 t ha^-1, annually for nine years. Before maize sowing, the sewage sludge was manually applied to the soil and incorporated at 10 cm depth. Soil samples (0-20 cm layer) for Zn, Cd and Pb analysis were collected 60 days after sowing. The successive applications of sewage sludge to the soil did not affect heavy metal (Cd and Pb) fractions in the soil, with exception of Zn fractions. The Zn, Cd and Pb distributions in the soil were strongly associated with humin and residual fractions, which are characterized by stable chemical bonds. Zinc, Cd and Pb in the soil showed low phytoavailability after nine-year successive applications of sewage sludge to the soil.     

外生菌根诱导油松根际土壤重金属形态变化

To understand the role of ectomycorrhizas in improving the tolerance of its host to excessive heavy metals in soil, this study was conducted to exam the patterns of four fractions （the exchangeable, the carbonate-bound, the Fe-Mn oxide- bound and the organically bound） of both Cu and Cd in the rhizosphere of Chinese pine （Pinus tabulaeformis） seedlings grown in excessive Cu and Cd environment. The results showed that the speciation of Cu and Cd in the rhizosphere was significantly influenced by inoculation of ectomycorrhizal fungus Boletus edulis. Compared to the rhizosphere, the content of exchangeable Cu slightly decreased in the mycorrhizosphere of the seedlings grown in 166 and 400 mg kg^-1 Cu contaminated soil, whereas the exchangeable Cd in the mycorrhizosphere decreased remarkably to only 33% and to 60% that of the rhizosphere at 0.75 and 1.50 mg kg^-1 Cd levels, respectively. These indicate the potential capacity of mycorrhizas to alleviate the damage of heavy metals to the host plants by reducing the bioavailability of heavy metals in soil. Distribution of the 4 tested fractions of Cu and Cd at different contamination levels showed that there was a strong tendency of changing from loosely associated fractions to strongly associated fractions in the mycorrhizosphere. The most stable Cd fraction, organically bound Cd, was significantly larger in the mycorrhizosphere than in the rhizosphere at different Cd contamination levels. This phenomenon was also observed for Cu but the difference was not statistically significant.     

施用污泥后石灰性土壤中铜、锌、镉的植物有效性

The toxicity of trace elements (TEs), such as copper (Cu), zinc (Zn), and cadmium (Cd), often restrict land application of sewage sludge (SS) and there was little information about soil-plant transfer of TEs in SS from field experiments in China. In this study pot and field experiments were carried out for 2 years to investigate the phytoavailability of TEs in calcareous soils amended with SS. The results of the pot experiment showed that the phytoavailability of Zn and Cu in the SS was equal to 53.4%-80.9% and 54.8%-91.1% of corresponding water-soluble metal salts, respectively. The results from the field experiment showed that the contents of total Zn, Cu, and Cd in the soils increased linearly with SS application rates. With increasing SS application rates, the contents of Zn and Cu in the wheat grains initially increased and then reached a plateau, while there was no significant change of Cd content in the maize grains. The bioconcentration factors of the metals in the grains of wheat and maize were found to be in the order of Zn > Cu > Cd, but for the straw the order was Cd > Cu > Zn. It was also found that wheat grains could accumulate more metals compared with maize grains. The results will be helpful in developing the critical loads of sewage sludge applied to calcareous soils.     

公路旁土壤中水分和重金属的迁移

Roads with very high traffic loads in regions where soils are low in both pH and sorption capacity might be a source of percolation water loaded with heavy metals. Looking at some ＂worst case＂ scenarios, this study focused on the input of traffic related pollutants and on Pb, Cd, Cu, Zn, Ni and Cr concentrations in the soil matrix and soil solution, respectively. The analysis also included pH and electrical conductivity and at some sites DOC. The investigations were carried out on sandy soils with more or less low pH values at four motorway sites in Germany. The average of daily traffic was about 50 000 up to 90 000 vehicles. Soil pore water was collected in two soil depths and at four distances from the road. The pH in general decreased with increasing distance from the roadside. The elevated pH near the roadside was presumably caused by deposition of dust and weathering residues of the road asphalt, as well as by infiltration of salt that was used during winter time. At these road sites, increased heavy metal concentrations in the soil matrix as well as in the soil solution were found. However, the concentrations seldom exceeded reference values of the German Soil Protection Act. The soil solution concentrations tended to increase from the road edge to 10 m distance, whereas the concentration in the soil matrix decreased. Elevated DOC concentrations corresponded with elevated Cu concentrations but did not substantially change this tendency. High soil water percolation rates were found near the roads. Thus, even low metal concentrations of percolation water could yield high metal loads in a narrow area beside the road.     

华北矿区残留态铜、铅在土壤剖面中的分布与迁移

Residual heavy metals are commonly considered to be immobile in soils, leading to an underestimation of their environmental risk. This study investigated the distribution and transport of residual heavy metals along soil profiles, using the Xiaoqinling gold mining region in North China as a case study. Soil samples were collected at three depths from three locations near the tailing heap. The speciation of copper (Cu) and lead (Pb) (exchangeable, carbonate-bound, Fe-Mn oxide-bound, organic matter-bound, and residual fractions) was determined using a sequential extraction procedure. The residual fraction’s morphology was observed using scanning electron microscopy (SEM). Results showed that metal fraction distributions along the soil profiles were influenced by each fraction’s mobility. Residual fraction with high chemical stability cannot be transformed from or into other fractions. This led to the conclusion that the high concentration of residual metals in soils mainly resulted from residual fraction transport.The SEM analysis showed that fine particles (submicrons) were mainly attached to large particles and were likely released and transported by water flow. The more sorptive fractions (non-residual fractions) were mainly retained in the top soil, and the more mobile fractions (residual fraction) were mainly leached to the deep soil. Cu and Pb concentrations in the residual fraction decreased slightly and those in the non-residual fractions decreased significantly with soil depth. These suggest a relatively higher residual metal mobility along the soil pro?les. Therefore, residual metals can be transported in soils and their environmental risk can not be ignored in assessing soil contamination.     

云南滇池沉积物中重金属的形态分布特征

Fractionation of heavy metals in sediments can help in understanding potential hazards of heavy metals. The present study analyzed total concentrations and fractions of selected heavy metals （Cd, Cr, Cu, Pb, and Zn） in surface sediments from Dianchi Lake, Yunnan Province, China, as well as factors that may affect distributions of the various heavy metal fractions. Total concentrations of the heavy metals decreased in the order Zn 〉 Cu 〉 Pb 〉 Cr 〉 Cd. These heavy metals, except Cr, were much higher than their background levels, indicating that Dianchi Lake was polluted by Cd, Zn, Pb, and Cu. Cadmium occurred mainly as the non-residual fraction （sum of the HOAc-soluble, reducible, and oxidizable fractions） （97.6%）, and Zn （55.7%） was also predominantly found in the non-residual fraction. In contrast, most of the Cr （88.5%）, Pb （81.8%）, and Cu （59.2%） occurred in the residual fraction. Correlation analysis showed that total heavy metal concentrations, organic matter and reducible Fe were the main factors affecting the distributions of the various heavy metal fractions. In the Walhai section of Dianchi Lake （comprising 97% of the lake area）, the concentrations of Cd, Zn, Pb, and Cu in the non-residual fraction were significantly lower （P ≤ 0.01 or 0.05） than those of the Caohal section （3% of the lake area）. This indicated that potential heavy metal hazards in the Caohai section were greater than the Waihai section.     

氧化节杆菌生物降解苯并芘

A pot experiment was conducted with multi-metal (Pb, Cd, Cu, and Zn) contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes (fly ash and steel slag). The efficiency of amendments-induced metal stabilization was evaluated by diffusive gradients in thin films (DGT), sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash (20 g kg-1 ) and steel slag (3 g kg-1 ) resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT (C DGT) and the metal uptake by Oryza sativa L. Significant correlations were found between C DGT and the concentration of a combination of metal fractions (exchangeable, bound to carbonates, and bound to Fe/Mn oxides), unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R (ratio of C DGT to pore water metal concentration) values, significantly decreased in the amended soils. The C DGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, Al and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.     

蚯蚓活动对城市生活污泥重金属的影响

采用塑料温棚内垄式堆积污泥培养蚯蚓方式,研究了蚯蚓处理对污泥重金属的影响。结果表明,污泥经蚯蚓处理后,理化性质发生了显著的变化,污泥的pH值、有机质、总氮和总磷都有不同程度的降低;蚯蚓能吸收富集污泥中的重金属,其中对重金属Cd有较强的富集能力;蚯蚓处理使污泥中重金属含量均出现不同程度的下降,重金属Cr、Zn、Pb、Cd、Cu、Ni分别减少27.98%、31.46%、32.81%、13.85%、23.86%和22.92%。利用盆栽试验,研究了污泥施用于土壤后生菜体内重金属积累的情况,结果表明,生菜体内重金属Zn、Cu、Pb和Ni的含量为污泥处理高于蚓粪处理;Cr和Cd则分别为差异不显著和略有降低。     

Determination of mobile heavy metal fraction in soil: Results of a pot experiment with sewage sludge

Abstract

The development of a method using a chelating resin to assess heavy metal mobility in soil and the first results obtained from a pot experiment with sewage sludge additions were studied. The resin was Chelex 100 with the calcium (Ca)‐form of the resin proving to be best suited for the extraction. The efficiency of recovery of the heavy metals from an aqueous solution ranged from 81.2% for cadmium (Cd) to 102% for copper (Cu) within 24 hours. For heavy metal extractions from a soil sample, a 96 hour extraction period was found to be optimum. The extracted heavy metal portion was comparable with the results obtained with an ammonium acetate (NH₄AOc) extraction. Total heavy metal contents in the substrate of the pot experiment did not show a significant influence due to the sewage sludge treatments, although considerable amounts of heavy metals were added by the sewage sludge. This effect can be both due to the incomplete recovery of heavy metals by an aqua regia extraction and leaching losses of these elements from the pots. Rape (Raphanus sativus L.) plants did not have any heavy metal contents which might indicate a high availability in soil, with the Cd and Cr contents in the rape biomass being partly lower in the sewage sludge‐treated pots than in the control plants; however, zinc (Zn) uptake slightly increased with increasing sewage sludge treatments. The Chelex 100 extraction procedure was correlated with Cd plant uptake, while the NH₄AOc extraction procedure was better related to the Zn uptake by rape plants.     

Removal of Heavy Metals from Soil Components and Soils by Natural Chelating Agents. Part II. Soil Extraction by Sugar Acids

Aqueous solutions of the natural chelatingagents D-gluconic acid and D-glucaric acid (D[+]-saccharic acid) were tested for their ability to remove heavy metals (Cd, Cr, Cu,Ni, Pb, Zn) from a soil polluted by long-term application of sewage sludge. Batch equilibrium experiments were performed undervariation of fundamental process parameters, i.e. pH value, sugaracid concentration, batch solution volume, solid:liquid ratioand number of treatment cycles.The extractability of heavy metals was low under near-neutral andslightly basic pH conditions. It increased drastically between pH12.0 and 13.0. Pb and Cu were preferentially extracted metals.Compared with the extraction efficiency of pH adequate puresodium hydroxide solutions, the sugar acids enhanced thesolubilisation of Pb and Cr especially. The metal depletion fromsoil was the highest when applying 20 or 50 g L^-1 solutionsof the chelating agents. Under strongly basic conditions solid:liquid ratios of 1:10 or 1:20 were proofed to be advantageous.Except Ni, multi-step extraction improved the metal removalstrongly. This effect was the greatest for Cr extraction. Underoptimised conditions the following metal extraction degrees wereachieved with strongly alkaline D-gluconic acid solutions: Ni 43%%, Cr 60%%, Cd 63%%,Zn 70%%, Pb 80%%, and Cu 84%%.     

GLDA淋洗参数对污泥中重金属去除效率的影响及其动力学分析

采用GLDA作为淋洗剂对工业污水污泥进行淋洗,确定淋洗的最优参数,为治理工业污泥提供参考依据。通过振荡淋洗研究了GLDA浓度（0.5% ~ 20%）、pH（2 ~ 10）、液固比（10∶1 ~ 80∶1）和淋洗时间（0 ~ 24 h）对污泥中重金属去除率的影响,利用动力学方程对实验数据进行拟合。结果表明,降低pH、增加液固比和延长淋洗时间均可提升重金属的淋洗效率,在pH为2,浓度5%,液固比60∶1,淋洗时间480 min时,GLDA对污泥中的重金属淋洗率达到最优,镍（Zn）、镍（Ni）、镉（Cd）和铬（Cr）的去除率分别为91.21%、76.34%、69.56%和65.01%。准二级动力学方程可以较好的拟合GLDA对4种重金属的淋洗过程,说明重金属淋洗过程以化学淋洗为主。综上所述,在进行淋洗参数优化的基础上,GLDA可用于工业污水污泥中重金属的去除。     

Assessment of Heavy Metals in Spinach (Spinacia oleracea L.) Grown in Sewage Sludge–Amended Soil

The assessment of heavy metals in spinach (Spinacia oleracea) grown in sewage sludge–amended soil was investigated. The results revealed that sewage sludge significantly (P < 0.01) increased the nutrients and heavy metals such as cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn) in the soil. The contents of metals were found to be below the maximum levels permitted for soils in India. The most agronomic performance and biochemical components of S. oleracea were found at 50% concentrations of sewage sludge in both seasons. The contents of Cd, Cr, Cu, Mn, and Zn in S. oleracea were increased from 5% to 100% concentrations of sewage sludge in both seasons. The order of contamination factor (Cf) of different heavy metals was Mn > Cd > Cr > Zn > Cu for soil and Cr > Cd > Mn > Zn > Cu for S. oleracea plants after application of sewage sludge. Therefore, use of sewage sludge increased concentrations of heavy metals in soil and S. oleracea.     

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。     

污泥与施污土壤重金属生物活性及生态风险评价

将城市污泥以不同质量比施于土壤中构成污泥混合土壤,研究各污泥配比土壤中重金属的生物活性,并采用三种重金属评价方法(地累积指数法、潜在生态风险指数法、综合毒性指数模型)和黑麦草对重金属的吸收富集效果来对施污土壤中重金属具有的生态风险性进行评价。结果表明:污泥的添加使土壤中生物活性态Cd、Cu和Zn含量显著增加,对三种重金属具有活化作用,但对Pb却起到钝化作用。生态风险评价结果表明:污泥的添加使土壤中Pb呈现无污染和低生态风险;Cu和Zn呈现中度污染和低生态风险;Cd达到强度污染和重度生态风险,重金属潜在生态风险(RI)总体处于强度生态风险水平。当污泥添加比例大于6:10(污泥S3处理)时,施污土壤中重金属的综合毒性指数高于土壤对照。黑麦草对Cd、Pb、Cu和Zn的富集浓度与施污土壤中对应重金属的生物活性态含量存在显著正幂指数关系,同时黑麦草对施污土壤中Cd、Cu和Pb的富集能力大小与地累积指数法和潜在生态风险指数法对三种重金属具有的生态风险性的评价结果具有一致性。     

Speciation of Metals in Sewage Sludge and Sludge-amended Soils

This study is aimed at ascertaining the chemical partitioning ofCu, Zn, Pb, Ni, Cr and Cd in sewage sludge and agricultural soils repeatedly amended with sludge. The operationally determined speciation was investigated by using selective five steps sequential extraction method for partitioning these metals into different chemicalforms, likely to be released in solution under various environmental conditions. It provides qualitative evidence regarding the form of the association of metals and indirectly of their bioavailability. It can help to explain the process by which metals are eliminated from sewagesludge and also indicate the impact of the use of sludge on agriculturalsoils, as amendments. Data obtained by extraction procedure showed different metal distribution trend among the fractions in sewage sludgeand sludge-amended soils. Comparison of distribution pattern of metals in sludge and sludge-applied soils shows that there is possible redistribution of metals among the different phases. The sum of the metal content in the fractions compared well with the total metal content in sewage sludge, the ratios averaging 1.02, 1.04, 1.07, 0.94, 1.06, and 1.12 for Cu, Zn, Pb, Ni, Cr, and Cd, respectively. The metal recovery efficiency in sludge-amended soils was found to be: 108±6%, 102±5%, 115±8%, 111±4%, 104±7%and 124±28% for Cu, Zn, Pb, Ni, Cr and Cd, respectively.     

Effect of sewage sludge on some chemical properties of calcareous sandy soils

Abstract

City sewage sludge was applied to the surface layer (0–10 cm) of two sandy soils, slightly calcareous with 8.9% CaCO₃ and moderately calcareous with 26.7% CaCO₃, at the rates of 0, 25, 50, 75, and 100 Mg ha^‐1. The effects of sewage sludge and its rates on total soluble salts, pH of soils and concentration and movement of some heavy metals within soils were investigated. Soil samples were packed at bulk density of 1.5 g cm^‐3 in PVC columns and incubated for 19 weeks. The results indicated that total soluble salts (EC) of the treated layer increased with increasing sewage sludge rates. Soluble salts also increased with an increase in soil depth for both soils. The pH values of treated layers in two soils decreased with increasing sewage sludge rates. With increasing sewage sludge rates, concentrations of heavy metals [cobalt (Co), nickel (Ni), cadmium (Cd), and leaf (Pb)] increased in the treated layers compared to the untreated layers and their mobility was restricted mostly to the upper 30‐cm depth. Movement of Co and Pb in both the soils was predominately limited up to a depth of 40 cm for Co and 5 cm for Pb below the treated soil layer. Nickel and Cd movement was mostly limited to a depth of 10 cm in slightly calcareous soil and 5 cm in moderately calcareous soil. Metal movement in the respective soils is ranked as Co>Ni=Cd>Pb and Co>Ni=Cd>Pb. The low concentrations of heavy metals and the restricted mobility with soil depth, suggest that this material may be used for agricultural crop production without any toxic effect on plants.