Characteristics of heavy metal accumulation on fly ash- and sewage sludge-amended calcific soil

Land disposal of fly ash(FA)and sewage sludge(SS)is a major problem due largely to their potentially harmful constituents.In this paper,a potting experiment was performed to evaluate the effects on the plant growth and to discuss in particular the potential hazard to soils and plants according to the characteristics of heavy metal accumulation and migration when FA and SS are used as the amendments of calcific soil in a limestone mining area. The results showed that the application of FA-SS mixture is capable of accelerating the growth of plants and improving the biomass production at either 1:1 or 1:2 FA-SS mixture:soil(w/w).The highest yields were obtained at 1:1(w/w)mixing ratio.When compared with the Element Background Values of Soils in China,the analysis on heavy metals indicated that the contents of Pb,Cr,Hg,Cd,As,Ni,Cu and Zn in the amended soils came up to the second-class environmental quality standards,only Hg and Cd showed significant accumulation.At the same time, though the metal concentrations in roots were higher than those for the control,the concentrations except Cu,Zn in shoots were lower.And all the heavy metal contents in the plants were substantially lower than the toxicity limits. The results indicated that the combined use of FA and SS at a rational rate of application should pose no danger to both soil and food chain based on the characteristics of the FS and SS,heavy metals and calcific soil.     

Relationship of chemical fractions of heavy metals with microbial and enzyme activities in sludge and ash-amended acid lateritic soil from India

The influence of metals, Cd, Cr, Cu, Ni, Pb and Zn, on the microbial biomass and enzyme activities of an amended acid lateritic soil were investigated under field conditions receiving a one-time application of 52 t ha^–1 of sludge, coal ash and their mixtures at 1:3, 1:1 and 3:1 proportions, and including control and chemical fertilizer treatment at crop-specific recommended doses. Paddies and peanuts were grown in the experimental plots and soil was sampled twice after 6 months and 1 year after amendment application. The heavy metals in the soil were fractionated using sequential extraction and the increments in their concentrations in amended soil with respect to the control were determined. Concentrations of Cd, Ni and Zn were determined to have increased in their mobile fractions and were more pronounced in soil collected during the second sampling, which was associated with a decrease in soil organic carbon. The size of the microbial biomass carbon and the soil enzyme activities increased with the addition of an amendment and was highest at equal proportions of coal ash and sludge. Further increase in the proportion of sludge resulted in a significant decrease in biomass carbon. Simple correlation revealed significant and strong negative relations of mobile fractions of Cd and Ni with the ratio between microbial biomass C and organic carbon in soil, while the organic carbon content and the pH were positively correlated. The microbial activities were determined to be sensitive to the concentrations of some heavy metals in mobile fractions and therefore indicated possibilities of being useful as indicators for evaluation of toxic effects of sludge-borne metals on soil organisms.     

高钙粉煤灰固化重金属污染土的工程性质试验研究

高钙粉煤灰是燃煤电厂排出的固体废物,其堆放不仅需占用大量土地,而且对周围环境存在严重威胁。通过系统的室内试验,着重研究了高钙粉煤灰固化铅与锌污染土的工程性质,揭示了其作用机制,探讨了利用高钙粉煤灰固化重金属污染土的可行性。试验结果表明,土体受到重金属离子污染后其无侧限抗压强度降低,掺入高钙粉煤灰可提高土体强度,并能抑制重金属离子的滤出;污染物浓度较低时,固化污染土中的Pb2+和Zn2+均能得到有效固化,污染物浓度较高时,Zn2+的固化效果优于Pb2+。干湿循环试验结果表明,高钙粉煤灰固化污染土的强度随干湿循环次数的增加,先增大后减小;固化土体中重金属离子浓度较低时,滤出液中金属离子浓度随干湿循环次数增加而增大;重金属离子浓度较高时,滤出液中金属离子浓度基本保持不变。     

Impact of treated sewage sludge application on phosphorus release kinetics in some calcareous soils

Treated sewage sludge contains significant amount of phosphorus and is widely used in agriculture. Kinetics of P release in soils is a subject of importance in soil and environmental sciences. There are few studies about P release kinetics in treated sewage sludge amended soils. For this purpose, sludge was mixed with ten soils at a rate equivalent to 100 Mg sludge ha⁻¹, and P desorption was determined by successive extraction using 0.01 M CaCl₂ over a period of 65 days at 25 ± 1°C. Phosphorus release rate was rapid at first (until about first 360 h) and then became slower until equilibrium was approached. Average of P released within 360 h for the unamended and amended soils was about 65 and 73% of the total desorbed P, respectively. Zero-order, first-order, second-order, power function, simplified Elovich and parabolic diffusion law kinetics models were used to describe P release. First-order, Elovich, power function and parabolic diffusion models could well describe P release in the unamended and amended soils. Correlation coefficients between P release rate parameters and selected soil properties showed that in the control soils, calcium carbonate equivalent and Olsen-extractable P; and in the amended soils, calcium carbonate equivalent, cation exchange capacity, organic matter and Olsen-extractable P were significantly correlated with P release parameters. The results of this study showed that application of sewage sludge can change P release characteristics of soils and increase P in runoff.     

Pollution of south of Tehran ground waters with heavy metals

The reuse of nutrients and organic matter in wastewater sludge via on agricultural lands application is a desirable goal. However, trace or heavy metals present in sludge pose the risk of human or phytotoxicity from land application. The aim of this research is possibility of ground water pollution of south of Tehran because of ten years irrigation with Ni, Cd and Pb borne waste water. For this purpose, 6 soil samples from southern parts of Tehran city and 2 ones from Zanjan city without lime and organic matter were selected. The soils differed in their texture from sandy to clayey. Each soil sample in duplicate and uniformly packed into PVC columns. Soil samples were irrigated with Cd, Pb and Ni-added wastewater. After irrigating, the columns were cut and the soils separated from sectioned pieces and their heavy metal concentrations (Pb, Cd and Ni) were measured by atomic absorption spectrophotometer by use of HNO₃ 4N solution. Because of high sorption capacity of these elements by soils, these metals were accumulated in surface layer of the soils. Movement in the soils without lime and organic matter were as low as other samples. Ni has had the most accumulation or the least vertical movement, and Pb the opposite ones.     

Assessment of nutrient and heavy metal content and speciation in sewage sludge from different locations in Iran

More than 80% of sewage sludge (SS) produced in Iran is landfilled with high environmental impact. The chemical properties of SS produced from wastewater plants of cites of Arak, Isfahan, Kermanshah, Rasht, Saveh, Shiraz, Sanandaj, Tehran, Takestan, and Toyserkan were studied to assess the potential beneficial effects of their application to agricultural soil as sustainable SS management. The pH and EC values, total content and water-soluble concentration of nutrients and heavy metals, their water-extractable pools were determined, and their speciation was done through the NICA–Donnan model using the Visual MINTEQ software. Relatively high contents of N, P, and physiologically active cations indicated potential beneficial effects of SS for land application in the agro-ecosystems, whereas the heavy metal content depended on the SS production site, with higher levels found in the SS of the Arak and Saveh wastewater treatment plants. The pH value was the main factor controlling the metal speciation, with Cu and Pb having the highest affinity for the organic matter, and Zn and Mn being mainly present as free ions or inorganic species. Results showed that SS from different locations in Iran differed in their main chemical properties and elemental composition and that speciation analysis could be used to predict potential beneficial and harmful effects of SS, particularly upon the modeling of metal–organic complexes by the NICA–Donnan approach. Globally, our results confirmed that while the SS produced in Iran has potential suitable chemical properties for use in agriculture, their heavy metals load should not be ignored.

     

Sources of very high heavy metal content in soils of volcanic island (La Réunion)

The objective of this study was to conduct an inventory of heavy metal concentrations (Cd, Cr, Cu, Hg, Ni, Pb and Zn) in the soils of La Réunion. 39 sampling sites were selected to cover the distribution of soils of the island. The results show that soils of La Réunion are rich in heavy metals: most of them exceed the French standard values beyond which sewage sludge spreading is not authorized. To identify the sources of heavy metals, we used: (i) the relationship between the heavy metal content in soils and the origin of the volcanic parent material; (ii) the comparison of heavy metal content between cultivated and uncultivated soils; and (iii) the heavy metal distribution in soil profiles. Cd and Pb evolution in soil profiles indicate an impact of human activities. High Hg concentrations in soils can be explained by the volcanic activity of the island. For Cr, Cu, Ni and Zn, we demonstrate that high concentrations in soils are mainly determined by the natural pedo-geochemical background.     

粉煤灰污泥添加剂对地下水质影响的模拟研究

通过测定土柱和淋洗液中重金属的含量,研究石灰岩质土壤应用粉煤灰污泥添加剂改良后重金属在土壤剖面上的分布移动特征及对地下水质的影响.结果表明:仅试验层内除As和Ni外,Zn、Cd、Pb、Cu、Cr、Hg含量明显增加,未出现明显向下移动的趋势;同时重金属淋出量明显增加,但未超过地下水Ⅲ级标准.初步认为与添加剂自身、重金属的特性及石灰岩质土壤滤层的截固作用相关.粉煤灰污泥经过合理的配施和预处理应用于石灰岩质矿区退化土壤的改良,短期内不会对地下水的质量产生明显的影响.     

Competitive adsorption behavior of selected heavy metals in three soil types of India amended with fly ash and sewage sludge

Laboratory batch experiments were carried out to study the competitive sorption behavior of metals in three types of Indian soils, differing in their physicochemical properties: acid laterite (SL1), red alfisol (SL2) and black vertisol (SL3) treated with different proportions of fly ash and sewage sludge mixture. Representative samples were equilibrated with 10 to 200 µM L ^-1 concentrations of metals simultaneously containing Cd, Cu, Ni, Pb and Zn in 5 mM of Ca(NO ₃) ₂ solution. In most of the cases the affinity sequence of metals was Pb>Cu>Zn>Ni>Cd based on their amount of sorption, which varied little with either metal equilibrating concentrations or the soil/mixture type. The observed metal affinity sequences in different soils amended with mixtures were compared to the predicted affinity sequences based on metal properties and a good match was found with those predicted by metal hydrolysis constants. This indicated that formation and subsequent sorption of metal hydrolysis products on soil surface is the predominant mechanism for sorption. In all the cases, Pb and Cu showed higher affinity followed by Zn, Ni or Cd. The increase in the metal additions further enhanced the competition among metals for exchange sites. Adsorption isotherms showed that metal sorption was linearly related to its concentration in the equilibrium solution. The distribution coefficients (K _D) computed from the slopes of linear regression for different metals were higher in SL3 than in both SL2 and SL1. All the mixture amended soils produced higher K _D values than their respective controls. Selectivity between metals resulted in the following affinities based on their K _D values—Pb>Cu>Zn>Ni or Cd—which was in line with the value of the hydrolysis constant of the metals under study.     

Soil improvement with coal ash and sewage sludge: a field experiment

A field experimental study was carried out successfully to improve the quality of the sandy soil by adding coal ash and sewage sludge. One ha of barren sandy soil field was chosen for the experiment in Shanghe County, Shandong Province, China. For soil amelioration and tree planting, two formulas of the mixture:coal ash, sewage sludge and soil, in ratios of 20:10:70 and 20:20:60, respectively, were used. Poplar trees were planted in pits filled with soils with additives (mixture of ash and sludge) as well as in the original sandy soil. In the 19th months after the trees were planted, the soils with additives were sampled and analyzed. The results show that the barren sandy soil was greatly improved after mixing with coal ash and sludge. The improved soils have remarkably higher nutrient concentrations, better texture, smaller bulk density, higher porosity and mass moisture content, and higher content of fine-grained minerals. During the first 22 months after planting, the annual increase in height of the trees grown in the soil with additives (4.78 m per year) was 55% higher than that of the control group (3.07 m per year), and the annual increase in diameter at the breast height (1.3 m) was 33 % higher (43.03 vs. 32.36 mm). Trees planted in soils with additives appeared healthier and shed leaves later than those in the control group. As the volume of the additives (30–40% in both formulas) is less than that of the sandy soil in and around the tree pits, it appears that the use of coal ash and sludge for tree planting and soil amelioration is environmentally safe even though the additives have relatively high heavy metal concentrations.     

Immobilization of Cd,Zn and Pb in sewage sludge using red mud

Sewage sludge is an inevitable end by-product of sewage treatment. Land application provides a cost-effective alternative for sewage sludge disposal. However, sewage sludge contains heavy metals that may limit its application. In this work, red mud was employed for the immobilization of heavy metals in sewage sludge. The effect of red mud amendment on heavy metal immobilization was evaluated using Toxicity Characteristic Leaching Procedure (TCLP) method. The TCLP results showed that the immobilization efficiency of Cd, Zn and Pb was 100, 92, and 82%, respectively, when sewage sludge was mixed with 10% red mud. Tests carried out in leaching columns demonstrated that heavy metal concentrations in the leachate of 10% red mud amended sludge were lower than those of the unamended sludge. Moreover, red mud decreased plant available heavy metal (Cd, Zn and Pb) content from 18.1, 17.2 and 14.6% to 6.9, 11.4 and 7.6%, respectively. Sequential chemical extraction experiments showed that after sludge was amended with 10% red mud, exchangeable fraction was reduced and iron and manganese oxides fraction was increased. Red mud amendment can effectively immobilize Cd, Zn and Pb in sewage sludge before land application.     

福建龙海土壤重金属含量特征及影响因素研究

为有效预防土壤重金属生态风险,以福建龙海市表层土壤为研究对象,应用经典统计分析、随机森林等方法,研究重金属元素含量特征及其影响因素。结果表明：(1)第四纪冲洪(海)积成因水稻土中多数重金属元素含量较高;(2)燕山期中酸性岩风化形成的残坡积红壤中重金属元素活动态含量较高;(3)As、Cu、Ni形态含量与全量相关性较好,而Cd、Cr、Hg的多数形态含量与全量相关性较差;(4)除元素全量外,土壤有机质对弱有机结合态重金属(不包括Ni、Pb元素)以及离子交换态、碳酸盐结合态Cd、Zn有重要影响,阳离子交换量对各形态Ni,(Fe×Al)/Si对各形态Cu具有重要影响,而土壤成因、土壤类型对重金属形态组成的影响较小。研究表明土壤重金属形态组成及其富集区与其全量不尽一致,土壤重金属生态风险评价应考虑土壤重金属形态分布特征。     

湖州市不同土壤重金属的污染现状

湖州市是主要的农产品基地，其主要土壤类型有四种，即黄泥土、青紫泥、白泥土和湖松土。样品分析表明重金属元素在黄泥土和青紫泥中较高，白泥土和湖松土中较低。大多数重金属元素相对下蜀土是富集的，超过自然背景值的元素有Cu,Cd及部门土壤中的Pb和Hg。有机质、pH值和Eh值对重金属的含量和化学形态有影响，有机质愈高，重金属的含量愈高；pH值接近中性，重金属的含量亦高。土壤的氧化条件可使大多数重金属变为高价离子，它们的化合物活性较低，但Cr^6 易被植物吸收。湖州土壤中重金属的高值点与工业污水排放和大气沉降有关。土壤中对农作物有危害的重金属元素为Cd和Hg，局部地方为Pb。     

The retention of heavy metals in sewage sludge applied to a freshwater tidal wetland

The hypothesis that freshwater tidal wetlands act as sinks for heavy metals was tested using sewage sludge applied biweekly from March to October 1981 at low treatment (25 g m^?2 wk^?1) and high treatment (100 g m^?1) levels. No differences in aboveground macrophyte standing crop were found except in June when high and low treatment sites had significantly higher (p=0.05) standing crops than control sites. Except for chromium, metal standing stocks in the vegetation on treatment sites did not increase as a result of sludge application. The March litter had significantly higher (p=0.05) concentrations of chromium, copper, lead, and nickel at all sites than the October vegetation, but only high and low treatment litter chromium levels were significantly higher (p=0.05) than control litter. When sludge application terminated in October, the top 5 cm of soil at the high and low treatment sites had retained, respectively, 47 and 43% of the cadmium, 53 and 28% of the chromium, 52 and 0% of the copper, 51 and 0% of the zinc, 31 and 0% of the lead, and 0 and 0% of the nickel applied; only cadmium (15 and 46%, respectively) and chromium (12 and 28%, respectively) were still retained the following March. Thus, freshwater tidal wetlands can retain significant quantities of heavy metals associated with sewage sludge. The vegetation and litter play minor roles while the soil plays a major role in heavy metal retention.     

An experimental study of heavy metal attenuation and mobility in sandy loam soils

Column flow-through experiments reacting wastewater solutions with sandy loam soil samples were performed to study heavy metal attenuation by two soils with different physical and chemical properties. Reacted soil columns were leached with synthetic acid rain to study the mobility of attenuated heavy metals under leaching conditions. This study demonstrates that cation exchange, surface adsorption, chelation with solid organic material, and precipitation were the important attenuation mechanisms for the heavy metals (Cd, Cr, Cu, Mo, Ph, and Zn). Adsorption on soil hydrous oxide surfaces was the primary attenuation mechanism for Cd and Zn in both soils, and for Cu in a soil with low organic matter content. Wastewater solution pH is also an important factor that influences the retention of heavy metals. Cadmium, Cu, Cr, and Zn became mobile after prolonged application of spiked wastewater solution, either through saturation of soil adsorption sites or due to decreasing pH. Only Cr, Pb, and Mo, which are attenuated primarily through precipitation, show significant net retention by soil. Acid rain water removed heavy metals left in the column residual pore solution and weakly sorbed heavy metals in the soils, and has the ability to mobilize some strongly attenuated heavy metals, especially when the soil organic matter content is high. The results have important applications in predicting heavy metal mobility in contaminated soil, the disposal of acid mine drainage, and assessing the risks of landfall leachate leakage.     

污泥和粉煤灰的循环利用及其对石漠化土壤质量的改善

本文通过在石漠化土壤中添加不同配比的城市污泥—粉煤灰混合物,研究其对石漠化区域土壤理化性质、持水性能,及在该石漠化土壤上所种植的高羊茅生长和重金属积累的影响。结果表明:施用粉煤灰能显著降低污泥Cu、Mn、Zn和Cd等重金属的含量并使土壤的pH得到提高,明显改善土壤的理化性质;土壤饱和含水率比对照提高1.95倍,持水时间提高7d左右,能增加土壤的N、P养分,并显著提高高羊茅的生物量,不失为促进石漠化地区生态恢复治理的一种有效方法。但由于重金属在环境中半衰期长、彻底清除难和生态毒害大等特点,不宜长期反复施用富含重金属的城市污泥。      

Utilization of fly ash for stabilization/solidification of heavy metal contaminated soils

Pozzolanic-based stabilization/solidification (S/S) is an effective, yet economic remediation technology to immobilize heavy metals in contaminated soils and sludges. In the present study, fly ash waste materials were used along with quicklime (CaO) to immobilize lead, trivalent and hexavalent chromium present in artificially contaminated clayey sand soils. The degree of heavy metal immobilization was evaluated using the Toxicity Characteristic Leaching Procedure (TCLP) as well as controlled extraction experiments. These leaching test results along with X-ray diffraction (XRD), scanning electron microscope and energy dispersive X-ray (SEM–EDX) analyses were also implemented to elucidate the mechanisms responsible for immobilization of the heavy metals under study. Finally, the reusability of the stabilized waste forms in construction applications was also investigated by performing unconfined compressive strength and swell tests. The experimental results suggest that the controlling mechanism for both lead and hexavalent chromium immobilization is surface adsorption, whereas for trivalent chromium it is hydroxide precipitation. Addition of quicklime and fly ash to the contaminated soils effectively reduced heavy metal leachability well below the nonhazardous regulatory limits. Overall, fly ash addition increases the immobilization pH region for all heavy metals tested, and significantly improves the stress-strain properties of the treated solids, thus allowing their reuse as readily available construction materials. The only potential problem associated with this quicklime–fly ash treatment is the excessive formation of the pozzolanic product ettringite in the presence of sulfates. Ettringite, when brought in contact with water, may cause significant swelling and subsequent deterioration of the stabilized matrix. Addition of minimum amounts of barium hydroxide was shown to effectively eliminate ettringite formation. Overall, due to the presence of very high levels of heavy metal contamination along with sulfates in the solid matrices under study, the results presented herein can be applied to the management of incinerator and coal fly ash, boiler slag and flue gas desulfurization wastes.     

Agricultural use of sewage sludge under sub-humid Mediterranean conditions: effect on growth,yield, and metal content of a forage plant

A field experiment was carried out in order to investigate the effects of sewage sludge application on the growth and yield components of triticale (X Triticosecale Wittmack). Five treatments were compared: a control (C) without application of sludge or nitrogen fertilization; a mineral fertilization treatment (MF) applied as ammonium nitrate; and three sewage sludge treatments (SS), 6, 12, and 18 t ha^?1, applied 15 days prior to triticale sowing. The main results showed that SS application improved plant growth by increasing leaf area index, tillering capacity, accumulated aboveground dry matter, and plant height of triticale. As a result, 18 t ha^?1 of SS could be recommended the suitable dose for triticale, where dry matter production was more than twofold above the control value. No toxic effects arising from the heavy metals in triticale plants were observed. The Cu concentration was the only trace element that increased in the straw tissues with sludge application, although the values recorded were below critical environmental thresholds. Furthermore, growth and yield responses of triticale to all SS rates are comparable even sometimes more important than those for mineral fertilizer.     

Ecotoxicological assessment of heavy metals in sewage sludge amended soils

Contamination of soils by potentially toxic elements (PTEs) (e.g. Zn, Cu, Ni, Cr, Pb, Cd) from amendments of sewage sludge is subject to strict controls within the European Community in relation to total permissible metal concentrations, soil properties and intended use. This paper highlights the need for ecotoxicological data for the assessment of PTE impacts in addition to geochemical data alone. The soil microflora plays an essential role in determining levels of soil fertility, being intimately associated with the biogeochemical cycling of essential plant nutrients and the turnover of organic carbon. The measurement of soil microbiological parameters can provide insight into the impact of PTEs upon soil fertility, where geochemical analysis alone can often be inadequate to assess contaminant effects on essential components of the soil ecosystem. Microbial investigations were conducted on soils sampled from a well-controlled field experiment previously amended with specific types and rates of sewage sludge. Key microbiological parameters measured included the activity of the dehydrogenase enzyme and the presence and number of effective nitrogen fixing cells of Rhizobium leguminosarum biovar trifolii capable of nodulating the host plant, white clover (Trifolium repens). Results were evaluated with respect to maximum permissible concentrations of PTEs in sludge amended soils, as stipulated under UK limit values and the European Directive 86/278/EEC. Important effects on the size of the Rhizobium population and dehydrogenase activity were apparent in soils samples in relation to the soil pH, sludge type, addition rates and the concentrations of PTE present.     

污泥屏障渗透性及重金属阻截效果试验研究

目前,废弃物处置场渗滤液中的重金属污染物只能依靠极低渗透性的水力屏障来控制,还不存在利用化学场专门拦截重金属污染物的反应型屏障。在有机结合生活污泥的低渗透性与丰富的有机质和厌氧微生物特性的基础上,提出“污泥屏障”的构想。研究利用柔性壁渗透仪测量不同有效应力作用下生活污泥试样的渗透系数,并对渗出液的化学性质进行了监测,验证污泥屏障的可行性。试验结果表明：随着有效应力的增大,污泥试样干密度提高,渗透系数的对数值随孔隙比的减小线性降低。试样内部微生物厌氧呼吸形成的生物膜和无机物沉淀以及黏土颗粒双电层厚度的增大,也是污泥渗透系数降低的原因,污泥渗透系数仅为 数量级。另外,污泥强烈吸附能力及厌氧微生物呼吸作用形成的中-弱碱性还原环境,对渗透液中的Zn和Cd都起到了很好的拦截作用。