Leaching characteristics and phytotoxic effects of sewage sludge biochar

Biochar was prepared via the pyrolysis of sewage sludge at temperatures ranging from 300 to 900 °C and the physical–chemical compositions of the biochars obtained were analyzed. Leaching tests were conducted using the biochars to investigate the release of the constituents and their phytotoxic effects on wheat (Triticum aestivum) seeds in a germination test. Multivariate analyses were used to evaluate the contributions of the constituents to the germination index (GI). The results showed that the biochars were rich in micronutrient contents and they improved the germination of wheat. The heavy metal contents were higher in the biochars than the sewage sludge and their levels increased with the pyrolysis temperature, but they were within the acceptable limits for land application, thereby suggesting that sewage sludge is suitable for use as a biochar substrate. The different components of the biochar leachates could promote and inhibit the germination of wheat seeds, where the GI was promoted at lower concentrations but inhibited at higher concentrations. Our results suggest that biochar is an effective and environmentally friendly fixative for the immobilization of heavy metals in sewage sludge when applied to land or disposed of in landfill, but its ecotoxicity needs to be assessed to ensure its environmental safety.     

Influence of temperature on product distribution and biochar properties by municipal sludge pyrolysis

Biochar has the potential to amend degraded soil and improve crop yield. An experiment involving municipal sludge pyrolysis was carried out in a horizontal quartz reactor over the temperature range of 300–700 °C. The aim of this work was to investigate the influence of pyrolysis temperature on product distribution and biochar properties required for agronomic applications. Results of the experiment showed that yield and energy conversion efficiency of biochar decreased as pyrolysis temperatures rose, while bio-oil and syngas increased gradually. Biochar aromaticity barely changed, while polarity gradually decreased and specific surface area increased with a rise in pyrolysis temperature. Nutritive elements showed different enriching characteristics in the sludge pyrolysis process: nitrogen failed to enrich in biochars, whereas both phosphorus and potassium were enriched. Heavy metals showed good stability in the pyrolysis process except chromium; the contents of all metals used in the biochar conformed to Chinese control standards for agronomic application.     

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

生物炭修复Cd,Pb污染土壤的研究进展

随着矿产开采、冶炼等工业活动以及污水灌溉、施用污泥和劣质化肥等农业活动的进行,Cd,Pb等有害重金属不断进入农业环境中,对农田、菜地等造成污染。生物炭作为重要的土壤改良剂,在对Cd,Pb污染土壤的修复中表现出巨大的潜力。从生物炭的特性及制备、修复效果及其影响因素、修复机理等方面,对近年来国内外有关生物炭修复Cd,Pb污染土壤的研究成果和现状进行了总结,并对生物炭修复Cd,Pb污染土壤的发展前景和未来研究方向进行了展望。     

Heavy metal removal from contaminated sludge for land application: a review

In recent years, various methods for heavy metal removal from sewage sludge have been extensively studied in order to minimize the prospective health risks of sludge during land application. In this paper, a comparative review and critical analysis of the application of chemical extraction, bioleaching, electroreclamation, and supercritical fluid extraction (SFE), in removing heavy metals from contaminated sludges is presented. Moreover, speciation studies, which can indicate ease of leachability of the different forms of heavy metals in sludge, are also presented. Experimental studies revealed a broad range in metal extraction efficiencies of the different extraction technologies. Acid treatment seemed to effectively remove Cd, attaining as much as 100% removal for some studies, as compared to bioleaching. SFE also gave higher removal efficiency than bioleaching. Cr, Pb and Ni seemed to be also effectively removed by the acid treatment. For the removal of Cu, Mn and Zn, the bioleaching process seemed to be appropriate with maximum removal efficiencies of 91%, 93% and 96% for the three metals, respectively, and as high as 64% minimum removal efficiency for Zn. The SFE process also gave good results for Cu, Mn and Zn removal. Electroreclamation exhibited better removal efficiency for Mn, but is still inferior to acid treatment and bioleaching processes. For chemical extraction, because of the adverse impacts that can result from the use of inorganic acids and complexing agents, interest can be directed more toward utilizing organic acids as extracting agents because of their biodegradability and capability to remove metals at mildly acidic condition, hence requiring less acid. The bioleaching process, although it seems to give a higher yield of metal extraction with lower chemical cost than chemical extraction, may be limited by the inability of the system to cope with the natural environmental conditions, requires strict monitoring of aeration rate and temperature and has applicability to only low sludge solids concentration. A full-scale study would be useful to better assess the efficiency of the process. The electroreclamation technology is limited by its relatively higher energy consumption and limited applicability to sludge. The SFE method, on the other hand, is limited by the complexity of the process and the cost of ligands suitable for effective metal extraction. Both of these technologies are still in their early stage of application and hence there is a need for further basic and applied studies. Finally, the common advantage for almost all treatment technologies studied is that the extraction efficiencies for some metals are high enough to remove metals from sludge to levels suitable for land application.     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

Toxicity of char residues produced in the co-pyrolysis of different wastes

Char residues produced in the co-pyrolysis of different wastes (plastics, pine biomass and used tyres) were characterized using chemical and toxicity assays. One part of the solid chars was submitted to extraction with dichloromethane (DCM) in order to reduce the toxicity of the char residues by removing organic contaminants. The different volatility fractions present in the extracted char (Char A) and in the raw char (Char B) were determined by progressive weight loss combustion. A selected group of heavy metals (Cd, Pb, Zn, Cu, Hg and As) was determined in both chars.The chars were subjected to the leaching test ISO/TS 21268 – 2, 2007 and the resulting eluates were further characterized by determining a group of inorganic parameters (pH, conductivity, Cd, Pb, Zn, Cu, Hg and As contents) and the concentrations of several organic contaminants (volatile aromatic hydrocarbons and alkyl phenols). An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri.The chemical and ecotoxicological results were analyzed according to the Council Decision 2003/33/CE and the criteria on the evaluation methods of waste ecotoxicity (CEMWE).The results obtained in this work indicated that the extraction with DCM is an effective method for the removal of organic contaminants of high to medium volatility from pyrolysis solid residues, thus decreasing their toxicity potential. Zn can be leached from the chars even after the DCM extraction treatment and can contribute to the ecotoxicity of the eluates obtained from chars.Both chars (treated and non treated with DCM) were classified as hazardous and ecotoxic wastes.     

Development of lightweight aggregate from dry sewage sludge and coal ash

In this study, dry sewage sludge (DSS) as the principal material was blended with coal ash (CA) to produce lightweight aggregate. The effects of different raw material compositions and sintering temperatures on the aggregate properties were then evaluated. In addition, an environmental assessment of the lightweight aggregate generated was conducted by analyzing the fixed rate of heavy metals in the aggregate, as well as their leaching behavior. The results indicated that using DSS enhanced the pyrolysis–volatilization reaction due to its high organic matter content, and decreased the bulk density and sintering temperature. However, the sintered products of un-amended DSS were porous and loose due to the formation of large pores during sintering. Adding CA improved the sintering temperature while effectively decreasing the pore size and increasing the compressive strength of the product. Furthermore, the sintering temperature and the proportion of CA were found to be the primary factors affecting the properties of the sintered products, and the addition of 18–25% of CA coupled with sintering at 1100 °C for 30 min produced the highest quality lightweight aggregates. In addition, heavy metals were fixed inside products generated under these conditions and the As, Pb, Cd, Cr, Ni, Cu, and Zn concentrations of the leachate were found to be within the limits of China’s regulatory requirements.     

A study of heavy metals and their fate in the composting of tannery sludge

Tannery waste is categorized as toxic and hazardous in Malaysia due to its high content of Cr (in excess of 500 mg/kg) and other heavy metals. Heavy metals, when in high enough concentrations, have the potential to be both phytotoxic and zootoxic. Heavy metals are found as contaminants in tannery sludge. This investigation aimed to identify the fate of chromium, cadmium, copper, lead, and zinc concentrations in tannery sludge throughout a 50-day composting cycle. The results of this study showed a general increase in the removal of Cr, Cd, Pb, and to a much smaller extent Zn and Cu, manifested by a decrease in their overall concentrations within the solid fraction of the final product (the decreases were likely the result of leaching). Furthermore, in using a sequential extraction method for sludge composting at different phases of treatment, a large proportion of the heavy metals were found to be associated to the residual fraction (70-80%) and fractions more resistant to extraction, X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of the metals were bound to bioavailable fractions X-(KNO3+H2O).     

脱硫用电石渣的重金属浸出特性及其对环境的影响

针对电厂用脱硫剂电石渣,分析了其基本组成及重金属浸出特性,为电厂脱硫设施的参数设计和环境影响评价提供依据和参考。研究结果表明,脱硫用电石渣主要成分为Ca（OH）2,含量在40%～50%之间;在8种重金属的含量中,只有Cd的含量超出土壤质量三级标准的要求,基本不会对土壤造成污染。浸出毒性试验表明,电石渣及其脱硫产物属于非危险废物,其各种重金属的浸出浓度主要受其本身重金属含量和最终pH的影响,这种影响在Pb、Cu和Cd上表现得较为突出,酸性环境下更有利于他们的浸出;碱性环境下有利于Pb和Ni的浸出。     

Sludge earthworm composting technology by Eisenia fetida

Prior to vermicompost application to the soils, there is a need to determine the heavy metal concentrations in the final vermicomposts. Acute toxicity on Eisenia fetida for copper (Cu) and cadmium (Cd) were conducted by artificial soils tests. The dosage of interest is typically the median lethal concentration (LC₅₀) that will kill 50 % of the population of organisms within the test period. The dry artificial soil is pre-moistened 1 or 2 days before the test by adding deionized water to obtain approximately half of the required final water content of 40–60 % of the maximum water holding capacity. The 14-day LC₅₀ values (95 % confidence interval) for Cu and Cd were 530 (450–624) and 1118 (988–1265) mg kg^?1, respectively. The vermicomposting was designed to evaluate the effects of earthworm activity on heavy metals in sewage sludge. Compared with the sludge before vermicomposting by Eisenia fetida, the results are as follows: (1) water content, the pH value and organic matter content decreased, (2) total nitrogen content increased, total phosphorus content and total potassium content decreased, (3) available nitrogen concentration, available phosphorus content increased, and (4) the total content of five metals (Cu, Ni, Cd, Pb and Zn) decreased, and the bioaccumulation factor shows that vermicomposting can efficiently remove heavy metals. Therefore, it can be concluded that the soil use of sludge of the Wastewater Treatment Plant in Huaibei is feasible.     

Waste paper and clinoptilolite as a bulking material with dewatered anaerobically stabilized primary sewage sludge (DASPSS) for compost production

Environmental problems associated with sewage sludge disposal have prompted strict legislative actions over the past few years. At the same time, the upgrading and expansion of wastewater treatment plants have greatly increased the volume of sludge generated. The major limitation of land application of sewage sludge compost is the potential for high heavy metal content in relation to the metal content of the original sludge. Composting of sewage sludge with natural zeolite (clinoptilolite) can enhance its quality and suitability for agricultural use. However, the dewatered anaerobically stabilized primary sewage sludge (DASPSS) contained a low concentration of humic substances (almost 2%), and the addition of the waste paper was necessary in order to produce a good soil conditioner with high concentrations of humics. The final results showed that the compost produced from DASPSS and 40-50% w/w of waste paper was a good soil fertilizer. Finally, in order to estimate the metal leachability of the final compost product, the generalized acid neutralization Capacity (GANC) procedure was used, and it was found that by increasing the leachate pH, the heavy metal concentration decreased. The application of the sequential chemical extraction indicated that metals were bound to the residual fraction characterized as a stabilize fractions.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液,考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr,Zn,Cu,Pb,Ni,As,Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中,醋酸缓冲溶液法的重金属浸出种类最多,且浸出量最大;Cd和Cr对环境具有较高的潜在危害性,Cu次之,Zn,Pb,Ni,As主要以残渣态形式存在,对环境的直接危害性较低。     

污泥灰中磷的湿化学法回收技术研究进展

从污泥灰中磷的提取、磷与重金属的分离和磷产品的制备3方面综述了国内外湿化学法回收污泥灰中磷的研究进展,重点分析了磷提取过程中的各种影响因素,并对今后污泥灰中磷的湿化学法回收技术的研究方向进行了展望。指出:利用萃取的方法将提取液中的无机强酸萃取出来并回收重复利用,可大幅降低酸的消耗量;在回收磷的同时可研究回收不同种类金属的方法,尤其是价值较大的重金属,以进一步提高污泥灰资源的回收价值。     

Vitrification as an alternative to landfilling of tannery sewage sludge

Due to high content of heavy metals such as chromium, tannery sewage sludge is a material which is difficult to be biologically treated as it is in the case of organic waste. Consequently, a common practice in managing tannery sewage sludge is landfilling. This poses a potential threat to both soil and water environments and it additionally generates costs of construction of landfills that meet specific environment protection requirements. Vitrification of this kind of sewage sludge with the addition of mineral wastes can represent an alternative to landfilling.The aim of this study was to investigate the possibility of obtaining an environmentally safe product by means of vitrification of tannery sewage sludge from a flotation wastewater treatment process and chemical precipitation in order to address the upcoming issue of dealing with sewage sludge from the tannery industry which will be prohibited to be landfilled in Poland after 2016. The focus was set on determining mixtures of tannery sewage sludge with additives which would result in the lowest possible heavy metal leaching levels and highest hardness rating of the products obtained from their vitrification.The plasma vitrification process was carried out for mixtures with various amounts of additives depending on the type of sewage sludge used. Only the materials of waste character were used as additives.One finding of the study was an optimum content of mineral additives in vitrified mixture of 30% v/v waste molding sands with 20% v/v carbonate flotation waste from the zinc and lead industry for the formulations with flotation sewage sludge, and 45% v/v and 5% v/v, respectively, for precipitation sewage sludge. These combinations allowed for obtaining products with negligible heavy metal leaching levels and hardness similar to commercial glass, which suggests they could be potentially used as construction aggregate substitutes. Incineration of sewage sludge before the vitrification process lead to increased hardness of the vitrificates and reduced leaching of some heavy metals.     

Dynamics of Cd, Cu and Pb added to soil through different kinds of sewage sludge

A greenhouse experiment was set up to study the distribution of Cd, Cu and Pb in three typical soils of the Pampas Region amended with sewage sludge. A sequential extraction procedure was used to obtain four operationally defined geochemical species: exchangeable, bound to organic matter, bound to carbonates, and residual. Two kinds of sewage sludge were used: pure sewage sludge and sewage sludge containing 30% DM of its own incinerated ash, at rates equivalent to a field application of 150 t DM ha(-1). Pots were maintained at 80% of field capacity through daily irrigation with distilled water. Soil samples were obtained on days 1, 60, 270 and 360, and then air-dried and passed through a 2 mm sieve for analysis. Results showed that sludge application increased the less available forms of Cd, Cu and Pb. The inorganic forms became the most prevalent forms for Cu and Pb, whereas Cd was only found in the residual fraction. The concentrations of OM-Cu and INOR-Cu in the amended soil samples were closely correlated with soil pH, whereas the chemical behavior of Cd and Pb did not depend on soil physico-chemical characteristics.     

Sequential extraction of metals from mixed and digested sludge from aerobic WWTPs sited in the south of Spain

The content of heavy metals is the major limitation to the application of sewage sludge in soil. However, assessment of the pollution by total metal determination does not reveal the true environmental impact. It is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, sequential extraction of metals from sludge before and after aerobic digestion was applied to sludge from five WWTPs in southern Spain to obtain information about the influence of the digestion treatment in the concentration of the metals. The percentage of each metal as residual, oxidizable, reducible and exchangeable form was calculated. For this purpose, sludge samples were collected from two different points of the plants, namely, sludge from the mixture (primary and secondary sludge) tank (mixed sludge, MS) and the digested-dewatered sludge (final sludge, FS). Heavy metals, Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn, were extracted following the sequential extraction scheme proposed by the Standards, Measurements and Testing Programme of the European Commission and determined by inductively-coupled plasma atomic emission spectrometry. The total concentration of heavy metals in the measured sludge samples did not exceed the limits set out by European legislation and were mainly associated with the two less-available fractions (27-28% as oxidizable metal and 44-50% as residual metal). However, metals as Co (64% in MS and 52% in FS samples), Mn (82% in MS and 79% in FS), Ni (32% in MS and 26% in FS) and Zn (79% in MS and 62% in FS) were present at important percentages as available forms. In addition, results showed a clear increase of the concentration of metals after sludge treatment in the proportion of two less-available fractions (oxidizable and residual metal).     

Heavy metals removal/stabilization from municipal solid waste incineration fly ash: a review and recent trends

Waste treatment using thermal technologies, such as incineration, leads to the production of pollutants and wastes, including fly ash (FA). Fly ash contains heavy metals (HMs) and other contaminants and can potentially pose high risks to the environment and negatively impact health and safety. Consequently, stabilizing fly ash prior to either use or landfilling is crucial. The toxicity of fly ash through heavy metal leaching can be assessed using leaching tests. The leaching rates of heavy metals primarily depend on the surrounding conditions as well as fly ash properties and metal speciation. Physical separation, leaching or extraction, thermal treatment and solidification/chemical stabilization are proposed as suitable approaches for fly ash treatment. Economic considerations, environmental concerns, energy consumption and processing times can define the efficiency and selection of the treatment approach. This review considers the latest findings and compares the advantages and shortcomings of different fly ash treatment methods with the aim of highlighting the recent advances in the field. The review concludes that the simultaneous implementation of various methods can lead to highly efficient heavy metals removal/stabilization while simultaneously taking economic and environmental considerations into account.

     

Leaching toxicity and heavy metal bioavailability of medical waste incineration fly ash

The aim of this study was to provide a comprehensive risk assessment for medical waste incineration fly ash from another aspect through various leaching methods. The differences and connections between leaching concentrations achieved via the toxicity characteristic leaching procedure (TCLP), the physiologically based extraction test (PBET) and the sequential extraction procedure were also described. Heavy metal contents of the used medical waste incineration fly ash were 1.7–31 times higher than that from Japan, indicating poor medical waste management in China. The fly ash leaching concentration in the TCLP test exceeded the regulation value and can be characterized as hazardous waste under current regulations. However, the PBET concentrations were only 1/10 of the TCLP value or even lower, and the calculated ingested contents of all heavy metals were lower than tolerable daily intake, demonstrating that TCLP might have overestimated the environment risk to some degree. The leaching metal content of TCLP ranged from exchangeable to residual forms, and the leaching percentage varied from 7.75 to 92.55 %, while the content for PBET was equal to or lower than the exchangeable form.     

Phosphate fertilizer from sewage sludge ash (SSA)

Ashes from sewage sludge incineration are rich in phosphorus content, ranging between 4% and 9%. Due to the current methods of disposal used for these ashes, phosphorus, which is a valuable plant nutrient, is removed from biological cycling. This article proposes the possible three-stage processing of SSA, whereby more than 90% of phosphorus can be extracted to make an adequate phosphate fertilizer. SSA from two Swiss sewage sludge incinerators was used for laboratory investigations. In an initial step, SSA was leached with sulfuric acid using a liquid-to-solid ratio of 2. The leaching time and pH required for high phosphorus dissolution were determined. Inevitably, dissolution of heavy metals takes place that would contaminate the fertilizer. Thus in a second step, leach solution has to be purified by having the heavy metals removed. Both ion exchange using chelating resins and sulfide precipitation turned out to be suitable for removing critical Cu, Ni and Cd. Thirdly, phosphates were precipitated as calcium phosphates with lime water. The resulting phosphate sludge was dewatered, dried and ground to get a powdery fertilizer whose efficacy was demonstrated by plant tests in a greenhouse. By measuring the weight of plants after 6 weeks of growth, fertilized in part with conventional phosphate fertilizer, fertilizer made from SSA was proven to be equal in its plant uptake efficiency.