Fixation and partitioning of heavy metals in slag after incineration of sewage sludge

Fixation of heavy metals in the slag produced during incineration of sewage sludge will reduce emission of the metals to the atmosphere and make the incineration process more environmentally friendly. The effects of incineration conditions (incineration temperature 500-1100°C, furnace residence time 0-60min, mass fraction of water in the sludge 0-75%) on the fixation rates and species partitioning of Cd, Pb, Cr, Cu, Zn, Mn and Ni in slag were investigated. When the incineration temperature was increased from 500 to 1100°C, the fixation rate of Cd decreased from 87% to 49%, while the fixation rates of Cu and Mn were stable. The maximum fixation rates for Pb and Zn and for Ni and Cr were reached at 900 and 1100°C, respectively. The fixation rates of Cu, Ni, Cd, Cr and Zn decreased as the residence time increased. With a 20min residence time, the fixation rates of Pb and Mn were low. The maximum fixation rates of Ni, Mn, Zn, Cu and Cr were achieved when the mass fraction of water in the sludge was 55%. The fixation rate of Cd decreased as the water mass fraction increased, while the fixation rate of Pb increased. Partitioning analysis of the metals contained in the slag showed that increasing the incineration temperature and residence time promoted complete oxidation of the metals. This reduced the non-residual fractions of the metals, which would lower the bioavailability of the metals. The mass fraction of water in the sludge had little effect on the partitioning of the metals. Correlation analysis indicated that the fixation rates of heavy metals in the sludge and the forms of heavy metals in the incinerator slag could be controlled by optimization of the incineration conditions. These results show how the bioavailability of the metals can be reduced for environmentally friendly disposal of the incinerator slag.     

Variations of metal distribution in sewage sludge composting

In the study, the variations of heavy metal distributions (of Cu, Mn, Pb, and Zn) during the sewage sludge composting process were investigated by sequential extraction procedures. The total content of Cu and Zn in the composted mixture increased after the composting process. Mn and Zn were mainly found in mobile fractions (exchangeable fraction (F1), carbonate fraction (F2), and Fe/Mn oxide fraction (F3)). Cu and Pb were strongly associated with the stable fractions (organic matter/sulfides fraction (F4) and residual fraction (F5)). These five metal fractions were used to calculate the metal mobility (bioavailability) in the sewage sludge and composted mixture. The mobility (bioavailability) of Mn, Pb, and Zn (but not Cu) increased during the composting process. The metal mobility in the composted mixture ranked in the following order: Mn>Zn>Pb>Cu.     

Fractionation of heavy metals in sludge from anaerobic wastewater stabilization ponds in southern Spain

The analysis of heavy metals is a very important task to assess the potential environmental and health risk associated with the sludge coming from wastewater treatment plants (WWTPs). However, it is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the Standard, Measurements and Testing Programme of the European Commission was applied to sludge samples collected from ten anaerobic wastewater stabilization ponds (WSPs) located in southern Spain. Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn were determined in the sludge extracts by inductively coupled plasma atomic emission spectrometry. In relation to current international legislation for the use of sludge for agricultural purposes, none of the metal concentrations exceeded maximum permitted levels. Overall, heavy metals were mainly associated with the two less-available fractions (34% oxidizable metal and 55% residual metal). Only Mn and Zn showed the highest share of the available (exchangeable and reducible) fractions (25-48%).     

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).     

Acidic bioleaching of heavy metals from sewage sludge

The overall objective of this study was to evaluate the use of controlled bio-acidification prior to land application as a decontamination process to remove heavy metals from sludge. The sulfur-oxidizing bacteria were naturally available in the sludge samples and were activated by providing sulfur and aeration at 28°C–30°C. Activation resulted in bio-acidification to pH 2 within 5–11 days. Successive inoculation of fresh sludges with 5% acidified samples reduced the acidification time to 2–3 days in most samples. Bio-acidification resulted in dissolving significant quantities of heavy metals from all sludge types tested. The maximum solubilization results were: 86%–97% for Ni; 48%–98% for Pb; 26%–71% for Cr; 18%–91% for Zn; 16%–90% for Cu; 7%–60% for Cd. Limited metal solubilization results were observed in the various control samples that accompanied the bio-acidified samples. The leaching results in the control samples were limited to 2%–19% for Ni, 0%–7% for Pb, 0%–5% for Cr, 0.3%–4% for Zn, 0.2%–4% for Cu and 0%–3% for Cd. The results confirmed that Ni and Pb were the easiest metals to dissolve from the various sludge types. On the other hand, the lowest solubilization results were observed for Cu and Cd, and moderate solubilization results were achieved for Cr. The bio-acidification process resulted in moderate gains in terms of improving the suitability of tested sludges for land application. Received: April 19, 1999 / Accepted: November 4, 1999     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.     

Effects of cement on redistribution of trace metals and dissolution of organics in sewage sludge and its inorganic waste-amended products

The suitability of using cement-stabilized sludge products as artificial soils in earth works was evaluated. The sludge products investigated were cemented sludge, cement-treated clay-amended sludge (SS+MC), and cement-treated copper slag-amended sludge (SS+CS). The leachability of lead (Pb), zinc (Zn), copper (Cu), and chromium (Cr) were assessed using the sequential extraction technique, toxicity characteristic leaching procedure (TCLP), NEN 7341 availability test, and column leaching test. The results indicated that Zn leachability was reduced in all the cement-stabilized sludge products. In contrast, Cu was transferred from the organic fraction to the readily leachable phases in the cement-stabilized sludge products and therefore exhibited increased leachability. The increased Cu leachability could be attributed to dissolution of humic substances in the sludge as a result of elevated pH. Good correlation between dissolved organic carbon (DOC) and heavy metal leaching from the cement-stabilized sludge products was observed in the column leaching experiment. Even with a cement percentage as small as 12.5%, calcium silicate hydrate (C-S-H) was formed in the SS+MC and SS+CS products. Inclusion of the marine clay in the SS+MC products could reduce the leaching potentials of Zn, and this was the great advantage of the marine clay over the copper slag for sludge amendment.     

An assessment of municipal solid waste compost quality produced in different cities of India in the perspective of developing quality control indices

A study was conducted to investigate physico-chemical properties, fertilizing potential and heavy metal polluting potentials of municipal solid waste composts produced in 29 cities of the country. Results indicated that except a very few samples, all other samples have normal pH and EC. Organic matter as well as major nutrients N and P contents in MSW composts are generally low as compared to the composts prepared from rural wastes. Heavy metal contents in composts from bigger cities (>1 million population) were higher by about 86% for Zn, 155% for Cu, 194% for Cd, 105% for Pb, 43% for Ni and 132% for Cr as compared to those from smaller cities (<1 million population). Composts prepared from source separated biogenos wastes contained, on average, higher organic matter (by 57%), total N (by 77%) and total P (by 78%), but lower concentrations of heavy metals Zn (by 63%), Cu (by 78%), Cd (by 64%), Pb (by 84%), Ni (by 50%), and Cr (by 63%) as compared to those prepared from mixed wastes. Partial segregation at the site of composting did not improve quality of compost significantly in terms of fertilizing parameters and heavy metal contents. Majority of MSW composts did not conform to the quality control guideline of ‘The Fertilizer (Control) Order 1985’ in respect of total organic C, total P, total K as well as heavy metals Cu, Pb and Cr. In order to enable the relevant stakeholders to judge overall quality, a scheme has been proposed for the categorization of composts into different marketable classes (A, B, C, and D) and restricted use classes (RU-1, RU-2, and RU-3) on the basis their fertilizing potential and as well as potential for contaminating soil and food chain. Under the scheme, ‘Fertilizing index’ was calculated from the values of total organic C, N, P, K, C/N ratio and stability parameter, and ‘Clean index’ was calculated from the contents of heavy metals, taking the relative importance of each of the parameters into consideration. As per the scheme, majority of the compost samples did not belong to any classes and hence, have been found unsuitable for any kind of use. As per the regulatory limits of different countries, very few compost samples (prepared from source separated biogenos wastes) were found in marketable classes (A, B, C and D) and some samples (11–14) were found suitable only for some restricted use.     

Volatility of heavy metals during incineration of tannery sludge in the presence of chlorides and phosphoric acid.

Knowledge of the behaviour of heavy metals in the combustion process is a most important factor in selecting disposal alternatives for waste materials. Accordingly, in this work, the vaporization behaviour of highly concentrated heavy metals (Pb, Zn, Cu and Cr) in tannery sludge were investigated experimentally. The sludge was spiked with various chlorine compounds (i.e. PVC, FeCl3, CaCl2 and NaCl) and pre-treated with phosphoric acid in order to evaluate the capacity of enhancement and weakening of the volatility of the heavy metals contained in tannery sludge. The experimental results show that the vaporization percentages increased with increasing ratio of Cl/sludge and temperature, and the accelerating and increasing effect of the addition of chlorides on the vaporization percentage of heavy metals was dependent on the release capacity of chlorine radicals. The vaporization percentages of lead and zinc increased by 15-20%, whereas those of copper and chromium increased by only about 3 and 10% at 800 degrees C. However, heavy metals were not expected to be completely released in the combustion process in spite of the high ratio of Cl/sludge. Alternately, heavy metals contained in tannery sludge can be immobilized effectively by pre-treatment with phosphoric acid. When the 85% phosphoric acid accounted for 10% of dry basis of tannery sludge, the phosphate-treated sludge showed the lowest vaporization percentage of about 3-15% with formation of Ca18Cu3(PO4)14, Ca9Cr(PO4)7, Ca19Zn2(PO4)14 and PbMgP2O7 in the bottom ash.     

添加CaO对燃煤重金属元素富集效果的影响

选取CaO作为吸附剂,探究了不同燃烧温度下添加CaO对重金属元素在燃煤灰渣中富集效果的影响规律。实验结果表明:添加CaO对重金属元素Cr未起到富集作用,而对Mn,Ni,Cu,Zn,As,Cd,Pb 7种重金属元素的富集效果显著;随燃烧温度的升高,CaO对各赋存形态的Mn,Ni,Cu,Zn,As的富集效果先变好而后变差,对各赋存形态的Cd和Pb的富集效果越来越好;CaO添加比(预处理后的CaO颗粒与预处理后的原煤的质量比)越大,CaO对Mn,Ni,Cu,Zn,As,Cd,Pb的富集效果越好,燃烧温度为850℃时的最佳CaO添加比为4%。     

城市污泥制备水中重金属吸附剂及其吸附特性研究

本实验利用城市污水厂的脱水污泥,通过化学活化法制备活性炭.研究活化温度、活化时间、固液比和活化剂浓度等因素对制备污泥活性炭的影响,确定氯化锌法制备污泥活性炭的最佳工艺为活化温度550 ℃、活化时间30 min、固液比1∶2、氯化剂浓度45％.将制备的污泥活性炭吸附Cu2＋,Cr6＋,Cd2＋3种重金属离子模拟废水,研究pH值、吸附时间、污泥投加量、温度等因素对吸附过程的影响.实验结果表明,剩余污泥对Cu2＋,Cr6＋,Cd2＋3种重金属离子都具有良好的吸附效果,在优化条件下,3种重金属离子去除率分别达到94％,76％,81％,吸附能力大小顺序为Cu2＋＞Cd2＋＞＋Cr6＋.     

Accumulation and fate of selected heavy metals in a biological wastewater treatment system

The aim of this research was to study the accumulation and removal of heavy metals (Cd, Cu, Pb, Zn) by a biological wastewater treatment system. Heavy metal contents in the influent and effluent wastewater were compared. Also, the heavy metal contents in the sludge before and after anaerobic digestion were compared. The results showed: (1) more pronounced variations in the contents of Cu and Zn than that of Cd and Pb, which showed that at 0.02 for Cd and 0.05 mg/l for Pb, the reduction in their contents was insignificant; (2) that removal of heavy metals was directly proportional to their initial contents in the influent wastewater. Corresponding to the influent contents, in increasing order, the reduction in heavy metal contents was: Cd相似文献   

Use of dewatered municipal sludge on Canna growth in pot experiments with a barren clay soil

The present study evaluated the possibility of using the dewatered municipal sludge for non-agricultural purposes. The sludge was amended with soil and was applied at 0, 165, 330, 495 and 660 t/ha to promote the growth of Canna. The results showed that the Canna growth pattern exhibited a pronounced positive growth response in the range of 165–495 t/ha, and the Canna could not survive at an amendment rate of 660 t/ha. The analysis of chlorophyll fluorescence parameters showed that sludge did no harm to Canna, while under the conditions of barren soil alone, the plants were put into nutrients stress conditions. Due to the application of sludge, the concentration of heavy metals (Cu, Zn, Cr, Cd, Pb and Ni) in soil increased. However, by planting of Canna, contents of Cd, Ni and Zn showed trends of decline; Cd and Ni have shown a significant decline in concentration, while Zn had only limit response. As a result, dewatered sludge might be used to amend the barren soil and Canna could be used for phytoremediation of sludge.     

Leaching behavior of heavy metals from municipal solid waste incineration bottom ash and its geochemical modeling

With the increase in the number of municipal solid waste incineration (MSWI) plants constructed in China recently, great attention has been paid to the heavy metal leaching toxicity of MSWI residues. In this study, the effects of various parameters, including extractant, leaching time, liquid-to-solid ratio, leachate pH, and heavy metal content, on the release properties of Cd, Cr, Cu, Ni, Pb, and Zn from MSWI bottom ash were investigated. Partial least-squares analysis was employed to highlight the interrelationships between the factors and response variables. Both experimental research and geochemical modeling using Visual MINTEQ software were conducted to study the pH-dependent leaching behavior of these metals in fresh and weathered bottom ash, considering precipitation/dissolution and surface complexation reactions (adsorption by hydrous ferric oxide and amorphous aluminum oxide/hydroxide). The results showed that leachate pH was the predominant factor influencing heavy metal leachability. The leaching of Cu, Pb, and Zn was mainly controlled by precipitation/dissolution reactions, whereas surface complexation had some effect on the leaching of Cr, Cd, and Ni for certain pH ranges. The modeling results aggreed well with the experimental results. Part of this work was presented at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

亚临界湿式氧化法脱除含油污泥中的重金属

采用亚临界湿式氧化法及金属络合剂协同亚临界湿式氧化法去除含油污泥中的重金属,考察了去除效果,优化了反应条件,并探讨了脱除重金属的含量上限。实验结果表明:在1 L反应釜内加入200 g含油污泥,在反应温度200℃、反应时间60 min、液固比(去离子水与含油污泥的质量比)0.30的优化条件下,Cu和Zn的去除率分别可达67.3%和22.0%;加入金属络合剂后,各重金属的去除率均有明显提高;在金属络合剂加入量为0.05mol/L的优化条件下,应用金属络合剂协同亚临界湿式氧化法可将2.5倍于CJ/T 309—2009《城镇污水处理厂污泥处置农用泥质》B级标准的重金属含量降至标准范围内。     

电镀污泥处理技术的研究进展

电镀污泥中含有大量的铬、镉、镍、锌等重金属，是一种典型的危险废物。综述了近年来国内外对电镀污泥处理技术的研究进展，包括固化／稳定化技术、热化学处理技术、有价金属回收技术和材料化技术等。对主要处理技术的应用前景进行了分析，认为热化学处理技术将成为未来电镀污泥处理领域内的一个重要研究方向。     

Heavy metals in source-separated compost and digestates

The production of compost and digestate from source-separated organic residues is well established in Europe. However, these products may be a source of pollutants when applied to soils. In order to assess this issue, composts, solid and liquid digestates from Switzerland were analyzed for heavy metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) addressing factors which may influence the concentration levels: the treatment process, the composition, origin, particle size and impurity content of input materials, the season of input materials collection or the degree of organic matter degradation.Composts (n = 81) showed mean contents being at 60% or less of the legal threshold values. Solid digestates (n = 20) had 20–50% lower values for Cd, Co, Pb and Zn but similar values for Cr, Cu and Ni. Liquid digestates (n = 5) exhibited mean concentrations which were approximately twice the values measured in compost for most elements. Statistical analyses did not reveal clear relationships between influencing factors and heavy metal contents. This suggests that the contamination was rather driven by factors not addressed in the present study.According to mass balance calculations related to Switzerland, the annual loads to agricultural soils resulting from the application of compost and digestates ranged between 2% (Cd) and 22% (Pb) of total heavy metal loads. At regional scale, composts and digestates are therefore minor sources of pollution compared to manure (Co, Cu, Ni, Zn), mineral fertilizer (Cd, Cr) and aerial deposition (Pb). However, for individual fields, fertilization with compost or digestates results in higher heavy metal loads than application of equivalent nutrient inputs through manure or mineral fertilizer.     

Sewage sludge ash to phosphorus fertiliser: variables influencing heavy metal removal during thermochemical treatment

The aim of this study was to improve the removal of heavy metals from sewage sludge ash by a thermochemical process. The resulting detoxified ash was intended for use as a raw material rich in phosphorus (P) for inorganic fertiliser production. The thermochemical treatment was performed in a rotary kiln where the evaporation of relevant heavy metals was enhanced by additives. The four variables investigated for process optimisation were treatment temperature, type of additive (KCl, MgCl(2)) and its amount, as well as type of reactor (directly or indirectly heated rotary kiln). The removal rates of Cd, Cr, Cu, Ni, Pb, Zn and of Ca, P and Cl were investigated. The best overall removal efficiency for Cd, Cu, Pb and Zn could be found for the indirectly heated system. The type of additive was critical, since MgCl(2) favours Zn- over Cu-removal, while KCl acts conversely. The use of MgCl(2) caused less particle abrasion from the pellets in the kiln than KCl. In the case of the additive KCl, liquid KCl - temporarily formed in the pellets - acted as a barrier to heavy metal evaporation as long as treatment temperatures were not sufficiently high to enhance its reaction or evaporation.     

Goods in the Anthroposphere as a Metal Emission Source A Case Study of Stockholm,Sweden

The aim of this study was to quantify the diffuse emissionsduring use of metal containing goods in the capital of Sweden,Stockholm. The following metals were studied: Cadmium (Cd), Chromium (Cr), Copper (Cu), Lead (Pb), Mercury (Hg), Nickel (Ni) and Zinc (Zn).A major part of the metals are found in a protected environmentwhere degrading processes like corrosion are most limited. However, during the lifetime of some goods the metal release to the environment is significant. The quantitatively most dominant emissions were found for Cu and Zn. The tap water system and roofs/fronts (Cu) represent goods with large exposedareas but with relatively small release rates per unit. In contrast, brake linings, aerial lines and electrical grounding (Cu) and tyres, brake linings and chemicals (Zn) are allgoods with high release rates but mostly limited exposed stocks.High yearly emissions are also found for Pb, ammunition andsinkers dominate the calculated emissions totally. For Cr and Ni, stainless steel represent the major part of the stocks, butcorrosion was estimated to give only a minor contribution to the emissions. Potential emission sources, i.e. stabilisers,pigments and plated goods dominate the exposed Cd stock. Theseemissions were not quantified due to lack of data. Hg is currently phased out, but one major source of emission, i.e. the use of amalgam, will be continuously significant for several decades. The importance of the traffic sector is obvious. The emissionsfrom brake linings (Cu, Zn and Pb), tyres (Zn, Pb, Cr and Ni)and asphalt wear (Cu, Zn, Cr, Ni and Pb) are all of large importance for the total emission from respectively metal.     

Nutrients and heavy metals distribution in thermally treated pig manure.

Ash from pig manure treated by combustion and thermal gasification was characterized and compared in terms of nutrient, i.e., potassium (K), phosphorus (P) and heavy metal, i.e., cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) contents. Total nutrient and metal concentrations were measured using energy dispersive X-ray fluorescence analysis. Acid (HNO3, H2SO4) and water-extractable concentrations were also measured both in non-classified ash and in selected ash particle size fractions using flame atomic absorption spectrometry and colorimetric spectrometry. Results indicate that ash from gasified manure contained more water-extractable K in comparison with combusted manure whereas the opposite was the case with respect to P. Heavy metals Ni, Cr and Cd were present in higher concentrations in the fine particle size fractions (< 30 microm of particle diameter), whereas K, P, Zn and Cu exhibited higher concentrations in the coarser particle size fractions (> 30 microm).