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).     

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.     

Neutralization of an extremely acidic sludge and stabilization of heavy metals in flyash aggregates

An extremely acidic, heavy metal-rich sludge (pH=-1.2) was scrubbed with a Class-F fly ash in order to simultaneously neutralize the acidity and stabilize the heavy metals contained in both wastes. This paper outlines the leaching behavior of the aggregate material generated by scrubbing. For proper fly ash/sludge ratios, the fly ash acted as an outstanding neutralizer for the acidic waste. Leaching of heavy metals from the aggregate samples was below the environmental limits within a pH range between 3 and 9. Subsequent washing of the leached aggregate with acidic CALWET solutions did not result in an additional release of heavy metals. It is proposed that coordinative bonding of the metal cations onto neutral surface sites and electrostatic adsorption led to stabilization of the heavy metals within the aggregate structure below hydrolysis pHs.     

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.     

Extractability and leachability of heavy metals in Technosols prepared from mixtures of unconsolidated wastes

Mixtures of wastes were prepared to improve on the characteristics of the individual ingredients as Technosols, with special attention given to heavy metal extractability. An anaerobic digested sewage sludge and a CaO-treated aerobic sludge were used. A mixture of the two sludges (50:50 DW basis) was also prepared to provide a third type of sludge. The residues were mixed with other types of waste, such as fly ash, Linz-Donowitz slag, foundry sand, shot blasting machine scrap, fettling and barley straw. Extractability of Cu, Cr, Ni, and Zn by 0.01 M CaCl(2) extraction (Me(CACI(2)) was carried out, and leachability of these elements was estimated by acidification of an aqueous suspension of the mixtures with 0.5 N acetic acid (Me(acetic)). The total concentrations of the metals were also determined (Me(T)). The Me(CACI(2)/Me(T) ratios for Cu and Ni (means: 4.0% and 3.1%) were higher than those for Cr and Zn (means: 0.07% each). The mean Me(acetic)/Me(T) ratios followed the order Ni, Zn, Cu, and Cr (19.5%, 4.1%, 3.7%, and 0.09%, respectively). The results highlight the existence of complex interactions among organic matter solubility, pH and heavy metal extractability.     

Agrochemical characterisation of the solid by-products and residues from the winery and distillery industry

The winery and distillery industry produces a great quantity of residues, whose management and disposal are environmental problems due to their seasonal character and some polluting characteristics. The main solid by-products and residues generated are grape stalk, grape pomace or marc, wine lee, exhausted grape marc and winery sludge. In this study, 87 samples of winery and distillery residues were collected from different Spanish wineries and distilleries. Electrical conductivity, pH, total organic matter, organic carbon, polyphenols and contents of plant nutrients and heavy metals were determined. The purpose of this research was to study the composition of these wastes and to find relationships in order to use easily analysable parameters to estimate their composition. In general, the winery and distillery residues showed low pH (mean values ranged from 3.8 to 6.8) and electrical conductivity values (1.62-6.15 dS m(-1)) and high organic matter (669-920 g kg(-1)) and macronutrient contents, especially in K (11.9-72.8 g kg(-1)). However, a notable polyphenol concentration (1.2-19.0 g kg(-1)) and low micronutrient and heavy metal contents were also observed, some of these properties being incompatible with agricultural requirements. Therefore, conditioning treatments are necessary prior to possible use of these wastes. In all wastes, significant correlations were found between easily determined parameters, such as pH, electrical conductivity and total organic matter, and most of the parameters studied. The regression models obtained are also discussed.     

Recovery of valuable metals from electronic and galvanic industrial wastes by leaching and electrowinning

In the present paper, a study on laboratory scale to perform a treatment for valuable metals recovery from electronic and galvanic industrial wastes, is reported. The characterisation of the waste, performed by XRD, SEM, EDX and chemical analysis, showed a high metals content in the sludge, such as Cu, Ni, Mn, Pb, Sn, W. A leaching process, coupled by electrowinning, is then proposed in order to reduce the volume of the waste material and to recover selectively valuable metals, such as Cu and Ni. During the leaching step, carried out by using H(2)SO(4), several factors were investigated (acid concentration, temperature and time of treatment). The leached liquor has been successfully treated with an electrowinning process, to recover copper and nickel. The copper and nickel depositions, were performed in acid and alkaline conditions, respectively. The Faraday yield was of about 95%. The energy consumption was 2.13 and 4.43 kWh per kg of copper and nickel recovered, respectively. At the end of the process, about 94-99% of the initial content of Cu and Ni was recovered at the cathode. The experimental results obtained, showed the technical feasibility of the process.     

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。     

Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

Behaviour of Cd,Cr, Mn,Ni, Pb,and Zn in sewage sludge incineration by fluidised bed furnace

Cd, Cr, Mn, Ni, Pb, and Zn behaviour during sewage sludge incineration was investigated in seven pilot tests using a circulating fluidised bed furnace. Dewatered sludge at a solids concentration of 15-18% was fed to the furnace either alone (two tests) or spiked with chlorinated organic compounds (five tests). The behaviour of metals in the fluidised bed furnace was studied by comparing metal concentrations in the two main ash streams: ash separated from the cyclone immediately following the fluidised bed furnace, and fly ash recovered in the final bag filter. A metal enrichment factor was defined as the ratio of metal concentration between filter ash and cyclone ash. Only Cd and Pb showed any significant enrichment. Their enrichment factors were mainly affected by chlorine concentration in the feed sludge. To check whether simple equilibrium models may explain and predict metal behaviour, experimental data were compared with percentage of the metal vaporisation in the combustion chamber predicted using a thermodynamic model. Discrepancies between model predictions and experimental results are accounted for by considering that kinetics may be a limiting factor in the formation of metal chloride gaseous species. Due to the very short sludge residence time in the fluidised bed furnace, the gaseous compounds have little chance to evolve completely.     

Assessment and analysis of industrial liquid waste and sludge disposal at unlined landfill sites in arid climate

Municipal solid waste disposal sites in arid countries such as Kuwait receive various types of waste materials like sewage sludge, chemical waste and other debris. Large amounts of leachate are expected to be generated due to the improper disposal of industrial wastewater, sewage sludge and chemical wastes with municipal solid waste at landfill sites even though the rainwater is scarce. Almost 95% of all solid waste generated in Kuwait during the last 10 years was dumped in five unlined landfills. The sites accepting liquid waste consist of old sand quarries that do not follow any specific engineering guidelines. With the current practice, contamination of the ground water table is possible due to the close location of the water table beneath the bottom of the waste disposal sites. This study determined the percentage of industrial liquid waste and sludge of the total waste dumped at the landfill sites, analyzed the chemical characteristics of liquid waste stream and contaminated water at disposal sites, and finally evaluated the possible risk posed by the continuous dumping of such wastes at the unlined landfills. Statistical analysis has been performed on the disposal and characterization of industrial wastewater and sludge at five active landfill sites. The chemical analysis shows that all the industrial wastes and sludge have high concentrations of COD, suspended solids, and heavy metals. Results show that from 1993 to 2000, 5.14+/-1.13 million t of total wastes were disposed per year in all active landfill sites in Kuwait. The share of industrial liquid and sludge waste was 1.85+/-0.19 million t representing 37.22+/-6.85% of total waste disposed in all landfill sites. Such wastes contribute to landfill leachate which pollutes groundwater and may enter the food chain causing adverse health effects. Lined evaporation ponds are suggested as an economical and safe solution for industrial wastewater and sludge disposal in the arid climate of Kuwait.     

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%).     

交联阳离子淀粉的合成及其对重金属离子的吸附

通过正交实验合成了取代度为0．568的交联阳离子淀粉。考察了溶液pH、螯合剂用量、重金属离子初始浓度对交联阳离子淀粉去除重金属离子效果的影响。当重金属离子初始质量浓度为50mg／L、螯合剂投加量为0．5g／U时,Pb^2 ,Cu^2 ,Cr^3 在溶液pH为6时的去除率达到最高,分别为97．94％,99．46％,84．30％,而Cd^ 在溶液pH为7时的去除率达到最高,为99．36％。实验结果表明,交联阳离子淀粉是一种有效去除废水中重金属的处理剂。     

Impacts of ultrasound on selective leaching recovery of heavy metals from metal-containing waste sludge

Lab synthesized metal-bearing sludge (LSMS) was used in series of designed lab tests to evaluate impacts of ultrasound on selective separation of heavy metals through acid leaching. The tests eliminated the potential of induced bias generated by utilizing field sludge that were produced from different location sources. The results showed that metal pairs of Cu and Fe, Cu and Cr, and Cr and Fe inside LSMS could be practically separated with one metal being contained in a liquid phase and another in a solid phase through acid leaching processes enhanced by ultrasound. With assistance of ultrasound, the acid leaching demonstrated a more efficient segregation between metals within LSMS than a conventional leaching that doesn’t have ultrasonic enhancement, and the tests provided in a generic means that ultrasonically enhanced acid leaching could cost-efficiently recover heavy metals from metal-containing waste sludge.     

Assessment of biotechnological strategies for the valorization of metal bearing wastes

The present work deals with the application of biotechnology for the mobilization of metals from different solid wastes: end of life industrial catalysts, heavy metal contaminated marine sediments and fluorescent powders coming from a cathode ray tube glass recycling process. Performed experiments were aimed at assessing the performance of acidophilic chemoautotrophic Fe/S-oxidizing bacteria for such different solid matrices, also focusing on the effect of solid concentration and of different substrata. The achieved results have evidenced that metal solubilization seems to be strongly influenced by the metal speciation and partitioning in the solid matrix. No biological effect was observed for Ni, Zn, As, Cr mobilization from marine sediments (34%, 44%, 15%, 10% yields, respectively) due to metal partitioning. On the other hand, for spent refinery catalysts (Ni, V, Mo extractions of 83%, 90% and 40%, respectively) and fluorescent powders (Zn and Y extraction of 55% and 70%, respectively), the improvement in metal extraction observed in the presence of a microbial activity confirms the key role of Fe/S oxidizing bacteria and ferrous iron. A negative effect of solid concentration was in general observed on bioleaching performances, due to the toxicity of dissolved metals and/or to the solid organic component.     

Review of environmental aspects and waste management of stone cutting and fabrication industries

Iran is the second largest stockholder of construction stones with 10 % of world production ;and there are more than 4000 stone cutting and fabrication industries (SCFIs). In the processing of raw stones, a considerable part of stone is turned into waste. Generated wastes include excess parts of different stones and sludge. The present paper reviews the state of SCFIs waste management using multiple data sources including site, analysis of effluent and sludge samples, and conducting interviews with people who are involved in 286 SCFIs in Qom and Tabriz. The results revealed that currently almost 35 to 52.5 % of raw stones were converted to solid wastes depending on stone cutting and processing methods, type of stones and their quality, which seemed a high percentage. Also, the effluents between 0.8 and 2.8 m³ were generated per ton of processed stone. Based on the analysis of heavy metals with atomic absorption spectroscopy, sludge samples contained a considerable amount of Pb, Cu, Cr, and Cd. It was also found that the lack of specific recycling, reuse and disposal programs and suitable supervision has led to uncontrolled disposal of stone wastes and sludge in different areas. However, there are good opportunities for reuse and recycling of the SCFIs wastes.     

Effect of composting process on phytotoxicity and speciation of copper, zinc and lead in sewage sludge and swine manure

The concentration and bioavailability of heavy metals in composted organic wastes have negative environmental impacts following land application. Aerobic composting procedures were conducted to investigate the influences of selected parameters on heavy metal speciation and phytotoxicity. Results showed that both of sewage sludge (SSC) and swine manure (SMC) composting systems decreased the pH, the content of organic matter (OM) and dissolved organic carbon (DOC), and total amounts of Cu, Zn and Pb. Sequential extraction showed that readily extractible fractions of exchangeable and carbonate in Cu and Zn increased during SSC composting but decreased during SMC composting, thus their bioavailability factors (BF) enhanced in SSC but declined in SMC. The fraction of reducible iron and manganese (FeMnOX) of Cu and Zn in SSC and FeMnOX-Cu in SMC decreased, but FeMnOX-Zn in SMC gradually increased in the process of compost. In contrast, the changes of Pb distributions were similar in two organic wastes. Pb was preferentially bound to the residual fraction and its BF decreased. The evolution of heavy metal distributions and BF depended on not only total metal concentrations but also the other properties, such as pH, decomposition of OM and decline of DOC. The germination rate (RSG), root growth (RRG) and germination index (GI) of pakchoi (Brassica Chinensis L.) increased during the composting process. Linear regression analysis demonstrated that GI, which could represent phytotoxic behavior to the plants, could be poorly predicted by BF or total amount of metals, i.e., BF-Zn, T-Cu. However, the inclusion of other physicochemical parameters (pH, OM and DOC) could enhance the linear regression significances (R).     

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.     

一株吡啶降解菌的筛选及其降解性能

以吡啶为唯一碳源,从焦化厂活性污泥中分离得到一株对吡啶具有高效降解能力的菌株B1,对其进行了菌种鉴定。通过单因素实验研究了菌株B1适宜的降解条件,对反应过程进行了动力学拟合,并考察了菌株B1对焦化废水中吡啶的降解效果。实验结果表明:菌株B1为革兰氏阴性菌,属于不动杆菌属(Acinetobacter sp.);菌株B1适宜的降解条件为降解温度30℃、初始pH为7、摇床转速150 r/min;菌株B1对吡啶的降解过程符合零级反应动力学模型,当初始吡啶质量浓度为300 mg/L时,降解速率常数最高达到21.103 mg/(L·h);用菌株B1对初始吡啶质量浓度为430 mg/L的实际焦化废水处理74 h后,吡啶降解率可达74.26%。     

厌氧折流板污泥对偶氮染料酸性大红GR的生物降解性能研究

研究了厌氧折流板反应器（ABR）活性厌氧污泥对偶氮染料酸性大红GR的吸附与生物降解性能,并与失活污泥进行了对比。试验结果表明,35℃时厌氧活性污泥2h、12h、6d的脱色率分别为78.2%、86.0%、98.9%。无论在反应初始阶段还是稳定阶段,ABR活性厌氧污泥对染料的去除效果都明显优于失活污泥。而且在初始COD为1152mg/L的,由于非有效吸附位置染料脱落等原因,反应期间,失活污泥混合液中染料浓度还会升高。情况下,活性厌氧污泥混合液出水COD为86.0mg/L,去除率约为92.5%。这说明ABR厌氧污泥微生物在短时间内便可以得到驯化,一旦厌氧微生物适应生长环境,生物降解便开始对染料发挥作用。