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).     

Evolution of heavy metals in municipal solid waste during bio-drying and implications of their subsequent transfer during combustion

Bio-drying has been applied to improve the heating value of municipal solid waste (MSW) prior to combustion. In the present study, evolution of heavy metals in MSW during bio-drying and subsequent combustion was studied using one aerobic and two combined hydrolytic-aerobic scenarios. Heavy metals were concentrated during bio-drying and transformed between different metal fractions, namely the exchangeable, carbonate-bound, iron- and manganese-oxides-bound, organic-matter-bound and residual fractions. The amounts of heavy metals per kg of bio-dried MSW transferred into combustion flue gas increased with bio-drying time, primarily due to metals enrichment from organics degradation. Because of their volatility, the partitioning ratios of As and Hg in flue gas remained stable so that bio-drying and heavy metal speciation had little effect on their transfer and partitioning during combustion. In contrast, the partitioning ratios of Pb, Zn and Cu tended to increase after bio-drying, which likely enhanced their release potential during combustion.     

An investigation on the potential of metal recovery from the municipal waste incinerator in Taiwan

This study aimed to identify distribution of metals and to estimate the amount of these metals that can be potentially recovered from incineration residues. First, the partitioning behavior of Cr, Cu, Fe, Cd, Al, Zn, and Pb in bottom ash and fly ash was investigated in one large municipal waste incinerator in Taiwan. In addition, the material flow analysis (MFA) method was used to estimate the material flux of metals within incinerator plant, and to calculate the amount of metal recovery. According to the findings of this study, six metals (Fe, Al, Cu, Zn, Cr, and Pb) concentrated in bottom ash mostly, while Cd existed primarily in fly ash. The weight percentages of Fe (4.49%), Al (5.24%), Cu (1.29%), Zn (2.21%), and Pb (0.58%) in incinerator ash are high, and even higher than the compositions of natural minerals. Finally, the amount of Cr, Cu, Fe, Cd, Al, Zn and Pb that can be potentially recovered from incineration residues will reach 2.69 x 10(2), 1.46 x 10(4), 4.91 x 10(4), 6.92 x 10(1), 5.10 x 10(4), 1.85 x 10(4) and 4.66 x 10(3) ton/yr, respectively.     

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%).     

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.     

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。     

Metal separation from mixed types of batteries using selective precipitation and liquid-liquid extraction techniques

The purpose of this paper is to study metal separation from a sample composed of a mixture of the main types of spent household batteries, using a hydrometallurgical route, comparing selective precipitation and liquid-liquid extraction separation techniques. The preparation of the solution consisted of: grinding the waste of mixed batteries, reduction and volatile metals elimination using electric furnace and acid leaching. From this solution two different routes were studied: selective precipitation with sodium hydroxide and liquid-liquid extraction using Cyanex 272 [bis(2,4,4-trimethylpentyl) phosphoric acid] as extracting agent. The best results were obtained from liquid-liquid extraction in which Zn had a 99% extraction rate at pH 2.5. More than 95% Fe was extracted at pH 7.0, the same pH at which more than 90% Ce was extracted. About 88% Mn, Cr and Co was extracted at this pH. At pH 3.0, more than 85% Ni was extracted, and at pH 3.5 more than 80% of Cd and La was extracted.     

Evaluation of Active Cap Materials for Metal Retention in Sediments

This study evaluated chemically active amendments used to construct active caps for remediating contaminated sediments. Three experiments assessed the effects of apatite, organoclay, zeolite, and biopolymers (chitosan and xanthan) on metal mobility, retention, and speciation. The first showed that the amendments individually and in mixtures (2 percent dry weight) reduced the concentrations of Cr, Co, Ni, and Pb in water extracts from reduced sediment. The second experiment, which used sequential extraction procedures to evaluate the effects of the amendments on metal speciation, showed that the amendments reduced the potentially mobile fractions of Pb, Zn, Ni, Cr, and Cd that are likely to be bioavailable. Last, column studies showed that active caps composed of the amendments prevented the diffusive transport of metals from contaminated sediment over six months. In addition, there was a “zone of influence” beneath the caps in which water extractable concentrations of metals declined substantially compared with untreated sediment. © 2014 Wiley Periodicals, Inc.     

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.     

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.     

Characteristics of element distributions in an MSW ash melting treatment system

Thermal treatment of municipal solid waste (MSW) has become a common practice in waste volume reduction and resource recovery. For the utilization of molten slag for construction materials and metal recovery, it is important to understand the behavior of heavy metals in the melting process. In this study, the correlation between the contents of elements in feed materials and MSW molten slag and their distributions in the ash melting process, including metal residues, are investigated. The hazardous metal contents in the molten slag were significantly related to the contents of metals in the feed materials. Therefore, the separation of products containing these metals in waste materials could be an effective means of producing environmentally safe molten slag with a low hazardous metals content. The distribution ratios of elements in the ash melting process were also determined. The elements Zn and Pb were found to have a distribution ratio of over 60% in fly ash from the melting furnace and the contents of these metals were also high; therefore, Zn and Pb could be potential target metals for recycling from fly ash from the melting furnace. Meanwhile, Cu, Ni, Mo, Sn, and Sb were found to have distribution ratios of over 60% in the metal residue. Therefore, metal residue could be a good resource for these metals, as the contents of Cu, Ni, Mo, Sn, and Sb in metal residue are higher than those in other output materials.     

Hydrometallurgical processing of Nd–Fe–B magnets for Nd purification

An evaluation of various metal purification processes subsequent to the leaching processing of the neodymium (Nd) product from neodymium–iron–boron (Nd–Fe–B) magnets has been conducted. These post-leaching purification processes included precipitation; replacement and electrolysis were studied in order to check the purity of the recovered neodymium. A hydrometallurgical investigation was adopted to digest the metal content of the scrap Nd–Fe–B magnets for the recovery of valuable Nd metal and other metals such as Fe, B, Co and Ni. The effect of leaching conditions such as solid-to-liquid ratio and temperature were optimized and 100 % Nd, 100 % Fe, 100 % B and 85.87 % Co leaching efficiencies were achieved under these conditions. The coating material of the magnet, Ni, achieved 50 % impregnation after increasing the reaction temperature to 70 °C. The metals present in the optimal leaching solution were recovered 99 % by pH adjustment. However, the replacement had the highest separation efficiency for the recovery of Nd metal. Further, the optimal leaching Nd–Fe–B solution was subjected to the electrolysis processes in order to verify the recovery efficiency for all metals.     

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.     

Metal Concentrations in Pore Water of the Lusatian Lignite Mining Sediments and Internal Metal Distribution in Juncus bulbosus

The aim of this study was to determine a suite of four metals (Fe, Mn, Zn, Cu) in the sediment, porewater and a pioneer plant (Juncus bulbosus) of Lusatian lignite mining lakes in eastern Germany. An attempt was made to understand the factors which affect element concentrations in the above- and below-ground biomass of Juncus bulbosus in an extreme environment. Water samples, sediments, porewater and plant material collected from two different mining lakes dominated by Juncus bulbosus species were analyzed for their elemental content. Additionally, scanning electron microscopy (SEM) and an energy-dispersive X-ray (EDX) detector were used to follow the internal metal distribution in the roots of Juncus plant. Results showed that sediment and porewater element concentrations in the lakes decreased in the order Fe > Mn > Zn and Cu. All the four elements were higher in the roots than in above-ground tissues, suggesting that iron plaque induced on roots under anaerobic conditions served as a metal reservoir, but not as an ultimate mechanism to control metal concentrations in the above-ground tissues. SEM and EDX analyses revealed that the rhizodermis, exodermis and endodermis cells regulate the traffic of transition metals and therefore avoid excess levels that are toxic to the plant in acidic mining-impacted lake sediments.     

A comparison study on high-temperature water–gas shift reaction over Fe/Al/Cu and Fe/Al/Ni catalysts using simulated waste-derived synthesis gas

A comparative study on Fe/Al, Fe/Al/Cu, and Fe/Al/Ni catalysts in high-temperature water–gas shift reaction (HT–WGS) using simulated waste-derived synthesis gas has been carried out. The metal oxide (Cu and Ni) and aluminum incorporated Fe catalysts were designed to get highly active HT–WGS catalysts. Despite the high CO concentration in the simulated waste-derived synthesis gas, Fe/Al/Cu catalyst exhibited the highest CO conversion (84 %) and 100 % selectivity to CO₂ at a very high gas hourly space velocity (GHSV) of 40,057 h^?1. The outstanding catalytic performance is mainly due to easier reducibility, the synergy effect of Cu and Al, and the stability of the magnetite.     

An overview of metals recovery from thermal power plant solid wastes

Thermal power plants (TPPs) that burn fossil fuels emit several pollutants linked to the environmental problems of acid rain, urban ozone, and the possibility of global climate change. As coal is burned in a power plant, its noncombustible mineral content is partitioned into bottom ash, which remains in the furnace, and fly ash, which rises with flue gases. Two other by-products of coal combustion air-pollution control technologies are flue gas desulfurization (FGD) wastes and fluidized-bed combustion (FBC) wastes. This paper analyzed and summarized the generation, characteristics and application of TPP solid wastes and discussed the potential effects of such solid wastes on the environment. On this basis, a review of a number of methods for recovery of metals from TPP solid wastes was made. They usually contain a quantity of valuable metals and they are actually a secondary resource of metals. By applying mineral processing technologies and hydrometallurgical and biohydrometallurgical processes, it is possible to recover metals such as Al, Ga, Ge, Ca, Cd, Fe, Hg, Mg, Na, Ni, Pb, Ra, Th, V, Zn, etc., from TPP solid wastes. Recovery of metals from such wastes and its utilization are important not only for saving metal resources, but also for protecting the environment.     

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.     

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%。     

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.