Speciation of Solutes in Drainage and Pore Waters of Two Former Lignite Mines (Germany)

An experimental speciation scheme consisting of ultra-filtration(1 kD), cation and anion exchange has been developed. Parallel calculations of the ion balances are performed using the computerroutine MINTEQA2. The experimental and computed ion balances suffer from non-equilibrium conditions, incalculability of metal-binding colloids or sub-colloids, inaccurate Eh measurements and analytical errors. In most samples colloidal or sub-colloidal structures of Fe oxy-hydroxides and/or gypsum influence the behavior of many trace elements. The comparison of theory and experiment has to be restricted to acid waters (pH < 5) where colloids (1–450 nm) and non-filterable colloids or sub-colloids (<1 nm) play a minor role. Yet, only a few transition metals such as Mn, Fe, Co, Ni, Cu, Zn, or Cd remain more or less free of colloidal influence in low pH waters. The effect of DOC on Al may be estimated by model substances like citrate.     

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.     

Chemical properties of heavy metals in typical hospital waste incinerator ashes in China

Incineration has become the main mechanism for hospital waste (HW) disposal in China after the outbreak of Severe Acute Respiratory Syndrome (SARS) in 2003. However, little information is available on the chemical properties of the resulting ashes. In the present study, 22HW ash samples, including 14 samples of bottom ash and eight samples of fly ash, were collected from four typical HW incineration plants located across China. Chemical analysis indicated that the HW ashes contained large amounts of metal salts of Al, Ca, Fe, K, Mg, Na with a concentration range of 1.8-315gkg(-1). Furthermore, the ashes contained high concentrations of heavy metals such as Ag, As, Ba, Bi, Cd, Cr, Cu, Mn, Ni, Pb, Ti, Sb, Sn, Sr, Zn with a vast range of 1.1-121,411mgkg(-1), with higher concentrations found in the fly ash samples. Sequential extraction results showed that Ba, Cr, Ni and Sn are present in the residual fraction, while Cd existed in the exchangeable and carbonate fractions. As, Mn, Zn existed in the Fe-Mn oxide fraction, Pb was present in the Fe-Mn oxide and residual fractions, and Cu was present in the organic matter fraction. Furthermore, toxicity characteristic leaching procedure (TCLP) results indicated that leached amounts of Cd, Cu and Pb from almost all fly ash samples exceeded the USEPA regulated levels. A comparison between the HW ashes and municipal solid waste (MSW) ash showed that both HW bottom ash and fly ash contained higher concentrations of Ag, As, Bi, Cd, Cr, Cu, Pb, Ti, and Zn. This research provides critical information for appropriate HW incineration ash management plans.     

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 metal mobility and potential availability in animal manure: using a sequential extraction procedure

In this study, dairy cow manure, goat manure, and chicken manure were collected from three farms and analyzed to find out the concentration of Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn. The concentration and potential of mobility and availability of heavy metals were studied in the animal manure samples. BCR Sequential extraction procedure was used to determine the binding forms of the metals. In this study, pseudo total concentrations of Mn and Zn were found out to be predominant in all the types of animal manure samples. According to the results, it was traced that Cr, Cu, and Ni were observed to be at the second highest level while Cd, Co, and Pb were seen at the lowest level in all the manure samples. When extractable amounts of heavy metals are taken into consideration, it is seen that the amount of the mobile fractions of heavy metals except for Cr and Ni are higher in comparison with that of immobile fraction in all the animal manure samples. It was also viewed that Mn, Cd, and Zn are more available in dairy cow manure and chicken manure whereas Cd, Co, and Mn are more available in goat manure.     

Vitrification for reclaiming spent alkaline batteries

The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification. Specimens were vitrified using an electrical heating furnace at 1400 °C and the output products included slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn, and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline batteries.     

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%).     

Salinity, organic content, micronutrients and heavy metals in pig slurries from South-eastern Spain

The increase in commercial pig production is an opportunity to reuse animal manures in arid and semiarid soils as a source of nutrients and organic matter. However, there are components in pig slurry that are potentially dangerous for the environment. In this study, pig slurries of 36 pig farms in South-eastern Spain were evaluated for salt content (electrical conductivity, chloride and sodium), organic load (BOD5 and COD), micronutrients (Fe, Cu, Mn and Zn), and heavy metals (Cd, Co, Cr, Ni and Pb). Except for electrical conductivity, Cu and Zn, components in pig slurries did not vary considerably between animal production stages, indicating similar management of diverse animal types. Assuming an application rate based on the maximum input of nitrogen from animal manure (210 kg total N/ha/yr), the estimates for soil annual load of Cl and Na, 415 kg/ha, could be a significant salinisation risk. Cu and Zn seemed to be the metals that could be accumulated most in soils where application of pig slurries is common (4 and 15 kg/ha/yr, respectively). The estimated heavy metal (Cd, Co, Cr, Ni and Pb) input to soils would be 260 g/ha/yr, with a relative contribution of Cr>Ni>Pb>Co>Cd.     

分步沉淀法处理酸性矿山废水

采用分步沉淀工艺处理酸性矿山废水,考察了工艺条件对废水中有价金属元素回收效果的影响。实验结果表明:Ca(OH)_2为适宜的废水pH调节剂;调节废水pH至4.00左右并投加0.05 mL/L的H_2O_2,可首先去除Fe~(2+)及Fe~(3+),得到富Fe渣(w(Fe)=51.00%);调节废水pH至6.00~6.50,先投加50 mg/L的Na_2S,去除废水中的Cu~(2+),获得富Cu渣(w(Cu)=10.89%),再将Na_2S的投加量增至100 mg/L,去除废水中的Zn与Mn,获得富Zn-Mn渣(w(Cu)=2.37%,w(Mn)=6.79%,w(Pb)=1.61%);进一步调节废水pH至8.40,可去除剩余的Zn、Mn及其他重金属。分步沉淀工艺处理后的废水可达标排放,产生的富Fe渣、富Cu渣及富Zn-Mn渣可直接出售或具有利用价值。分步沉淀工艺可实现有价金属元素的高效回收,大幅度降低废水处理的实际成本,值得工程应用与推广。     

Thermodynamic estimation of minor element distribution between immiscible liquids in Fe-Cu-based metal phase generated in melting treatment of municipal solid wastes

Waste electrical and electronic equipment (WEEE) has become an important target in managing material cycles from the viewpoint of not only waste management and control of environmental pollution but also resource conservation. This study investigated the distribution tendency of trace elements in municipal solid waste (MSW) or incinerator ash, including valuable non-ferrous metals (Ni, Co, Cr, Mn, Mo, Ti, V, W, Zr), precious group metals (PGMs) originated from WEEE (Ag, Au, Pd, Pt), and others (Al, B, Pb, Si), between Fe-rich and Cu-rich metal phases by means of simple thermodynamic calculations. Most of the typical alloying elements for steel (Co, Cr, Mo, Nb, Ni, Si, Ti, V, and W) and Rh were preferentially distributed into the Fe-rich phase. PGMs, such as Au, Ag, and Pd, were enriched in the Cu-rich phase, whereas Pt was almost equally distributed into both phases. Since the primary metallurgical processing of Cu is followed by an electrolysis for refining, and since PGMs in crude copper have been industrially recovered from the resulting anode slime, our results indicated that Ag, Au, and Pd could be effectively recovered from MSW if the Cu-rich phase could be selectively collected.     

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.     

Leaching of metals from fly ashes in the presence of complexing agents

The leachability of some metals (Al, As, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Ti, Zn) from fly ashes was studied in the presence of ethylenediamine tetraacetic acid (EDTA) and naturally occurring complexing agents-humic acids (HAs). Secondary complex-forming equilibria taking place in the leachates increase significantly the leached amounts of most metals. Kinetic experiments showed that almost the whole "available" amounts of metals are leached from fly ash within a time period of several hours (mostly within 20 h), with exceptions of matrix constituents (typically aluminium), which are released more slowly.     

黄钠铁矾法氧化去除废锂电池硫酸浸出液中的铁

废锂电池中含有的Co、Ni和Cu等金属具有回收价值,Fe的存在降低了有价金属的回收效率。为去除废锂电池硫酸浸出液中的Fe,采用黄钠铁矾法分别以氯酸钠和过氧化氢作为氧化剂氧化除Fe,并优化了过氧化氢作为氧化剂的除Fe工艺参数。实验结果表明:过氧化氢作为氧化剂的除Fe效果好于氯酸钠;在n(H2O2)∶n(Fe)=0.5、初始溶液pH为1.8、终点pH为2.5、反应时间为2.0 h、搅拌速率为500 r/min的最佳工艺条件下,初始ρ(Fe)为0.212g/L的硫酸浸出液经除Fe处理后ρ(Fe)小于0.004 g/L,Fe去除率达98.0%,Co、Ni和Cu的损失率分别为1.04%、2.17%和1.41%。     

Effect of nine years of animal waste deposition on profile distribution of heavy metals in Abeokuta,south-western Nigeria and its implication for environmental quality

Uncontrolled deposition of waste from animal farms is a common practice in south-western Nigeria, and the presence of heavy metals in soil constitutes environmental and health hazards by polluting the soil, ground water, adjoining streams and rivers. The study investigated the profile distribution of Mn, Pb, Cd, Zn, Fe, Cu, Ni and Cr in some tropical Alfisols in south-western Nigeria after nine years disposal of animal wastes. The amount of these metals in the soil horizons was high enough to cause health and phytotoxic risks. All the metals except Zn and Cr increased down the profile, while Mn, Pb, Cd, Fe, Cu and Ni accumulated at 80–120 cm depth. The increment of these metals at this depth over the top soil were 26%, 143%, 72%, 47%, 328% for Mn, Pb, Cd, Cu and Ni, respectively. It thus, shows their mobility and the possibility of polluting ground water. The Mn content at the poultry and cattle waste sites increased by 127% and 25%, respectively over the control, while that of cattle and swine dump site for Cd content were 9.82 and 15.63 mg kg^?1, respectively. Lead content also increased by 8.52 and 5.25 mg kg^?1, respectively.There was the accumulation of Zn and Cu at the swine dump site while the cattle dump site had the highest amounts of nickel and chromium. The least amount of Fe was recorded at the swine waste dump site. The reduction in organic matter with depths together with the reduced pH might have favored the mobility of the metals. The ranking of pollution among the sites was poultry > swine > cattle > sheep and could be due to the type of ration fed, the vaccination programmes, sanitation programmes and other management practices.     

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.     

Biosorption of copper from aqueous solutions utilizing agricultural wastes

The purpose of this study was to determine the copper (Cu) biosorption capacities of several agricultural wastes from aqueous solutions. Samples of agricultural wastes were tested unaltered and after hydrochloric acid (HCl) treatment. Additional parameters tested include sample dose, contact time, particle size, mixing temperature, and the concentrations and pH of the Cu solutions. Desorption studies were performed to determine if the removed Cu could be recovered. In addition, tests were conducted to determine if the agricultural waste samples (AWS) could be reused for additional Cu biosorption cycles. The results of this study demonstrate a wide range of Cu biosorption proficiencies ranging from 0% to 100% removal. The parameters that resulted in higher Cu removal include higher pH and lower Cu solution concentration. Desorption results showed a 58% to 86% Cu recovery rate. Three of the five reused AWS were effective at removing Cu during subsequent trials. Therefore, these AWS types can be reused for additional Cu biosorption cycles. Hence, it is possible that using those AWS for metal treatment could reduce hazardous waste disposal inefficiencies and costs by avoiding disposing of spent AWS following each Cu biosorption cycle.     

Removal of substituted phenols onto iron‐treated Nostoc sp. biomass

This study explored the possibility of removing 4‐nitrophenol (4‐NP) and 2,4‐dichlorophenol (2,4‐DCP) from water by using a dead blue‐green algae, Nostoc sp., dried and untreated and dried and treated with iron (Fe‐treated with 0.1 M ferric chloride solution for 1 day). The Nostoc sp. untreated and Fe‐treated biomass were used to study the sorption and desorption of 4‐NP and 2,4‐DCP. The effects of solute concentration, ionic strength, and temperature on sorption and desorption in the presence of untreated and treated Nostoc sp. biomass were investigated. The Fe‐treated Nostoc sp. biomass sorbed higher amounts of both 4‐NP and 2,4‐DCP than the untreated biomass. The percent cumulative desorption decreased from 6.41% to 0.28% and 1.84% to 0.19%, respectively, for 4‐NP and 2,4‐DCP for the Fe‐treated biomass. Biosorption of 4‐NP and 2,4‐DCP onto untreated and Fe‐treated Nostoc sp. biomass conformed to Freundlich isotherms. Iron treatment of Nostoc sp. biomass increased the value of ln K from 8.07 to 8.59 for 4‐NP and from 8.04 to 8.51 for 2,4‐DCP but decreased their desorption. An increase in ionic strength (0.003–0.03) increased the biosorption of both substituted phenols and decreased their percent desorption. An increase in temperature in the range of 15–35°C decreased the sorption of 4‐NP and 2,4‐DCP onto both untreated and Fe‐treated Nostoc sp. biomass and increased their desorption, indicating that the biosorption of both substituted phenols onto untreated and Fe‐treated Nostoc sp. biomass was principally a physical process. The results of this study suggest that Fe‐treated dried Nostoc sp. biomass could be explored as an inexpensive and eco‐friendly material for the effective removal of these phenols and, potentially, other chemicals from industrial wastewater and contaminated groundwater.     

Investigation of potentially toxic heavy metals in different organic wastes used to fertilize market garden crops

The benefits of using organic waste as fertilizer and soil amendment should be assessed together with the environmental impacts due to the possible presence of heavy metals (HMs). This study involved analysing major element and HM contents in raw and size-fractionated organic wastes (17 sewage sludges and composts) from developed and developing countries. The overall HM concentration pattern showed an asymmetric distribution due to the presence of some wastes with extremely high concentrations. HM concentrations were correlated with the size of cities or farms where the wastes had been produced, and HM were differentiated with respect to their origins (geogenic: Cr–Ni; anthropogenic agricultural and urban: Cu–Zn; anthropogenic urban: Cd–Pb). Size fractionation highlighted Cd, Cu, Zn and Pb accumulation in fine size fractions, while Cr and Ni were accumulated in the coarsest. HM associations with major elements revealed inorganic (Al, Fe, etc.) bearing phases for Cr and Ni, and sulfur or phosphorus species for Cd, Cu Pb and Zn.     

Solidification with water as a treatment method for air pollution control residues

The process of solidification with water was studied on air pollution control (APC) residues from incineration of refuse-derived fuel (RDF) regarding mechanical strength and leaching behaviour of solidified material. Factorial design in two levels was applied to investigate the impact of water addition, time, and temperature to mechanical strength of solidified material. Factors time and temperature, as well as the interaction between the addition of water and time significantly (alpha=0.05) influenced the mechanical strength of solidified material. The diffusion-leaching test NEN 7345 was performed to investigate if the leaching behaviour of elements from solidified material was determined by diffusion. Since it was found that leaching is not diffusion controlled, the long-term leaching behaviour was not assessed. However, the investigation showed that some of the studied components (Al, Hg, Mn, Pb, Si, and Zn) could be considerably demobilised by solidification with water. Concentrations of As, Cd, Co, Cu, Fe, and Ni were either below or not quite above the detection limits to be included in the analysis of leaching behaviour. The elements least demobilised by solidification were Cl, Cr, K, and Na.     

Leaching behaviour of bottom ash from RDF high-temperature gasification plants

This study investigated the physical properties, the chemical composition and the leaching behaviour of two bottom ash (BA) samples from two different refuse derived fuel high-temperature gasification plants, as a function of particle size. The X-ray diffraction patterns showed that the materials contained large amounts of glass. This aspect was also confirmed by the results of availability and ANC leaching tests. Chemical composition indicated that Fe, Mn, Cu and Cr were the most abundant metals, with a slight enrichment in the finest fractions.Suitability of samples for inert waste landfilling and reuse was evaluated through the leaching test EN 12457-2. In one sample the concentration of all metals was below the limit set by law, while limits were exceeded for Cu, Cr and Ni in the other sample, where the finest fraction showed to give the main contribution to leaching of Cu and Ni.Preliminary results of physical and geotechnical characterisation indicated the suitability of vitrified BA for reuse in the field of civil engineering. The possible application of a size separation pre-treatment in order to improve the chemical characteristics of the materials was also discussed.