Bacterial leaching of metals from sewage sludge by indigenous iron-oxidizing bacteria

Bioleaching of metals can be achieved in sewage sludge using Thiobacillus ferrooxidans, which obtains its energy requirements from the oxidation of added ferrous iron. The purpose of this study was to verify the presence of indigenous T. ferroxidans and to evaluate their adaptive capacity and leaching potential. Nineteen sludges (primary, secondary, aerobically and anaerobically digested, oxidation pond) were tested and all of them contained indigenous iron-oxidizing bacteria. The acclimation of these organisms by successive transfers allowed a rise of sludge redox potential over 450 mV and a decrease of sludge pH between 3.8 and 2.2 over a 10-day incubation period. The metal solubilization efficiencies were Cd: 55-98%, Cr: 0-32%, Cu: 39-94%, Mn: 71-98%, Ni: 37-98%, Pb: 0-31% and Zn: 66-98%, were reached with these indigenous strains. The results obtained show that the metal bioleaching may be easily realized by direct acclimation of sludge microflora.     

废旧镍镉电池的生物沥滤处理——沥滤停留时间的影响研究

用污泥加硫酸化液沥滤镍镉电池中的重金属是一种全新的工艺,该工艺主要由生物酸化反应器和金属沥滤反应器两个反应器组成.生物酸化反应器中产生的酸液就是沥滤电池中重金属的反应液.研究表明,酸化液在沥滤反应池的停留时间对沥滤的效果有显著影响.在1、4、7、12 d 4个停留时间中,4 d的效果是最好的,对金属Cd和Ni都用40 d左右基本实现了全部滤除;1d略微慢一些,Cd用了40 d,Ni用了45 d;7 d和12 d的沥滤时间都长于50 d.4 d产生的金属废液量是1 d的1/4,考虑到后续处理金属沥滤废液的工作量,选择4d的停留时间要优于1d.     

氧化亚铁硫杆菌浸出废弃线路板中铜的研究

对废弃线路板中的铜进行了细菌浸出、只有硫酸亚铁环境下的浸出及酸浸出实验，研究了不同条件对比浸出效果，研究结果表明，细菌浸出比只有硫酸亚铁存在的浸出和酸浸要快得多。研究了在线路板粉末浓度12、24、40、60和120 g/L下浸出速率的变化，结果表明， 在考察范围内，浸出速度随着加入的废弃线路板粉末浓度的升高而降低，当线路板粉末的浓度＞60 g/L时，浸出速度维持在较低水平，选取24 g/L作为浸出的线路板粉末的浓度。分别在细菌培养0、24、48和72 h时加入线路板粉末24 g/L进行浸出实验，结果表明，细菌培养时间长，使得浸出过程进行得也更快。     

Integrated bioleaching of copper metal from waste printed circuit board—a comprehensive review of approaches and challenges

Waste electrical and electronic equipment (e-waste) is the most rapidly growing waste stream in the world, and the majority of the residues are openly disposed of in developing countries. Waste printed circuit boards (WPCBs) make up the major portion of e-waste, and their informal recycling can cause environmental pollution and health risks. Furthermore, the conventional disposal and recycling techniques—mechanical treatments used to recover valuable metals, including copper—are not sustainable in the long term. Chemical leaching is rapid and efficient but causes secondary pollution. Bioleaching is a promising approach, eco-friendly and economically feasible, but it is slower process. This review considers the recycling potential of microbes and suggests an integrated bioleaching approach for Cu extraction and recovery from WPCBs. The proposed recycling system should be more effective, efficient and both technically and economically feasible.     

生物淋滤-Fenton对印染污泥脱水性能的影响

采用嗜酸性硫杆菌生物淋滤联合Fenton氧化法对印染污泥脱水性能进行了研究。结果表明,生物淋滤过程中pH下降速率随着硫粉添加量增加而变快,经生物淋滤处理后污泥的脱水性能在一定程度上得到了改善。对生物淋滤后的污泥进行了Fenton氧化处理,获得的最佳反应条件为反应时间2 h,H2O2和Fe2+添加量分别为6 g/L和0.5 g/L。在该条件下,污泥上清液中总有机碳(TOC)由20.8 mg/L增加到356.6 mg/L;污泥比阻(SRF)和滤饼含水率分别由5.98×1011s2/g和88.75%减少至1.26×1011s2/g和82.85%。生物淋滤-Fenton氧化法在污泥破解程度和脱水性能改善方面均优于单独Fenton氧化法。     

Characterization of spent nickel–metal hydride batteries and a preliminary economic evaluation of the recovery processes

Valuable metal materials can be recovered from spent nickel–metal hydride (NiMH) batteries. However, little attention has been paid to the metal compositions of individual components of NiMH batteries, although this is important for the selection of the appropriate recycling process. In this study, NiMH batteries were manually disassembled to identify the components and to characterize the metals in each of these. A preliminary economic analysis was also conducted to evaluate the recovery of valuable metals from spent NiMH batteries using thermal melting versus simple mechanical separation. The results of this study show that metallic components account for more than 60% of battery weight. The contents of Ni, Fe, Co, and rare earth elements (REEs) (i.e., valuable metals of interest for recovery) in a single battery were 17.9%, 15.4%, 4.41%, and 17.3%, respectively. Most of the Fe was in the battery components of the steel cathode collector, cathode cap, and anode metal grid, while Ni (>90%) and Co (>90%) were mainly in the electrode active materials (anode and cathode metal powders). About 1.88 g of REEs (Ce, La, and Y) could be obtained from one spent NiMH battery. The estimated profits from recovering valuable metals from spent NiMH batteries by using thermal melting and mechanical processes are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. The findings of this study are very useful for further research related to technical and economic evaluations of the recovery of valuable metals from spent NiMH batteries. Implications: The spent nickel–metal hydride (NiMH) batteries were manually disassembled and their components were identified. The metals account for more than 60% of battery weight, when Ni, Fe, Co, and rare earth elements (REEs) were 17.9%, 15.4%, 4.41%, and 17.3%, respectively, in a single battery. The estimated profits of recovering valuable metals from NiMH batteries by using thermal melting and mechanical processing are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. These findings are very useful to develop or select the recovery methods of valuable metals from spent NiMH batteries.     

Effect of different types of elemental sulfur on bioleaching of heavy metals from contaminated sediments

The application of two different types of elemental sulfur (S0) was studied to evaluate the efficiency on bioleaching of heavy metals from contaminated sediments. Bioleaching tests were performed in suspension and in the solid-bed with a heavy metal contaminated sediment using commercial sulfur powder (technical sulfur) or a microbially produced sulfur waste (biological sulfur) as substrate for the indigenous sulfur-oxidizing bacteria and thus as acid source. Generally, using biological sulfur during suspension leaching yielded in considerably better results than technical sulfur. The equilibrium in acidification, sulfur oxidation and metal solubilization was reached already after 10-14 d of leaching depending upon the amount of sulfur added. The metal removal after 28 d of leaching was higher when biological sulfur was used. The biological sulfur added was oxidized with high rate, and no residual S0 was detectable in the sediment samples after leaching. The observed effects are attributable to the hydrophilic properties of the biologically produced sulfur particles resulting in an increased bioavailability for the Acidithiobacilli. In column experiments only poor effects on the kinetics of the leaching parameters were observed replacing technical sulfur by biological sulfur, and the overall metal removal was almost the same for both types of S0. Therefore, under the conditions of solid-bed leaching the rate of sulfur oxidation and metal solubilization is more strongly affected by transport phenomena than by microbial conversion processes attributed to different physicochemical properties of the sulfur sources. The results indicate that the application of biological sulfur provides a suitable means for improving the efficiency of suspension leaching treatments by shortening the leaching time. Solid-bed leaching treatments may benefit from the reuse of biological sulfur by reducing the costs for material and operating.     

Selective Leaching of Valuable Metals from Waste Printed Circuit Boards

Abstract

This study was carried out to recover valuable metals from the printed circuit boards (PCBs) of waste computers. PCB samples were crushed to smaller than 1 mm by a shredder and initially separated into 30% conducting and 70% nonconducting materials by an electrostatic separator. The conducting materials, which contained the valuable metals, were then used as the feed material for magnetic separation, where it was found that 42% of the conducting materials were magnetic and 58% were nonmagnetic. Leaching of the nonmagnetic component using 2 M H₂SO₄ and 0.2 M H₂O₂ at 85 °C for 12 hr resulted in greater than 95% extraction of Cu, Fe, Zn, Ni, and Al. Au and Ag were extracted at 40 °C with a leaching solution of 0.2 M (NH₄)₂S₂O₃, 0.02 M CuSO₄, and 0.4 M NH₄OH, which resulted in recovery of more than 95% of the Au within 48 hr and 100% of the Ag within 24 hr. The residues were next reacted with a 2 M NaCl solution to leach out Pb, which took place within 2 hr at room temperature.     

Bioleaching of heavy metals from sediment: significance of pH

Bioleaching process, which causes acidification and solubilization of heavy metals, is one of the promising methods for removing heavy metals from contaminated sediments. The solubilization of heavy metals from contaminated sediments is governed by the sediment pH. In the present study, the significance of pH in bioleaching of heavy metals from contaminated sediment was evaluated at different solid contents of sediments in a bench-scale reactor. Results showed that a temporal change of pH in the bioleaching process was effected by the buffering capacity of the sediment particulates. The variations of pH in this bioleaching process were calculated by a modified logistic model. It was observed that solubilization of heavy metals from sediments is highly pH-dependent. In addition, a non-linear equation for metal solubilization relating pH value in the bioleaching process was established. This allows an easier and faster estimate of metal solubilization by measuring pH in the bioleaching process.     

污泥生物沥滤工艺优化和重金属分配研究

为了得到嗜酸硫细菌沥滤污泥中重金属的最佳工艺参数,对沥滤过程进行3因素4水平的正交实验研究。3种影响因素的水平设置分别为:污泥浓度35、25、15和5 g/L,单质硫投加量15、10、5和1 g/L,接种量15、10、5和3 g/L。对沥滤过程污泥中7种重金属(As、Cd、Cr、Cu、Ni、Pb和Zn)的去除率进行极差分析,提出了因素影响程度依次为单质硫投加量污泥浓度接种量,且最佳工艺条件为:污泥浓度25 g/L,单质硫投加量10 g/L,接种量为5%。采用超声波-离心方法,分步提取污泥胞外聚合物(EPS)的2种形态:松散结合态(LB)和紧密结合态(TB)。分析其中的重金属浓度,提出沥滤后重金属在污泥EPS的赋存以LB为主。     

Influence of initial pH on bioleaching of heavy metals from contaminated soil employing indigenous Acidithiobacillus thiooxidans

Bioleaching of heavy metals from contaminated soil was carried out employing indigenous sulfur oxidizing bacterium Acidithiobacillus thiooxidans. Experiments were carried out to assess the influence of initial pH of the system on bioleaching of chromium, zinc, copper, lead and cadmium from metal contaminated soil. pH at the end of four weeks of bioleaching at different initial pH of 3-7 was between 0.9 and 1.3, ORP between 567 and 617mV and sulfate production was in the range of 6090-8418mgl(-1). Chromium, zinc, copper, lead and cadmium solubilization ranged from "59% to 98%" at different initial pH. A. thiooxidans was not affected by the increasing pH of the bioleaching system towards neutral and it was able to utilize elemental sulfur. The results of the present study are encouraging to develop the bioleaching process for decontamination of heavy metal contaminated soil.     

Highly efficient recovery of molybdenum from spent catalyst by an optimized process

ABSTRACT

Disposal of spent catalyst in an economical and green way has become a great concern for industrial production. We developed a process including acid leaching, solvent extraction and stripping in order to recycle spent catalyst. In this study, we conducted selective recovery of molybdenum through focus on finding an optimized extraction and stripping process by comparing different extractants and stripping agents. To separate molybdenum from other metals efficiently and figure out the mechanism of extraction process, the five different extractants of methyl trioctyl ammonium chloride, tri-n-octylamine, tris (2-ethylhexyl) amine, bis (2-ethylhexyl) phosphate, and tributyl phosphate with different functional groups were examined; the extraction ability and extraction mechanism of these five extractants were systematically studied under the same system for the first time. It was found that more than 98% of the molybdenum could be extracted with an organic phase consisting of tri-n-octylamine or methyl trioctyl ammonium chloride under the optimal conditions. The result indicated that the tri-n-octylamine and methyl trioctyl ammonium chloride possess excellent molybdenum extraction ability, the extraction capacity of the rest extractants was in the order of bis (2-ethylhexyl) phosphate > tris (2-ethylhexyl) amine > tributyl phosphate. In the stripping process, NH₄OH, NaOH, and H₂SO₄ were chosen as stripping agent to strip the molybdenum from the loaded tri-n-octylamine organic phase. The stripping ability of the three studied stripping agents was in the order NaOH > NH₄OH > H₂SO₄. The Fourier transform infrared (FTIR) spectra showed that the structure of the tri-n-octylamine organic phase was stable during the extraction and stripping process. Results showed that molybdenum could be highly and efficiently recovered by optimized extraction and stripping process.

Implications: A series of different extractants and stripping agent have been systematically studied in order to compare their extraction and stripping ability under the same system. Based on the obtained results, an optimized extraction and stripping process was proposed to recycle molybdenum from spent catalyst efficiently. It is possible to dispose spent catalysts in an economic and environmental way by this developed metal recovery process.     

复合纳米材料对土壤重金属离子吸持固化的模拟研究

土壤中过量重金属离子可通过食物链和地表水系统危害人群健康。通过土柱淋溶模拟实验,研究了SiO2-Al2O3-Fe2O3等复合纳米材料对土壤溶液中Cu2+、Cd2+、Pb2+、Zn2+和Ni2+的吸持与固化特征。分别向重金属含量4倍于土壤二级标准(GB15618-1995)的土壤中添加0%、4%、6%和10%的复合纳米材料,分析不同深度土壤渗滤液以及土柱上栽培植物不同部位中重金属的含量。结果表明,碱性壤质土壤中重金属向下的迁移量很少;在含4%复合纳米材料土柱中,其吸持固化土壤溶液中63%的Cu、79%的Cd、68%的Pb、89%的Zn和76%的Ni;在含6%复合纳米材料土柱中,其吸持固化土壤溶液中82%的Cu、92%的Cd、76%的Pb、91%的Zn和88%的Ni;再增加土柱中复合纳米材料的含量,其吸持固化效果并不再显著增加。     

微生物沥浸法去除底泥中的重金属

以硫酸亚铁盐为底物,培养以氧化亚铁硫杆菌为主要菌种的土著沥滤微生物,采用批式方法对湘江长沙段底泥进行微生物沥浸实验。实验结果表明,底物投加量与底泥固体浓度比(Sd/Sc)为1.5时已能满足底泥的微生物沥浸要求,进一步研究发现底泥固体浓度为13%、底物投加量为19.5 g/L、沥浸时间为6 d时,底泥中超标重金属Cd、Zn和Cu的去除率可分别达到83.1%、75.3%和61.2%;沥浸后底泥中大部分重金属以残渣态存在,且含量低于农用污泥中污染物控制标准,其中硫化物有机结合态Cu浸出较Zn、Cd需更低的pH,且Cu以间接机理浸出为主;以Fe2+为底物的沥浸体系中,黄铁矾的重吸附或共沉淀是沥浸实验后期重金属浸出率下降的原因之一。     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Temporal variations and bioaccumulation of heavy metals in different Suaeda salsa marshes of the Yellow River estuary,China

To understand the temporal variations and bioaccumulation of heavy metals in the coastal marshes, the concentrations of heavy metals (Cr, Ni, Pb, and Cu) in the two Suaeda salsa marshes [middle S. salsa marsh (MM) and low S. salsa marsh (LM)] of the Yellow River estuary were determined from May to November in 2008 by in situ sampling and inductively coupled plasma mass spectrometry (ICP-MS) analysis. Results showed that heavy metal concentrations in S. salsa of MM and LM were generally in the order of Cu?>?Cr?>?Pb?>?Ni, while those in sediments fell in the order of Cr?>?Ni?>?Cu?>?Pb. Heavy metal concentrations of S. salsa in MM and LM were different, and significant differences were observed in stems (F?=?4.797, p?=?0.046) and litters (F?=?6.799, p?=?0.026) for Ni. Litter was the main stock of heavy metals, and the allocations of Cr, Ni, and Pb reached 31.25–51.31, 28.49–42.58, and 29.55–66.79 % (in MM) and 36.73–48.60, 41.70–57.87, and 33.30–60.64 % (in LM), respectively. The ratios of roots/leaves (R/L) and roots/stems (R/S) for Cr and Ni in MM were mostly greater than 1, while those ratios in LM were mostly less than 1, indicating that Cr and Ni in S. salsa at LM had greater mobility compared with those at MM. Moreover, the [accumulation factor, AF]_plant of Cr, Ni, Cu, and Pb in LM, especially [AF]_root and [AF]_stem of Cr and [AF]_litter of Ni, was also higher than that in MM. These indicated that S. salsa grown in LM was more suitable for potential biomonitor or phytoremediation of Cr, Ni, Cu, and Pb if intertidal sediments were seriously contaminated with an increase of pollutant loading (especially heavy metals) in the Yellow River estuary. The use of biomonitor (S. salsa) living and growing in LM could yield valuable information not only on the presence of anthropogenic stressors, but, more importantly, on the adverse influence the stressors are having on the environment.     

Ascorbic acid, β-carotene,sugars, phenols,and heavy metals in sweet potatoes grown in soil fertilized with municipal sewage sludge

Municipal sewage sludge (MSS) used for land farming typically contains heavy metals that might impact crop quality and human health. A completely randomized experimental design with three treatments (six replicates each) was used to monitor the impact of mixing native soil with MSS or yard waste (YW) mixed with MSS (YW +MSS) on: i) sweet potato yield and quality; ii) concentration of seven heavy metals (Cd, Cr, Mo, Cu, Zn, Pb, and Ni) in sweet potato plant parts (edible roots, leaves, stem, and feeder roots); and iii) concentrations of ascorbic acid, total phenols, free sugars, and β-carotene in sweet potato edible roots at harvest. Soil samples were collected and analyzed for total and extractable metals using two extraction procedures, concentrated nitric acid (to extract total metals from soil) as well as CaCl₂ solution (to extract soluble metals in soil that are available to plants), respectively. Elemental analyses were performed using inductively coupled plasma mass spectrometry (ICP-MS). Overall, plant available metals were greater in soils amended with MSS compared to control plots. Concentration of Pb was greater in YW than MSS amendments. Total concentrations of Pb, Ni, and Cr were greater in plants grown in MSS+YW treatments compared to control plants. MSS+YW treatments increased sweet potato yield, ascorbic acid, soluble sugars, and phenols in edible roots by 53, 28, 27, and 48%, respectively compared to plants grown in native soil. B-carotene concentration (157.5 μg g^?1 fresh weight) was greater in the roots of plants grown in MSS compared to roots of plants grown in MSS+YW treatments (99.9 μg g^?1 fresh weight). Concentration of heavy metals in MSS-amended soil and in sweet potato roots were below their respective permissible limits.     

去除污泥中重金属铬的生物淋滤反应器设计与应用

用微生物方法去除污泥中重金属（生物淋滤法）是近年来发展的新技术，探索工程化的条件有重要的应用价值。设计了一套容积为1m^3的生物淋滤反应器，由生物淋滤池、搅拌器、曝气器和空气压缩机等构成。其中，搅拌叶轮由平叶桨和斜叶桨组合而成。利用制革污泥进行了半连续的生物淋滤试验，结果表明，在反应器中污泥与菌体和营养物质能充分混匀，经过2-5d的处理，污泥pH持续下降到2．0以下，污泥中铬的溶出率达90％-99．5％。     

Heavy metal availability,bioaccessibility, and leachability in contaminated soil: effects of pig manure and earthworms

A pot experiment and a leaching experiment were conducted to investigate the effects of earthworms and pig manure on heavy metals (Cd, Pb, and Zn) immobility, in vitro bioaccessibility and leachability under simulated acid rain (SAR). Results showed manure significantly increased soil organic carbon (SOC), dissolved organic carbon (DOC), available phosphorus (AP), total N, total P and pH, and decreased CaCl₂-extractable metals and total heavy metals in water and SAR leachate. The addition of earthworms significantly increased AP (from 0.38 to 1.7 mg kg^?1), and a downward trend in CaCl₂-extractable and total leaching loss of heavy metals were observed. The combined earthworm and manure treatment decreased CaCl₂-extractable Zn, Cd, and Pb. For Na₄P₂O₇-extractable metals, Cd and Pb were decreased with increasing manure application rate. Application of earthworm alone did not contribute to the remediation of heavy metal polluted soils. Considering the effects on heavy metal immobilization and cost, the application of 6% manure was an alternative approach for treating contaminated soils. These findings provide valuable information for risk management during immobilization of heavy metals in contaminated soils.

     

SGA对垃圾焚烧飞灰中重金属的固化性能研究简

根据EPA 1311、HJ/T 299-2007、HJ/T 300-2007和HJ 557-2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthio guanidine acid，SGA）、二甲基二硫代氨基甲酸盐（sodium dimethyl dithio carbamate，SDD）和Ca（OH）₂浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的Cd、Ni、Pb和Zn浓度分别超过国家危险废物鉴别标准（GB5085.3-2007）规定值的4.75倍、1.47倍、6.72倍和2.20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0.1 mol/kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）₂；当固化剂SGA、SDD和Ca（OH）₂加入量为0.5 mol/kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB 5085.3-2007）中的规定值。与SDD和Ca（OH）₂相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。