Application of ionic liquids for the removal of heavy metals from wastewater and activated sludge

This paper presents the results of adsorption studies on the removal of heavy metals (Cr, Cu, Cd, Ni, Pb and Zn) from standard solutions, real wastewater samples and activated sewage sludge using a new technique of liquid-liquid extraction using quaternary ammonium and phosphonium ionic liquids (ILs). Batch sorption experiments were conducted using the ILs [PR4][TS], [PR4][MTBA], [A336][TS] and [A336][MTBA]. Removal of these heavy metals from standard solutions were not effective, however removal of heavy metals from the industrial effluents/wastewater treatment plants were satisfactory, indicating that the removal depends mainly on the composition of the wastewater and cannot be predicted with standard solutions. Removal of heavy metals from activated sludge proved to be more successful than conventional methods such as incineration, acid extraction, thermal treatment, etc. For the heavy metals Cu, Ni and Zn, ≥90% removal was achieved.     

The sorption of lead, cadmium, copper and zinc ions from aqueous solutions on a raw diatomite from Algeria

The adsorption of Cu(2+), Zn(2+), Cd(2+) and Pb(2+) ions from aqueous solution by Algerian raw diatomite was studied. The influences of different sorption parameters such as contact pH solution, contact time and initial metal ions concentration were studied to optimize the reaction conditions. The metals ions adsorption was strictly pH dependent. The maximum adsorption capacities towards Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were 0.319, 0.311, 0.18 and 0.096 mmol g(-1), respectively. The kinetic data were modelled using the pseudo-first-order and pseudo-second-order kinetic equations. Among the kinetic models studied, the pseudo-second-order equation was the best applicable model to describe the sorption process. Equilibrium isotherm data were analysed using the Langmuir and the Freundlich isotherms; the results showed that the adsorption equilibrium was well described by both model isotherms. The negative value of free energy change ΔG indicates feasible and spontaneous adsorption of four metal ions on raw diatomite. According to these results, the high exchange capacities of different metal ions at high and low concentration levels, and given the low cost of the investigated adsorbent in this work, Algerian diatomite was considered to be an excellent adsorbent.     

Biological treatment of heavy metals in acid mine drainage using sulfate reducing bioreactors.

The uncontrolled release of acid mine drainage (AMD) from abandoned mines and tailing piles threatens water resources in many sites worldwide. AMD introduces elevated concentrations of sulfate ions and dissolved heavy metals as well as high acidity levels to groundwater and receiving surface water. Anaerobic biological processes relying on the activity of sulfate reducing bacteria are being considered for the treatment of AMD and other heavy metal containing effluents. Biogenic sulfides form insoluble complexes with heavy metals resulting in their precipitation. The objective of this study was to investigate the remediation of AMD in sulfate reducing bioreactors inoculated with anaerobic granular sludge and fed with an influent containing ethanol. Biological treatment of an acidic (pH 4.0) synthetic AMD containing high concentrations of heavy metals (100 mg Cu(2+)l(-1); 10 mg Ni(2+)l(-1), 10 mg Zn(2+)l(-1)) increased the effluent pH level to 7.0-7.2 and resulted in metal removal efficiencies exceeding 99.2%. The highest metal precipitation rates attained for Cu, Ni and Zn averaged 92.5, 14.6 and 15.8 mg metal l(-1) of reactor d(-1). The results of this work demonstrate that an ethanol-fed sulfidogenic reactor was highly effective to remove heavy metal contamination and neutralized the acidity of the synthetic wastewater.     

Heavy metal adsorption changes of EAF steel slag after phosphorus adsorption

A kind of electric arc furnace (EAF) steel slag was phosphated, and its isothermal and dynamic adsorptions of copper, cadmium, and lead ions were measured to determine if heavy metal adsorption changes after phosphorus adsorption. The surface area increased greatly after the slag was phosphated. Isothermal adsorption experiments showed that the theoretical Q(max) of the EAF steel slag on Cu(2+), Cd(2+), and Pb(2+) improved 59, 50, and 89% respectively after it was phosphated. Dynamic adsorption results showed that the greatest adsorption capacities of unit volume of Cu(2+), Cd(2+), and Pb(2+) were 2.2, 1.8, and 1.8 times that of the column packed with original EAF steel slag when the column was packed with phosphate EAF steel slag at the same heavy metal ion concentration. The breakthrough time, the exhaustion time and elution efficiency of the column also increased when the column was packed with phosphated EAF steel slag compared with that packed with original EAF steel slag. Phosphorus adsorption could further improve the heavy metal ion adsorption of the EAF steel slag.     

Use of sesame stalk biomass for the removal of Ni(II) and Zn(II) from aqueous solutions

In this study an agricultural residue, sesame stalk, was evaluated for the removal of Ni(II) and Zn(II) metal ions from aqueous solutions. Biosorption studies were carried out at different pH, biosorbent dosage, initial metal ion concentrations, contact time, and solution temperature to determine the optimum conditions. The experimental data were modeled by Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherm models. Langmuir model resulted in the best fit of the biosorption data. The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data and to evaluate rate constants. The best correlation was provided by the second-order kinetic model. The thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated for predicting the nature of adsorption. The experimental results showed that sesame stalk can be used as an effective and low-cost biosorbent precursor for the removal of heavy metal ions from aqueous solutions.     

Evaluation of heavy metal inhibition of activated sludge by TTC and INT-electron transport system activity tests.

TTC and INT-electron transport system activity tests were compared for assessing heavy metal inhibition of activated sludge. The median inhibitory concentrations (IC50s) of Cu2+, Zn2+, Cd2+, Hg2+, Ni2+, Pb2+ and Ag+ measured via TTC test were lower than those measured via INT test, which indicates that the INT-electron transport system activity test was less sensitive to heavy metal toxicity than the TTC test. Tested heavy metals brought about similar decrease in TTC-electron transport system activity and COD removal rate, but less decrease in INT-electron transport system activity than COD removal rate, which suggests that the TTC-electron transport system activity is a better parameter for reflecting heavy metal inhibition of activated sludge than INT-electron transport system activity. The ranking of tested heavy metals in order of decreasing toxicity based on TTC test was Hg2+, Cd2+, Cu2+, Ag+, Zn2+, Ni2+ and Pb2+, and the ranking based on INT test was Hg2+, Ag+, Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+.     

Modification of granular activated carbon using low molecular weight polymer for enhanced removal of Cu(2+) from aqueous solution.

Palm shell activated carbon was modified via surface impregnation with polyethyleneimine (PEI) to enhance removal of Cu(2+) from aqueous solution in this study. The effect of PEI modification on batch adsorption of Cu(2+) as well as the equilibrium behavior of adsorption of metal ions on activated carbon were investigated. PEI modification clearly increased the Cu(2+) adsorption capacities by 68% and 75.86% for initial solution pH of 3 and 5 respectively. The adsorption data of Cu(2+) on both virgin and PEI-modified AC for both initial solution pH of 3 and 5 fitted the Langmuir and Redlich-Peterson isotherms considerably better than the Freundlich isotherm.     

The influence of heavy metals on the production of extracellular polymer substances in the processes of heavy metal ions elimination.

Wastewaters from a chemical industry polluted by heavy metal ions represent a hazard for all living organisms. It can mean danger for ecosystems and human health. New methods are sought alternative to traditional chemical and physical processes. Active elimination process of heavy metals ions provided by living cells, their components and extracellular products represents a potential way of separating toxic heavy metals from industrial wastewaters. While the abilities of bacteria to remove metal ions in solution are extensively used, fungi have been recognized as a promising kind of low-cost adsorbents for removal of heavy-metal ions from aqueous waste sources. Yeasts and fungi differ from each other in their constitution and in their abilities to produce variety of extracellular polymeric substances (EPS) with different mechanisms of metal interactions. The accumulation of Cd(2+), Cr(6+), Pb(2+), Ni(2+) and Zn(2+) by yeasts and their EPS was screened at twelve different yeast species in microcultivation system Bioscreen C and in the shaking Erlenmayer's flasks. This results were compared with the production of yeast EPS and the composition of yeast cell walls. The EPS production was measured during the yeast growth and cell wall composition was studied during the cultivations in the shaking flasks. At the end of the process extracellular polymers and their chemical composition were isolated and amount of bound heavy metals was characterized. The variable composition and the amount of the EPS were found at various yeast strains. It was influenced by various compositions of growth medium and also by various concentrations of heavy metals. It is evident, that the amount of bound heavy metals was different. The work reviews the possibilities of usage of various yeast EPS and components of cell walls in the elimination processes of heavy metal ions. Further the structure and properties of yeasts cell wall and EPS were discussed. The finding of mechanisms mentioned above is necessary to identify the functional groups entered in the metals elimination processes.     

共存重金属离子对好氧活性污泥活性影响的实验研究

采用序批式实验研究了铜、锌、镍离子共存条件下,对活性污泥表观产率、生物吸附降解能力、污泥絮凝沉降性能和耗氧速率等方面的影响,并测定了两种重金属离子共存的情况下,不同浓度重金属离子之间的相互作用。实验结果表明:Cu2+和Zn2+、Cu2+和Ni2+、Zn2+和Ni2+3种离子共存总浓度分别为5、5、10 mg/L以内,对污泥表观产率的影响不是很大,系统可以稳定运行。3种离子共存总浓度分别为5、3、3 mg/L以内,对CODCr的去除率没有影响,MLSS都可以稳定的增加,大于这个基点,系统都无法正常的运行;Cu2+和Ni2+共存的情况下对微生物的呼吸有协同抑制的作用。     

南昌市湖泊重金属源识别及污染特征风险评价

为了解南昌市湖泊重金属污染特征现状,论文以青山湖、象湖及前湖为研究对象,在分析湖泊水体及沉积物重金属Cr、Ni、Cu、Zn、Cd、Pb水平的基础上,采用因子分析、地质累积指数与综合潜在生态风险指数对湖泊重金属污染水平进行评价,并结合主成分分析等统计方法判别各研究水域重金属污染源。结果表明水域中Cr、Cd与Pb为主要重金属污染元素,前湖面临着最为严重的水体重金属污染。沉积物中Ni、Cu、Zn、Cd、Pb存在不同程度风险,各湖泊中沉积重金属风险程度从大到小均为Cd>Cu>Pb>Ni>Zn。前湖生态风险程度最大,其次是象湖。主成分分析表明湖泊重金属主要来源于交通运输与废水废气排放。因此为避免进一步污染,应合理规划交通,控制汽车尾气排放,提升污水治理水平。     

Comparative MCDM Analysis for AMD Treatment Method Selection

Robule Lake, located in Eastern Serbia, near the city of Bor, is being influenced by waste materials from mining activities. For the purification of water from Robule Lake, contaminated with various metal ions (Fe, Cu, Zn, Mn, Cd, Ni, etc.), acid mine drainage (AMD) treatment methods such as: passive treatment method, sequential neutralization, ion exchange, adsorption process based on low cost adsorbents, adsorption process based on natural zeolits, electrodialysis, filtration with nanofiltration membranes, and reverse osmosis, were evaluated by the following MCDM methods: TOPSIS, VIKOR, MOOSRA, WASPAS, and CoCoSo. Criteria used for the evaluation were: efficiency in the metal ions removal and the quality of the purified water, necessity of pre-treatment and / or post-treatment of treated water, possibility of using the generated waste, capital costs, operating and maintenance costs, needed area, and sensitivity of the method. The results of the MCDM analysis showed that sequential neutralization was the most appropriate method for this wastewater, while passive treatment system and ion exchange were ranked as second and third, respectively.

After the selection of AMD treatment method, neutralization tests with lime were carried out with the water sample from Robule Lake. The results of sequential neutralization testing showed that concentration of Fe ions could be lowered to 1 mg/L at pH 4. The values of Cu, Zn, and Ni ions concentration obtained at pH 7 were 0.04, 0.65, and 0.21 mg/L, respectively, while the values of Mn and Cd ions concentration of 0.01 and 0.0001 mg/L, were obtained at pH 10.

     

Effects of sorption, sulphate reduction, and Phragmites australis on the removal of heavy metals in subsurface flow constructed wetland microcosms.

The removal of Co, Ni, Cu and Zn from synthetic industrial wastewater was studied in subsurface flow constructed wetland microcosms filled with gravel or a gravel/straw mixture. Half of the microcosms were planted with Phragmites australis and half were left unplanted. All microcosms received low-strength wastewater (1 mg L(-1) of Co, Ni, and Zn, 0.5 mg L(-1) Cu, 2,000mg L(-1) SO4) during seven 14-day incubation batches. The pore water was regularly monitored at two depths for heavy metals, sulphate, organic carbon and redox potential. Sorption properties of gravel and straw were assessed in a separate experiment. A second series of seven incubation batches with high-strength wastewater (10 mg L(-1) of each metal, 2,000 mg L(-1) SO4) was then applied to saturate the substrate. Glucose was added to the gravel microcosms together with the high-strength wastewater. Sorption processes were responsible for metal removal during start-up, with the highest removal efficiencies in the gravel microcosms. The lower initial efficiencies in the gravel/straw microcosms were presumably caused by the decomposition of straw. However, after establishment of anaerobic conditions (Eh approximately -200 mV), precipitation as metal sulphides provided an additional removal pathway in the gravel/straw microcosms. The addition of glucose to gravel microcosms enhanced sulphate reduction and metal removal, although Phragmites australis negatively affected these processes in the top-layer of all microcosms.     

Removal of lead(II) and copper(II) from aqueous solution using foitite from Linshou mine in Hebei, China

Foitite from Linshou mine in China's Hebei province was investigated as an adsorbent to remove Pb(II) and Cu(II) from aqueous solution. The results showed that foitite can readily remove heavy metal ions from aqueous solution. The data shows that the metal uptake for Pb(II) increases rapidly, accounting for 74.47% when contact time was 2 min. In contrast to Pb(ll), there was a worse capability for adsorption of Cu(II). In the first 4 min, the metal uptake accounted for 34.7%. According to the analytical results obtained from X-ray diffraction, laser Raman spectrum, X-ray energy dispersive spectrometer, and Zeta potential, the removal mechanism of Pb(II) and Cu(II) by using foitite can be explained as following: firstly, the existence of an electrostatic field around foitite particles can attract heavy metal ions and consequently combine heavy metal ions with OH; secondly, heavy metal ions in the solution are exchanged with the Fe3+ and Al3+ in the foitite.     

Characterisation of heavy metal tolerance and biosorption capacity of bacterium strain CPB4 (Bacillus spp.).

A heavy metal resistant bacterium Bacillus spp. strain CPB4 was isolated from heavy metal contaminated soil in Korea and further characterised. The CPB4 strain showed a high capacity for uptake of heavy metal Pb (Pb > Cd > Cu > Ni > Co > Mn > Cr > Zn) both in single and in mixed heavy metal solution. Optimal conditions for heavy metal uptakes of CPB4 strain were 20-40 degrees C culture temperature, 5-7 pH and 24 h pre-culture times. TEM showed that large amounts of the electron-dense granules (heavy metal complexes) were found mainly on the cell wall and cell membrane. Furthermore, more than 90% of adsorbed heavy metals were distributed both in cell wall and in cell membrane fractions. The amount of heavy metal uptake was remarkably decreased by reducing the crude protein contents when cells were treated by alkali solutions. Therefore, this study showed one of the possible examples for useful bioremediation.     

Enhancement of removal efficiency of heavy metal ions by polyaniline deposition on electrospun polyacrylonitrile membranes

This paper describes the preparation of a membrane of polyacrylonitrile(PAN) and its corresponding membrane coated with polyaniline(PANI) for the adsorption of heavy metal ions.Scanning electron microscopy micrographs revealed that all the membranes exhibited nanofibrous morphology.The prepared membranes were characterized by Fourier transform infrared spectroscopy(FTIR).The prepared membranes were used as an adsorbent for hazardous heavy metal ions Pb~(2+) and Cr_2 O_7~(2-).The adsorption capacity and the removal efficiency of the membranes were examined as function of the initial adsorbate concentration and pH of the medium.Coated membranes with PANI showed better adsorption performance and their direct current(DC) conductivities were correlated to heavy metal ion concentrations.Adsorption isotherms were also performed,and the adsorption process was tested according to the Langmuir and Freundlich models.The regeneration and reuse of the prepared membranes to re-adsorb heavy metal ions were also investigated.The enhancement in adsorption performance and reusability of PANI-coated membranes in comparison with non-coated ones is fully discussed.The results show that the maximum adsorption capacities of lead and chromate ions on the PANI-coated membranes are 290.12 and 1 202.53 mg/g,respectively.     

氨基功能化CaCO3粉末材料吸附重金属离子的研究

用直接沉淀法和包覆法相结合,制得氨基功能化CaCO3粉末材料,并对其作为某些重金属离子(Pb2+、Cu2+和Mn2+)的有效吸附剂进行表征及测定。X射线衍射(XRD)、能谱分析和扫描电子显微镜(SEM)证明该材料含有CaCO3,通过红外测定可知,功能性基团(-NH2)已成功包覆于CaCO3粉末材料上。氨基对重金属离子的吸附起主要作用,考察了吸附时间、重金属离子的初始浓度和溶液的pH值对吸附的影响。     

Application of mulch for treating metals in urban runoff: batch and column test.

Among the many methods available for the removal of heavy metals in urban nonpoint source pollution (NSP), adsorption has been shown to be an economically feasible alternative. To adsorb the amount of heavy metals in runoff, filtration of runoff through a specially constructed filter system is one possible treatment method. The mulch layer in a specially constructed filter system functions through adsorptive-filtration, where some pollutants are immobilised through sorption and some pollutants associated with suspended solids are immobilised through filtration. Therefore, the major interest of this study was to investigate the possibility of utilising mulch for the adsorption of heavy metals such as cadmium, copper, lead and zinc for a solution typical of those found in urban runoff using the flask-type adsorption batch tests and laboratory column tests. From the equilibrium sorption batch tests, it was observed that the adsorption of heavy metals on mulch with the same initial concentrations of metals in the solution decreased in the order Pb(II) > Cu(II) > Zn(II) > Cd(II) regardless of changes in pH. In column tests, the breakthrough curves for various heavy metals' adsorption by mulch showed that the binding strength of the following metal ions onto mulch was as follows: Pb(II) > Cu(II) > Zn(II) > Cd(II).     

Simultaneous copper, cobalt and phenol removal from aqueous solutions by alternating biosorption and biodegradation

A strategy for removal of heavy metals and phenol from wastewaters is proposed. It involves consecutive cation biosorption by fungi, phenol biodegradation by the yeast association Candida sp. 2326 + Candida sp. 2327 and regeneration. Copper and cobalt removal from aqueous solutions containing 80-120 mg/L phenol by biosorption, using Rhizopus archizus cells immobilized onto poly (vinyl alcohol), was investigated by conducting a series of batch experiments. The removal efficiencies were 81% for Cu and 5% for Co. The residual concentrations of Cu (1.9 mg/L) and of Co (9.5 mg/L) did not change the biodegradation dynamics of phenol. A quantitative biodegradation of 120 mg/L phenol proceeded within 22 h. After biodegradation of phenol, the removal efficiencies achieved by biosorption after regeneration were 90% for Cu and 44% for Co. It was found that copper and cobalt form positively charged complexes with phenol. This complex formation hinders the retention of Cu and Co by the biosorbent and reduces the uptake of their cations.     

Enhanced heavy metals removal without phosphorus loss from anaerobically digested sewage sludge

Heavy metals removal without phosphorus loss from anaerobically digested sewage sludge was investigated by conducting batch experiments using hydrogen peroxide and/or iron sulphate under acidified conditions at pH 3. The addition of hydrogen peroxide to the sludge improved the elution efficiencies of As, Cd, Cu and Zn with phosphorus loss from the sludge. The optimum initial concentrations of hydrogen peroxide were. Respectively. 0.1% for As, Cd, Mn and Zn and 0.5% for Cu and Ni. The combined process of 0.1% hydrogen peroxide and 1 g Fe/L ferric sulphate enhanced the initial elution rate of Cu and Cr compared to the addition of either ferric sulphate or hydrogen peroxide, indicating that oxidants stronger than hydrogen peroxide were produced in the sludge. Furthermore, the combined process immobilised phosphorus in the sludge due to co-precipitation with ferric hydroxide or precipitation as ferric phosphate. It was concluded that there is a possibility that the combined process could remove heavy metals effectively without phosphorus loss from anaerobically digested sewage sludge.     

Two-stage anaerobic digestion enables heavy metal removal.

To fully exploit the environmental benefits of the biogas process, the digestate should be recycled as biofertiliser to agriculture. This practice can however be jeopardized by the presence of unwanted compounds such as heavy metals in the digestate. By using two-stage digestion, where the first stage includes hydrolysis/acidification and liquefaction of the substrate, heavy metals can be transferred to the leachate. From the leachate, metals can then be removed by adsorption. In this study, up to 70% of the Ni, 40% of the Zn and 25% of the Cd present in maize was removed when the leachate from hydrolysis was circulated over a macroporous polyacrylamide column for 6 days. For Cu and Pb, the mobilization in the hydrolytic stage was lower which resulted in a low removal. A more efficient two-stage process with improved substrate hydrolysis would give lower pH and/or longer periods with low pH in the hydrolytic stage. This is likely to increase metal mobilisation, and would open up for an excellent opportunity of heavy metal removal.