Removal of heavy metals from acid mine drainage (AMD) using coal fly ash, natural clinker and synthetic zeolites

Acid mine drainage (AMD) is a widespread environmental problem associated with both working and abandoned mining operations, resulting from the microbial oxidation of pyrite in presence of water and air, affording an acidic solution that contains toxic metal ions. The generation of AMD and release of dissolved heavy metals is an important concern facing the mining industry. The present study aimed at evaluating the use of low-cost sorbents like coal fly ash, natural clinker and synthetic zeolites to clean-up AMD generated at the Parys Mountain copper-lead-zinc deposit, Anglesey (North Wales), and to remove heavy metals and ammonium from AMD. pH played a very important role in the sorption/removal of the contaminants and a higher adsorbent ratio in the treatment of AMD promoted the increase of the pH, particularly using natural clinker-based faujasite (7.70-9.43) and the reduction of metal concentration. Na-phillipsite showed a lower efficiency as compared to that of faujasite. Selectivity of faujasite for metal removal was, in decreasing order, Fe>As>Pb>Zn>Cu>Ni>Cr. Based on these results, the use of these materials has the potential to provide improved methods for the treatment of AMD.     

In situ measurements of labile Al and Mn in acid mine drainage using diffusive gradients in thin films

The technique of diffusive gradients in thin films (DGT) can be used for in situ measurements of labile metal species in water, but the application for this method on acid mine drainage (AMD) is complicated due to reduced sampler adsorption of metals at low pH. This study evaluates the use of DGT on labile Al and Mn in AMD (pH 3.1-4.2). DGT measurements were performed both in standard solutions in the laboratory and in situ in the field. Laboratory results show that DGT can be used in water with pH as low as 3.0 for Al and 4.0 for Mn without correcting for reduced adsorption. Below pH 4.0, the adsorption of Mn showed a linearly decrease with pH to approximately 55% at pH 3.0. Taking this correction into account revealed that 84-100% of the total dissolved Al and Mn measured in the field was DGT-labile. Measurements using DGT agreed well with predictions using the speciation program WHAM VI. This study shows that the use of DGT can be extended below the previously reported pH working range for Al, and for Mn using a simple linear correction with respect to pH, and demonstrates that the technique can be applied for monitoring time-integrated labile metal concentrations at AMD sites.     

Phosphorus removal performance of acid mine drainage from wastewater

Acid mine drainage (AMD) in Yunfu iron sulfide mine contain Fe(2+), Fe(3+), and Al(3+) up to 8000, 1700 and 1200 mg/L, respectively. Phosphorus removal from synthetic wastewater with 10mg/L of total phosphorus (TP) concentration and second municipal effluent with 3.5-4.0mg/L of TP concentration were conducted with the AMD by jar tests. Dosage of the AMD and initial pH of water are the two most important parameters affecting the performance of phosphorus removal of the AMD. The optimal phosphorus removal efficiency and residual iron ions (TFe) concentration are 97.0% and 3.0mg/L, respectively, at 1.61 Fe/P molar ratio and pH 8.03 for synthetic wastewater, and 92.1% and 0.32 mg/L, respectively, for second municipal effluent at 1.41 Fe/P molar ratio and pH 7.3. Resultant heavy metal concentration in effluents and precipitate was very low, and the risk of resultant heavy metal contamination was very small. The phosphorus removal performance of the AMD was much similar to that of ferric sulfate (FS) and polyferric sulfate (PFS), and better than that of FeSO(4). And residual TFe concentration in treated water arising from utilization of the AMD was similar to that of FeSO(4), and higher than that of FS and PFS. The AMD could be used as coagulant for phosphorus removal from wastewater directly due to the presence of Fe(2+), Fe(3+), and Al(3+) largely.     

Removal of chromium and toxic ions present in mine drainage by Ectodermis of Opuntia

This work presents conditions for hexavalent and trivalent chromium removal from aqueous solutions using natural, protonated and thermally treated Ectodermis of Opuntia. A removal of 77% of Cr(VI) and 99% of Cr(III) can be achieved. The sorbent material is characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, infrared spectroscopy, thermogravimetric analysis, before and after the contact with the chromium containing aqueous media. The results obtained from the characterization techniques indicate that the metal ion remains on the surface of the sorbent material. The percentage removal is found to depend on the initial chromium concentration and pH. The Cr(VI) and Cr(III) uptake process is maximum at pH 4, using 0.1g of sorbent per liter of aqueous solution. The natural Ectodermis of Opuntia showed a chromium adsorption capacity that was adequately described by the Langmuir adsorption isotherm. Finally, an actual mine drainage sample that contained Cd, Cr, Cu, Fe Zn, Ni and Pb was tested under optimal conditions for chromium removal and Ectodermis of Opuntia was found to be a suitable sorbent material. The use of this waste material for the treatment of metal-containing aqueous solutions as well as mine drainage is effective and economical.     

Reduction of acidity and removal of metal ions from coal mining effluents using chitosan microspheres

Effluents from coal mining operations are not only highly acid but also depict elevated concentrations of metals which may contaminate the environment. Due to the polybasic characteristic of chitosan, this biopolymer is capable of both neutralizing and removing iron, aluminum and copper ions from such effluents. The present study aimed at evaluating the use of chitosan microspheres for their importance in continuous systems. The microspheres were prepared by the phase inversion method. Their average diameter and morphology were determined. Water samples from decantation pool (DP) and acidic mine drainage (AMD) effluents were treated using different amounts of microspheres. The pH and concentration of Fe, Al and Cu ions were evaluated both before and after treatment of effluent samples. The results revealed that the microspheres were capable of increasing the pH of DP and AMD samples from 2.34 and 2.58, respectively, to 6.20, i.e., close to neutrality. The treatment also resulted in full removal of the metals investigated.     

Bioassessment of a combined chemical-biological treatment for synthetic acid mine drainage

In this work, ecotoxicological characteristics of synthetic samples of acid mine drainage (AMD) before and after a combined chemical-biological treatment were investigated by using Lepidium sativum and Daphnia magna. AMD treatment was performed in a two-column apparatus consisting of chemical precipitation by limestone and biological refinement by sulphate reducing bacteria. Synthetic samples of AMD before treatment were toxic for both L. sativum (germination index, G, lower than 10%) and D. magna (100% immobility) due to acid pH and presence of copper and zinc. Chemical treatment (raising pH to 5-6 and eliminating copper) generated effluents with reduced toxicity for L. sativum (G=33%), while 100% immobility was still observed for D. magna. Dynamic trends of toxicity for the first and fifth outputs of the biological column denoted a gradual improvement leading to hormesis for Lepidium (after the initial release of organic excess), while a constant residual toxicity remained for Daphnia (probably due to H(2)S produced by sulphate reducing bacteria).     

Removal of nickel from aqueous solutions by sawdust

The main parameters influencing Nickel (II) metal sorption on maple sawdust were: initial metal ion concentration, amount of adsorbent, and pH value of solution. The maximum percent metal removal was attained after about 1h. The greatest increase in the rate of adsorption of metal ions on sawdust was observed for pH changes from 2 to 5. An empirical relationship has been obtained to predict the percentage Nickel (II) removal at any time for known values of sorbent and initial sorbate concentration. The experimental results provided evidence for chelation ion exchange as the major adsorption mechanisms for binding metal ions to the sawdust. The adsorbent can be effectively regenerated using 0.1 M strong acid and reused.     

Grafting of ion-imprinted polymers on the surface of silica gel particles through covalently surface-bound initiators: a selective sorbent for uranyl ion

A new ion imprinted polymer coated silica gel sorbent has been prepared using the radical "grafting from" polymerization method through surface-bound azo initiators for selective uranyl uptake. The introduction of azo initiator onto the silica surface was achieved by the reaction of surface amino groups with 4,4'-azobis(4-cyanopentanoic acid chloride). The grafting step was then carried out in a stirred solution of initiator-modified silica particles in the presence of uranyl ion and functional and cross-linking monomers. The prepared sorbent was characterized using FT-IR spectroscopy, scanning electron microscopy (SEM), elemental analysis (EA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and BET adsorption isotherm analysis. The influence of the uranyl concentration, pH, and flow rate of solution on the grafted polymer affinity has been investigated. Maximum uptake of uranyl ion was observed at a pH 3.0. The rebinding behavior of the sorbent has been successfully described by the Langmuir-Freundlich isotherm. The dynamic column capacity of sorbent and enrichment factor for uranyl ion were 52.9 +/- 3.4 micromol g(-1) and 52, respectively. It was found that imprinting results in increased affinity of the sorbent toward uranyl ion over strong competitor metal ions such as Fe(III) and Th(IV). The sorbent was repeatedly used and regenerated for 3 months without any significant decrease in polymer binding affinities. Finally the sorbent was applied to the preconcentration and determination of uranyl ion in real water samples.     

Sulfidogenic biotreatment of synthetic acid mine drainage and sulfide oxidation in anaerobic baffled reactor

The treatment of synthetic acid mine drainage (AMD) water (pH 3.0-6.5) containing sulfate (3.0-3.5 g L(-1)) and various metals (Co, Cu, Fe, Mn, Ni, and Zn) was studied in an ethanol-fed sulfate-reducing 4-compartment anaerobic baffled reactor (ABR) at 32°C. The reactor was operated for 160 days at different chemical oxygen demand (COD)/sulfate ratios, hydraulic retention times (HRT), pH, and metal concentrations to study the robustness of the process. The last compartment of the reactor was aerated at different rates to study the bio-oxidation of sulfide to elemental sulfur. The highest sulfate reduction efficiency (88%) was obtained with a feed sulfate concentration of 3.5 g L(-1), COD/sulfate mass ratio of 0.737, feed pH of 3.0 and HRT of 2 days without aeration in the 4th compartment. The corresponding COD removal efficiency was about 92%. The alkalinity produced in the sulfidogenic ethanol oxidation neutralized the acidic mine water from pH 3.0-4.5 to pH 7.0-8.0. Effluent soluble and total heavy metal concentrations were substantially reduced with removal efficiencies generally higher than 99%, except for Mn (25-77%). Limited aeration in the 4th compartment of ABR promoted incomplete oxidation of sulfide to elemental sulfur rather than complete oxidation to sulfate. Depending on the aeration rate and HRT, 32-74% of produced sulfide was oxidized to elemental sulfur. This study demonstrates that by optimizing operating conditions, sulfate reduction, metal removal, alkalinity generation, and excess sulfide oxidation can be achieved in a single ABR treating AMD.     

Sulfide oxidation and acid mine drainage formation within two active tailings impoundments in the Golden Quadrangle of the Apuseni Mountains, Romania

Sulfidic mine tailings have to be classified as one of the major source of hazardous materials leading to water contamination. This study highlights the processes leading to sulfide oxidation and acid mine drainage (AMD) formation in the active stage of two tailings impoundments located in the southern part of the Apuseni Mountains, in Romania, a well-known region for its long-term gold-silver and metal mining activity. Sampling was undertaken when both impoundments were still in operation in order to assess their actual stage of oxidation and long-term behavior in terms of the potential for acid mine drainage generation. Both tailings have high potential for AMD formation (2.5 and 3.7 wt.% of pyrite equivalent, respectively) with lesser amount of carbonates (5.6 and 3.6 wt.% of calcite equivalent) as neutralization potential (ABA=-55.6 and -85.1 tCaCO(3)/1000 t ) and showed clear signs of sulfide oxidation yet during operation. Sequential extraction results indicate a stronger enrichment and mobility of elements in the oxidized tailings: Fe as Fe(III) oxy-hydroxides and oxides (transformation from sulfide minerals, leaching in oxidation zone), Ca mainly in water soluble and exchangeable form where gypsum and calcite are dissolved and higher mobility of Cu for Ribita and Pb for Mialu. Two processes leading to the formation of mine drainage at this stage could be highlighted (1) a neutral Fe(II) plume forming in the impoundment with ferrihydrite precipitation at its outcrop and (2) acid mine drainage seeping in the unsaturated zone of the active dam, leading to the formation of schwertmannite at its outcrop.     

An investigation into the sorption of heavy metals from wastewaters by polyacrylamide-grafted iron(III) oxide

An adsorbent for heavy metals was synthesized by introducing carboxylate functional group into polyacrylamide-grafted hydrous iron(III) oxide. The product exhibits a very high adsorption potential for Pb(II), Hg(II) and Cd(II). The removal of metal ions by adsorption on adsorbent has been found to be contact time, concentration, pH and temperature dependent. The process follows first-order reversible kinetics. The intraparticle diffusion of metal ions through pores in the adsorbent was shown to be the main rate-limiting step. The optimum pH range for the removal of metal ions was found to be 5.0-6.0. The thermodynamic parameters such as free energy change, enthalpy change and entropy change have been calculated to predict the nature of adsorption. The adsorption data were fitted using the Langmuir equation and maximum adsorption for each metal was estimated using their respective Langmuir equation constants. The method was applied for synthetic wastewaters. NaCl regeneration has been tried for several cycles with a view to recover the adsorbed metal ions and also to restore the sorbent to its original state.     

Solar photocatalytic removal of Cu(II), Ni(II), Zn(II) and Pb(II): speciation modeling of metal-citric acid complexes

The present study is targeted on solar photocatalytic removal of metal ions from wastewater. Photoreductive deposition and dark adsorption of metal ions Cu(II), Ni(II), Pb(II) and Zn(II), using solar energy irradiated TiO2, has been investigated. Citric acid has been used as a hole scavenger. Modeling of metal species has been performed and speciation is used as a tool for discussing the photodeposition trends. Ninety-seven percent reductive deposition was obtained for copper. The deposition values of other metals were significantly low [nickel (36.4%), zinc (22.2%) and lead (41.4%)], indicating that the photocatalytic treatment process, using solar energy, was more suitable for wastewater containing Cu(II) ions. In absence of citric acid, the decreasing order deposition was Cu(II)>Ni(II)>Pb(II)>Zn(II), which proves the theoretical thermodynamic predictions about the metals.     

Removal and recovery of lead (II) ions from contaminated licorice extracts using oxidized multi-walled carbon nanotubes

A column with oxidized multi-walled carbon nanotubes (MWNTs) has been studied as a sorbent for removing and accumulating lead (II) from contaminated Licorice extracts. Under optimized situation, the adsorption capacity of lead (II) on oxidized MWNTs was 17 mg g(-1) at pH 7.0, and the lead (II) was eluted with 10 ml of 1% hydrochloric acid. Additionally, the effects of adsorptive parameters, including pH of the solution, sample volume, flow rates of the sample, matrix ions, and eluent type were investigated for optimization of the presented procedure. A fluorescence spectrophotometer was employed to determine the contents of lead (II). High-performance liquid chromatography (HPLC) was developed for the quantitative determination of main constituents of Licorice extracts. Oxidized MWNT cartridges were used to remove lead ions from contaminated Licorice extracts, high adsorption capacity, adsorption reversibility of lead (II), and low loss of major constituents. The results suggested that the oxidized MWNT column has the potential to remove heavy metal ions from herbal extracts.     

Comparison of adsorption capacity of young brown coals and humic acids prepared from different coal mines in Anatolia

Binding of Zn2+ and Cd2+ cations to relatively young brown coals YBC (lignite), humic acids (HAs) and commercial humic acid (CHA) were studied in aqueous media at pH 2.7-6 by polarographic method. This study was conducted to evaluate the removal of heavy metals in an aquatic system without prior treatment. The general principles of cation binding to YBC and humic materials are discussed. Sorption of heavy metal ions (Zn2+ and Cd2+) on samples of YBCs from three areas (Ilgin, Beysehir, and Ermenek) in the vicinity of the city of Konya in Anatolia (Turkey) were compared with sorption of these metal ions on HAs, prepared from these YBCs. The ability of both types of sorbent to remove metals from aqueous solutions was studied as a function of pH and concentration of initial metal solutions. Sorption depends strongly on pH, the origin of the YBC and on the nature of the metal ion. Whereas, for YBCs the main ligand groups seem to be carboxylate ions, this is not the case for the HA polymers, prepared from three YBCs, which differ substantially from properties of commercial samples of "HA". The process is very efficient especially in the case of low concentrations of pollutants in water, where common methods are either economically unfavorable or technically complicated. Of the two metal ions examined, Cd2+ was found to form the most stable HA complexes, followed by Zn. Effective removal of metals was demonstrated at pH-values of 5-5.7. The adsorption isotherm was measured at 25 degrees C, using adsorptive solutions at the optimum pH-value to determine the adsorption capacity. An important aspect of the proposed method was that the removal was performed on several metals at a pH-range in which a given metal undergoes an adsorption process making the method useful for wastewater treatment.     

Sorption of uranium(VI) using oxime-grafted ordered mesoporous carbon CMK-5

A new sorbent for uranium(VI) has been developed by functionalizing ordered mesoporous carbon CMK-5 with 4-acetophenone oxime via thermally initiated diazotization. The sorption of U(VI) ions onto the functionalized CMK-5 (Oxime-CMK-5) was investigated as a function of sorbent dosage, pH value, contact time, ionic strength and temperature using batch sorption techniques. The results showed that U(VI) sorption onto Oxime-CMK-5 was strongly dependent on pH, but to a lesser extent, on ionic strength. Kinetic studies revealed that the sorption process achieved equilibrium within 30 min and followed a pseudo-first-order rate equation. The isothermal data correlated with the Langmuir model better than the Freundlich model. Thermodynamic data indicated the spontaneous and endothermic nature of the process. Under current experimental conditions, a maximum U(VI) sorption capacity was found to be 65.18 mg/g. Quantitative recovery of uranium was achieved by desorbing the U(VI)-loaded Oxime-CMK-5 with 1.0 mol/L HCl and no significant decrease in U(VI) sorption capability of Oxime-CMK-5 was observed after five consecutive sorption-desorption cycles. The sorption study performed in a simulated nuclear industry effluent demonstrated that the new sorbent showed a desirable selectivity for U(VI) ions over a range of competing metal ions.     

Isotherms and thermodynamics for the sorption of heavy metal ions onto functionalized sporopollenin

In this study, sporopollenin of Lycopodium clavatum spores was used for the sorption experiment. Glutaraldehyde (GA) immobilized sporopollenin (Sp), is employed as a sorbent in sorption of selected heavy metal ions. The sorbent prepared by sequential treatment of sporopollenin by silanazing compound and glutaraldehyde is suggested for sorption of Cu(II), Zn(II) and Co(II) from aqueous solutions. Experimental conditions for effective sorption of heavy metal ions were optimized with respect to different experimental parameters using batch method in detail. Optimum pH range of Cu(II) has occurred at pH ≥ 5.5 and Zn(II), Co(II) at pH ≥ 5.0, for the batch method. All of the metal ions can be desorbed with 10 cm³ of 0.5 mol dm⁻³ of ethylenediaminetetraacetic acid (EDTA) solution. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm equations were applied to the experimental data. Thermodynamic parameters such as free energy (ΔG^o), entropy (ΔS^o) and enthalpy (ΔH^o) were also calculated from the sorption results used to explain the mechanism of the sorption. The results indicated that this sorbent is successfully employed in the separation of trace Cu(II), Zn(II) and Co(II) from the aqueous solutions.     

CCB-based encapsulation of pyrite for remediation of acid mine drainage

Acid mine drainage (AMD) from abandoned coal mines continues to be one of the most significant environmental problems. Remediation of AMD requires an addition of lime source to decrease the acidity, and grouting the entire mine and encapsulating the pyrite by calcium-rich additives is often employed. Utilization of alkaline coal combustion by-products (CCBs) has gained acceptance in such remediation applications because of their cost-effectiveness. A study was conducted to investigate the effectiveness of CCBs to abate acid mine drainage by encapsulation of pyrite. Geomechanical, hydraulic, and environmental tests were performed on grouts prepared with various ratios of CCBs as well as an alternative free lime source, lime kiln dust (LKD). The results indicated that the mechanical properties of grouts were dependent on their free lime contents. Hydraulic conductivities of pyrite-grout columns were relatively high due to the coating of the pyrite rock with the grout rather than the filling of all of the void spaces, as commonly experienced in field applications. The leaching tests indicated that the presence of high amounts of lime in a grout is not solely sufficient to improve the quality of AMD, since the rate of dissolution of a high lime content grout may be slow due to its rapid hardening. Therefore, it is recommended that grouts be selected with consideration of their hardening capacities, as well as the percentage of lime content present in the mixture.     

Biosorption of heavy metal ions from aqueous solution by red macroalgae

Biosorption is an effective process for the removal and recovery of heavy metal ions from aqueous solutions. The biomass of marine algae has been reported to have high biosorption capacities for a number of heavy metal ions. In this study, four species of red seaweeds Corallina mediterranea, Galaxaura oblongata, Jania rubens and Pterocladia capillacea were examined to remove Co(II), Cd(II), Cr(III) and Pb(II) ions from aqueous solution. The experimental parameters that affect the biosorption process such as pH, contact time and biomass dosage were studied. The maximum biosorption capacity of metal ions was 105.2mg/g at biomass dosage 10 g/L, pH 5 and contact time 60 min. The biosorption efficiency of algal biomass for the removal of heavy metal ions from industrial wastewater was evaluated for two successive cycles. Galaxaura oblongata biomass was relatively more efficient to remove metal ions with mean biosorption efficiency of 84%. This study demonstrated that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for lowering the heavy metal pollution in the environment.     

Effect of pH on solar photocatalytic reduction and deposition of Cu(II), Ni(II), Pb(II) and Zn(II): speciation modeling and reaction kinetics

The present study is targeted on the effect of pH on solar photocatalytic removal of metal ions from wastewater. Photoreductive deposition and dark adsorption of metal ions Cu(II), Ni(II), Pb(II) and Zn(II), using solar energy irradiated TiO(2), has been investigated at pH values 2, 4, 7, 8 and 10. Modeling of metal species at the studied pH values has been performed and speciation is used as a tool for discussing the photodeposition. The decreasing order of metal deposition at pH 2 and 4 was found to be Pb(II)>Cu(II)>Ni(II) congruent with Zn(II). In the neutral and alkaline pH conditions (pH 7, 8 and 10) the order was Cu(II)>Zn(II)>Ni(II)>Pb(II).     

Enhanced biosorption of nickel(II) ions by silica-gel-immobilized waste biomass: biosorption characteristics in batch and dynamic flow mode

Batch and dynamic flow biosorption studies were carried out using the waste biomass entrapped in silica-gel matrix for the removal of nickel(II) ions from synthetic solutions and real wastewater. Batch biosorption conditions were examined with respect to initial pH, S/L ratio, contact time, and initial nickel ion concentration. Zeta potential measurements showed that immobilized biosorbent was negatively charged in the pH range of 3.0-8.0. The immobilized biomass was found to possess relatively high biosorption capacity (98.01 mg g(-1)), and biosorption equilibrium was established in a short time of operation (5 min). The equilibrium data were followed by Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models. Scanning electron microscope analysis was used to screen the changes on the surface structure of the waste biomass after immobilization and nickel(II) biosorption. Sorbent-sorbate interactions were confirmed by Fourier transform infrared spectroscopy. The applicability of sorbent system was investigated in a continuous mode, and column studies were performed under different flow rate, column size, and biosorbent dosage. Also, the proposed sorbent system was successfully used to remove the nickel ions from industrial wastewater in dynamic flow treatment mode. The results showed that silica-immobilized waste biomass was a low-cost promising sorbent for sequester of nickel(II) ions from synthetic and real wastewater.