Biological treatment of highly contaminated acid mine drainage in batch reactors: Long-term treatment and reactive mixture characterization

Passive bioreactors involving sulphate-reducing bacteria (SRB) are a practical alternative technology to treat acid mine drainage (AMD). Careful selection of the organic carbon source is important to ensure performance and long-term efficiency of the treatment. However, a rigorous and methodical characterization to predict the biodegradability of organic substrates by SRB still needs to be investigated. In the present study, four natural organic materials were thoroughly characterized to assess their ability to serve as substrates and to find a parameter that links organic carbon sources with their biodegradability. Three reactive mixtures were then comparatively evaluated for their performance to treat a highly contaminated AMD in long-term (152 days) batch experiments. All three mixtures were successful for sulphate reduction and metal (Fe, Ni, Cd, Zn, and Mn) removal (91.8-99.8%). Higher efficiencies were observed in the reactors with 30% (w/w) cellulosic wastes (maple wood chips and sawdust) which decreased sulphate concentrations from 5500 mg/L to <1mg/L, than in reactors with 2-3% cellulosic wastes, where final sulphate concentrations were in the range 2000-2750 mg/L. Organic material characterization indicated that higher C/N ratios, chemical oxygen demand (COD)/SO(4)(2-) ratios and dissolved organic carbon (DOC)/SO(4)(2-) ratios were associated with better sulphate-reducing conditions and metal removal. This work suggests that C/N and DOC/SO(4)(2-) ratios considered together are key parameters to assess the biodegradability of natural organic wastes under sulphate-reducing conditions.     

Use of response surface methodology (RSM) in the evaluation of growth and copper(II) bioaccumulation properties of Candida utilis in molasses medium

The influential factors on simultaneous growth and copper(II) bioaccumulation by growing cells of Candida utilis yeast under various ambient conditions, such as changing concentrations of molasses sucrose and copper(II) were tested. The highest growth rate of 0.133 h(-1) was obtained at an initial sucrose concentration of 15 g l(-1) in absence of copper(II). For each constant sucrose concentration chosen between 5 and 15 g l(-1), the increase in initial copper(II) concentration up to 500 mg l(-1) resulted in a decrease in the percentage uptake of copper(II) and moreover all copper(II) concentrations tested inhibited the yeast growth. On the other hand, at each constant copper(II) concentration studied, both the growth and copper(II) uptake yield enhanced with raising sucrose concentration up to 15 g l(-1). Maximum uptake yield of 34.2% was observed in 15 g l(-1) sucrose and 50 mg l(-1) copper(II) containing growth medium. The binary effects of initial sucrose and copper(II) concentrations on the specific growth rate and copper(II) uptake yield of yeast were analyzed by experimental design method and two model equations for predicting the growth rate and copper(II) uptake yield of yeast due to arbitrarily chosen sucrose and copper(II) concentrations were developed by using response surface methodology (RSM).     

Removal of arsenite from water by synthetic siderite: behaviors and mechanisms

Synthetic siderite has been used as adsorbent for As(III) removal in this study. Effects of contact time, temperature, pH, co-existing anions on As(III) adsorption were intensively investigated. Adsorption mechanisms were also studied using the X-ray absorption technique. Results show that the maximum adsorption capacity is up to 9.98 mg g(-1) at 25°C at a siderite dosage of 2 g L(-1). Adsorption kinetics agrees with the Lagergren pseudo-second order model. Arsenic(III) adsorption can be better described by Langmuir isotherm model for As(III) adsorption at 55°C, indicating that the coverage of the adsorption sites is in the form of monolayer, although Freundlich isotherm yields a better fit to the experimental data at 25, 35 and 45°C. Thermodynamic study indicates that As(III) adsorption on the synthetic siderite is spontaneous and endothermic in nature. The adsorption capacity is enhanced with the increase in reaction temperature. The adsorption is independent on solution pH between 3.0 and 9.6. The presence of NO(3)(-), SO(4)(2-), PO(4)(3-) or SiO(3)(2-) with element concentrations less than 20 mg L(-1) does not have adverse effect on As(III) adsorption. XANES spectra indicate that As mainly occurs as As(V) in the As adsorbed-materials, and the fraction of oxidized As(III) increases with the decrease in As(III) concentration. The formation of Fe hydroxide minerals (such as lepidocrocite and goethite) followed by As(III) oxidation and adsorption is shown to be the main mechanism of As(III) removal by the synthetic siderite.     

Effects of tri-valent (Cr(III)) and hexa-valent (Cr(VI)) chromium on the growth of activated sludge

The effects of Cr(VI) and Cr(III) species on the activated sludge growth rate have been assessed for a batch growth system, for a range of chromium concentration between 0 and 320 mg l(-1). Cr(VI) was found to stimulate microbial growth for concentrations up to about 25 mg l(-1), exhibiting maximum growth stimulation at 10 mg l(-1), whilst the lethal dose was found to be between 80 and 160 mg l(-1). On the other hand, Cr(III) was also found to stimulate microbial growth for concentrations up to about 15 mg l(-1), (with a maximum stimulation concentration at 10 mg l(-1)), whilst the lethal dose was found to lie between 160 and 320 mg l(-1). The results indicate that Cr(VI) is more toxic to biomass at relatively high concentrations (higher than 70 mg l(-1)) whilst it has a more pronounced growth stimulation effect at relatively smaller concentrations (less than 25 mg l(-1)), compared with Cr(III).     

Characterization of arsenic (V) and arsenic (III) in water samples using ammonium molybdate and estimation by graphite furnace atomic absorption spectroscopy

Arsenic (V) is known to form heteropolyacid with ammonium molybdate in acidic aqueous solutions, which can be quantitatively extracted into certain organic solvents. In the present work, 12-molybdoarsenic acid extracted in butan-1-ol is used for quantification of As (V). Total arsenic is estimated by converting arsenic (III) to arsenic (V) by digesting samples with concentrated nitric acid before extraction. Concentration of As (III) in the sample solutions could be calculated by the difference in total arsenic and arsenic (V). The characterization of arsenic was carried out by GFAAS using Pd as modifier. Optimization of the experimental conditions and instrumental parameters was investigated in detail. Recoveries of (90-110%) were obtained in the spiked samples. The detection limit was 0.2 microg l(-1). The proposed method was successfully applied for the determination of trace amount of arsenic (III) and arsenic (V) in process water samples.     

Effects of adsorbent dose, its particle size and initial arsenic concentration on the removal of arsenic, iron and manganese from simulated ground water by Fe3+ impregnated activated carbon

This paper presents the observations of the study on arsenic removal from a contaminated ground water (simulated) by adsorption onto Fe³⁺ impregnated granular activated carbon (GAC-Fe). Fe²⁺, Fe³⁺ and Mn²⁺ have also been considered along with arsenic species in the water sample. Similar study has also been done with untreated granular activated carbon (GAC) for comparison. The effects of adsorbent dose, particle size of adsorbent and initial arsenic concentration on the removal of As(T), As(III), As(V), Fe²⁺, Fe³⁺ and Mn²⁺ have been discussed. Under the experimental conditions, the optimum adsorbent doses for GAC-Fe and GAC have been found to be 8 g/l and 24 g/l, respectively with an agitation time of 15 h. Particle size of the adsorbents (both GAC and GAC-Fe) has shown negligible effect on the removal of arsenic and Fe species. However, for Mn removal the effect of adsorbent particle size is comparatively more. Percentage removal of As(T), As(V) and As(III) increase with the decrease in initial arsenic concentration (As₀). However, the increase in percentage removal of all the arsenic species with decrease in As₀ are less for higher value of As₀ (3000–500 ppb) than those of the lower value of As₀ (500–10 ppb). The % removal of As(T), As(III), As(V), Fe, and Mn were 95%, 92.4%, 97.6%, 99% and 41.2%, respectively when 8 g/l GAC-Fe was used at the As₀ value of 200 ppb. However, for GAC these values were 55.5%, 44%, 71%, 98% and 97%. The pH and temperature of the study were 7 ± 0.1 and 30 ± 1 °C, respectively.     

Adsorption characteristics of As(V) on iron-coated zeolite

The sorption characteristics of arsenic(As(V)) on iron-coated zeolite (ICZ) were investigated through batch and column studies. As(V) was completely removed within 30 min in a concentration of 2mg/l, with a 100g/l dose of ICZ. Optimum dose of ICZ was 33.3g/l at a concentration of 20.12 mg/l and the effect of solution pH was negligible at a pH range of 3.0相似文献   

Synthesis,characterization and kinetic of a surfactant-modified bentonite used to remove As(III) and As(V) from aqueous solution

In this study, organobentonites were prepared by modification of bentonite with various cationic surfactants, and were used to remove As(V) and As(III) from aqueous solution. The results showed that the adsorption capacities of bentonite modified with octadecyl benzyl dimethyl ammonium (SMB3) were 0.288 mg/g for As(V) and 0.102 mg/g for As(III), which were much higher compared to 0.043 and 0.036 mg/g of un-modified bentonite (UB). The adsorption kinetics were fitted well with the pseudo-second-order model with rate constants of 46.7 × 10⁻³ g/mg h for As(V) and 3.1 × 10⁻³ g/mg h for As(III), respectively. The maximum adsorption capacity of As(V) derived from the Langmuir equation reached as high as 1.48 mg/g, while the maximum adsorption capacity of As(III) was 0.82 mg/g. The adsorption of As(V) and As(III) was strongly dependent on solution pH. Addition of anions did not impact on As(III) adsorption, while they clearly suppressed adsorption of As(V). In addition, this study also showed that desorbed rates were 74.61% for As(V) and 30.32% for As(III), respectively, after regeneration of SMB3 in 0.1 M HCl solution. Furthermore, in order to interpret the proposed absorption mechanism, both SMB3 and UB were extensively characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) analyses.     

Toxic effects of dissolved heavy metals on Desulfovibrio vulgaris and Desulfovibrio sp. strains

Biological treatment of metal-containing wastewaters with sulphate-reducing bacteria (SRB) is an attractive technique for the bioremediation of this kind of medium. In order to design a suitable engineering process to address this environmental problem, it is crucial to understand the inhibitory effect of dissolved heavy metals on these bacteria. Batch studies were carried out to evaluate the toxic effects of several heavy metal ions [Cr(III), Cu(II), Mn(II), Ni(II) and Zn(II)] on two cultures of SRB (Desulfovibrio vulgaris and Desulfovibrio sp.). The experimental data indicate that SRB show different responses to each metal. At the highest metal concentration tolerated for each metal, the precipitation levels for D. vulgaris were as follows: 24.7%-15 ppm Cr(III), 45%-4 ppm Cu(II), 60%-10 ppm Mn(II), 96%-8.5 ppm Ni(II) and 9%-20 ppm Zn(II). The corresponding values for Desulfovibrio sp. were: 25.5%-15 ppm Cr(III), 71%-4 ppm Cu(II), 66.2%-10 ppm Mn(II), 96.1%-8.5 ppm Ni(II) and 93%-20 ppm Zn(II). Results obtained in batch studies will be taken into account for the subsequent design of a sulphate-reducing bioreactor to reduce levels of heavy metals present in different types of contaminated media.     

Adsorptive removal of As(V) and As(III) from water by a Zr(IV)-loaded orange waste gel

Orange waste, produced during juicing has been loaded with zirconium(IV) so as to examine its adsorption behavior for both As(V) and As(III) from an aquatic environment. Immobilization of zirconium onto the orange waste creates a very good adsorbent for arsenic. Adsorption kinetics of As(V) at different concentrations are well described in terms of pseudo-second-order rate equation with respect to adsorption capacity and correlation coefficients. Arsenate was strongly adsorbed in the pH range from 2 to 6, while arsenite was strongly adsorbed between pH 9 and 10. Moreover, equimolar (0.27 mM) addition of other anionic species such as chloride, carbonate, and sulfate had no influence on the adsorption of arsenate and arsenite. The maximum adsorption capacity of the Zr(IV)-loaded SOW gel was evaluated as 88 mg/g and 130 mg/g for As(V) and As(III), respectively. Column adsorption tests suggested that complete removal of arsenic was achievable at up to 120 Bed Volumes (BV) for As(V) and 8 0BV for As(III). Elution of both arsenate and arsenite was accomplished using 1 M NaOH without any leakage of the loaded zirconium. Thus this efficient and abundant bio-waste could be successfully employed for the remediation of an aquatic environment polluted with arsenic.     

Speciation of dissolved inorganic arsenic by diffusive gradients in thin films: selective binding of AsIII by 3-mercaptopropyl-functionalized silica gel

A diffusive gradients in thin films (DGT) technique for selectively measuring As(III) utilizes commercially available 3-mercaptopropyl-functionalized silica gel. Deployment of the new technique alongside the Metsorb-DGT for total inorganic arsenic allows the calculation of As(III) directly and As(V) by difference. Uptake of As(III) by mercapto-silica was quantitative and elution with a mixture of 1 mol L(-1) HNO(3) and 0.01 mol L(-1) KIO(3) gave a recovery of 85.6 ± 1.7%. DGT validation experiments showed linear accumulation of As(III) over time (R(2) > 0.998). Accumulation was unaffected by varying ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) and pH (3.5-8.5). Deployment of mercapto-silica DGT and Metsorb DGT in seawater spiked with As(III) and As(V) demonstrated the ability of the combined approach to accurately quantify both species in the presence of potential competing ions. Ferrihydrite DGT, which has been previously reported for the measurement of total inorganic arsenic, was evaluated in seawater and shown to underestimate both As(III) and As(V) at longer deployment times (72 h). Reproducibility of the new mercapto-silica DGT technique was good (relative standard deviations < 9%), and the average method detection limit was sufficiently low to allow quantification of ultratrace concentrations of As(III) (0.03 μg L(-1); 72 h deployment).     

Oxidation of arsenic bearing fly ash as pretreatment before solidification.

When a waste fly ash, containing large amounts of As(2)O(3), is solidified using cement and lime, the arsenic concentration in the leachate (extraction test DIN 38 414 S4) is determined by the solubility of CaHAsO(3) and can be lowered to a value of ca. 5 mg/l, in a saturated solution of Ca(OH)(2). One of the criteria for landfilling of hazardous waste is, however, that the arsenic concentration in the leachate must be lower than 1 mg/l. In this paper, it is shown that oxidation of the waste before solidification, whereby As(III) is oxidised to As(V) using H(2)O(2), lowers the leaching of arsenic, and other contaminants, from the solidified product. With the speciation program MINTEQA2, it is calculated that the solubility of As(V) in the presence of a pure Ca(3)(AsO(4))(2) precipitate is lower than the solubility of As(III) in the presence of a pure CaHAsO(3) precipitate. The arsenic concentration in the presence of both a Ca(OH)(2) and a Ca(3)(AsO(4))(2) precipitate can even be lowered to 0.47 mg/l (pH 12.5). The As concentration in the leachate of the extraction test on an oxidised S/S sample was indeed lowered to ca. 0.5 mg/l, which is a reduction by a factor of 10 compared to the concentration of ca. 5 mg/l, obtained in the leachate of the extraction test on a non-oxidised S/S sample. This is in very good agreement with the calculated value of 0.47 mg/l. Also, the pretreatment decreased the cumulative fraction of arsenic released over the entire test period of a semi-dynamic leach test by a factor of 7. At all times during the test, the As concentration did not exceed the norm of 1 mg/l.     

Arsenic adsorption by polyvinyl pyrrolidone K25 coated cassava peel carbon from aqueous solution

Sorption of arsenic from aqueous solution was carried out using polyvinyl pyrrolidone K25 coated cassava peel carbon (PVPCC). Batch experiments were conducted to determine the effect of contact time, initial concentration, pH and desorption. Batch sorption data's were fitted to Lagergren kinetic studies. Column studies were also conducted using PVPCC as adsorbent. The optimized flow rate of 2.5 mL min(-1) and bed height 10 cm were used to determine the effect of metal ion concentration on removal of As(V). BDST model was applied to calculate the adsorption capacity (N(0)) of column. The N(0) value of 2.59 x 10(-5), 4.21 x 10(-5), 4.05 x 10(-5), 4.26 x 10(-5) and 3.2 x 10(-5) mg g(-1) were obtained for 0.5, 1.0, 1.5, 2.0 and 2.5 mg L(-1) of As(V), respectively. The batch sorption proved to be more efficient than the column sorption. The sorption of As(V) and the nature of the adsorbent was examined by Fourier transmission infrared spectroscopy (FTIR) and X-ray diffraction (XRD) studies, respectively.     

Arsenic removal by a waste metal (hydr)oxide entrapped into calcium alginate beads

In this work, a solid waste material from an electroplating industrial plant has been investigated for As(III) and As(V) sorption. This sorbent, a mixture of mainly Fe(III) and Ni(II) (hydr)oxides, has been used both in its native form and entrapped in calcium alginate. The effect of sorbent concentration in the gel bead, solution pH, contact time and As(III) and As(V) concentration on sorption has been studied. Furthermore the effect of the gel matrix has been investigated. A 10% (w/v) of (hydr)oxide in the gel beads was found to provide both spherical beads shape and good sorption performance. Solution pH was found to exert a stronger influence in As(V) than in As(III) sorption. The optimum pH range resulted to be within 5-10 for As(III) and within 6-9 for As(V). Taking into account these results, pH 8 was chosen for further sorption experiments. Equilibrium was reached after 48 h contact time for the studied systems. Kinetics data of both As(III) and As(V) onto native (hydr)oxide (O) and entrapped in calcium alginate beads (10% O-CA) were successfully modelled according to pseudo-first and pseudo-second order equations. Sorption equilibrium data were evaluated by the Langmuir isotherm model and the maximum capacity q(max) were 77.4 and 126.5 mg g(-1) for As(III) on O and 10% O-CA, and 26.8 and 41.6 mg g(-1) for As(V) on O and 10% O-CA, respectively. The entrapment of the (hydr)oxide in a calcium alginate gel matrix improved the As(III) and As(V) sorption by 60%.     

Asymmetric Redox-Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic

Advanced redox-polymer materials offer a powerful platform for integrating electroseparations and electrocatalysis, especially for water purification and environmental remediation applications. The selective capture and remediation of trivalent arsenic (As(III)) is a central challenge for water purification due to its high toxicity and difficulty to remove at ultra-dilute concentrations. Current methods present low ion selectivity, and require multistep processes to transform arsenic to the less harmful As(V) state. The tandem selective capture and conversion of As(III) to As(V) is achieved using an asymmetric design of two redox-active polymers, poly(vinyl)ferrocene (PVF) and poly-TEMPO-methacrylate (PTMA). During capture, PVF selectively removes As(III) with exceptional uptake (>100 mg As/g adsorbent), and during release, synergistic electrocatalytic oxidation of As(III) to As(V) with >90% efficiency can be achieved by PTMA, a radical-based redox polymer. The system demonstrates >90% removal efficiencies with real wastewater and concentrations of arsenic as low as 10 ppb. By integrating electron-transfer through the judicious design of asymmetric redox-materials, an order-of-magnitude energy efficiency increase can be achieved compared to non-faradaic, carbon-based materials. The study demonstrates for the first time the effectiveness of asymmetric redox-active polymers for integrated reactive separations and electrochemically mediated process intensification for environmental remediation.     

A combined treatment approach using Fenton's reagent and zero valent iron for the removal of arsenic from drinking water

Studies on the development of an arsenic remediation approach using Fenton's reagent (H2O2 and Fe(II)) followed by passage through zero valent iron is reported. The efficiency of the process was investigated under various operating conditions. Potable municipal water and ground water samples spiked with arsenic(III) and (V) were used in the investigations. The arsenic content was determined by ICP-QMS. A HPLC-ICPMS procedure was used for the speciation and determination of both As(III) and (V) in the processed samples, to study the effectiveness of the oxidation step and the subsequent removal of the arsenic.The optimisation studies indicate that addition of 100 microl of H2O2 and 100 mg of Fe(II) (as ferrous ammonium sulphate) per litre of water for initial treatment followed by passing through zero valent iron, after a reaction time of 10 min, is capable of removing arsenic to lower than the US Environmental Protection Agency (EPA) guideline value of 10 microg/l, from a starting concentration of 2 mg/l of As(III). Using these suggested amounts, several experiments were carried out at different concentrations of As(III). Residual hydrogen peroxide in the processed samples can be eliminated by subsequent chlorination, making the water, thus, processed, suitable for drinking purposes. This approach is simple and cost effective for use at community levels.     

A laboratory study for the treatment of arsenic, iron, and manganese bearing ground water using Fe(3+) impregnated activated carbon: effects of shaking time, pH and temperature

This paper deals with the experimental investigation related to removal of arsenic from a simulated contaminated ground water by the adsorption onto Fe(3+) impregnated granular activated carbon (GAC-Fe) in presence of Fe(2+), Fe(3+), and Mn(2+). Similar study has also been done with granular activated carbon (GAC) for comparison. The effects of shaking time, pH, and temperature on the percentage removal of As(T), As(III), As(V), Fe(2+), Fe(3+), and Mn have been discussed. The shaking time for optimum removal of arsenic species has been noted as 8h for GAC-Fe and 12h for GAC, respectively. As(T) removal was less affected by the change in pH within the pH range of 2-11. Maximum removal of As(V) and As(III) was observed in the pH range of 5-7 and 9-11, respectively, for both the adsorbents. Under the experimental conditions at 30 degrees C, the optimum removal of As(T), As(III), As(V), Fe, and Mn are 95.5%, 93%, 98%, 100%, and 41%, respectively, when GAC-Fe is used. For GAC these values are 56%, 41%, 71%, 99%, and 98%. The adsorbent dose (AD) and its particle size (PS) for both GAC and GAC-Fe were 30 g/l and 125-150 mum, respectively. The initial arsenic concentration in the synthetic water sample was 200 ppb.     

Effect of carbon dioxide and bicarbonate as inorganic carbon sources on growth and adaptation of autohydrogenotrophic denitrifying bacteria

Acclimation of autohydrogenotrophic denitrifying bacteria using inorganic carbon source (CO(2) and bicarbonate) and hydrogen gas as electron donor was performed in this study. In this regard, activated sludge was used as the seed source and sequencing batch reactor (SBR) technique was applied for accomplishing the acclimatization. Three distinct strategies in feeding of carbon sources were applied: (I) continuous sparging of CO(2), (II) bicarbonate plus continuous sparging of CO(2), and (III) only bicarbonate. The pH-reducing nature of CO(2) showed an unfavorable impact on denitrification rate; however bicarbonate resulted in a buffered environment in the mixed liquor and provided a suitable mean to maintain the pH in the desirable range of 7-8.2. As a result, bicarbonate as the only carbon source showed a faster adaptation, while carbon dioxide as the only carbon source as well as a complementary carbon source added to bicarbonate resulted in longer acclimation period. Adapted hydrogenotrophic denitrifying bacteria, using bicarbonate and hydrogen gas in the aforementioned pH range, caused denitrification at a rate of 13.33 mg NO(3)(-)-N/g MLVSS/h for degrading 20 and 30 mg NO(3)(-)-N/L and 9.09 mg NO(3)(-)-N/g MLVSS/h for degrading 50mg NO(3)(-)-N/L.     

First-step nucleation growth dependence of InAs/InGaAs/InP quantum dot formation in two-step growth

First-step nucleation growth has an important impact on the two-step growth of high-quality mid-infrared emissive InAs/InGaAs/InP quantum dots (QDs). It has been found that an optimized growth rate for first-step nucleation is critical for forming QDs with narrow size distribution, high dot density and high crystal quality. High growth temperature has an advantage in removing defects in the QDs formed, but the dot density will be reduced. Contrasting behavior in forming InAs QDs using metal-organic vapor phase epitaxy (MOVPE) by varying the input flux ratio of group-V versus group-III source (V/III ratio) in the first-step nucleation growth has been observed and investigated. High-density, 2.5 × 10(10)?cm(-2), InAs QDs emitting at>2.15?μm have been formed with narrow size distribution, ～1?nm standard deviation, by reducing the V/III ratio to zero in first-step nucleation growth.