Removal and recovery of Cr(VI) from wastewater by maghemite nanoparticles

Hexavalent chromium existing in the effluent is a major concern for the metal-processing plant. In this study, a new method combining nanoparticle adsorption and magnetic separation was developed for the removal and recovery of Cr(VI) from wastewater. The nanoscale maghemite was synthesized, characterized, and evaluated as adsorbents of Cr(VI). Various factors influencing the adsorption of Cr(VI), e.g., pH, temperature, initial concentration, and coexisting common ions were studied. Adsorption reached equilibrium within 15 min and was independent of initial Cr concentration. The maximum adsorption occurred at pH 2.5. The adsorption data were analyzed and fitted well by Freundlich isotherm. Cr(VI) adsorption capacity of maghemite nanoparticles was compared favorably with other adsorbents like activated carbon and clay. Competition from common coexisting ions such as Na+, Ca2+, Mg2+, Cu2+, Ni2+, NO3-, and Cl- was ignorable, which illustrated the selective adsorption of Cr(VI) from wastewater. Regeneration studies verified that the maghemite nanoparticles, which underwent six successive adsorption-desorption processes, still retained the original metal removal capacity. In addition, the adsorption mechanisms were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopic techniques.     

Simultaneous adsorption and biodegradation processes in sequencing batch reactor (SBR) for treating copper and cadmium-containing wastewater

The application of simultaneous adsorption and biodegradation processes in the same reactor is known to be effective in the removal of both biodegradable and non-biodegradable contaminants in various kinds of wastewater. The objective of this study is to evaluate the efficacy of the two processes under sequencing batch reactor (SBR) operation in treating copper and cadmium-containing synthetic wastewater with powdered activated carbon (PAC) as the adsorbent. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in the ratio of 0.5: 3.5: 1.0: 0.75 :0.25 for a cycle time of 6 h. In the presence of 10 mg/L Cu(II) and 30 mg/L Cd(II), respectively, the average COD removal efficiencies were above 85% with the PAC dosage in the influent solution at 143 mg/L compared to around 60% without PAC addition. Copper(II) was found to exert a more pronounced inhibitory effect on the bioactivity of the microorganisms compared to Cd(II). It was observed that the combined presence of Cu(II) and Cd(II) did not exert synergistic effects on the microorganisms. Kinetic study conducted for the REACT period showed that the addition of PAC had minimized the inhibitory effect of the heavy metals on the bioactivity of microorganisms.     

Enhanced chitosan beads-supported Fe-nanoparticles for removal of heavy metals from electroplating wastewater in permeable reactive barriers

The removal of heavy metals from electroplating wastewater is a matter of paramount importance due to their high toxicity causing major environmental pollution problems. Nanoscale zero-valent iron (NZVI) became more effective to remove heavy metals from electroplating wastewater when enhanced chitosan (CS) beads were introduced as a support material in permeable reactive barriers (PRBs). The removal rate of Cr (VI) decreased with an increase of pH and initial Cr (VI) concentration. However, the removal rates of Cu (II), Cd (II) and Pb (II) increased with an increase of pH while decreased with an increase of their initial concentrations. The initial concentrations of heavy metals showed an effect on their removal sequence. Scanning electron microscope images showed that CS-NZVI beads enhanced by ethylene glycol diglycidyl ether (EGDE) had a loose and porous surface with a nucleus-shell structure. The pore size of the nucleus ranged from 19.2 to 138.6 μm with an average aperture size of around 58.6 μm. The shell showed a tube structure and electroplating wastewaters may reach NZVI through these tubes. X-ray photoelectron spectroscope (XPS) demonstrated that the reduction of Cr (VI) to Cr (III) was complete in less than 2 h. Cu (II) and Pb (II) were removed via predominant reduction and auxiliary adsorption. However, main adsorption and auxiliary reduction worked for the removal of Cd (II). The removal rate of total Cr, Cu (II), Cd (II) and Pb (II) from actual electroplating wastewater was 89.4%, 98.9%, 94.9% and 99.4%, respectively. The findings revealed that EGDE-CS-NZVI-beads PRBs had the capacity to remediate actual electroplating wastewater and may become an effective and promising technology for in situ remediation of heavy metals.     

Use of porous volcanic rocks for the adsorptive removal of copper

Low‐cost adsorbents, pumice (VPum) and scoria (VSco) were investigated for the removal of Cu(II) as function of various parameters. Batch experiments were conducted to evaluate the influence of Cd(II) and Ni(II) on the adsorptive removal of Cu(II) from aqueous solutions. Kinetic data showed a trend of fast removal at initial stages, thereby achieving maximum adsorption after 1 h agitation. The adsorption process well explained by pseudo‐second‐order kinetics for both adsorbents. Adsorption capacity were found 1.432 and 1.015 mg/g using VPum and VSco, respectively. This work showed the promising nature of pumice and scoria to effectively remove copper from water.     

Removal of metal ions by modified Pinus radiata bark and tannins from water solutions

Pinus radiata bark and tannins, chemically modified with an acidified formaldehyde solution were used for removing metal ions from aqueous solutions and copper mine acidic residual waters. The adsorption ability to different metal ions [V(V), Re(VII), Mo(VI), Ge(IV), As(V), Cd(II), Hg(II), Al(III), Pb(II), Fe(II), Fe(III), Cu(II)] and the factors affecting their removal from solutions were investigated. Effect of pH on the adsorption, desorption, maximum adsorption capacity of the adsorbents, and selectivity experiments with metal ion solutions and waste waters from copper mine were carried out. The adsorbents considerably varied in the adsorption ability to each metal ion. The adsorption depends largely upon the pH of the solution. Modified tannins showed lower adsorption values than the modified bark. For the same adsorbent, the maximum capacity at pH 3 for the different ions were very different, ranging for modified bark from 6.8 meqg⁻¹ for V to 0.93 meqg⁻¹ for Hg. Waste waters were extracted with modified bark as adsorbent and at pH 2. The ions Cu(II) (35.2 mgL⁻¹), Fe(III) (198 mgL⁻¹), Al(III) (83.5 mgL⁻¹) and Cd(II) (0.15 mgL⁻¹) were removed in 15.6%, 46.9%, 83.7% and 3.3%, respectively, by using 1 g of adsorbent/10 mL of waste water. In general, a continuous adsorption on a packed column gave higher adsorbed values than those observed in the batchwise experiment.     

Removal of estrone and 17beta-estradiol from water by adsorption

Endocrine disrupting chemicals (EDCs) are the focus of current environment concern, as they can cause adverse health effects in an intact organism, or its progeny, subsequent to endocrine function. The paper reports on the removal of estrone (E1) and 17beta-estradiol (E2) from water through the use of various adsorbents including granular activated carbon (GAC), chitin, chitosan, ion exchange resin and a carbonaceous adsorbent prepared from industrial waste. The results show that the kinetics of adsorption were adsorbent and compound-dependent, with equilibration being reached within 2 h for a waste-derived carbonaceous adsorbent to 71 h for an ion-exchange resin for E1, and within 7 h for the waste-derived carbonaceous adsorbent to 125 h for GAC for E2. Of all the adsorbents tested, the carbonaceous adsorbent showed the highest adsorption capacity, with a maximum adsorption constant of 87500 ml/g for E1 and 116000 ml/g for E2. The GAC also had a very high adsorption capacity for the two compounds, with a maximum adsorption constant of 9290 ml/g for E1 and 12200 ml/g for E2. The effects of some fundamental environmental parameters including adsorbent concentration, pH, salinity and the presence of humic acid and surfactant on adsorption were studied. The results show that adsorption capacity of activated carbon was decreased with an increase in adsorbent concentration and by the presence of surfactant and humic acid. The results have demonstrated excellent performance of a waste derived adsorbent in removing E1 and E2 from water, and indicated the potential of converting certain solid waste into useful adsorbents for pollution-control purposes.     

Heavy metal removal with Mexican clinoptilolite: multi-component ionic exchange

This paper describes the interactions of Pb(II), Cd(II), and Cr(VI) competing for ion-exchange sites in naturally occurring clinoptilolite. Dissolved Pb and Cd were effectively removed within 18 h in batch reactors, with higher removal efficiencies (> 95%) in the acidic pH range. The presence of Cr(VI), which can interact with these metals to form anionic complexes, significantly diminished the Pb and Cd removal efficiencies. A decrease in the efficiency of clinoptilolite to remove Pb was also observed in the high (> or = 10) pH range. This was attributed to the formation of anionic hydroxo-complexes with little affinity for cationic ion exchange sites. Pb outcompeted Cd for ion exchange sites in a flow-through column packed with clinoptilolite (contact time = 10 s). The preferential removal of Pb in column, but not in batch reactors, reflects that competitive retention can be affected by contact time because diffusion kinetics may influence the removal efficiency to a greater extent than equilibrium partitioning. Phenol, which was tested as a representative organic co-contaminant, slightly hindered heavy metal removal in batch reactors. This was attributed to the formation of organometallic complexes that cannot penetrate the zeolite exchange channels. Altogether, these results show that natural zeolites hold great potential to remove cationic heavy metal species from industrial wastewater. Nevertheless, process efficiency can be hindered by the presence of ligands that form complexes with reduced accessibility and/or affinity for ion exchange.     

Purification of chromium(VI) finishing wastewaters using calcined and uncalcined Mg-Al-CO3-hydrotalcite

The applicability of calcined and uncalcined hydrotalcite for the purification of industrial effluents has been studied using chromium finishing wastewaters. Using a batch method, the influence of the initial concentration of chromium (10-450mg/l), hydrotalcite (HT) dose (0.5-5g/l) and time (0.5-72h) has been evaluated. The process could be described by the Langmuir model and gave a maximum removal of chromium of 16.3mg Cr(VI)/g on uncalcined HT and 128mg Cr(VI)/g on calcined hydrotalcite (C-HT). Removal using the calcined product provided an effective system to treat chromium finishing wastewaters with the most stringent discharge limit for such industrial streams being achieved with between two and four consecutive removal cycles on C-HT at a dose of 2g/l.     

Hexavalent chromium removal from aqueous solution by adsorption on aluminum magnesium mixed hydroxide

A series of sols consisting of aluminum magnesium mixed hydroxide (AMH) nanoparticles with various Mg/Al molar ratios were prepared by coprecipitation. The use of AMH as adsorbent to remove Cr(VI) from aqueous solution was investigated. Adsorption experiments were carried out as a function of the Mg/Al molar ratio, pH, contact time, concentration of Cr(VI) and temperature. It was found that AMH with Mg/Al molar ratio 3 has the largest adsorption efficiency due to the smallest average particle diameter and the highest zeta potential; AMH was particularly effective for the Cr(VI) removal in a pH range from acid to slightly alkaline, even though the most effective pH range was between 2.5 and 5.0. The adsorption of Cr(VI) on AMH reached equilibrium within 150 min. The saturated adsorption capacities of AMH for Cr(VI) were 105.3-112.0 mg/g at 20-40 °C. The interaction between the surface sites of AMH and the Cr(VI) ions may be a combination of both anion exchange and surface complexation. The pseudo-second-order model best described the adsorption kinetics of Cr(VI) onto AMH. The results showed that AMH can be used as a new adsorbent for Cr(VI) removal which has higher adsorption capacity and faster adsorption rate at pH values close to that at which pollutants are usually found in the environment.     

天然气液化厂站脱汞的探讨

分析了吸附脱汞和氧化型吸收剂的脱汞效果,吸附脱汞的吸附剂包括煤基活性炭、活性炭纤维、活性焦、钙基吸附剂、壳聚糖类吸附剂.介绍了天然气脱汞的国内外工程实例.     

A study of Cr(VI) and NH4+adsorption using greensand (glauconite) as a low‐cost adsorbent from aqueous solutions

This paper investigates the removal of Cr(VI) and NH⁴⁺ from aqueous solutions using greensand (glauconite). The effects of adsorbent dosage, contact time, initial Cr(VI) and NH⁴⁺ concentrations, and pH were investigated in batch experiments. The results show that these parameters influenced Cr(VI) and NH⁴⁺ removal using glauconite considerably. Pseudo‐first‐order, pseudo‐second‐order and intraparticle diffusion kinetic models were applied to explain the kinetic data, and the pseudo‐second‐order model achieved good agreement. The equilibrium isotherm data are coordinated with the Freundlich, Langmuir models, Temkin and Dubinin–Radushkevich; the Freundlich model proved most best suitable. The removal efficiency of Cr(VI) and NH₄⁺ were 12.21 mg/g (54% at pH 3) and 19.24 mg/g (77.08% at pH 7). All in all, the results showed that the adsorption process on glauconite could be used as an effective method for removing Cr(VI) and NH⁴⁺ from aqueous solutions.     

Biosorption of chromium(VI) from aqueous solutions by green algae Spirogyra species.

Biosorption of heavy metals is an effective technology for the treatment of industrial wastewaters. Results are presented showing the sorption of Cr(VI) from solutions by biomass of filamentous algae Spirogyra species. Batch experiments were conducted to determine the adsorption properties of the biomass and it was observed that the adsorption capacity of the biomass strongly depends on equilibrium pH. Equilibrium isotherms were also obtained and maximum removal of Cr(VI) was around 14.7 x 10(3) mg metal, kg of dry weight biomass at a pH of 2.0 in 120 min with 5 mg/l of initial concentration. The results indicated that the biomass of Spirogyra species is suitable for the development of efficient biosorbent for the removal and recovery of Cr(VI) from wastewater.     

Deploying a metal adsorbent in situ: a technique for indicating bioavailable Cd(II) in marine waters

This paper reports a study into the deployment of a metal adsorbent in situ to estimate bioavailable Cd(II) in marine waters. Eight adsorbents were screened in the laboratory to test their ability to accumulate Cd(II) from deionised water and artificial seawater, and an oxidised activated carbon was selected for further investigation. The adsorption isotherm at Cd(II) concentrations 0.16-38 microgl(-1) and at salinity 15 followed the Freundlich equation. The adsorbent was contained in nylon bags (pore size 35 microm) and dialysis tubes (membrane pore size 2 nm) to produce deployable devices and to investigate the effect of housing material on Cd(II) accumulation. The devices were tested in the laboratory and deployed at four field sites for up to 3 weeks. The adsorbent in the nylon bags reached equilibrium towards the end of this period and the measured contents were in good agreement with expected contents predicted from known seawater Cd(II) concentrations and the adsorption isotherm. The dialysis tubes accumulated significantly lower amounts of Cd(II) than the nylon bags, probably due to an initial lag as Cd(II) diffused into the dialysis bag and due to biofouling which reduced diffusion. The relationship between concentrations of Cd(II) accumulated by the mussels (indicating the bioavailable Cd(II) fraction) and the devices at different field sites could be described by the Freundlich model. The goodness of fit of this relationship was better for the dialysis tubes than the nylon bags. The adsorbent in the nylon bags may have collected small particles from seawater which affected the Cd(II) analysis. Both devices demonstrate potential as indicators of the relative bioavailable fraction of Cd(II) to Mytilus edulis in marine waters.     

The removal of chromium(VI) from dilute aqueous solution by activated carbon

The removal of chromium(VI) by activated carbon, filtrasorb 400, is brought by two major interfacial reactions: adsorption and reduction. Chemical factors such as pH and total Cr(VI) that affect the magnitude of Cr(VI) adsorption were investigated. The adsorption of Cr(VI) exhibits a peak value at pH 5–6. The particle size of carbon and the presence of cyanide species do not change the magnitude of chromium removal. The reduced Cr(VI), e.g. Cr(III) is less adsorbable than Cr(VI).The free energy of specific chemical interaction, ΔG^chem was computed by the Gouy-Chapman-Stern-Grahame model. The average values of ΔG^chem are −5.57 RT and −5.81RT, respectively, for Cr(VI) and CN. These values are significant enough to influence the overall magnitude of Cr(VI) and CN adsorption. Results also indicate that HCrO⁻₄ and Cr₂O²⁻₇ are the major Cr(VI) species involved in surface association.     

Removal of chromium (VI) from wastewater using bentonite-supported nanoscale zero-valent iron

Bentonite-supported nanoscale zero-valent iron (B-nZVI) was synthesized using liquid-phase reduction. The orthogonal method was used to evaluate the factors impacting Cr(VI) removal and this showed that the initial concentration of Cr(VI), pH, temperature, and B-nZVI loading were all importance factors. Characterization with scanning electron microscopy (SEM) validated the hypothesis that the presence of bentonite led to a decrease in aggregation of iron nanoparticles and a corresponding increase in the specific surface area (SSA) of the iron particles. B-nZVI with a 50% bentonite mass fraction had a SSA of 39.94 m²/g, while the SSA of nZVI and bentonite was 54.04 and 6.03 m²/g, respectively. X-ray diffraction (XRD) confirmed the existence of Fe⁰ before the reaction and the presence of Fe(II), Fe(III) and Cr(III) after the reaction. Batch experiments revealed that the removal of Cr (VI) using B-nZVI was consistent with pseudo first-order reaction kinetics. Finally, B-nZVI was used to remediate electroplating wastewater with removal efficiencies for Cr, Pb and Cu > 90%. Reuse of B-nZVI after washing with ethylenediaminetetraacetic acid (EDTA) solution was possible but the capacity of B-nZVI for Cr(VI) removal decreased by approximately 70%.     

Removal of textile basic dye from aqueous solutions using sawdust as bio‐adsorbent

The ability of low cost bio‐adsorbent sawdust to remove basic dye (methylene blue) from aqueous solution is investigated using it in two different forms: in raw form and in chemically treated (with sulphuric acid) form. The effect of contact time, dye concentration, adsorbent dose and the kinetics of adsorption were studied in batch experiments. At neutral pH and 4?gm/l of chemically activated and raw sawdust adsorbents, removal of 98.12% and 97.18% of methylene blue dye (at 100?mg/l concentration) from the aqueous solution, was the best result obtained during study. An average percentage removal difference of less than 5%, between two adsorbents was achieved under different conditions in the experiments. The data fit well in Freundlich isotherm.     

Removal of emerging contaminants of concern by alternative adsorbents

The effective removal of emerging contaminants of concern (ECCs) such as endocrine-disrupting chemicals, pharmaceutically active compounds, personal care products, and flame retardants is a desirable water treatment goal. In this study, one activated carbon, one carbonaceous resin, and two high-silica zeolites were studied to evaluate their effectiveness for the removal of an ECC mixture from lake water. Adsorption isotherm experiments were performed with a mixture of 28 ECCs at environmentally relevant concentrations (200–900 ng/L). Among the tested adsorbents, activated carbon was the most effective, and activated carbon doses typically used for taste and odor control in drinking water (<10 mg/L) were sufficient to achieve a 2-log removal for most of the tested ECCs. The carbonaceous resin was less effective than the activated carbon because this adsorbent had a smaller volume of pores in the size range required for the adsorption of many ECCs (6–9 Å). For the removal of ECC mixture constituents, zeolites were less effective than the carbonaceous adsorbents. Because zeolites contain pores of uniform size and shape, a few of the tested ECCs with matching pore size/shape requirements were well removed, but the adsorptive removal of others was negligible, even at zeolite doses of 100 mg/L. The results of this study demonstrate that effective adsorbents for the removal of a broad spectrum of ECCs from water should exhibit heterogeneity in pore size and shape and a large pore volume in the 6–9 Å size range.     

Studies on removal and recovery of Cr(VI) from electroplating wastes

Phosphate treated sawdust shows remarkable increase in sorption capacity of Cr(VI) as compared to untreated sawdust. The adsorption process is pH dependent. 100% adsorption of Cr(VI) was observed in the pH range <2 for the initial Cr(VI) concentration of 8–50 mg 1⁻¹. The effect of various adsorbent doses at pH 2 confirms Langmuir adsorption isotherms. 100% removal of Cr(VI) from synthetic waste as well as from electroplating waste containing 50 mg 1⁻¹ Cr(VI) was achieved by batch as well as by column processes. The adsorbed Cr(VI) on phosphate treated sawdust was recovered (87%) using 0.01 M sodium hydroxide.     

The use of indigenous coal reserves for the removal of lead(II) from the aquatic environment by adsorption

Activated carbon was prepared as an adsorbent from low cost Lakhra coal (LC) (Lignite grade) by chemical activation for the removal of Pb(II) from aqueous solution. The variables of pH, adsorbent dose, agitation time, ionic strength and temperature were investigated. The sorption process followed pseudo-first-order kinetics, intra-particle diffusion and Langmuir isotherm models. Evaluation of thermodynamic parameters affirmed the spontaneity of the process. The study also included the surface properties of activated Lakhra coal (ALC) by FTIR, scanning electron microscope and energy dispersive spectroscopy. The maximum Pb(II) removal capacity of ALC was 758?±?8?mg?g^?1 at 32?°C, approximately 300 times higher than without activation. This value was higher than other previously reported values. Thus, this study demonstrated that indigenous LC has excellent potential to be used as an economically feasible adsorbent after activation for the treatment of wastewater bearing Pb(II).     

Removal of heavy metals from aqueous solution by nonliving Ulva seaweed as biosorbent

The growth of dense green seaweed mats of Ulva spp. is an increasing problem in estuaries and coasts worldwide. The enormous amount of Ulva biomass thus becomes a troublesome waste disposal problem. On the other hand, it has been revealed that nonliving seaweed biomass, particularly brown seaweeds, has a high capacity for assimilating heavy metals. In this study, the possibility of using Ulva seaweed biomass as a biosorbent for the removal of heavy metals was examined. After processing, the biomass material was very easy to separate from the aqueous solution using a mesh. The sorption capacity of Cd on Ulva biomass increased upon pretreatment with alkali solution. The outstanding function of the biosorbent was demonstrated at around pH 8. On the basis of the Langmuir isotherms of Cd, Zn and Cu using the alkali-pretreated biomass, the parameters q(m) and b were determined to be within the narrow range of 60-90 mg/g and 0.03-0.04 L/mg, respectively, for each metal. Given the q(m) and b values, Ulva seaweed is a good biosorbent material for removing heavy metals. In an experiment using artificial wastewater containing Cd, Zn, Cu, Cr and Ni, it was possible to remove each metal simultaneously using Ulva biomass. Adsorption by Ulva biomass is effective for the removal of heavy metals from wastewater.