Biosorption of copper from aqueous solutions utilizing agricultural wastes

The purpose of this study was to determine the copper (Cu) biosorption capacities of several agricultural wastes from aqueous solutions. Samples of agricultural wastes were tested unaltered and after hydrochloric acid (HCl) treatment. Additional parameters tested include sample dose, contact time, particle size, mixing temperature, and the concentrations and pH of the Cu solutions. Desorption studies were performed to determine if the removed Cu could be recovered. In addition, tests were conducted to determine if the agricultural waste samples (AWS) could be reused for additional Cu biosorption cycles. The results of this study demonstrate a wide range of Cu biosorption proficiencies ranging from 0% to 100% removal. The parameters that resulted in higher Cu removal include higher pH and lower Cu solution concentration. Desorption results showed a 58% to 86% Cu recovery rate. Three of the five reused AWS were effective at removing Cu during subsequent trials. Therefore, these AWS types can be reused for additional Cu biosorption cycles. Hence, it is possible that using those AWS for metal treatment could reduce hazardous waste disposal inefficiencies and costs by avoiding disposing of spent AWS following each Cu biosorption cycle.     

Removing cadmium from aqueous solutions utilizing agricultural wastes

The purpose of this study was to determine the cadmium (Cd) biosorption capacities of several agricultural wastes from aqueous solutions. Samples were tested unaltered and after hydrochloric acid treatment. Additional parameters tested include sample dose, contact time, particle size, mixing temperature, and the concentrations and pH of the Cd solutions. Desorption studies were performed to determine if the removed Cd could be recovered. In addition, tests were conducted to determine if the agricultural waste samples (AWS) could be reused for additional Cd biosorption cycles. The results of this study demonstrate a wide range of Cd biosorption proficiencies ranging from 33 to 100% removal. The parameters that resulted in higher Cd removal include higher sample dose, higher pH, and lower Cd solution concentration. Desorption results showed a 36–56% Cd recovery rate. Reused AWS were effective at removing Cd during subsequent trials. Therefore, all AWS types tested in this study can be reused for additional Cd biosorption cycles. Hence, it is possible that using AWS for metal treatment could reduce hazardous waste disposal inefficiencies and costs by avoiding disposing of spent AWS following each Cd biosorption cycle.     

Sunflower stalk, an agricultural waste, as an adsorbent for the removal of lead and cadmium from aqueous solutions

Sunflower residue, an agricultural waste material for the removal of lead (Pb) and cadmium (Cd) from aqueous solutions were investigated using a batch method. Adsorbent was prepared by washing sunflower residue with deionized water until the effluent was colorless. Batch mode experiments were carried out as a function of solution pH, adsorbent dosage, initial concentration and contact time. The results indicated that the adsorbent showed good sorption potential and maximum metal removal was observed at pH 5. Within 150 min of operation about 97 and 87 % of Pb and Cd ions were removed from the solutions, respectively. Lead and Cd sorption curves were well fitted to the modified two-site Langmuir model. The adsorption capacities for Pb and Cd at optimum conditions were 182 and 70 mg g^?1, respectively. The kinetics of Pb and Cd adsorption from aqueous solutions were analyzed by fitting the experimental data to a pseudo-second-order kinetic model and the rate constant was found to be 8.42 × 10^?2 and 8.95 × 10^?2 g mg^?1 min^?1 for Cd and Pb, respectively. The results revealed that sunflower can adsorb considerable amount of Pb and Cd ions and thus could be an economical method for the removal of Pb and Cd from aqueous systems.     

Olive mill solid residues as heavy metal sorbent material: a preliminary study

Biosorption of heavy metals is an innovative and alternative technology to remove these pollutants from aqueous solutions using inactive and dead biomasses such as agricultural and industrial wastes, algae and bacteria. In this study olive mill solid residue was used as heavy metal adsorbent material for its wide availability as agricultural waste and also for its cellulosic matrix, rich of potential metal binding active sites. Preliminary studies concerned with the removal of different heavy metals (Hg, Pb, Cu, Zn and Cd), the effect of pre-treatments by water and n-hexane and the regeneration possibility. Olive mill solid residue resulted able to remove heavy metals from aqueous solutions with an affinity series reflecting the hydrolytic properties of the metallic ions, but also a particular affinity for copper. It can be supposed that biosorption phenomenon occur by a general ion exchange mechanism combined with a specific complexation reaction for copper ions. Water pre-treatment is sufficient to reduce COD release in the effluent according to the law limit, while n-hexane pre-treatment strongly reduces also the adsorption properties of this material. Experimental isotherms obtained under different operating conditions were fitted using a non linear regression method for the estimation of the Langmuir parameters. Moreover a simple Scatchard plot analysis was performed for a preliminary investigation of the active sites, showing the presence of two different site affinities depending on the metal concentration, according to the previous hypothesis of two kinds of uptake mechanisms for copper biosorption. Regeneration tests gave good results in terms of yield of regeneration and also concentration ratios.     

Activated carbon from Ceiba pentandra hulls, an agricultural waste, as an adsorbent in the removal of lead and zinc from aqueous solutions

The ability of low-cost activated carbon prepared from Ceiba pentandra hulls, an agricultural waste material, for the removal of lead and zinc from aqueous solutions has been investigated. In the batch tests experimental parameters were studied, including solution pH, contact time, adsorbent dose and initial metal ions concentration. The adsorbent exhibited good sorption potential at pH 6.0. Maximum removal of lead (99.5%) and of zinc (99.1%) with 10 g/l of sorbent was observed at 50 mg/L sorbate concentration. Removals of about 60-70% occurred in 10 min, and equilibrium was attained at around 50 min for both metals. The functional groups (CO, SO,-OH) present on the carbon surface were responsible for the adsorption of metal ions. The adsorption parameters were analysed using both the Freundlich and Langmuir models. The data are better fitted by the Freundlich isotherm as compared to Langmuir model, and the adsorption capacities for lead and zinc were 25.5 and 24.1 mg/g, respectively. Kinetics of adsorption obeyed a second order rate equation and the rate constant was found to be 2.71 x 10(-2) and 2.08 x 10(-2) g/mg/min for lead and zinc, respectively. The desorption studies were carried out using dilute HCl, and the effect of HCl concentration on desorption was studied. Maximum desorptions of 85% for lead and 78% for zinc were attained with 0.15 M HCl.     

Partial characterization of the exopolysaccharide from Oscillatoria trichoides Szafer and the role of released polysaccharide in sequestration of Cr6+

The structural investigation and the chromium adsorptive potential of an exopolysaccharide (EPS) released during the growth of an indigenous cyanobacterium, Oscillatoria trichoides Szafer, were investigated in a laboratory‐scale study. The results showed that, of the total EPS produced, 410.53 milligrams/gram (mg g^?1) were released polysaccharides (RPS) and 11.36 mg g^?1 were capsular polysaccharides (CPS). The sorption of hexavalent chromium (Cr⁶⁺) by the RPS achieved a maximum amount of metal removal (q_max) value of 76.92 mg g^?1 of polysaccharide dry weight. The highest coefficient of determination (0.9742) for the Langmuir adsorption model indicates best fitness of the model in explaining the sorption as a unilayer process. Equilibrium studies indicated that 30 to 40 milligrams per liter initial chromium concentration and a pH of 2 were optimal for biosorption of chromium by the RPS. Scanning electron microscopy with energy‐dispersive X‐ray spectroscopy analysis of Cr⁶⁺‐treated RPS showed the presence of 3.76% bound chromium. Compositional analysis of the EPS showed the presence of carbohydrates, proteins, pyruvic acid, and hexosamines. High‐performance liquid chromatography analysis demonstrated the presence of hexoses, as neutral sugars and glucuronic acid as an acidic sugar. The presence of carboxylic groups was also detected by infrared spectroscopy. The presence of these chemical constituents may serve as binding sites for the metal ions; therefore, the RPS of this species appears to be a promising biosorbent for Cr⁶⁺.     

Combining Ion‐exchange (IX) technology and biological reduction for perchlorate removal

Ion‐exchange (IX) resin is perhaps the most promising technology to remove the contaminant perchlorate (ClO₄^?) from waters. However, ion exchange is only a separation technology that transfers the perchlorate from waters to the waste solutions used to regenerate the resins. The waste solutions contain high perchlorate concentrations, and treatment technologies for these regenerant solutions are needed. In this article, we review the latest knowledge on perchlorate removal by ion‐exchange resins; propose three systems that combine ion‐exchange resins (for perchlorate removal) and biological reduction for treating the waste solutions resulting from resin regeneration; and discuss the challenges and research needed to fully develop the proposed technology. © 2002 Wiley Periodicals, Inc.     

Eco-Friendly, Vascular Shape and Interpenetrating Poly (Acrylic Acid) Grafted Pectin Hydrogels; Biosorption and Desorption Investigations

The synthesis and characterization of poly (acrylic acid) grafted pectin hydrogel followed by biosorption and desorption characteristics of cadmium, as a model heavy metal, have been studied. The grafted eco-friendly pectin based interpenetrating hydrogel was prepared in the presence of gluteraldehyde crosslinker under N₂ atmosphere and characterized using ¹H-NMR, FTIR, TGA and SEM techniques. Gluteraldehyde was found to form one-arm and two-arm crosslinks in the copolymer. Upon grafting, two-dimensional sheet structures bounded to tubular and vascular cylindrical rods were observed. The biosorption and desorption data, determined experimentally, were fitted to pseudo-second order reaction kinetics. At higher ionic strength values, the maximum metal uptake value (q _max) was lowered and pseudo-second order rate constant (k ₂) was increased. Whereas, at higher pH values the maximum metal uptake value (q _max) was increased and Pseudo-second order rate constant (k ₂) was decreased. 0.1?M HCl solution was a suitable eluent to regenerate the hydrogel surface and recover the adsorbed cadmium metal ions. Pectin based copolymer could be used as an efficient candidature biosorbent for the recovery of cadmium metal ions from aqueous solutions.     

Treatment of Perchlorate‐Contaminated Groundwater Using Highly Selective,Regenerable Ion‐Exchange Technology: A Pilot‐Scale Demonstration

Treatment of perchlorate‐contaminated groundwater using highly selective, regenerable ion‐exchange technology has been recently demonstrated at Edwards Air Force Base, California. At an influent concentration of about 450 μg/l ClO₄^?, the bifunctional anion‐exchange resin bed treated approximately 40,000 empty bed volumes of groundwater before a significant breakthrough of ClO₄^? occurred. The presence of relatively high concentrations of chloride and sulfate in site groundwater did not appear to affect the ability of the bifunctional resin to remove ClO₄^?. The spent resin bed was successfully regenerated using the FeCl₃^?HCl regeneration technique recently developed at the Oak Ridge National Laboratory, and nearly 100 percent of sorbed ClO₄^? was displaced or recovered after elution with as little as about two bed volumes of the regenerant solution. In addition, a new methodology was developed to completely destroy ClO₄^? in the FeCl₃^?HCl solution so that the disposal of perchlorate‐containing hazardous wastes could be eliminated. It is therefore anticipated that these treatment and regeneration technologies may offer an efficient and cost‐effective means to remove ClO₄^? from contaminated groundwater with significantly reduced generation of waste requiring disposal. © 2002 Wiley Periodicals, Inc.     

Phosphorus recovery from secondary effluent and side-stream liquid in a sewage treatment plant using zirconium-loaded saponified orange waste

Zirconium was loaded onto orange waste, a cheap and available agricultural waste in Japan, to investigate the feasibility of its utilization for phosphorus recovery from secondary effluent and side-stream liquid, which contain 5.9 and 68.2 mg/dm³ phosphorus, respectively. The phosphorus removal from side-stream liquid by using zirconium-loaded saponified orange waste (Zr-SOW) gel increased with an increasing solid/liquid ratio, and it was found that Zr-SOW gel showed better performance than zirconium ferrite. The prepared adsorbent was effective for phosphorus removal and exhibited a reasonably high adsorption capacity, twice than that of zirconium ferrite. The secondary effluent was treated in a column packed with Zr-SOW gel, and an dynamic adsorption capacity of 1.3 mol-P/kg was attained. The adsorbed phosphorus from the column was successfully eluted as a concentrated form by using a small amount of 0.2 M NaOH. Throughout the elution process, zirconium was not leaked from the adsorption gel.     

Ecotoxicity of wastes in avoidance tests with Enchytraeus albidus,Enchytraeus crypticus and Eisenia fetida (Oligochaeta)

Contact bioassays are important for testing the ecotoxicity of solid materials. However, survival and reproduction tests are often not practical due to their duration which may last for several weeks. Avoidance tests with soil invertebrates may offer an alternative or extension to the classic test batteries due to their short duration (days rather than weeks) and due to a sensitive sub-acute endpoint (behavior). The aims of our study were: (a) to evaluate the effects of three solid industrial wastes (incineration ash, contaminated wood chips and contaminated soil) on three Oligochaeta species (enchytraeids Enchytraeus albidus, Enchytraeus crypticus and earthworm Eisenia fetida) in avoidance tests; (b) to compare the sensitivity among the species and to compare results of avoidance test to reproduction tests; (c) to elucidate if measuring the weight in the earthworm avoidance test could be reasonable additional endpoint. Avoidance mostly increased with the increasing percent of waste in the mixture showing a dose–response curve. E. fetida was the most sensitive species and E. crypticus the least one. An additional endpoint, (changes in weight after two-day exposure) was not found to be more sensitive than avoidance reaction, but it confirmed that earthworms staying in the highest concentrations of the waste mixture were affected showing apparent weight reduction. Our results indicate that avoidance tests with earthworms and enchytraeids are feasible for waste testing.     

Evaluation of a Slag and Portland Cement Mix to Simulate Treatment of Acidic Waste via Solidification/Stabilization in a Deep Soil Mix Application

Site investigations at an oil and gas facility identified a highly acidic waste referred to as residual acid tar that resulted in the transport of dissolved nickel toward the point of compliance at concentrations that exceeded site environmental screening levels. Solidification/stabilization (S/S) via deep soil mixing was selected as the remedial approach and a mixture of ground granulated blast furnace slag cement and Portland cement was subjected to treatability testing to evaluate the reagent mix's ability to achieve treatment objectives. Results from the treatability test showed a cement mix dose of 21 percent was sufficient to raise the pH above the target of 6.0 and reduce dissolved nickel concentrations to below site screening levels in leachate from treated samples of residual acid tar and material impacted by residual acid tar. Cement mix doses of 21 percent or greater were sufficient to achieve target strengths in the unimpacted shallow overburden. However, none of the doses tested were able to achieve target strengths in the residual acid tar or peaty material impacted by the residual acid tar. Results showed soil strengths increased significantly when the pH in leachate from the treated samples approached 12, suggesting the presence of organic acids related to the peaty soils may interfere with the cement set. Recommendations from the study include additional treatability testing to evaluate pre‐treatment with hydrated lime to satisfy acid neutralization requirements prior to dosing with the cement mix. ©2016 Wiley Periodicals, Inc.     

Efficiency of Modified Composite Biosorbent for Bioremoval of Phosphate Ions in Aqueous Area: Process Modeling Studies

This paper was focused on the biosorption of phosphate ions from aqueous solution onto the cetyltrimethylammonium bromide (CTAB) modified multi-component biosorbent composed of pine, oak, hornbeam and fir sawdust biomasses. A series of batch tests were conducted and the effects of solution pH, ion concentration, quantity of biosorbent and contact time on the bioremoval of phosphate ions were investigated. The biosorption data of kinetic and equilibrium were modeled using various mathematical equations. The phosphate removal increased with increased ion concentration and decreased with increased pH and biosorbent quantity values. The equilibrium state was reached within 120 min of exposure time. The process kinetics was best described by Elovich model while the isotherm data of biosorption best obeyed Freundlich equation. The obtained results revealed that the use of CTAB modified mix sawdust biosorbent presented interesting options for bioremediation of contaminated environments and waste recycling (as nutrient fertilizer and compost material).     

Hydrothermal solidification behavior of municipal solid waste incineration bottom ash without any additives

Municipal solid waste incineration (MSWI) bottom ash could be solidified with and without slaked lime (calcium hydroxide) addition by a hydrothermal method under steam pressure of 1.56 MPa at 200 °C for up to 72 h. Experimental results showed that CSH gel or tobermorite exerted a main influence on strength development, and without any additives CSH gel was easy to form, while slaked lime addition favored to form tobermorite. Tobermorite seemed to exert a larger effect on the strength development than CSH gel. Leaching results showed that the concentrations of heavy metals dissolved from the solidified specimens were effectively reduced after hydrothermal processing. The immobilization was mainly due to the tobermorite or CSH gel formation, and Pb²⁺ and Zn²⁺ seemed to be fixed more readily than Cr⁶⁺, which might be the reason that the structural Ca²⁺ within tobermorite or CSH gel was exchanged by Pb²⁺ and Zn²⁺ more easily than Cr⁶⁺. In addition, there existed a close relationship between leaching concentration and strength enhancement, and a higher strength seemed to exert a larger effect on immobilization of heavy metals.     

Biosorption of Hg(II) Ions From Aqueous Solution Using the Aquatic Weed Water Hyacinth With Equilibrium and Kinetic Modeling

The potential for biosorption of Hg(II) ions from aqueous solutions using water hyacinth was studied. The effect of the retention period (0, 1, 3, 7, and 15 days), pH (3, 5, 7, and 9), initial concentration of Hg(II) ions (5, 10, and 15 mg/L), and organic loading rate (25, 50, and 75 percent) on biosorption were investigated. The physicochemical parameters were also analyzed at various concentrations of Hg(II) ions before and after treatment. The maximum biosorption rate was obtained at 15 days with the initial concentration of 10 mg/L at a pH of 7 and organic loading rate of 50 percent. The maximum biosorption capacity of both water hyacinth roots and shoots were 5.5 mg/L and 3.8 mg/L, respectively. The Hg(II) biosorption data were analyzed using the first‐ and second‐order kinetic models. Pseudo second‐order kinetics was considered the most appropriate model for predicting the biosorption capacity of both water hyacinth roots and shoots, and the modeled results were compared to the experimental results. Langmuir and Freundlich isotherms were used to evaluate the experimental data, and their constants were derived. Biosorption equilibrium data were best described by the Langmuir isotherm model followed by the Freundlich model. © 2013 Wiley Periodicals, Inc.     

Biosorption of Malachite Green from Aqueous Solutions onto Polylactide/Spent Brewery Grains Films: Kinetic and Equilibrium Studies

Batch experiments were conducted to study the biosorption of Malachite Green (MG) onto polylactide (PLA)/spent brewery grains (SBGs) films. Films were prepared by solvent-casting method using dichloromethane. Effects of contact time, pH, salt concentration, and optimal experimental condition was evaluated. At pH 6.89 and low salt concentration, Malachite Green was removed effectively. The isotherm data fitted the Freundlich model with 0.969 R² value and 0.738 slope implying chemisorptions process. The biosorption process followed pseudo-second order kinetics with calculated adsorption capacity at equilibrium (qe) of 0.572?mg/g at 23?°C. The investigation showed that PLA/SBGs films are effective in dye removal from textile, paper and leather industries effluents.     

Treatment of mixed contamination in water using cyclodextrin‐based materials

This study investigated the effectiveness of a cyclodextrin‐based solid material for the removal of mixed dissolved contaminants. The solid material was prepared by condensation of α‐cyclodextrin. The removal efficiency was found to be 70 percent for total heavy metals (cadmium, lead, chromium, iron, nickel, cobalt, and mercury) to 98 percent for polychlorinated biphenyls (PCBs). The optimum pH for heavy metal removal was approximately 5 and for PCBs it was in the range of 5–7. All of these heavy metals were successfully recovered from the spent cyclodextrin‐based material using nitric acid, allowing the material to be reused for further passes. The results also showed that the presence of alkaline and alkaline earth metals did not have a significant effect on the removal efficiency, indicating that the cyclodextrin‐based material could selectively remove the heavy metals of concern without being consumed by alkaline and alkaline‐earth metals. © 2006 Government of Canada.     

Adsorption of malachite green on groundnut shell waste based powdered activated carbon

In the present technologically fast changing situation related to waste management practices, it is desirable that disposal of plant waste should be done in a scientific manner by keeping in view economic and pollution considerations. This is only possible when the plant waste has the potential to be used as raw material for some useful product. In the present study, groundnut shell, an agricultural waste, was used for the preparation of an adsorbent by chemical activation using ZnCl2 under optimized conditions and its comparative characterisation was conducted with commercially available powdered activated carbon (CPAC) for its physical, chemical and adsorption properties. The groundnut shell based powdered activated carbon (GSPAC) has a higher surface area, iodine and methylene blue number compared to CPAC. Both of the carbons were used for the removal of malachite green dye from aqueous solution and the effect of various operating variables, viz. adsorbent dose (0.1-1 g l(-1)), contact time (5-120 min) and adsorbate concentrations (100-200 mg l(-1)) on the removal of dye, has been studied. The experimental results indicate that at a dose of 0.5 g l(-1) and initial concentration of 100 mg l(-1), GSPAC showed 94.5% removal of the dye in 30 min equilibrium time, while CPAC removed 96% of the dye in 15 min. The experimental isotherm data were analyzed using the linearized forms of Freundlich, Langmuir and BET equations to determine maximum adsorptive capacities. The equilibrium data fit well to the Freundlich isotherm, although the BET isotherm also showed higher correlation for both of the carbons. The results of comparative adsorption capacity of both carbons indicate that groundnut shell can be used as a low-cost alternative to commercial powdered activated carbon in aqueous solution for dye removal.     

Biosorption potential and kinetic studies of vegetable waste mixture for the removal of Nickel(II)

Biosorption potential of new low cost biosorbent prepared from vegetable waste, composed of 1:1 mixture of potato and carrot peels for the removal of Ni(II) from aqueous solution was determined. The residual metallic ion concentrations were determined using an atomic absorption spectrophotometric technique (AAS). Batch experiments were conducted to optimize parameters such as initial pH, temperature, contact time, initial metal ion concentration and biosorbent dose and the results showed that maximum adsorption of Nickel (79.32 %) occurs when the contents were stirred for 75 min with 3.0 g of biosorbent at 35 °C and pH 4. Kinetic studies of the reaction revealed that it follows a pseudo-second order reaction. The experimental results were analyzed in terms of Langmuir and Freundlich isotherms. The Langmuir isotherm model fits well to data of Ni(II) biosorption by the prepared biomass as compared to the model of Freundlich. Both neat and Ni loaded biosorbent samples were analyzed by AAS using a dry ashing process in a furnace and also by use of a FT-IR spectrophotometer and an X-Ray florescence spectrometer in order to confirm the biosorption of Ni(II) and the results have revealed that a significant amount of Ni is present in the spent biosorbent.     

Design parameters for fixed bed reactors of activated carbon developed from fertilizer waste for the removal of some heavy metal ions

Activated carbon, developed from fertilizer waste, has been used for the removal of Hg²⁺, Cr⁶⁺, Pb²⁺, and Cu²⁺. Mass transfer kinetic approach has been successfully applied for the determination of various parameters necessary for designing a fixed-bed absorber. Parameters selected are the length of the (PAZ) primary adsorption zone (δ), total time involved for the establishment of primary adsorption zone (t_x), mass rate of flow to the absorber (F_m), time for primary adsorption zone to move down its length (t_δ), amount of adsorbate adsorbed in PAZ from breakpoint to exhaustion (M_s), fractional capacity (f), time of initial formation of PAZ (t_f) and per cent saturation of column at break point. Chemical regeneration has been achieved with 1 M HNO₃.