A review on economically adsorbents on heavy metals removal in water and wastewater

Heavy metals contamination in water has been an issue to the environment and human health. The persisting contamination level has been observed and concerned by the public due to continuous deterioration of water quality. On the other hand, conventional treatment system could not completely remove the toxic metals in the water, thus alternative purification methods using inexpensive materials were endeavor to improve the current treatment process. Wide ranges of low cost adsorbents were used to remove heavy metal in aqueous solution and wastewater. The low cost adsorbents were usually collected from agricultural waste, seafood waste, food waste, industrial by-product and soil. These adsorbents are readily available in a copious amount. Besides, the pretreatment are not complicated to be conducted on the raw products, which is economically sound for an alternative treatment. The previous studies have provided much evidence of low cost adsorbents’ efficiency in removing metal ions from aqueous solution or wastewater. In this review, several low cost adsorbents in the recent literature have been studied. The maximum adsorption capacity, affecting factors such as pH, contact times, temperature, initial concentration and modified materials were revised and summarized in this review for further reference. Comparisons of the adsorbent between the modified and natural products were also demonstrated to provide a clear understanding on the kinetic uptake of the selected adsorbents. Some of the natural adsorbents appeared as good heavy metal removal, while some were not and require further modifications and improvements to enhance the adsorption capacity. SWOT analysis (strength, weakness, opportunities, threat) was also performed on the low cost adsorbents to identify the advantages of using low cost adsorbents and solve the weaknesses encountered by the utilization of low cost materials. This tool helps to determine the potential quality of low cost materials in the application for water and wastewater treatment.     

Agricultural waste material as potential adsorbent for sequestering heavy metal ions from aqueous solutions - a review

Heavy metal remediation of aqueous streams is of special concern due to recalcitrant and persistency of heavy metals in environment. Conventional treatment technologies for the removal of these toxic heavy metals are not economical and further generate huge quantity of toxic chemical sludge. Biosorption is emerging as a potential alternative to the existing conventional technologies for the removal and/or recovery of metal ions from aqueous solutions. The major advantages of biosorption over conventional treatment methods include: low cost, high efficiency, minimization of chemical or biological sludge, regeneration of biosorbents and possibility of metal recovery. Cellulosic agricultural waste materials are an abundant source for significant metal biosorption. The functional groups present in agricultural waste biomass viz. acetamido, alcoholic, carbonyl, phenolic, amido, amino, sulphydryl groups etc. have affinity for heavy metal ions to form metal complexes or chelates. The mechanism of biosorption process includes chemisorption, complexation, adsorption on surface, diffusion through pores and ion exchange etc. The purpose of this review article is to provide the scattered available information on various aspects of utilization of the agricultural waste materials for heavy metal removal. Agricultural waste material being highly efficient, low cost and renewable source of biomass can be exploited for heavy metal remediation. Further these biosorbents can be modified for better efficiency and multiple reuses to enhance their applicability at industrial scale.     

改性微生物吸附剂在重金属废水处理中的应用进展

高效、低耗、环境友好的重金属废水处理方法是当前的研究热点之一,微生物吸附法因具有优良的吸附性能、不产生二次污染、环境友好性等优点,在重金属废水处理中有巨大的应用潜力。细菌、真菌、藻类等微生物可通过静电吸附、络合作用等将重金属结合到细胞壁表面。但未经处理的微生物往往吸附效果不佳,通过对微生物进行物理、化学等方法的改性处理,能显著增加微生物与重金属离子结合的活性位点,提高去除效果。本文对国内外微生物的改性方法以及改性微生物吸附剂对废水中重金属的吸附能力和影响因素进行阐述,讨论微生物吸附剂存在的相关问题,并对其未来的研究方向做简要展望。     

Removal of heavy metal ions from wastewater by chemically modified plant wastes as adsorbents: a review

The application of low-cost adsorbents obtained from plant wastes as a replacement for costly conventional methods of removing heavy metal ions from wastewater has been reviewed. It is well known that cellulosic waste materials can be obtained and employed as cheap adsorbents and their performance to remove heavy metal ions can be affected upon chemical treatment. In general, chemically modified plant wastes exhibit higher adsorption capacities than unmodified forms. Numerous chemicals have been used for modifications which include mineral and organic acids, bases, oxidizing agent, organic compounds, etc. In this review, an extensive list of plant wastes as adsorbents including rice husks, spent grain, sawdust, sugarcane bagasse, fruit wastes, weeds and others has been compiled. Some of the treated adsorbents show good adsorption capacities for Cd, Cu, Pb, Zn and Ni.     

Heavy metal removal from contaminated scallop waste for feed and fertilizer application

The present work elucidates environmental friendly removal process of heavy metals by using biomass waste and natural product. The process consists of the following three steps: (1) leaching of all metals including heavy metals by dilute sulfuric acid, (2) removal of turbid organic materials from the leach liquor by means of coagulation using astringent persimmon extract enriched with persimmon tannin leaving all heavy metal ions in the leach liquor and (3) adsorptive removal of heavy metals by means of adsorption onto the gel prepared from apple waste. The operational conditions at these three steps were discussed in detail, among which the pH adjustment is the key factor; i.e. the lower the pHs the higher the efficiency of the leaching, while reverse was the case for the adsorption.     

Synergistic Removal of Pb(II), Cd(II) and Humic Acid by Fe3O4@Mesoporous Silica-Graphene Oxide Composites

The synergistic adsorption of heavy metal ions and humic acid can be very challenging. This is largely because of their competitive adsorption onto most adsorbent materials. Hierarchically structured composites containing polyethylenimine-modified magnetic mesoporous silica and graphene oxide (MMSP-GO) were here prepared to address this. Magnetic mesoporous silica microspheres were synthesized and functionalized with PEI molecules, providing many amine groups for chemical conjugation with the carboxyl groups on GO sheets and enhanced the affinity between the pollutants and the mesoporous silica. The features of the composites were characterized using TEM, SEM, TGA, DLS, and VSM measurements. Series adsorption results proved that this system was suitable for simultaneous and efficient removal of heavy metal ions and humic acid using MMSP-GO composites as adsorbents. The maximum adsorption capacities of MMSP-GO for Pb(II) and Cd (II) were 333 and 167 mg g⁻¹ caculated by Langmuir model, respectively. HA enhances adsorption of heavy metals by MMSP-GO composites due to their interactions in aqueous solutions. The underlying mechanism of synergistic adsorption of heavy metal ions and humic acid were discussed. MMSP-GO composites have shown promise for use as adsorbents in the simultaneous removal of heavy metals and humic acid in wastewater treatment processes.     

Surface modification of natural fibers using bacteria: depositing bacterial cellulose onto natural fibers to create hierarchical fiber reinforced nanocomposites

Triggered biodegradable composites made entirely from renewable resources are urgently sought after to improve material recyclability or be able to divert materials from waste streams. Many biobased polymers and natural fibers usually display poor interfacial adhesion when combined in a composite material. Here we propose a way to modify the surfaces of natural fibers by utilizing bacteria ( Acetobacter xylinum) to deposit nanosized bacterial cellulose around natural fibers, which enhances their adhesion to renewable polymers. This paper describes the process of modifying large quantities of natural fibers with bacterial cellulose through their use as substrates for bacteria during fermentation. The modified fibers were characterized by scanning electron microscopy, single fiber tensile tests, X-ray photoelectron spectroscopy, and inverse gas chromatography to determine their surface and mechanical properties. The practical adhesion between the modified fibers and the renewable polymers cellulose acetate butyrate and poly(L-lactic acid) was quantified using the single fiber pullout test.     

Metal-Induced Production of a Novel Bioadsorbent Exopolysaccharide in a Native Rhodotorula mucilaginosa from the Mexican Northeastern Region

There is a current need to develop low-cost strategies to degrade and eliminate industrially used colorants discharged into the environment. Colorants discharged into natural water streams pose various threats, including: toxicity, degradation of aesthetics and inhibiting sunlight penetration into aquatic ecosystems. Dyes and colorants usually have complex aromatic molecular structures, which make them very stable and difficult to degrade and eliminate by conventional water treatment systems. The results in this work demonstrated that heavy metal-resistant Rhodotorula mucilaginosa strain UANL-001L isolated from the northeast region of Mexico produce an exopolysaccharide (EPS), during growth, which has colorant adsorption potential. The EPS produced was purified by precipitation and dialysis and was then physically and chemically characterized by Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, and chemical elemental analysis. Here, the ability of the purified EPS produced to adsorb methylene blue (MB), which served as a model colorant, is studied. MB adsorption by the EPS is found to follow Langmuir Adsorption Isotherm kinetics at 25°C. Further, by calculating the Langmuir constant the adsorption capabilities of the EPS produced by the Rhodotorula mucilaginosa strain UANL-001L is compared to that of other adsorbents, both, microbially produced and from agroindustrial waste. The total adsorption capacity of the EPS, from the Rhodotorula mucilaginosa strain UANL-001L, was found to be two-fold greater than the best bioadsorbents reported in the literature. Finally, apart from determining which heavy metals stimulated EPS production in the strain, the optimal conditions of pH, heavy metal concentration, and rate of agitation of the growing culture for EPS production, was determined. The EPS reported here has the potential of aiding in the efficient removal of colorants both in water treatment plants and in situ in natural water streams.     

Removal of chromium on Polyalthia longifolia leaves biomass

Adsorption is an environmental friendly process for removal and/or recovery of heavy metals from wastewater. In recent years, it has been substantiated as a popular technique to treat industrial waste effluents, with significant advantages. In this work, batchwise removal of chromium (III) ions from water by Polyalthia longifolia leaves was studied as a function of adsorbent dose, pH, contact time, and agitation speed. Surface characteristics of the leaves were evaluated by recording IR spectra. The Langmuir, Freundlich, and Temkin adsorption isotherms were employed to explain the sorption process. It was found that one gram of leaves can remove 1.87 mg of trivalent chromium when working at pH 3.0. It has been concluded that Polyalthia longifolia leaves can be used as cost-effective and benign adsorbents for removal of Cr(III) ions from wastewater.     

Study on the Adsorption of Cr3+ by Peanut Shell: Adsorption Kinetics,Thermodynamics, and Isotherm Properties

The pollution of heavy metals in soil to the environment is becoming more and more serious, resulting in the reduction of crop production and the occurrence of medical accidents. In order to remove heavy metal ions from soil and reduce the harm of heavy metals to the environment, modified peanut shell was used to adsorb Cr³⁺ in this article. The effects of different adsorption conditions on the adsorption rate and adsorption capacity of Cr³⁺ on ZnCl₂ modified peanut shell were studied, the best adsorption conditions were explored, and the relationship of kinetics, thermodynamics and adsorption isotherm properties of adsorption process were explored. The results showed that the optimum adsorption pH value, dosage, initial concentration, adsorption temperature and contact time of ZnCl₂ modified peanut shell were 2.5, 2.5 g/L, 75 μg/mL, 25 °C and 40 min, respectively. The prepared materials were characterized and analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD) analyzer. It was concluded that the modified peanut shell had a good adsorption capacity to Cr³⁺. The kinetic study showed that the adsorption process of Cr³⁺ on peanut shell modified by zinc chloride was in accordance with the quasi-second-order kinetic model. The adsorption process belonged to exothermic reaction and belonged to spontaneous reaction process. In summary, it is proved that zinc chloride modified peanut shell can efficiently adsorb Cr³⁺, which can be used for the treatment of heavy metal wastes in industry, which is beneficial to environmental protection and avoid heavy metal pollution.     

Removal of selected metal ions from aqueous solution using modified corncobs

The objective of this study was to convert corncobs to metal ion adsorbents for wastewater treatment. Ground corncobs were modified with either 0.6 M citric acid (CA) or 1.0 M phosphoric acid (PA) to help improve their natural adsorption capacity. The effect of a combination of wash and modification treatment was tested for corncob adsorption efficiency with five different metal ions (cadmium, copper, lead, nickel, zinc) individually or in a mixed solution containing each metal at a 20 mM concentration. Results were compared to those of commercial resins Amberlite IRC-718, Amberlite 200, Duolite GT-73 and carboxymethylcellulose (CMC). Modified corncobs showed the same adsorption efficiency as Duolite GT-73 for cadmium, copper, nickel and zinc ions and had greater adsorption than CMC for nickel and zinc ions. For mixed metals, the modified corncobs exhibited the same adsorption efficiency as Duolite GT-73 for cadmium and copper ions and the same or higher adsorption than Amberlite IRC-718 for lead ions. Adsorption capacities of modified samples were compared to those of Amberlite IRC-718, Amberlite 200 and Duolite GT-73. Commercial resins generally had higher adsorption capacities than modified corncobs. However, the adsorption capacity of modified corncobs for copper and lead ions was equivalent to Duolite GT-73, but was lower than for Amberlite IRC-718 or Amberlite 200. Depending on the specific metal ion and the presence or absence of other metal ions, chemically modified corncobs were at least equivalent in adsorption properties to all of the commercial cation exchange resins examined in this study.     

Carbon from Cassava peel, an agricultural waste, as an adsorbent in the removal of dyes and metal ions from aqueous solution

Cassava (Manihot esculenta) is a short lived erect perennial shrub, planted vegetatively from hard wood stem cuttings. It is an important crop across a wide range of tropical environments and is a significant component of cropping systems. Cassava peel is an agricultural waste from the food processing industry. Activated carbons prepared from waste cassava peel employing physical and chemical methods were tested for their efficiency in the removal of dyes and metal ions from aqueous solution. While both of these were efficient as adsorbents for dyes and metal ions, the material impregnated with H₃PO₄ showed higher efficiency than the heat treated materials.     

Development of specific adsorbents for human tumor necrosis factor-alpha: influence of antibody immobilization on performance and biocompatibility

To develop adsorbents for the specific removal of tumor necrosis factor-alpha (TNF) in extracorporeal blood purification, cellulose microparticles were functionalized either with a monoclonal anti-TNF antibody (mAb) or with recombinant human antibody fragments (Fab). The TNF binding capacity of the adsorbents was determined with in vitro batch experiments using spiked human plasma (spike: 1200 pg TNF/mL; 1 mg particles in 250 muL plasma). Random immobilization of the full-sized monoclonal antibody to periodate-activated cellulose yielded particles with excellent adsorption capacity (258.1 +/- 48.6 pg TNF per mg adsorbent wet weight). No leaching of antibody was detectable, and the adsorbents retained their activity for at least 12 months at 4 degrees C. We found that the conditions used during immobilization of the antibody (pH, nature of the reducing agent) profoundly influenced the biocompatibility of the resulting adsorbents, especially with respect to activation of the complement system. Particles obtained by random immobilization of the monovalent Fab fragments on periodate-activated cellulose using the same conditions as for immobilization of the mAb exhibited only low adsorption capacity (44 +/- 7 pg/mg adsorbent wet weight). Oriented coupling of the Fab fragments on chelate-epoxy cellulose via a C-terminal histidine tag, however, increased the adsorption capacity to 178.3 +/- 8.6 pg TNF/mg adsorbent wet weight. Thus, in the case of small, monovalent ligands, the orientation on the carrier is critical to retain full binding activity.     

Advances in water treatment by adsorption technology

Among various water purification and recycling technologies, adsorption is a fast, inexpensive and universal method. The development of low-cost adsorbents has led to the rapid growth of research interests in this field. The present protocol describes salient features of adsorption and details experimental methodologies for the development and characterization of low-cost adsorbents, water treatment and recycling using adsorption technology including batch processes and column operations. The protocol describes the development of inexpensive adsorbents from waste materials, which takes only 1-2 days, and an adsorption process taking 15-120 min for the removal of pollutants. The applications of batch and column processes are discussed, along with suggestions to make this technology more popular and applicable.     

Adsorption of heavy metal ion from aqueous single metal solution by chemically modified sugarcane bagasse

This work describes the preparation of new chelating materials derived from sugarcane bagasse for adsorption of heavy metal ions in aqueous solution. The first part of this report deals with the chemical modification of sugarcane bagasse with succinic anhydride. The carboxylic acid functions introduced into the material were used to anchor polyamines, which resulted in two yet unpublished modified sugarcane bagasse materials. The obtained materials were characterized by elemental analysis and infrared spectroscopy (IR). The second part of this reports features the comparative evaluation of the adsorption capacity of the modified sugarcane bagasse materials for Cu(2+), Cd(2+), and Pb(2+) ions in aqueous single metal solution by classical titration. Adsorption isotherms were studied by the Freundlich and Langmuir models.     

Microwave-assisted preparation of bagasse and rice straw for the removal of emulsified oil from wastewater

The present study was carried out to examine modified bagasse and rice straw as absorbents for the removal of emulsified oil by a microwave-assisted technique. The raw adsorbents were chemically modified with sodium hydroxide and surfactant solution for better adsorption of oil. The surface modification was confirmed through Fourier transform infrared (FTIR) spectroscopy and scanning electron microscope (SEM) analysis. Batch studies were performed to identify the influence of contact time, pH, dosage, speed, and temperature on the percentage of removal of emulsified oil from the wastewater. A maximum oil removal of 98.07% and 98.72% was achieved in microwave-assisted bagasse and rice straw at 313 K. The obtained data were compared with isotherm and kinetic models to understand the mechanism behind the adsorption. From the Langmuir isotherm model, a maximum adsorption capacity of 192.58 and 276.82 mg/g was observed for modified bagasse and rice straw. The oil-loaded raw and microwave-assisted adsorbents can act as a potential energy source for renewable energy.     

Effects of moisture content and initial pH in composting process on heavy metal removal characteristics of grass clipping compost used for stormwater filtration

Heavy metals are common contaminants in stormwater runoff. One of the devices that can be used to effectively and economically remove heavy metals from runoff is a yard waste compost stormwater filter. The primary goal of composting is to reduce waste volume rather than to produce stormwater filter media. Moisture content (MC) and initial pH, the two important parameters in composting, were studied for their effects on yard waste volume reduction and heavy metal adsorption performances of the compost. The main objective of this investigation was to examine whether the conditions that provided high yard waste volume reduction would also result in compost with good heavy metal removal performances. Manila grass was composted at different initial pHs (5–9) and MCs (30–70%) and the composts were used to adsorb cadmium, copper, lead and zinc from water. Results indicated that MC is more critical than initial pH for both volume reduction and production of compost with high metal adsorption performances. The most optimal conditions for the two attributes were not exactly the same but lower MCs of 30–40% and pH 7 or higher tended to satisfy both high volume reduction and effective metal adsorption.     

Removal of cesium ions from aqueous solutions using various separation technologies

Cesium is the major fission product of uranium, which widely exists in radioactive wastewater. Radiocesium has potential adverse effects on human health and ecological environment. Different methods such as chemical precipitation, coagulation/co-precipitation, solvent extraction, membrane process, chemical reduction, and adsorption have been used to remove radioactive cesium from aqueous solution. However, the development of innovative technologies capable of selectively removing radioactive cesium is still imperative yet challenging. This review focused on cesium removal using various separation technologies, including chemical precipitation, solvent extraction, membrane separation, and adsorption. The key restraints for cesium removal, as well as the recent progress of these methods have also been discussed. Particular attention has been paid to the adsorption methods, which has been highlighted by introducing the latest advances in inorganic adsorbents (such as metal hexacyanoferrates, clay minerals, carbon-based-adsorbents, and ammonium molybdophosphate), organic adsorbents (such as ion exchange resin, metal–organic frameworks and supramolecular/indicator grafting adsorbents), and biosorbents (such as agroforestry wastes and microbial biomass). Adsorption-based methods are high efficient in separation of cesium ions from aqueous streams, and adsorption of cesium ions has been investigated intensively and even used in practical applications, there is still considerable scope for improvement in terms of adsorption capacity and selectivity.

     

Tannin‐Adsorbents for Water Decontamination and for the Recovery of Critical Metals: Current State and Future Perspectives

Biosorption is known as an effective way to clean‐up water from organic and inorganic contaminants and has also emerged as a promising technology to recover critical substances. Tannins are renewable materials, coming from multiple vegetable sources. A variety of biosorbents have been developed from tannins, including tannin resins, rigid foams, composites with mesoporous silica, cellulose, collagen, and magnetic adsorbents. These materials have shown an excellent ability to uptake heavy‐metal cations (Cd(II), Cu(II), Pb(II), Ni(II), Cr(III)), owning to the chelating ability provided by the plentiful adjacent hydroxyl groups. In addition, tannin‐adsorbents have shown exceptional ability to remove Cr(VI), and to uptake Au(III) and Pd(II) from strong acidic solutions, which has evident application in the recovery of precious metals from e‐wastes leaching. The fact that tannin‐adsorbents can reduce the oxidation state of these adsorbates to Cr(III) and to elemental species of Au and Pd is interesting. Adsorption of dyes, surfactants, pharmaceuticals and antimony is also feasible, but the removal of certain metalloid species, such as arsenic and phosphate, seems to be limited even after applying chemical modifications. This article presents a systematic review on the preparation of tannin‐adsorbents and their application in water decontamination and in the recovery of critical metals.     

Removal of heavy metals from water effluents using supermacroporous metal chelating cryogels

Applications of IDA in, for example, immobilized metal ion affinity chromatography for purification of His-tagged proteins are well recognized. The use of IDA as an efficient chelating adsorbent for environmental separations, that is, for the capture of heavy metals, is not studied. Adsorbents based on supermacroporous gels (cryogels) bearing metal chelating functionalities (IDA residues and ligand derived from derivatization of epoxy-cryogel with tris(2-aminoethyl)amine followed by the treatment with bromoacetic acid (defined as TBA ligand)) have been prepared and evaluated on capture of heavy metal ions. The cryogels were prepared in plastic carriers, resulting in desired mechanical stability and named as macroporous gel particles (MGPs). Sorption and desorption experiments for different metals (Cu2+, Zn2+, Cd2+, and Ni2+ with IDA adsorbent and Cu2+ and Zn2+ with TBA adsorbent) were carried out in batch and monolithic modes, respectively. Obtained capacities with Cu2+ were 74 μmol/mL (TBA) and 19 μmol/mL gel (IDA). The metal removal was higher for pH values between pH 3 and 5. Both adsorbents showed improved sorption at lower temperatures (10°C) than at higher (40°C) and the adsorption significantly dropped for the TBA adsorbent and Zn2+ at 40°C. Desorption of Cu2+ by using 1 M HCl and 0.1 M EDTA was successful for the IDA adsorbent whereas the desorption with the TBA adsorbent needs further attention. The result of this work has demonstrated that MGPs are potential treatment alternatives within the field of environmental separations and the removal of heavy metals from water effluents.