Application of Agro‐Based Biomasses for Zinc Removal from Wastewater – A Review

Zinc remediation of aqueous streams is of special concern due to its highly toxic and persistent nature. Conventional treatment technologies for the removal of zinc 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 of metal ions from aqueous solutions. Mechanisms involved in the biosorption process include chemisorption, complexation, adsorption–complexation on surface and pores, ion exchange, microprecipitation, heavy metal hydroxide condensation onto the bio surface, and surface adsorption. Biosorption largely depends on parameters such as pH, the initial metal ion concentration, biomass concentration, presence of various competitive metal ions in solution, and to a limited extent on temperature. Biosorption using biomass such as agricultural wastes, industrial residues, municipal solid waste, biosolids, food processing waste, aquatic plants, animal wastes, etc., is regarded as a cost‐effective technique for the treatment of high volume and low concentration complex wastewaters containing zinc metal. Very few reviews are available where readers can get an overview of the sorption capacities of agro based biomasses used for zinc remediation together with the traditional remediation methods. The purpose of this review article is to provide the scattered available information on various aspects of utilization of the agro based biomasses for zinc metal ions removal. An extensive table summarizes the sorption capacities of various adsorbents. These biosorbents can be modified using various methods for better efficiency and multiple reuses to enhance their applicability at industrial scale. We have incorporated most of the valuable available literature on zinc removal from waste water using agro based biomasses in this review.     

Demobilization of Heavy Metals from Mine Waters

The present study elucidates the remediation of mine waters by means of geochemical barriers („active barriers“). Active barrier systems (ABS) are developed, which can prevent heavy metal dispersion by introducing the barrier into the mine. Therefore, low‐cost materials are investigated which can remove contaminants by chemical, and/or physical mechanisms from water. The materials investigated are industrial by‐products (e.g. fly ash, red mud, scale arrears), natural wastes (e.g. tree bark), and relatively cheap natural products (bentonite, zeolites). Red mud and fly ash show the best results for the removal of Zn, Cd, Ni, and Mn from model water. Cd seems to have the strongest binding of the investigated metals on the sorption sites. The main mechanisms of metal removal from solution in this case are sorption and precipitation. Both materials have very good sorption and acid neutralization capacities (ANC), but ANC seems to be the determining factor.     

Nanoporous polystyrene fibers for oil spill cleanup

The development of oil sorbents with high sorption capacity, low cost, scalable fabrication, and high selectivity is of great significance for water environmental protection, especially for oil spillage on seawater. In this work, we report nanoporous polystyrene (PS) fibers prepared via a one-step electrospinning process used as oil sorbents for oil spill cleanup. The oleophilic-hydrophobic PS oil sorbent with highly porous structures shows a motor oil sorption capacity of 113.87 g/g, approximately 3-4 times that of natural sorbents and nonwoven polypropylene fibrous mats. Additionally, the sorbents also exhibit a relatively high sorption capacity for edible oils, such as bean oil (111.80 g/g) and sunflower seed oil (96.89 g/g). The oil sorption mechanism of the PS sorbent and the sorption kinetics were investigated. Our nanoporous material has great potential for use in wastewater treatment, oil accident remediation and environmental protection.     

Reuse of Drinking Water Treatment Waste for Remediation of Heavy Metal Contaminated Groundwater

Lime softening produces an estimated 10,000 metric tons of dry drinking water treatment wastes (DWTW) per year, costing an estimated one billion dollars annually for disposal worldwide. Lime softening wastes have been investigated for reuse as internal curing agents or supplementary cementitious materials in concrete as well as a high-capacity sorbent for heavy metal removal. Lead, cadmium, and zinc are common heavy metals in groundwater contaminated by mine tailings. Cement-based filter media (CBFM) are a novel material-class for heavy metal remediation in groundwater. This study investigated the incorporation of DWTW as a recycled, low-cost additive to CBFM for the removal of lead, cadmium, and zinc. Jar testing at three different metal concentrations and breakthrough column testing using synthetic groundwater were performed to measure removal capacity and reaction kinetics. Jar testing results show as DWTW content increases at low concentrations, removal approaches 100% but at high metal concentrations removal decreases due to saturation or exhaustion of the removal mechanisms. Removal occurs through the formation of metal carbonate precipitates, surface sorption, and ion exchange with calcium according to the preferential series Pb⁺² > Zn⁺² > Cd²⁺. Removal kinetics were also measured through column testing and exceeded estimated calculations derived from batch jar testing isotherms due to the large formation of oolitic metal carbonates. Lead, cadmium, and zinc was concentrated in the column precipitates from 0.29, 0.23, and 20.0 μg/g in the influent solution to approximately 200, 130, 14,000 μg/g in the reacted DWTW-CBFM. The control and DWTW-CBFM columns had statically similar removal for zinc and lead. In the DWTW-CBFM, cadmium had decreased removal of approximately 25% due to proportionately decreased hydroxide content from cement replacement with 25% DWTW. This study shows the potential for DWTW as an enhancement to CBFM, thereby valorizing an otherwise waste material. Furthermore, the concentrative abilities of CBFM through precipitate and oolitic mineral formation could provide a minable waste product and close the waste-product cycle for DWTW.     

Removal of Cu2+ and Pb2+ Ions Using CMC Based Thermoresponsive Nanocomposite Hydrogel

In this study, carboxymethylcellulose (CMC) based thermoresponsive nanocomposite hydrogel was synthesized for the removal of Cu²⁺ and Pb²⁺ ions from aqueous solutions. To prepare nanocomposite hydrogel, graft copolymerization of N‐isopropyl acrylamide (NIPAm) and acrylic acid (AA) onto CMC was carried out in Na‐montmorillonite (MMT)/water suspension media and ammonium persulfate (APS) used as initiator. The chemical structures of hydrogels were characterized by Fourier transform infrared (FT‐IR) and X‐ray diffraction spectroscopy (XRD). Lower critical solution temperature (LCST), pH responsivity, swelling, and deswelling properties of the hydrogels were also examined. In addition competitive and non‐competitive removal of Cu²⁺ and Pb²⁺ studies were carried out. According to heavy metal sorption studies results, removal capacities of nanocomposite hydrogel for both metal ions were found to be higher than those of pure hydrogel. The analyzed adsorption data showed that the adsorption process of Cu²⁺ and Pb²⁺ could be explained by pseudo‐second order kinetic model. Moreover, according to competitive sorption studies, it is found to be that both hydrogels are more selective to Cu²⁺ ion rather than Pb²⁺.     

基于梯度扩散薄膜技术(DGT)的氨基生物炭覆盖沉积物水界面铜、铅释放研究

湖泊沉积物的重金属污染防治一直是环境领域的热点问题.本研究采用氨基生物炭作为覆盖材料,利用梯度扩散薄膜技术(DGT),研究了上覆水不同pH及水流扰动条件下Cu(Ⅱ)、Pb(Ⅱ)在沉积物水界面间的原位释放特征,以及氨基生物炭对湖泊沉积物重金属污染的原位修复效果.研究结果表明,在0 r/min或100 r/min水动力条件下,可移动态重金属离子有不断由沉积物向其他介质扩散的趋势,1.81 kg/m 2的氨基生物炭覆盖强度可降低Cu(Ⅱ)、Pb(Ⅱ)释放通量达89%以上,有效减小了水环境中重金属的潜在生态风险.在pH=5的酸性及pH=9的碱性水环境中原位修复效果较差,水体中大量的H+或络合物均会削弱氨基生物炭对重金属离子的吸附,当上覆水在pH=7的中性条件时原位修复效果最佳.100 r/min水流扰动下的上覆水Cu(Ⅱ)、Pb(Ⅱ)含量在释放平衡时较0 r/min条件下高出0.036~0.096μg/mL,说明高强度的水流扰动易造成覆盖材料的扬起和浮动,导致覆盖材料与重金属发生解吸.     

Development of Polymeric and Polymer‐Based Hybrid Adsorbents for Chromium Removal from Aqueous Solution

Ferric oxide‐loaded hybrid sorbents are environmentally benign and exhibit sorption behaviors for chromium removal from waters. In the current study, glycidyl methacrylate‐based polymer (GMD) and nanosized ferric oxide loaded glycidyl methacrylate‐based polymer (GMDFe) were prepared and assayed to examine the effect of ferric oxide loading on chromium sorption from aqueous solution for the first time from the equilibrium and kinetic points of view. The experimental equilibrium data, suitably fitted by the Langmuir and Freundlich isotherms, have shown that ferric oxide loaded hybrid sorbent exhibits higher adsorption capacity than glycidyl methacrylate‐based polymer (GMD). The Langmuir isotherm model was found to be the most suitable one for the Cr(VI) adsorption. The maximum adsorption capacities of GMD and GMDFe sorbents were determined at pH 4 as 109.54 and 157.52 mg/g, respectively. A series of column experiments was carried out to determine the breakthrough curves. The column was regenerated by eluting Cr(VI) using NaOH (10% w/v) solution after adsorption studies.     

Importance of Nonequilibrium Sorption Conditions: Contaminated Soil

When modeling the fate and transport of chemicals in ground water, a common assumption is that sorption equilibrium is achieved rapidly. This local equilibrium assumption is valid when the rate of chemical sorption to soil particles is more rapid than the rate of aqueous chemical change by other processes. However, for some chemicals (e.g., weathered hydrocarbons) this assumption is not necessarily correct. As a result, an increasing body of knowledge related to the extent and rate of release (ROR) of hydrocarbons from soil has been generated.
When evaluating site remediation options, it is important to know when nonequilibrium sorption conditions may have a significant impact on such decisions. In this study, a tiered procedure was developed to consistently evaluate the importance of ROR information at a site. The procedure consists of three tiers, each requiring more information and computational effort than the previous one. The first tier employs three power-law relationships between site parameters and the importance of ROR kinetics to quickly and easily estimate the importance of ROR information at a site. The second tier involves running and evaluating the deterministic component of a ground water fate and transport model. The third tier involves running and evaluating the probabilistic component of the ground water model. Given the sequential nature of the procedure, it is not necessary to perform Tier II (or Tier III) unless the Tier I (or Tier II) evaluation indicates that ROR kinetics may be important at the specific site under consideration. An example of applying the Tier I analysis to a specific site is provided. The results illustrate the influence of the chemical removal processes (e.g., advection and biodegradation) on the predicted importance of ROR kinetics. For the site considered, ROR kinetics had an important impact on model predictions when the biodegradation rate was high.     

Sorption of ionic forms of metals on suspension in the case of a volley of wastewater into a channel flow

The sorption kinetics of heavy metal ions by organic suspension is considered in the case of a volley of wastewater into a channel flow. The characteristic time scales of the major kinetic stages of ionic sorption are estimated by using a model of matter sorption by particulate matter involving macrokinetic parameters and field data. The sorption on organic suspension and iron hydroxides is virtually instantaneous, whereas the characteristic time of sorption on clay particles is of the order of hours and days. A concept of sorption capacity of natural water is introduced. This capacity depends on the concentration of the sorbing suspension and the distribution coefficient of the dissolved forms of substances that can be sorbed, in particular, heavy metals. When the sorption capacity is small or sorption kinetics is slow, the dilution of wastewater becomes the main mechanism reducing the concentration of metal ionic forms.     

Sorption site capacities for Cs on the sedimentary rock in Horonobe area

The sorption behavior of radionuclides depends on the content of minerals in geological media. The sorption of radionuclides on minerals has been interpreted as the uptake on the sorption sites on mineral surfaces. However, conventional investigations such as X-ray diffraction analysis cannot avoid large errors in quantification of minerals. Furthermore, the discrepancies of sorption behavior have been often found even on the same kind of minerals. Therefore, the sorption site capacity cannot be effectively estimated by the quantification of minerals. In this study, the sorption site on sedimentary rock sampled in Horonobe area, where the Horonobe Underground Research Center, JAEA, is located, was estimated from the Cs sorption isotherms obtained by sorption experiments. To deduce the fitting parameters, illite content estimated from the amount of extracted K by alkylammonium treatment and smectite content estimated from the cation exchange capacity measurement were introduced to the fitting procedure. The result shows that the sorption site capacities of smectite and illite in the sedimentary rock in Horonobe area are 1.3–1.7 × 10⁻⁴ and 1.4–4.0 × 10⁻⁵ eq/g, respectively.     

Ein einfaches Modell zur Simulation der Schwermetallmigration im Boden

The heavy-metal ions are bonded in the soil in different ways. With increasing concentration in the soil the soluble share of heavy-metal ions which is transported by the percolation water into lower soil layers and finally into the ground-water grows. The decrease of the distribution quotients and sorption capacities in the lead > cadmium series can be explained by the form of bonding at the soils which is specific to heavy metals. The elements are fixed as monohydroxo complexes. The heavy-metal retention capacity decreases with increasing time of introduction. For the estimation of the migration of heavy metals in agriculturally used soils it is recommended to combine accumulation models with migration models.     

Sorption von Schwermetallen durch Eisenphosphat-Kolloide in essigsauren Bodenextrakten

Sorption of Heavy Metals from Acetic Acid Extracts by Ferric Phosphate Colloids A conceivable procedure to remedy heavy metal contaminated soil materials is given with extraction of organic acids, i. e. by the use of a biological degradable extraction agent. The following concentration step of heavy metal extracts should be carried out to a great extent without a change of the low pH values. A conventional precipitation of the heavy metals by rising the pH should be avoided in order to introduce no large amounts of salts into the wastewaters of the process and furthermore, to reduce the amount of sludge to be deposited. The process scheme developed with the objective of heavy metals recycling consists of the following steps: the extraction of the heavy metal contaminated soils with weak organic acids like acetic acid or citric acid, the electrolysis of the extract, and a concentration step in order to treat metal concentrations not fully removed by electrolysis. This third step, e.g. could contain sorption on iron phosphate colloids and precipitation within the acidic environment. It has been examined whether a removal of the heavy metals Pb, Cd, Cu, Sb, Cr, Ni and Zn from acetic aqueous solutions of pH between 2 and 3 can be carried out.     

Removal of Heavy Metals from Synthetic Mixture as well as Pharmaceutical Sample Via Cation Exchange Resin Modified with Rhodamine B: Its Thermodynamic and Kinetic Studies

A new sorbent was prepared by loading rhodamine B on Amberlite IR‐120. Various physico‐chemical parameters such as effects of adsorbate concentration, contact time, pH, and temperature on the sorption of the dye have been studied. Thermodynamic parameters (ΔH° and ΔS°) were also evaluated for the sorption of dye. Kinetic studies revealed that the sorption of the dye was best fit for pseudo‐second‐order kinetic. The metal ion uptake in different solvent systems has been explored through column studies. On the basis of distribution coefficient (K_d), some heavy metal ions of analytical interest from binary mixtures have been separated. The limit of detection (LOD) for the Ni²⁺ and Fe³⁺ metal ions was 0.81 and 0.60 µg L^?1, and the limit of quantification (LOQ) was found to be 2.72 and 2.0 µg L^?1. This sorbent has also been successfully applied in the analysis of multivitamin formulation. The applicability of the modified resin in the separation of heavy metals constituting real and synthetic samples has been explored.     

Biosorption of Heavy Metals in Leachate Derived from Gold Mine Tailings Using Aspergillus fumigatus

Leachate derived from bioleaching process contains high amount of metals that must be removed before discharging the water. Aspergillus fumigatus was isolated from a gold mine tailings and its ability to remove of As, Fe, Mn, Pb, and Zn from aqueous solutions and leachate of bioleaching processes was assessed. Batch sorption experiments were carried out to characterize the capability of fungal biomass (FB) and iron coated fungal biomass (ICFB) to remove metal ions in single and multi‐solute systems. The maximum sorption capacity of FB for As(III), As(V), Fe, Mn, Pb, and Zn were 11.2, 8.57, 94.33, 53.47, 43.66, and 70.4 mg/g, respectively, at pH 6. For ICFB, these values were 88.5, 81.3, 98.03, 66.2, 50.25, and 74.07 mg/g. Results showed that only ICFB was found to be more effective in removing metal ions from the leachate. The amount of adsorbed metals from the leachate was 2.88, 21.20, 1.91, 0.1, and 0.08 mg/g for As, Fe, Mn, Zn, and Pb, respectively. The FT‐IR analysis showed involvement of the functional groups of the FB in the metal ions sorption. Scanning electron microscopy revealed that surface morphological changed following metal ions adsorption. The study showed that the indigenous fungus A. fumigatus was able to remove As, Fe, Mn, Pb, and Zn from the leachate of gold mine tailings and therefore the potential for removing metal ions from metal‐bearing leachate.     

Adsorption of Zinc using Tea Factory Waste: Kinetics,Equilibrium and Thermodynamics

In India, the annual production of tea is ca. 857,000 tonnes, which is 27.4% of the total world production. The amount of tea factory waste (TFW) produced per annum after processing is ca. 190,400 tonnes. TFW can be used as a low cost adsorbent for the removal of toxic metals from the aqueous phase. An investigation was carried out to study the feasibility of the use of TFW as an adsorbent for the removal of the heavy metal, zinc. Equilibrium, kinetic and thermodynamic studies were reported. The straight line plot of log (q_e–q) versus time t for the adsorption of zinc shows the validity of the Lagergren equation. The various steps involved in adsorbate transport from the solution to the surface of the adsorbent particles were dealt with by using a Weber‐Morris plot, q_e versus t^0.5 for the TFW. The rate controlling parameters, k_id,1 and k_id,2, were determined and it was found that the macro‐pore diffusion rate was much larger than micro‐pore diffusion rate. A batch sorption model, which assumes the pseudo‐second‐order mechanism, was used to predict the rate constant of sorption, the equilibrium sorption capacity and the initial sorption rate with the effect of initial zinc (II) ion concentration. Equilibrium data obtained from the experiments were analyzed with various isotherms, i. e., Freundlich, Langmuir, Redlich‐Peterson and Tempkin. The adsorption equilibrium was reached in 30 min and the adsorption data fitted well to all models. The maximum adsorption capacity of TFW for zinc (II) ions was determined to be 14.2 mg/g. The capacity of adsorption on Zn(II) increased with increasing temperatures and pH. The maximum uptake level of zinc was observed at pH of 4.2. The various thermodynamic parameters, i. e., ΔG°, ΔH° and ΔS°, were estimated. The thermodynamics of the zinc ion/TFW system indicated a spontaneous, endothermic and random nature of the process. The results showed that the TFW, which has low economical value, is a suitable adsorbent for the removal of zinc (II) ions from aqueous solutions.     

Competitive Sorption of Antimony with Zinc,Nickel, and Aluminum in a Seaweed Based Fixed‐bed Sorption Column

The removal of heavy metals such as Ni(II), Zn(II), Al(III), and Sb(III) from aqueous metal solutions was investigated using novel, cost effective, seaweed derived sorbents. Studies with a laboratory scale fixed‐bed sorption column, using a seaweed waste material (referred to as waste Ascophyllum product (WAP)) from the processing of Ascophyllum nodosum as biosorbent, demonstrated high removal efficiencies (RE) for a variety of heavy metals including Ni(II), Zn(II) and Al(III), with 90, 90 and 74% RE achieved from initial 10 mg/L metal solutions, respectively. The presence of Sb(III) in multi component metal solutions suppressed the removal of Ni(II), Zn(II) and Al(III), reducing the RE to 28, 17 and 24%, respectively. The use of Polysiphonia lanosa as a biosorbent showed a 67% RE for Sb(III), both alone and in combination with other metals. Potentiometric and conductometric titrations, X‐ray photoelectron and mid‐infrared spectroscopic analysis demonstrated that carboxyl, alcohol, sulfonate and ether groups were heavily involved in Sb(III) binding by P. lanosa. Only carboxyl and sulfonate groups were involved in Sb(III) binding by WAP. Furthermore, a greater amount of weak acidic groups (mainly carboxylic functions) were involved in Sb(III) binding by P. lanosa, compared to WAP which involved a greater concentration of strong acidic groups (mainly sulfonates).     

Accumulation of Metals in Naturally Grown Weeds (Aquatic Macrophytes) Grown on an Industrial Effluent Channel

The ability of seven hyperaccumulator macrophytes which grow naturally in the heavy metal contaminated channels of three different industries (Hindustan Aeronautical Ltd., Eveready Ltd., and Scooter India Ltd.) to accumulate heavy metals was recorded. All these industries use electroplating processes in their manufacturing and are located in the inner area of Lucknow City, U.P., India. Of the three industries monitored, effluent released from Eveready Ltd. contained the highest concentration of heavy metals. In general, accumulations of heavy metals depend upon the plant species and the metal concentration in the media. All plant samples showed heterogeneous metal accumulations, except for Fe or Cd. It was observed that some plant species accumulated high level of metals, e. g., Eichhornnia crassipes for Fe (4052.44 μg/g), Mn (788.42 μg/g), and Cu (315.50 μg/g), and Spirodela polyrhiza for Cd (12.75 μg/g), Pb (20.25 μg/g), and Cr (128.27 μg/g), even when the metal concentrations were not high in the effluent. In summary, these two plants were found to be the best accumulators at each contaminated site. The results will be helpful in the selection of plant species which can be used as bioaccumulators or bioindicators.     

Sorptive Potential of Beach Sand to Remove Ni(II) Ions: An Equilibrium Isotherm Study

The potential to remove Ni(II) ions from aqueous solutions using sea beach sand, a carbonate‐quartz mineral, was thoroughly investigated. The effects of relevant parameters such as solution pH, adsorbent dose, metal ions concentration, and temperature on Ni(II) sorption onto beach sand were examined. The sorption data followed the Langmuir, Freundlich and Dubinin‐Radushkevich (D‐R) isotherms. The adsorption was endothermic in nature at ambient temperature and the computation of the parameters, ΔH, ΔS and ΔG indicated the interactions between sorbate and sorbent to be thermodynamically favorable. Equilibrium was achieved very quickly within 30 min of shaking. A pseudo‐first order Lagergren equation was used to test the adsorption kinetics. Other kinetic models, e. g., the Morris‐Weber and Reichenberg equations, were used to calculate the rate constant of intraparticle diffusion and the fate of the diffusion process, respectively. The influence of some of the common cations and anions were also a subject of this study.     

Cd(II), Pb(II) and Zn(II) Removal from Contaminated Water by Biosorption Using Activated Sludge Biomass

Biosorption using activated sludge biomass (ASB) as a potentially sustainable technology for the treatment of wastewater containing different metal ions (Cd(II), Pb(II) and Zn(II)) was investigated. ASB metal uptake clearly competed with protons consumed by microbial biomass compared with control tests with non‐activated sludge biomass. Biosorption tests confirmed maximum exchange between metal ions and protons at pH 2.0–4.5. It was revealed by the study that the amount of metal ions released from the biomass increased with biomass sludge concentration. The result showed that maximum absorption of metal ions was observed for Cd(II) at pH 3.5, Pb(II) at pH 4.0, and pH 4.5 for Zn(II) ions. The maximum absorption capacities of ASB for Cd(II), Pb(II) and Zn(II) were determined to be 59.3, 68.5 and 86.5%, respectively. The biosorption of heavy metals was directly proportional to ASB stabilization corresponding to a reduction in heavy metals in the order of Cd < Pb < Zn. The order of increase of biosorption of metal ions in ASB was Zn(II) < Pb(II) < Cd(II), and this was opposite to that of non active sludge. The results indicate that ASB is a sustainable tools for the bioremediation of Cd(II), Pb(II) and Zn(II) ions from industrial sludge and wastewater treatment plants.     

Quantification of in situ nutrient and heavy metal remediation by a small pearl oyster (Pinctada imbricata) farm at Port Stephens, Australia

The use of pearl oysters has recently been proposed as an environmental remediation tool in coastal ecosystems. This study quantified the nitrogen, phosphorus and heavy metal content of the tissue and shell of pearl oysters harvested from a small pearl oyster farm at Port Stephens, Australia. Each tonne of pearl oyster material harvested resulted in approximately 703 g metals, 7452 g nitrogen, and 545 g phosphorus being removed from the waters of Port Stephens. Increasing current farm production of 9.8 tyr(-1) to 499 tyr(-1) would balance current nitrogen loads entering Port Stephens from a small Sewage Treatment Plant (STP) located on its southern shores. Furthermore, manipulation of harvest dates to coincide with oyster condition would likely remove substantially greater quantities of nutrients. This study demonstrates that pearl aquaculture may be used to assist in the removal of pollutants from coastal waters while producing a commercially profitable commodity.