Abstract
With the increasing industrialization, the heavy metal contamination has become a serious environmental issue. Different activities, such as fertilizer, pharmaceutical, chemical, automobile, petroleum, and textile units, discharge a large amount of heavy metals laden effluent that contaminates the water streams. Traditional processes such as precipitation, ion exchange, membrane technology, and advance oxidation have been utilized for the remediation of heavy metal contamination. These processes could not be attractive for commercial applications because of their poor removal rate, problem of disposal, and high operating cost. Biosorption is now becoming a good alternative and environmentally friendly option. Biosorption of heavy metals is a metal uptake process by using ion exchange, precipitation, surface complexation, etc.. Various sources of waste biomaterials are utilized for the treatment of metal-contaminated wastewater stream. As natural biosorbents are not giving higher efficiency, modifications are done by physical and chemical activation of the biomaterials. Scientific developments were done for improving the efficiency, but limited research was conducted for the regeneration or reuse of the biosorbents. In recent years, researchers are paying attention on the reuse of the spent biosorbents by using eluent solutions such as acids, bases, chelating agents, etc. and getting the potential results. This makes the biosorption process more efficient and economic than the other conventional methods for the treatment of metal-tainted effluent. This chapter highlights the toxic metals and the various sources of biomaterials which are utilized for heavy metal removal.
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Keywords
- Biosorption
- Heavy metal ions
- Wastewater
- Agricultural biosorbents
- Bacterial biomass
- Fungal biomass
- Algal biomass
- Regeneration
14.1 Introduction
Heavy metal contamination with the surface and groundwater becomes a serious problem nowadays. The toxic metals which have higher specific gravity (>5) are known as heavy metals. The metals such as Hg, Pb, Cu, Co, Cd, As, Fe, Se, V, Ni, Cr, and Zn make various toxic effects to the human health. The toxic metals coming out from various industries like mining operations, refining process, fertilizer processing, tanneries, battery manufacturing, paper mill, and pesticides are contaminating water bodies (Celik and Demirbas 2005; Kjellstrom et al. 1977; Pastircakova 2004). To avoid such problems, various national and international regulatory bodies have fixed some standard limit for heavy metals before discharging [Table 14.1]. Conventional methods for heavy metal elimination from water stream are precipitation, advance oxidation, ion- exchange process, membrane separation, biosorption, etc. Among these processes, biosorption is an effective process due to its economical operation, abundant availability of biomaterials, easy operating process, and high competence of metal eradication. This section focuses on the effect of toxic metals, the metal removal options available in literature, and the adsorbents which are utilized for metal removal.
14.2 Sources of Heavy Metals and Their Hazardous Effect
Heavy metals such as Cr, Pb, Cu, Co, Hg, Cd, As, Fe, Se, V, Ni, and Zn have great hazardous effects on living beings. The metals are mainly discharged from various industries like mining, fertilizer, pesticides, and chemical manufacturing which are responsible directly or indirectly for the contamination of surface and groundwater. Major sources of discharging various hazardous heavy metals and their health effects are presented in Table 14.2.
14.3 Conventional Methods for Hazardous Heavy Metal Eradication
14.3.1 Chemical Precipitation
It has simple operating procedure, higher efficiency, and low operating cost, so it is considered as the good process for metal removal (Ku and Jung 2001). The coagulant is added to the metal-contaminated wastewater, and then the metal gets precipitated which is separated by using sedimentation or filtration process. Coagulants have long-chained polymers consisting of cationic and anionic charge which react with metal ion and bind the molecules together. There are mainly two types of chemical precipitation processes where one is hydroxide precipitation and the other is sulfide precipitation. Various chemical precipitation processes found in the literature are illustrated in Table 14.3.
14.3.2 Ion-Exchange Process
An ion-exchange process is an important treatment process which has great removal capacity, and it is used commercially for large-scale treatment processes (Kang et al. 2004). Several types of resins are utilized in treatment processes. In metal removal process, exchange between the cation of the resin and metal ion is the reason of removal. In literature, various ion-exchange processes are reported as described in Table 14.4. In this process, synthetic resins get the preference for the large-scale application because of their higher efficiency (Alyuz and Veli 2009). Solution pH, temperature, and the concentration of the metal ion play an important role for the removal of metal ion (Gode and Pehlivan 2006). Another important factor that affects ion-exchange process is ionic charge. The effect of ionic charge was evaluated by some researchers (Abo-Farha et al. 2009). They utilized Ce4+, Fe3+, and Pb2+, and the adsorption sequence was found as Ce4+ > Fe3+ > Pb2+. Similar type of results was also observed by Kang and his group (Kang et al. 2004) where they utilized Co2+, Ni2+, and Cr3+. Utilization of the zeolites was also reported in literature which gave the efficient results (Motsi et al. 2009). Many researchers used iron oxide with clinoptilolite to improve the process (Doula 2009).
14.3.3 Membrane Filtration
Though membrane filtration is a costly process, it is very efficient for the remotion of heavy metals. Ultrafiltration technique is operated at low pressure while removing the contaminants from wastewater. It is somewhere inefficient for removing small particle as the pore size is large. In order to improve the efficiency of this process, two types of techniques are used. The first one is micellar-enhanced ultrafiltration, and the second one is polymer-enhanced ultrafiltration. In this process, various complex agents were utilized as reported in literature which includes polyacrylic acid, poly (acrylic acid) sodium, polyethyleneimine, poly-ammonium acrylate, and humic acid. It is an efficient process and also requires low energy. Reverse osmosis process is another important membrane separation process where semipermeable membranes are utilized. The process is very efficient and capable to remove the dissolved specie from aqueous solution. Drinking water manufacturing companies are using the reverse osmosis techniques commercially. The system requires high power as pump is utilized for the operation which makes the process uneconomical for wastewater treatment.
Nanofiltration is considered as one of the most efficient processes among the membrane filtration processes. It was found as the efficient process for removal of Cr (VI) (Muthukrishnan and Guha 2008), Ni(II) (Murthy and Chaudhari 2008), and Cu(II) (Csefalvay et al. 2009; Ahmad and Ooi 2010). The literature review suggests it was utilized for rejection of smaller particles of arsenic also (Nguyen et al. 2009; Figoli et al. 2010). The nanofiltration is nowadays a very effective method because of its higher efficiency and low energy requirement (Erikson 1988). Researchers utilized NF90 and N30F resins in this process for the treatment of arsenic-loaded water (Figoli et al. 2010). Others (Murthy and Chaudhari 2008) used composite polyamide membrane, and 98% Ni(II) was removed. Other group of researchers (Murthy and Chaudhari 2009) utilized nanofiltration for binary mixture of cadmium and nickel at a concentration of 5 mg/L, and the removal percentages were 98.94% and 82.69%, respectively. Nanofiltration and reverse osmosis were also effective for copper removal (Csefalvay et al. 2009). Treatment of metal-contaminated effluent coming out from metallurgical industry was done using this method by Liu and his group (Feini et al. 2008). The literature study suggests that for the recovery of the precious metal like silver, nanofiltration or reverse osmosis was utilized (Koseoglu and Kitis 2009).
14.3.4 Coagulation and Flocculation
It is another useful choice for heavy metal remediation. In this process, various coagulants such as ferrous sulfate and aluminum sulfate are utilized. Researchers used poly-aluminum chloride to remove the toxic heavy metals (El Samrani et al. 2008). In this process, doses of coagulants are optimized on the basis of the concentration of the impurities. Chang and Wang utilized polyethyleneimine for this purpose (Chang and Wang 2007). In flocculation process, the impurities are separated by filtration or flotation process. The recent research trend utilizes polyacrylamide and polyferric sulfate in flocculation process. Various flocculants were reported in literature where these were utilized for the removal of metal ion.
14.3.5 Flotation
Flotation is an important treatment method and is widely used in large-scale application. In this process, the metal is removed through bubble which is floated over the solution. For the flotation, sometimes air is introduced to the solution, and sometimes precipitation and flotation are used. Here, metals are attached with the microbubbles, and due to lower density, it floats. The floating bubbles bearing metal ion are separated as sludge (Lundh et al. 2000). The researchers were using the flotation process for the long time, and efficient results were observed (Tassel et al. 1997, 1998). Yuan and his team (Yuan et al. 2008) utilized bio-surfactant for the separation of Cd, Pd, and Cu where the removal percentages were 71.17%, 89.95%, and 81.13%. Medina et al. tested the process for removal of trivalent chromium where 96.2% removal was observed (Medina et al. 2005). Though the process is good, the process alone is not capable to give the higher removal efficiency in many times.
14.3.6 Electrochemical Treatment
Electrochemical treatment is another efficient treatment process which is widely used in recent research. The method is very useful to maintain the discharge limit of the metal ions as instructed by the various regulatory bodies (Wang et al. 2007). As electrocoagulation is the part of the electrochemical treatment process, the researchers utilized aluminum or iron electrodes in this treatment process (Chen 2004). In this process, hydrogen gas is generated which helps the impurities to float. Researchers (Heidmann and Calmano 2008) applied this process by using aluminum electrodes to remove the zinc, copper, nickel, and chromium. Zn and Ni were removed by utilizing electrochemical treatment, and 100% removal was found (Kabdasli et al. 2009). Nanseu-Njiki et al. utilized the electrochemical process for the removal of mercury where 99.9% removal was observed (Nanseu-Njiki et al. 2009). The applications of the EC process for the removal of various metal ions are shown in Table 14.5.
14.4 Biosorption
From economical point of view, adsorption is now becoming a sustainable option for the treatment of wastewater. A large number of adsorbents were utilized for treatment of metal-contaminated wastewater as reported in literature. Biosorption is an important process where the efficiencies are good and regeneration processes are also easier. Nonliving plant biomass such as wheat shell, cork biomass, food waste, coconut shell, different leafs, rice husk, sago waste, wood sawdust, rice straw, rubber wood, papaya wood, and many more were used as biosorbents. Biomasses such as bacteria, algae, and fungi play a vital role for the treatment of tainted water. Different chitosan-based materials also show remarkable efficiency for heavy metal remediation. Different categories of the biosorbents are utilized for finding an efficient and economical option of the remediation of heavy metals in literature.
14.4.1 Agricultural Biosorbents
Various low-cost adsorbents were tested to know their metal adsorption capacity [Table 14.6]. Many reviews were done where agricultural adsorbents were utilized for elimination of hazardous heavy metals. Sud et al. reported employment of agricultural waste materials for the remediation of metal ions (Sud et al. 2008). Rice bran was tested for the treatment of copper, zinc, lead, and cadmium, and the removal percentages were above 80% (Montanher et al. 2005). Rubber wood sawdust was applied for removal of hexavalent chromium and found an efficient removal of 60–70% (Karthikeyan et al. 2005).
14.4.2 Carbonaceous Biosorbents
Activated carbon is commercially used for drinking water production. It has high surface area which makes the adsorbent efficient for the removal of the contaminants. Many researchers utilized the activated carbon for the removal of metal ions and got the promising results (Kang et al. 2008). Various activation processes are available in the literature where waste materials were utilized for the preparation of the carbonaceous biosorbents (Dias et al. 2007). It was found that eucalyptus bark was utilized to remove the Cu and Pb (Kongsuwan et al. 2009). Carbon nanotube was utilized for the removal of Pb by researchers (Wang et al. 2007; Kabbashi et al. 2009). Others removed the Cd and Cr by carbon nanotube (Kuo and Lin 2009; Pillay et al. 2009).It was also used for the removal of Cu as reported by Li et al. (2010). Various activated carbons which were utilized to remove the heavy metal ions are illustrated in Table 14.7.
14.4.3 Bacterial Biomass Biosorbents
Bacterial biomass is now becoming an effective biosorbents for treatment of heavy metal contamination. In case of bacterial biomass, researchers used Bacillus cereus and Escherichia coli for the treatment of metal-contaminated wastewater (Pan et al. 2007). Metal biosorption capacity of various bacterial biomasses is presented in Table 14.8. Pseudomonas aeruginosa, Bacillus sp., Pseudomonas putida, and Corynebacterium glutamicum have been tested for lead ions where they display good adsorption capacity. Other species of the bacteria such as Pseudomonas putida, Thiobacillus, Pseudomonas, and Aeromonas caviae were also tested by other researchers. In case of low metal ion concentration, the bacterial biomasses show the higher efficiency.
14.4.4 Fungal Biomass Biosorption
Biosorption by using fungal biomass is a noble and economical process for the treatment of metal-contaminated water source. Various studies were reported in literature as summarized in Table 14.9 where fungal biomass shows the higher metal adsorption capacity. In these studies, many species of fungal biomasses, such as Penicillium chrysogenum, Penicillium spp., Aspergillus niger (live), Penicillium chrysogenum, and Aspergillus terreus (immobilized in polyurethane foam) were tested. Various fungal biomasses such as Aspergillus niger (Dursun 2006) and Saccharomyces cerevisiae (Cojocaru et al. 2009) were used for the removal of metal ion. Metabolic activities of fungi depend on the presence of metal ion. There are many instances where fungal biomass shows the higher metal binding efficiencies.
14.4.5 Algal Biomass Biosorbents
Many algae show potential capacity of metal ion adsorption. As it is available in large quantities in nature, it has been used as an economical biosorbent. The researchers used dried marine green algae for the elimination of copper and zinc (Ajjabi and Chouba 2009). According to Brinza et al. 2007, brown algae show the higher metal adsorption capacity than the other forms (Brinza et al. 2007). Various studies from literature are reported in Table 14.10. Adsorption of lead by algal biomass was reported by Deng et al. (2007).
14.4.6 Chitosan Composite Biosorbents
Chitosan is basically a biopolymer and capable to remove the metal ions effectively from the wastewater. For the increasing of the adsorption capacity, various modifications of the chitosan were done and reported in literature. Various chitosan composites which are reported in literature are shown in Table 14.11. Some researchers utilized the chitosan for the treatment of copper, chromium, lead, and zinc (Sun et al. 2009). The utilization of the mixture of sand and chitosan was found for the removal of copper (Kalyani et al. 2005). As the surface areas of the chitosan composites are large, the adsorbents are capable to give higher adsorption capacity.
14.5 Chemical Modification of the Biosorbents
Many instances are reported in literature where biosorption capacities of natural biosorbents were increased by various chemical treatments. As reported in the literature, modification of the adsorbents was done by utilizing acids such as nitric acid, hydrochloric acid, sulfuric acid, citric acid, etc. Chemical modifications of the adsorbents were also made by using calcium hydroxide, sodium hydroxide, sodium carbonate, etc. Some organics such as formaldehyde, ethylenediamine, etc. were involved in the modification of the adsorbents. Hydrogen peroxide was also used for modification of the raw adsorbents. Chemically modified adsorbents which were utilized to remove the metal ions are presented in Table 14.12. Hydrochloric acid was utilized for the modification of oak tree sawdust (Argun et al. 2007). Peanut husk was modified by using sulfuric acid and utilized for the treatment of copper, chromium, and lead (Li et al. 2007). Some researchers modified banana pith by the treatment with nitric acid (Low et al. 1995).
14.6 Responsible Functional Groups
Biosorption of metal ion depends on the active groups. Various components such as cellulose, chitin, and glycol present in the biosorbents bind the metal ion. Some functional groups such as hydroxyl, amino, ester, sulfhydryl, carbonyl, and carboxyl group participate for the binding of metal ions as described in Table 14.13. For the determination of the metal uptake by the active sites of the biosorbent, various instruments such as Infrared spectroscopy, X-ray diffraction analysis, electron dispersive spectroscopy, nuclear magnetic resonance, etc. are utilized.
14.7 Regeneration of Biosorbents
Desorption of metal ions from adsorbent has an important significance for the reuse of the adsorbent. Regeneration study is required to check the economical feasibility of the biosorbent. Now, in recent trend, regeneration of the adsorbents is carried out by elution processes where acids, bases, and other chemicals are utilized. Elutent is an important factor in regeneration study, and the selection of the elutent is done based on its high efficiency, low cost, and environmentally friendly nature. Regeneration efficiencies of different biosorbents were investigated by various researchers as described in Table 14.14. Scientists (Bai and Abraham 2003) reported the regeneration of immobilized fungal biomass by using 0.01 N NaOH and Na2CO3 where 78% and 91.91 ± 3.9% regeneration were achieved. Others (Saeed et al. 2005a, b) utilized 0.1 N HCl for desorption of copper, cadmium, and zinc ions from the papaya wood and obtained the efficiency of 99.4%, 98.5%, and 99.3% after fifth cycle. Some researchers (Gupta and Nayak 2012) utilized nitric acid for the regeneration of orange peel powder with Fe3O4 and got the regeneration efficiency of 98.28% even after fifth cycle. Furthermore, it can be concluded that regeneration of the biosorbent makes bisorption process more effective and efficient.
14.8 Conclusion
To combat the environmental degradation in a sustainable way, many technologies have been developed. Among them, biosorption in considered as an efficient and economical process for its easy operation, local availability, and low cost. Some of the waste biomasses which are locally available in abundant quantities are utilized as biosorbents. Natural biosorbents such as activated carbon, wood sawdust, leaf powder, bacterial biomass, algal biomass, and fungal biomass were utilized for treatment of metal-tainted effluent. As most of the natural biosorbents have low adsorption capacity, researchers attempted to increase the adsorption capacity by a number of pretreatment techniques. These pretreatment includes physical and chemical activation where in physical treatment, the adsorbents are heated at high temperature with controlled rate of heating. In chemical treatment, various acids, bases, and other chemicals are utilized. Chemical modification increases the binding sites and modifies the functional groups of the adsorbent resulting enhancement of the adsorption capacity as well as their mechanical strength. Literature review suggests utilization of various biosorbents for the removal of heavy metals and their adsorption capacity were investigated at laboratory scale. The results are promising, but the real application of those bioadsorbent is very limited. So to increase the industrial applications of the biosorbents, more pilot-scale studies are required.
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Biswas, S., Nag, S. (2021). Biomass-Based Absorbents for Heavy Metal Removal. In: Inamuddin, Ahamed, M., Lichtfouse, E., Asiri, A. (eds) Green Adsorbents to Remove Metals, Dyes and Boron from Polluted Water. Environmental Chemistry for a Sustainable World, vol 49. Springer, Cham. https://doi.org/10.1007/978-3-030-47400-3_14
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