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Kyomuhimbo, H.D.; Feleni, U.; Haneklaus, N.H.; Brink, H. Application of Enzyme-Nanoparticle-Polymer Composites in Wastewater Treatment. Encyclopedia. Available online: https://encyclopedia.pub/entry/49115 (accessed on 08 May 2024).
Kyomuhimbo HD, Feleni U, Haneklaus NH, Brink H. Application of Enzyme-Nanoparticle-Polymer Composites in Wastewater Treatment. Encyclopedia. Available at: https://encyclopedia.pub/entry/49115. Accessed May 08, 2024.
Kyomuhimbo, Hilda Dinah, Usisipho Feleni, Nils H. Haneklaus, Hendrik Brink. "Application of Enzyme-Nanoparticle-Polymer Composites in Wastewater Treatment" Encyclopedia, https://encyclopedia.pub/entry/49115 (accessed May 08, 2024).
Kyomuhimbo, H.D., Feleni, U., Haneklaus, N.H., & Brink, H. (2023, September 13). Application of Enzyme-Nanoparticle-Polymer Composites in Wastewater Treatment. In Encyclopedia. https://encyclopedia.pub/entry/49115
Kyomuhimbo, Hilda Dinah, et al. "Application of Enzyme-Nanoparticle-Polymer Composites in Wastewater Treatment." Encyclopedia. Web. 13 September, 2023.
Application of Enzyme-Nanoparticle-Polymer Composites in Wastewater Treatment
Edit

Different water treatment technologies such as photochemical degradation, biodegradation, electrochemical degradation, reverse osmosis, and membrane separation have been used to get rid of water pollutants. Enzymatic treatments have received great attention due to several advantages compared to physical and chemical treatments, such as mild operating conditions and high catalytic efficiency without harsh side effects. Oxidase and peroxidase enzymes from different sources have been immobilized on metal and metal oxide-polymer composites and used in the degradation of pollutants.

enzyme-nanoparticle-polymer composites wastewater pollutants

1. Introduction

In recent decades, the global community has increasingly recognized the formidable challenge posed by water pollution arising from the unregulated release of municipal and industrial waste [1][2]. Many industries including petrochemical, paints and explosives, food, pharmaceutical, leather and textile, pulp and paper, and cosmetics have contributed to this cause [3][4]. These discharges cause serious problems to aquatic life due to their high biochemical oxygen demand (BOD), chemical oxygen demand, and blockage of sunlight [5][6].
One of the industries producing the highest level of toxic chemicals from dyeing, printing, and finishing is the leather and textile industry [1]. The conversion of skin into leather in textile industries generates huge amounts of wastewater containing a variety of organic and inorganic chemicals such as dyes, neutral salts, phenols, and biogenic matter of skins [7][8]. The complex aromatic structures of these chemicals, especially the dyes, make them highly soluble in water and stable against light, aerobic decomposition, and oxidizing reagents [9]. Therefore, their accumulation leads to serious environmental concerns for aquatic life and human beings due to their adverse effects of toxicity, carcinogenicity, and mutagenicity [10]. Another industrial sector that has developed rapidly in the last century is the pesticide industry, as it is an important component of modern global agricultural systems for controlling pests and increasing crop yield [11]. These pesticides are applied in much higher doses than those required to kill the pests, and end up accumulating in water bodies via run off and percolation [12]. Unfortunately, these agrochemical residues not only pollute the aquatic systems and damage biodiversity, they cause serious health hazards to humans and may even directly or indirectly lead to death [13][14]. Moreover, these compounds have very long half-lives and can remain in the environment for several decades [15][16].
The growth of the pharmaceutical industry (veterinary and human medicines) in the past years has also led to rising amounts of drugs, antibiotics, and hormones. These medicines are not fully metabolized by living organisms and when these end up in wastewater treatment plants, they are difficult to biodegrade, since most of them are fat soluble [17][18][19]. For example a study conducted by Joss et al. [20] indicated that biological degradation of pharmaceuticals using activated sewage sludge from municipal wastewater could only degrade 4 out of 35 compounds by over 90% and 17 compounds by less than 50%. These compounds have increased in the environment due to their increased consumption and direct discharge into the environment. The presence of pharmaceuticals, cosmetics, and their metabolites in municipal waste and industrial effluents presents a significant challenge, as these compounds cannot be effectively eliminated using conventional techniques, and consequently are released to the receiving environment [21][22]. While in the environment, they accumulate or transform into metabolites under certain environmental conditions, and these secondary metabolites may even be more toxic than the parent compounds [12][23]. These make pathogenic organisms develop resistance against them over time, which is a high risk to human health [24].
The continued release, spread, and accumulation of persistent organic pollutants in the water environment from these industries, including polychlorinated biphenyls and polycyclic aromatic hydrocarbons from the petrochemical industries, have become a major threat to human health due to their toxic, mutagenic, and carcinogenic properties [25][26][27]. The emission of these pollutants occurs at the manufacturing stage, after consumption and disposal of unused products. These products are hard to be tracked or controlled in most situations and are resistant to natural biodegradation [12][28]. Most of these compounds are phenolic and, therefore, bio-recalcitrant, carcinogenic, and easily accumulate in plants and animals. They should, therefore, be removed prior to wastewater discharge [17][29][30].
Different water treatment technologies such as photochemical degradation, biodegradation, electrochemical degradation, reverse osmosis, and membrane separation have been used to get rid of these pollutants. However, these techniques are costly, consist of complicated procedures, do not entirely remove the pollutants, and lead to secondary contaminants that also need to be redisposed of [31][32]. Enzymatic treatments of these pollutants have received great attention due to several advantages compared to physical and chemical treatments, such as mild operating conditions and high catalytic efficiency without harsh side effects [33][34]. Hence, the use of biocatalysts in wastewater treatment has gained momentum due to their ability to target a wide range of pollutants [35]. Enzymes immobilized onto supports are often used in the treatment of wastewaters to ensure improved thermal and pH stability and repeatability, which is rarely achieved with free enzymes [36]. Various pollutants including drugs, dyes, pesticides, polycyclic aromatic hydrocarbons (PAHs), and even heavy metals have been degraded using enzyme/metal-polymer biocatalysts, as demonstrated in Figure 1. Oxidase and peroxidase enzymes from different sources have been immobilized on metal and metal oxide-polymer composites and used in the degradation of pollutants, as observed in Figure 1
Figure 1. Different pollutants that have been degraded by enzyme-nanoparticle-polymer composites. A—Laccase, B—Horse radish peroxidase, C—Lignin peroxidase, D—Chloroperoxidase, E—Glucose oxidase, F—Glucose oxidase/laccase, G—S. cerevisiae enzyme, H—Glycerophosphodiesterase, I—Manganese peroxidase, * 0–6 h, # 6–24 h, ɸ over 24 h.

2. Laccase-Based Nanocomposite Biocatalysts for Degradation of Pollutants

Laccase is the most explored enzyme in wastewater treatment due to its ability to degrade a wide range of micro pollutants including dyes, pharmaceuticals, and endocrine-disrupting chemicals [37][38][39]. Unlike other oxidoreductases, laccase does not require hydrogen peroxide or other cofactors for substrate cleavage [40][41][42] and its range of compounds for oxidation can be increased with redox mediators [43][44]. Laccase-based composite biocatalysts show great potential in wastewater treatment as they have demonstrated high pollutant degradation rates with high reusability (Table 1). For example, Laccase/Fe2O3/PEI biocatalyst completely degraded sulfa drugs (Sulfadiazine, Sulfamethazine and Sulfamethoxazole) within 30 min and could still degrade 82.8% after 10 cycles in the same time frame [24]. Laccase/Ca-alginate beads degraded 99% bisphenol A [19] and dyes (aniline purple–86%, lanset grey G–85%, and reactive black 5–80%) [45] in 2 h and 24 h, respectively.
Table 1. Application of enzyme-nanoparticle-polymer composites in degradation of organic pollutants for application in wastewater treatment.
Nanocomposite (NC) Immobilization Method Pollutants Removed Degradation (%) Degradation Time Reusability Ref.
TiO2/polyvinylidene fluoride (PVDF) Crosslinking of TiO2/PVDF membrane using APTES and glutaraldehyde followed by immersion in laccase solution Bisphenol A 95 5 h 91.7% (96 h of continuous use) [46]
TiO2/bacterial cellulose (BC) Physical adsorption of TiO2 on BC followed by crosslinking with glutaraldehyde and immersion in laccase solution Reactive red X-3B in presence of ABTS 80 60 min 70% and 57% (6 and 10 cycles, respectively) [1]
Calcium alginate Physical entrapment of enzyme in nanocomposite Fluoranthene in a fluidized bed reactor 81.06 8 h 66.845% (60 days of storage) [27]
Fe2O3/poly(ethylene glycol)/concovalin A Chemical co-precipitation followed by crosslinking with glutaraldehyde and immersion in laccase solution Sulfadiazine 100 30 min 82.8% (10 consecutive cycles) [24]
Sulfamethazine
Sulfamethoxazole
(all in presence of syringaldehyde mediator)
MNPs/chitosan Physical mixing of NPs and chitosan followed by crosslinking with glutaraldehyde and immersion in laccase solution Reactive black 5 90 30 min 47% (10 cycles) [47]
Evans blue 60 30 min
Tryphan blue 80 40 min
Direct blue 15 70 60 min
MNPs/polydopamine Functionalized MNP-polydopamine NC with dialdehyde starch followed by immersion in laccase solution 2,4-dichlorophenol 72 3 h 77% (8 cycles) [48]
91 12 h
Fe2O3/Cu-alginate Physical entrapment of enzyme in nanocomposite Triclosan 89.6 8 h 86.9% (3 cycles in acetate buffer) [4]
53.2 8 h (wastewater)
Remazol Brilliant Blue R (RBBR) 75.8 8 h
55 25 h (wastewater)
35 25 h (waste water)
Cu (II)-chitosan-graft-poly (glycidyl methacrylate)/poly (ethylene imine) Physical adsorption of laccase on nanocomposites Phenol in presence of ABTS 80 4 h 50% (8 cycles) [30]
MNPs/chitosan Crosslinking with glutaraldehyde followed by immersion in laccase solution 2,4-Dichlorophenol 91.4 12 h 75.8% and 57.4% (2,4-DCP and 4-CP after 10 cycles) [33]
4-Chlorophenol 75.5
MNPs/SiO2/poly (glycidyl methacrylate)-S-SH Physical adsorption of enzyme on the nanocomposite Meloxicam 92 48 h 82.3%, 88.9%, and 87.5% (meloxicam, piroxicam and Cd2+, respectively, after 5 cycles) [21]
Piroxicam 95
Cd2+ 94
MNPs/Poly(p-Phenylenediamine) Covalent immobilization using glutaraldehyde for crosslinking Reactive blue 19 80 1 h 43% (8 cycles) [6]
MNPs@MoS2/polyethyleneimine Physical adsorption of laccase on nanocomposite Malachite green 82.7 Overnight 62% (10 cycles) [25]
Bisphenol A 87.6
Bisphenol F
(all in presence of ABTS)
70.6
Cu-alginate Physical entrapment of enzyme in nanocomposite Fuschin blue 65 (HOBT) 4 h 100% and 95% (120 h continuous use and 15 days storage, respectively) [8]
Congo red 27 (ABTS)
Tryphan blue 51(syringaldehyde)
Malachite green 60 (ABTS)
Erichrome black T 50 (HOBT)
Crystal violet
(all in different mediators)
32 (HOBT)
Textile effluent in a continuous flow packed bed bioreactor 66 (colour)
90 (BOD)
98 (COD)
MNPs/chitosan Physical entrapment of enzyme in presence of ionic liquid and ABTS 2,4-dichlorophenol 100 4 h 93.2% (for 2,4-DCP after 6 cycles) [49]
Bisphenol A 100 72 h
Indole 70.5 72 h
Anthracene 93.3 72 h
MNPs/polyethylenimine Crosslinking of NPs with PEI using glutaraldehyde followed by chelation of laccase with Cu(II) Phenol in a fixed bed reactor 72.93% at a flowrate of 25 μL/min - - [34]
MNPs/Cu2+-PEG In situ oxidation of metal salt using PEG followed by physical adsorption of laccase Malachite green 100 (ABTS) 120 min 99.9, 90.1, 89.4, 94.6, 76.5, 80.1, 74.6, and 66.1% (respectively, for the dyes after 10 cycles) [10]
Brilliant green 96.5 (ABTS)
Crystal violet 95.2 (ABTS)
Azophloxine 97.7 (TEMPO)
Red MX-5B 86.6 (ABTS)
Methyl orange 92.7 (VLA)
Reactive blue 19 96 (TEMPO)
Alizarin red 83.7 (TEMPO)
TiO2/Zn-alginate Physical entrapment of enzyme in nanocomposite Alizarin red 61 5 h 100% (14 cycles) [50]
Tryphan blue 96
Malachite green 100
Indigo carmine 100
Ca-alginate Physical entrapment with crosslinking of enzyme prior to entrapment Bisphenol A 99 2 h 70% (10 successive cycles) [19]
Ca-alginate Physical entrapment of enzyme in nanocomposite Aniline purple 86.1 24 h - [51]
Ca-alginate Physical entrapment of enzyme in nanocomposite Reactive Red 180 67.2 11 days - [52]
Reactive Blue 21 88.05
Ca-alginate Physical entrapment of enzyme in nanocomposite Reactive T. Blue 92 72 h 22.3% (6 cycles) [53]
Ca-alginate Physical entrapment of enzyme in nanocomposite RBBR 85 2 h 52.1% and 70% (Bismarck brown and all the others, respectively) [45]
Reactive Black 5 80 24 h
Bismarck Brown R 55 24 h
Lancet Grey G 85 24 h
Cu-alginate Physical entrapment of enzyme in nanocomposite Acid dye 38% 24 h - [54]
MNPs/chitosan Crosslinking with glutaraldehyde followed by adsorption in laccase solution Reactive yellow 2 85 10 h - [55]
Reactive blue 4 60 12 h
MNPs/poly(GMA-MMA)/Cu-Poly(4-vinyl pyridine Polymer grafting with Cu chelation followed by adsorption of enzyme Reactive green 19 60 18 h 63%, 76%, and 59% (green, red, and brown dyes, respectively) [56]
Reactive red 2 88
Reactive brown 10 90
Cu-alginate Physical entrapment of enzyme in nanocomposite phenol model solution containing tannic acid, gallic acid, ferulic acid, resorcinol, and pyrogallol 75 6 h 35% (8 cycles) [57]
FScubes/PDA@PVDF Prepared the FS/PDA@PVDF membrane using solvothermal process followed by covalent immobilization of laccase using glutaraldehyde as cross linker Congo red 97.1 3 h 85% and 76% (7 days and 5 cycles, respectively) [58]

3. Horse Radish Peroxidase (HRP)-Based Nanocomposite Biocatalysts for Degradation of Pollutants

Another commonly explored peroxidase on nanoparticle-polymer composite materials is horse radish peroxidase (HRP), due to its ability to oxidize a wide range of phenolic compounds in the presence of hydrogen peroxide [59]. It oxidizes phenolic compounds by adding hydrogen peroxide to form corresponding radicals which spontaneously interact to form insoluble polymers that can be easily removed from the wastewater [60]. HRP/nanoparticle-polymer composite biocatalysts have been explored in the degradation of phenols, dyes, and endocrine-disrupting compounds, as illustrated in Table 2. For example, HRP/MNPs/polyvinyl alcohol/poly acrylic acid could completely degrade estrone after 40 min [18], and HRP/TiO2/polydopamine completely removed 2,4-dicholorphenol in Zhaohe wastewater samples in only 30 min [61]. Interestingly, the HRP/TiO2/polydopamine biocatalyst retained 100% and 90% degradation activity after 15 and 25 reuses, respectively.
Table 2. Application of enzyme-nanoparticle-polymer composites in degradation of organic pollutants for application in wastewater treatment.
Nanocomposite (NC) Immobilization Method Pollutants Removed Degradation (%) Degradation Time Reusability Ref.
TiO2/polydopamine In situ polymerization of dopamine on TiO2NPs followed by covalent crosslinking of enzyme with glutaraldehyde 2,4-dichlorophenol 100 30 min 100%, 90%, and 63.6% (15, 25, and 40 reuses, respectively) [61]
MNPs/poly(glycidylmethacrylate-co-methylmethacrylate) (poly(GMA-MMA)) Crosslinking of enzyme and nanocomposite beads using glutaraldehyde phenol 86 2 h 84% (8 weeks), 92%, and 79% (phenol and p-chlorophenol, respectively, after 48 h of continuous use) [3]
p-chlorophenol
(in the presence of H2O2)
59  
Fe2O3/poly (amido amine) (PAMAM)/silk fibroin Crosslinking of enzyme with nanocomposites using glutaraldehyde Bisphenol A in presence of H2O2 80 120 min - [62]
Calcium alginate Physical entrapment of enzyme in nanocomposite Acid blue 113 76 240 min Can be recycled up to 3 times [7]
Aluminosilicate halloysite nanotubes/chitosan Crosslinking of enzyme with nanocomposites using glutaraldehyde Phenol in presence of hydrogen peroxide 98.8 30 min 60% (4 cycles) [63]
MNPs/polyacrylonitrile Crosslinking of enzyme with nanocomposites using glutaraldehyde Phenol 85.2 - 52% (5 cycles) [29]
MNPs/poly(vinyl alcohol)/poly(acrylic acid) Physical adsorption of enzyme on nanocomposites Estrone 100 40 min 56.2% (7 cycles) [18]
MNPs/polymethyl methacrylate Physical entrapment of enzyme in nanocomposite Phenol in presence of hydrogen peroxide 55 50 min - [64]
MNPs/poly(glycidylmethacrylate-co-methylmethacrylate) (poly(GMA-MMA)) Crosslinking of enzyme with nanocomposite beads using glutaraldehyde Phenol 86 2 h 91% and 79% (phenol and chlorophenol, respectively, after 48 h of continuous operation) [3]
p-Chlorophenol
(in presence of hydrogen peroxide in a fluidized bed reactor)
59  

4. Other Oxidase and Peroxidase-Based Nanocomposite Biocatalysts for Degradation of Pollutants

Other enzymes such as chloroperoxidase, manganese peroxidase, and lignin peroxidase immobilized on composite materials, though not very popular, prove that they can offer wonderful materials for pollutant degradation (Table 3). For example, when lignin peroxidase was immobilized on MNPs@SiO2/polydopamine, it was able to degrade tetracycline and other phenolics such as 5-chlorophenol, phenol, and dibutyl phthalate completely within 24 h [32]. Manganese peroxidase immobilized on MNPs/chitosan degraded 96% of methylene blue in synthetic wastewater in just 50 min [2], glucose oxidase immobilized on NiFe2O4/tannin could degrade 98.6% of indigo carmine in presence of UV light within 90 min [31], and chloroperoxidase/TiO2/polydopamine nanocomposites degraded over 95% of aniline blue and crystal violet in 2 min [61].
Table 3. Application of enzyme-nanoparticle-polymer composites in degradation of organic pollutants for application in wastewater treatment.
Nanocomposite (NC) Enzyme Immobilization Method Pollutants Removed Degradation (%) Degradation Time Reusability Ref.
iO2/polydopamine Chloroperoxidase (CPO) Covalent crosslinking of enzyme with nanocomposites using glutaraldehyde Aniline blue 97.58 2 min 90.3%, 78.2%, and 53.71% (10, 15, and 20 reuses, respectively) [61]
Crystal violet 98.98 2 min
NiFe2O4/tannin Glucose oxidase Physical adsorption of enzyme on nanocomposite Indigo carmine in presence of UV light 98.6 90 min 85.57% (5 cycles) [31]
MnFe2O4/calcium alginate Glucose oxidase and
Laccase
Physical adsorption of enzymes on the nanocomposite Methylene blue 82.13 1 h - [9]
Indigo 25.09
Acid red 14 20.42
MNPs/PAMAM Glycerophosphodiesterase (GpdQ) Crosslinking of enzyme with nanocomposites using glutaraldehyde Organophosphate pesticide 44.5 120 days Used as a filter in a Pasteur pipette between two layers of sand [14]
MNPs@SiO2/polydopamine Lignin peroxidase Physical adsorption of enzymes on the nanocomposite Tetracycline 100 24 h 80.3% and 67.5% (7 and 14 days of storage), 70% and 30% (4 and 8 cycles, respectively) [32]
Dibutyl phthalate 100 24 h
5-chlorophenol 100 24 h
Phenol 100 24 h
Phenanthrene 79 24 h
Fluoranthene 73 24 h
Benzo(a)pyrene 65 24 h
MNPs/chitosan Manganese peroxidase Crosslinking of enzyme with nanocomposites using glutaraldehyde Methylene blue 96 50 min 91.7% and 86.7% (5 cycles-methylene blue and reactive orange, respectively) [2]
Reactive orange 16 98
Fe2O3/chitosan Saccharomyces cerevisiae enzyme Adsorption of chitosan on the NPs surface followed by crosslinking with enzyme using glutaraldehyde Cu(II) 96.8 60 min - [65]

 

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