Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 Contents lists available at ScienceDirect Journal of Environmental Chemical Engineering journal homepage: www.elsevier.com/locate/jece Efficiency of various recent wastewater dye removal methods: A review ⁎ T Vanitha Katheresan, Jibrail Kansedo , Sie Yon Lau Department of Chemical Engineering, Faculty of Engineering and Science, Curtin University Malaysia, CDT 250, 98009 Miri, Sarawak, Malaysia A R T I C LE I N FO A B S T R A C T Keywords: Wastewater dye removal Adsorbents Activated carbon Enzyme peroxidase Combined adsorbents Dye effluents released from numerous dye-utilizing industries are harmful towards the environment and living things. Consequently, existence of dye effluent in environmental water bodies is becoming a growing concern to environmentalists and civilians. A long term sustainable and efficient dye effluent treatment method should be established to eliminate this issue. Dye wastewater should be treated first before release to minimize its negative impacts towards the environment and living things. However, due to lack of information on efficient dye removal methods, it is difficult to decide on a single technique that resolves the prevailing dye effluent issue. Therefore, this paper reviews existing research papers on various biological, chemical and physical dye removal methods to find its efficiency through percentage of dye removal. Although there are numerous existing tried and tested methods to accomplish dye removal, most of them have a common disadvantage which is the generation of secondary pollution to the environment. This paper highlights enzyme degradation (biological) and adsorption (physical) dye removal as these are known as one of the most efficient dye removal techniques these days. This paper also suggests the usage of a combined adsorbent as it is envisioned that this technique has better efficiency and is able to remove dyes at a faster rate. 1. Introduction Synthetic dyes are a necessity in various significant industries such as the leather, paper as well as textile industries for its colour-giving properties. It is estimated that 700 000 tonnes of various colouring from about 100 000 commercially accessible dyes are manufactured each year [1,29,49,58,100]. Often, once dyes have served their purpose, most of them are discarded without further care into environmental water bodies. Five major industries, shown in Fig. 1, are known to be responsible for the presence of dye effluents in the environment. The textile industry (54%) releases the highest amount of dye effluent, contributing to more than half of the existing dye effluents seen in the environment around the world. The dyeing industry (21%), paper and pulp industry (10%), tannery and paint industry (8%) and the dye manufacturing industry (7%) too are known to produce high amounts of dye effluents from various associated processes [32,85]. The exact amount of dye effluents ejected by each industry into the environment is unknown but it can be said that the number is quite large to result as a significant environmental issue. Among other dye-utilizing industries, the textile industry is said to utilize the highest amount of dyestuff at approximately 10 000 tonnes per year worldwide [104]. Besides that, this industry is also known to produce around 100 tonnes of dye effluent per year, the highest amount ⁎ of dye wastewater from one industry alone [114]. High usage of dyestuff in various processes of textile industries result in generation of huge amounts of dye wastewater. Besides that, textile industries produces high amounts of dye effluents due to the tremendous water requirement by the industry [3,22,25,105]. For various processes in the textile industry, specific mixtures of chemicals, dyestuff and water is prepared. Once the process is complete, the leftover mixture (dye effluent) is discharged into the environment. For instance, 85% dye effluent is ejected from the dyeing process. This dye effluent is the leftover of the total amount of dye mixture prepared at the beginning of the dyeing process. The percentage of dye mixture ejected at the end of each process of the textile industry is shown in Fig. 2. It is deduced that dye effluents from the textile industry exist due to the inability of the dye mixture (dye molecules and chemicals) to completely attach itself onto a fabric or textile [103]. Generally, only a maximum 80% of dye and chemical molecules from dye mixtures are able to be adsorbed by materials intended for colouring [92]. Fabrics in particular, can only absorb a maximum 25% of dye mixture onto its body due to its limited absorption capacity [39]. Dye effluents, better known as dye wastewater, is rich with numerous hazardous chemicals shown in Fig. 3. Dye effluents can endanger the lives of animals and humans as they are toxic by nature. It is Corresponding author. E-mail address: jibrail.k@curtin.edu.my (J. Kansedo). https://doi.org/10.1016/j.jece.2018.06.060 Received 27 February 2018; Received in revised form 26 May 2018; Accepted 26 June 2018 Available online 26 June 2018 2213-3437/ © 2018 Elsevier Ltd. All rights reserved. Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. Fig. 1. Industries responsible for the presence of dye effluent in the environment [102]. Fig. 2. Discharge percentage of dye mixture from each process of the textile industry [22]. paper is to review studies on different dye removal methods according to its dye removal percentage. This paper was composed due to the lack of information on the efficiency of available dye removal methods in literature. Following that, this paper highlights the most suitable dye removal technique based on the review conducted. This paper highlights enzyme degradation (biological) and adsorption (physical) dye removal as these are known as one of the most efficient dye removal techniques these days. The highlighted methods are believed to efficiently remove dye particles from wastewater in a short period of time with no harmful by-products. easy to spot water bodies containing dye effluents as its colour gives it away [7,72]. Presence of dye effluents in water sources are unacceptable as water is required by animals and humans for daily activities such as bathing, cooking, drinking and washing [132]. Nowadays, removal of dye molecules from water sources has not only become a major environmental concern but also a challenge [58,59,75]. Techniques of recovering and reusing dye wastewater received the limelight recently as clean water sources might soon begin to deplete rapidly if no dependable solution is found. Developing a fixed solution to permanently eliminate dye particles from textile effluents would greatly benefit the environment [98,130]. Currently, various dye removal methods have been established in countless research papers claiming successful dye removal. Although there are a variety of applicable dye removal techniques, not all of them are successful or even suitable to be practiced due to their disadvantages [43,78]. An ideal dye removal method should be able to efficiently remove large quantities of dye from wastewater in a short time span without producing secondary pollution. It is encouraged to remove pollutants from wastewater with a method that does not produce more hazardous by-products (secondary pollution) [104]. This paper describes different types of dyes as well as dye removal methods biologically, chemically and physically. The focal aim of this 2. Dyes Dyes are colourful substances designed to give materials such as fabrics, papers, or any colourable materials a hue. This is possible as dyes can attach themselves onto any amenable materials [138,140]. Dyes have been utilized by humans for over a thousand years for various applications. Those days, dyes were usually produced on a small scale from naturally available material such as insects or plants and are known as natural dyes [63]. However, the drawback with natural dyes was its limited variety as well as muted tones which fades when exposed to sunlight and washing [114]. 4677 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. Fig. 3. Hazardous chemicals used along with dyes by dye-utilizing industries [55,63,86]. detergents or any other washing agents [7]. Dye molecules can withstand degradation even when exposed to extreme heat sources, oxidising agents or strong light [29,43,59,98]. Synthetic dyes were only recently discovered and its production in large scales started due to the rise in dye demand. An extensive range of synthetic dyes was invented by WH Perkins in the year 1856 spotting various brilliant, colourfast tones for numerous uses [63]. This invention solved the problem natural dyes retained but new issues arose whereby dye-utilizing industries ejected dye wastewater into the environment without proper treatment. This presented dire consequences as presence of dyes in water sources posed a threat to living things in the environment due to its toxic nature [47]. Although it seems that resuming the usage of natural dyes are a better alternative, it was found that this scenario was just as bad as utilizing synthetic dyes alone. This is because in order to make sure the natural dyes bond with fabrics, a mordant is required [104]. Mordants are a kind of binding agent that aid in the attachment of natural dye to materials. Mordents are very much toxic and more dangerous than synthetic dyes [63]. Nowadays, synthetic dyes have become a crucial ingredient widely used to give colour to textiles, cosmetics, plastics and printing [1,4,92]. This is due to the fact that dyes are naturally recalcitrant substances and degrading it is not easy nor possible. Synthetic dye molecules are complex as well as stable structures due to the presence of auxochromes (water soluble bonding compound) and chromophores (colour giving compound) it contains [25,97,105]. This quality of dyes complicate its degradation process using straightforward methods. The reason as to why dyes are created this way is so that the colour of a dyed material does not fade easily [35]. They are made as complex organic substances so that they can resist getting degraded upon contact with water, 2.1. Types of dyes There are many types of synthetic dyes and they can be classified based on their molecular structure as tabulated in Table 1, as is commonly done. Sometimes, dyes are classified by their application or even by their solubility. Acid, basic, direct, mordant and reactive dyes are examples of soluble dyes while azo, disperse, sulphur and vat dyes are example of insoluble dyes [102]. Among all dye types, azo dyes are the highest produced dye type at 70% production rate and it is the most frequently utilized dye worldwide [28]. Regardless of its structure, all synthetic dyes have a common disadvantage which is its hazardous nature [86]. Due to this, synthetic dyes should not be allowed to enter the environment untreated to blend with water sources. Due to its noxiousness, dyes have caused grave concern to environmentalists and water consumers. Therefore, efforts in methods and technologies that can permanently remove one or more dye types from water bodies are greatly welcomed [72,85,132]. 3. Importance of dye removal Dye-utilizing industries usually store dye effluents as industrial waste after dyes have fulfilled their role in colouring materials [114]. 4678 4679 Inks, medicine, modified nylon, modified polyester, paper, polyacrylonitrile, polyester, silk, tanninmordanted cotton and wool Cotton, leather, nylon, rayon, silk and paper Acetate, acrylic fibres, cellulose, cellulose acetate, nylon, polyamide, polyester, polyester-cotton and plastic All fibres, oils, paints, plastics and soaps as well as detergents Food, drug, and cosmetics Basic (cationic dye) (water soluble) Direct (water soluble) Disperse (water insoluble) Fluorescent brighteners Food, drug, and cosmetics Mordant Oxidation bases Fats, gasoline, inks, lacquers, lubricants, oils, plastics, stains, varnishes and waxes Cotton, leather, paper, polyamide fibres, rayon, silk and wood Cotton, cellulosic fibres, polyester-cotton, rayon and wool Solvent (water insoluble) Sulphur Vat (water insoluble) Cellulosic, cotton, nylon, silk and wool Reactive (water soluble) Anodized aluminium, natural fibres, leather and wool Cotton, fur and hair Cosmetics, food, leather, modified acrylics, nylon, paper, printing ink, silk and wool Acetate, cellulose, cotton, rayon and polyester Acid (water soluble) Azo Applications Type Table 1 Various types and applications of dyes [3,49,58,117]. Aromatic substrate vatted with sodium sulfide and reoxidized to insoluble sulfur-containing products on fibre Water-insoluble dyes solubilized by reducing with sodium hydrogen sulphite, then exhausted on fibre and reoxidized Along with chromium salts The substrate is oxidised with aromatic amines and phenols Reaction between functional group on fibre and reactive site on dye. Covalently bonding under the influence of heat and an alkaline pH Substrate dissolution Anthraquinone, azo, carotenoid and triarylmethane. Mixing Anthraquinone (including polycyclic quinines) and indigoids Indeterminate structures Vat Blue 4 (indanthrene). Solvent red 26, Solvent blue 35 Sulphur black 1 Reactive Blue 5 Anthraquinone, azo, basic, oxazine, formazan, triphenylmethane and phthalocyanine Anthraquinone, azo, phthalocyanine and triphenylmethane Mordant Red 11 Direct Blue Disperse Blue 27, Disperse Red 4, Disperse Yellow 3 4,4′-bis (ethoxycarbonylvinyl) stilbene Food Yellow 4 and tartrazine Direct Orange 26 Methylene Blue Bluish red azo dye Acid Yellow 36 Example Anthraquinone and azo Aniline black and indeterminate structures Anthraquinone, azo, benzodifuranone, nitro and styryl Coumarin, naphthylamides, pyrazolos and stilbene Acridine, anthraquinone, azine, azo, cyanine, diazahemicyanine, diphenylmethane, hemicyanine, thiazine, triarylmethane, oxazine and xanthene Azo, phthalocyanine, polyazo, stilbene, and oxazine Azo (including premetallized), anthraquinone, azine, nitro, nitroso, triphenylmethane and xanthene Azo Chemicals Required In dye baths with neutral or slightly alkaline conditions with additional electrolyte. Padded on cloth and either baked or thermofixed at high pressure and temperature or low temperature carrier methods Mass dispersion, solution or suspension Coupling component used to impregnate fibre and a solution of stabilized diazonium salt is used for treatment In dye baths with acidic conditions In dye baths with neutral to acidic conditions Application Method V. Katheresan et al. Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. These wastes are then purged into the environmental water bodies changing colourless clean water into contaminated coloured water. The appropriate act that should be performed by these industries before releasing dye wastewater into the environment is treating it. Water pollution due to the presence of dyes are unacceptable to environmentalists as well as the public because they are hazardous toxic substances [104]. Sometimes, concentrated dye effluents with high pH (acidic) and temperature are released immediately after dyeing processes. The oxygen transfer mechanism and the self-purification process of environmental water bodies will get disturbed by this phenomenon [19,63]. When released into the environment after usage, these effluents pose a threat to the ecosystem by polluting water sources disabling water usage. Dye effluents mixed with natural water source produces a foul odour besides creating an eye sore to people. Beginning with the aquatic animals and plants, textile effluents can harm living things on land as well [57,75,140]. When dye effluents blend with water sources, the turbidity of water increases as dye effluents tend to form a visible layer above the water surface due to their lower density at 0.8 kg/m3 compared to the density of water, 1.0 kg/m3. This blocks the penetration of sunlight required by living things below the water for processes like photosynthesis and respiration ceasing its existence [25,49,102]. Next, damage to the soil productivity will occur if the dye effluent finds its way into forests or fields proceeding to clog soil pores [122]. The quality of water will persistently deteriorate and become a breeding ground for bacteria and viruses making it unsuitable for daily usage or consumption. Animals utilizing this water source will suffer the lack of clean drinking water. Villagers and indigenous people solely depending on rivers as their source of water will be deprived of water supply or worse, unknowingly consume the contaminated water and fall sick [4,59]. Releasing dye effluents into the environment does nothing but gradually degrade the environment and induce human health issues. Dye effluents that comes in contact with skin can cause skin irritation. If dye effluents comes into contact with one’s eye, eye burns or even permanent eye injury may result for animals and humans alike [103]. Chemicals present in dye effluents dumped into water sources can evaporate into the surrounding and upon inhalation, shortness of breath or difficulty in breathing can be experienced [104]. Ingesting dyes can cause extreme sweating, confusion, methemoglobinemia, mouth burns, nausea or vomiting [100,105]. Dyes are also conventional carcinogens and long term effects to one’s body or unborn child is unavoidable. Therefore, treating wastewater with detrimental dye effluents is significant to prevent its destructive impacts on receiving waters, animals and humans [7,8,63,131]. Dumping dye wastewater into the environment was not given much consideration in the past. This issue only got the deserved attention after health troubles started to arise sometime in the past 30 years [29,49]. Following that, information on dyes, its application, and methods to remove it were delved into to find solutions. These solutions were then implemented by dye manufacturers, dye utilizing industries and even the government to remove dye particles from water sources [92]. Recently, the environmental legislature set a law on the presence of toxic coloured wastewater in water bodies [45,72]. As per this law, dyeutilizing industries have to ensure wastewater released from their factories abide by The International Dye Industry Wastewater Discharge Quality Standards were adopted from the Zero Discharge of Hazardous Chemicals Programme (ZDHC) [35]. Textile wastewater is rich with pollutants such as biological oxygen demand (BOD), chemical oxygen demand (COD), colours, hazardous chemicals, and dissolved salts (TDS and TSS) [58,117]. The international permissible standard dye effluent pollutant discharge is shown in Table 2. Levels of biological oxygen demand (BOD), chemical oxygen demand (COD), colour, pH, suspended solids and temperature of the Table 2 International standard of dye effluent discharge into the environment [17,78,85]. Factor Standard allowed Biological oxygen demand Chemical oxygen demand Colour pH Suspended solids Temperature Toxic pollutants Below 30 mg/L Below 50 mg/L Below 1 ppm Between 6–9 Below 20 mg/L Below 42 °C Not allowed to be released dye effluent released should be below the amount permissible to be released. Toxic pollutants are certainly not allowed to be released into the environment due to its dreadful consequences. Industries producing dye wastewater should start rectifying the damage and harm they are inflicting towards the environment as well as living things. Along with researchers working to eliminate dye wastewater from the environment, dye-utilizing industries too should make an effort to avoid releasing dye wastewater in to the environment. Dye-utilizing industries should stop causing pollution and start establishing dye effluent treatment plans instead [102]. As for some of the more responsible dye-utilizing industries, it is strongly recommended that they reuse treated dye wastewater in their dyeing processes instead of disposing it into the environment. That is a more economical concept than buying and using fresh water for dyeing processes repeatedly. Fresh water, at the amount required by dyeing industries does not come cheap and cost cutting is usually a desired factor by all industries [132]. 4. Methods of dye removal In the late 90’s, dye removal methods include only preliminary water purification processes such as equalisation and sedimentation due to the fact that there were no dye effluent discharge limit [103]. After permissible dye effluent release standards were established, improvements were made by introducing more effective dye removal methods such as dye degrading filter beds and activated sludge processes [82]. Following that, a system for dye wastewater treatment shown in Fig. 4 was introduced. This system, known as the traditional dye removal method, was implemented by the concerning industries for some time till it was stopped due to its high cost of operation and maintenance [3]. Currently, numerous researches are being done to find the ideal dye removal method so that dye wastewater can be recovered and reused according to that [107]. Existing methods of dye removal can be separated into three categories namely the biological, chemical, and physical treatments [122]. Although many dye removal methods have been researched in the past 30 years, only several are truly being implemented by the concerning industries these days because of limitations posed by majority of the methods [32,100,138]. 4.1. Biological dye removal methods In most countries, the typical biological method is the commonly and extensively utilized dye removal method to treat dye wastewater. Generally known as the conventional method, a combination of aerobic and anaerobic process is carried out before dye effluents are released to the environment [7]. This method was chosen as the go-to dye removal method mainly because it is very cheap and can be accomplished easily [103]. As a matter of fact, this treatment alone is insufficient to completely remove hazardous particles from textile dye wastewater which is why coloured water is still seen in the environment [97]. Although the conventional method does treat the chemical oxygen demand present in the wastewater, it does not make the water dye-free or toxicfree. Besides this method, other conventional biological dye removal 4680 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. removal methods are advanced oxidation process, electrochemical destruction, Fenton reaction dye removal, oxidation, ozonation, photochemical and ultraviolet irradiation. The mentioned methods are tabulated along with its description, advantages and disadvantages in Table 4. Most of the chemical dye removal methods are costly compared to biological and physical dye removal methods with an exception to the electrochemical degradation dye removal method. Chemical dye removal methods are also commercially unattractive, requires specific equipment and requires high electrical energy [35]. High electrical energy is required to power equipment or reactors in which chemical dye removal takes place. Besides that, chemical as well as reagent consumption on a large scale is an issue commonly reported by users of chemical dye removing methods [29]. Another undesirable characteristic of this method is the generation of toxic secondary pollution resulting at the end of a chemical dye removal processes presenting an additional disposal problem [131]. 4.3. Physical dye removal methods Physical dye removal methods are usually straightforward methods commonly accomplished by the mass transfer mechanism. Conventional physical dye removal methods are adsorption, coagulation or flocculation, ion exchange, irradiation, membrane filtration, nano filtration or ultra-filtration and reverse osmosis. These methods are tabulated along with its description, advantages and disadvantages in Table 5. Among the three methods (biological, chemical and physical), branches of physical dye removal are the most commonly used methods. These methods are often chosen for its simplicity and efficiency. By far, this method requires the least amount of chemicals compared to the biological or chemical dye removal methods [69]. This method does not deal with living organisms hence is considered to be more predictable than the other two dye removal methods. 4.4. Efficiency of dye removal methods The mentioned dye removal methods biologically, chemically and physically are methods that have been tried and tested by numerous researches. It should be noted that not all dye removal methods can guarantee a successful dye removal. Sometimes, the conditions set for dye removal can influence the results obtained at the end of a dye removal process. Table 6 provides a list of research done by other authors on the various dye removal methods with an exception of the membrane filtration (physical) method as this method was found be an inefficient method of dye removal. Table 6 compares research papers on various dye removal techniques in terms of their dye removal percentage. The average success rate of each method was displayed for easier efficiency comparison. As shown in Table 6, chemical dye removal processes displayed the highest percentage of dye removal ranging from 88.8 to 99%. However, chemical dye removal methods often possess intolerable disadvantages as shown in Table 4. Besides that, chemical dye removal processes with the exception to upcoming electrochemical destruction technologies depend on the dye solution pH and in most cases pose the issue of secondary pollution generation. Due to the heavy weightage of disadvantages in chemical dye removal methods, these methods should be not be considered for dye removal if possible [130]. Dye removal by biological or physical methods are fairly successful. Biological dye removal methods have a removal percentage ranging from 76 to 90.1% with the enzyme degradation method ranking highest on the list. The enzymatic dye degradation method is an adequate and reliable dye removal method. This method is cheap, efficient, non-toxic and very importantly reusable. Its only disadvantage is its unreliable amount of enzyme production but this issue can be easily solved with the selection of a proper raw material and extraction method. Physical dye removal methods have a removal percentage ranging Fig. 4. Traditional wastewater treatment system [95]. methods are adsorption by microbial biomass, algae degradation, enzyme degradation, fungal cultures, microbial cultures as well as pure and mixed culture. The mentioned methods are tabulated along with its description, advantages and disadvantages in Table 3. Biological dye removal methods incorporates some form of living organism in its process. This method should be used with caution and engineering ethics should be uphold. Utilization of enzyme to remove dye is becoming quite famous these days as it is believed that branches of biological dye removal methods are the cheapest as well as safest methods of dye removal [114]. Since this method deals with living things, its major disadvantage is its growth rate. System instability is common in biological dye removal processes as predicting its growth rate and reactions can be tricky at times. 4.2. Chemical dye removal methods Chemical dye removal methods are methods utilizing chemistry or its theories in accomplishing dye removal. Conventional chemical dye 4681 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. Table 3 Various biological dye removal methods along with its advantages and disadvantages [3,25,78,85,117]. Method Description Advantages Disadvantages Adsorption by microbial biomass Mixture of organic living organisms fashioned to adsorb dye molecules. Algae consumes dye particle for self-growth. Selected dyes have an exceptional affinity towards microbial biomass Not an effective method for all dyes Able to consume dyes. Cheap. Easily assessable. Environmental friendly process. Able to fairly decolourize a variety of dye types. Cheap. No foam formation. Unstable system. Algae degradation Aerobic-anaerobic combination (conventional method) A prepared sludge breaks down complex dye molecules. Enzyme degradation. Extracted enzyme used to degrade dye molecules. Fungal cultures Fungus breaks down dye molecules and consumes them for self-growth. Bacteria mixed with chemicals or other bacteria to remove dye particles. Mixtures of algae, bacteria or fungus with necessary chemicals to remove dye. Microbial cultures such as mixed bacterial Pure and mixed culture Cheap. High efficiency. Non-toxic. Possesses the ability to degrade dyes using enzymes. Reusable. Can eliminate various types of dyes at once. Flexible method. Takes a maximum of 30 h in decolourization of dye wastewater which is considered fast. Reusable. Suitable only for azo dye removal. Does not completely eliminate all dye particles. Formation of methane and hydrogen sulphide as by-products. Inflexible method. Large land area requires. Produces sludge. Takes long time. Unreliable amount of enzyme production. Lengthy growth phase. Needs a nitrogen confined area to grow. Requires large reactors for complete dye removal. Unstable system. Effective to a limited number of dyes. Large scale application is preferred due to high cost. Colourless toxic by-products. Produces sludge. Requires conventional method as post-treatment. Table 4 Various chemical dye removal methods along with its advantages and disadvantages [43,49,59,105,142]. Method Description Advantages Disadvantages Advanced oxidation process Multiple oxidation process done simultaneously to remove dye particles. Expansive. Not flexible. Production of undesirable by-products. pH dependent. Electrochemical destruction Electro-coagulation or non-soluble anodes are used to eat up dye molecules. Can eliminate toxic materials. Can remove dye in unusual conditions. Good dye removal method. Chemicals do not get consumed and no sludge build-up. Fairly suitable soluble and insoluble dye removal method. Fenton reaction Fenton’s reagent (mixture of catalyst and hydrogen peroxide) to remove dye particles from wastewater. Oxidation Oxidising agents used to treat dye effluents. Agents break down complex dye molecules to carbon dioxide and water. Usage of catalyst can further enhance the process. Ozone produced from oxygen is used to eliminate dye particles. Ozonation Photochemical Ultraviolet irradiation Fenton reaction coupled with ultraviolet light to remove dye molecules from wastewater. Usage of UV light to decompose dye particles in wastewater. Fairly suitable dye removal method for soluble and insoluble dyes. Removes all toxins in water. Suitable for dyes wastewater with solid content Can completely degrade dyes. Common chemical dye removal method. Short reaction time. Straightforward application Can be used in its gaseous state. Does not increase wastewater volume. Effective dye removal method. No sludge generation. Quick reaction. Effective dye removal method. No foul odours production. No sludge production. Hazardous chemical required. No sludge production. Weakens foul odours. Additional hazardous material production. High cost of electricity. Less effective dye removal compared to other methods due to high flow rates. Cannot remove disperse and vat dyes. High iron sludge generation. Long reaction time. Works only on low pH. Costly. Difficult to activate hydrogen peroxide agent. pH dependent. Requires catalyst for efficient removal. Has an extremely short half-life for only 20 min. High cost. Produces toxic by-products. Unstable method. Expansive. Forms a lot of by-products Energy depletion. High cost. Limited treatment times. of dyestuff [3,29,100,105,117]. This method can even be used to purify industrial wastewater or to clean drinking water. It is common knowledge that synthetic dyes cannot be removed from dye wastewater through conventional methods due to its inefficiency in completely removing dye from dye wastewater [104]. This leaves adsorption as one of the ideal methods to remove dye. Dye effluents treated by the adsorption method resulted in the production of higher treated water quality compared to other dye removal methods [55,75,142]. The one disadvantage this method had was its high cost of adsorbents but with the discovery of cheap but equally efficient adsorbents, this method rose to become an economical method of dye removal worldwide [4,63,85]. Adsorption is a mass transfer process whereby elements gather at the interface of two similar or different phases for instance gas-liquid, gas-solid, liquid-liquid and liquid-solid [32,138]. Adsorption is an efficient equilibrium separation process commonly utilised for water purification operations. Adsorption is a non-reactive process whereby a solid surface is concentrated by a substance initially present in a from 86.8 to 99% with the adsorption method ranking highest on the list. The adsorption dye removal method is an outstanding dye removal method capable of degrading almost any dye or a mixture of dyes easily. Similar to the enzyme degradation method, the adsorption method too can be repeatable several times until the adsorbent is spent. The only disadvantage of this method is certain adsorbents can be quite expansive due to naturally high efficiency of the method. This issue can be solved by selecting low cost raw materials to be fashioned as alternative adsorbents. Seeing that both the enzyme degradation and adsorption methods are efficient in dye removal, merging of these methods into a single dye removal technique should be considered for future dye removal technologies. 5. Dye removal through adsorption Among the numerous tried and tested dye removal methods, adsorption (physical method) emerged as one of the preferred technique of dye removal due to its outstanding ability to remove almost any type 4682 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. Table 5 Various physical dye removal methods along with its advantages and disadvantages [55,58,63,132,138]. Method Description Advantages Disadvantages Adsorption Adsorbents fashioned from high adsorption capacity materials to adsorb dye molecules. Coagulation/flocculation inducing agents are added to dye wastewater where dye particles clump together. Clumps can then be removed through filtration. A reversible chemical process whereby ions from the dye wastewater swaps with similar ions attached to a stationary solid surface. Radiation is used to remove dye molecules from dye wastewater. Dye wastewater is passed through a membrane which separates dye particles from clean water. Excellent removal method for a wide variety of dyes. Re-generable adsorbent. Cheap. Robust method. Suitable only for disperse, sulphur and vat dye effluents. Adsorbents can be costly Coagulation and flocculation Ion exchange Irradiation Membrane filtration Nano filtration and ultra-filtration Reverse osmosis Dye wastewater is passed through a thin-pored membrane which separates dye particles from clean water. Pressure driven system where water is passed through an extremely thin membrane leaving contaminants on one side and water on the other. Can be regenerated. Good dye removal method. Produces high quality water. Effective at laboratory scale. Effective for water recovery and reusing. Can remove any type of dye Common water recycling method. Effective for decolouring and desalting a variety of dyes. Produces clean and pure water. Generation of huge amounts of concentrated sludge. Not suitable for acid, azo, basic, and reactive dye effluents. Sometimes expansive due to requirement of special chemicals. pH dependent system. Effective to a limited number of dyes A huge amount of dissolved oxygen is required. Expansive. Costly initial investment. Easy membrane fouling. Produces concentrated sludge. Unsuitable for dye removal. High cost. High energy consumption. Membrane pores constantly clogged by dye molecules. Requires high pressure. Short life span. Costly. Requires high pressure. significant parameters affecting adsorption along with the effects of the parameter in dye removal [1,3,58,138]. gaseous or liquid surrounding [59,92]. This process lowers the concentration of dissolved particles from an effluent. The substance that gets adsorbed is called the adsorbate while the substance used to adsorb the adsorbate is the adsorbent. Adsorption can be accomplished by two approaches, chemical sorption (chemisorption) and physical sorption (physisorption) [122]. Often, adsorption is conducted through physisorption with minor exceptions where chemisorption is used instead. In physisorption, other forces such as dipole-dipole, hydrogen bonds and polar bonds can also ensure adsorption occurs. In most solid-liquid systems (a mixture of solid adsorbent and dye effluent), the end result would be a colourless treated solution. The adsorbent works by separating dye particles (solutes) from dye solution hence accumulating it on its surface. Once all the dye molecules have been adsorbed onto the adsorbent, the system is said to be in dynamic equilibrium. Adsorption is an exceptional dye removal technique as it does not require any additional special equipment and is easy to conduct [132]. Besides that, no pre-treatment is required for the commencement of adsorption. Sometimes the adsorption technique is used as post-treatment after using the conventional method to decolourize dyes effluents as shown in Fig. 4. The adsorption process is best conducted with porous materials so that dye removal is efficient [31,45]. One desirable quality of the adsorption technique is that no additional hazardous material will result at the end of the process making it suitable for pollution control applications [19,100]. To ensure the production of high quality treated effluents, proper design of adsorption system is crucial. Furthermore, in order to ensure a higher rate of adsorption, the factors affecting adsorption should be acknowledged and used as guidance. 6. Adsorbents for adsorption dye removal method An adsorbent is a porous insoluble sponge-like substance with the ability to capture and trap adsorbate particles onto itself [1,69]. An adsorbent is not necessarily made of solid raw materials but can be fashioned from any other raw materials deemed suitable. Liquids-based raw materials such as enzymes too can be synthesized into an adsorbent. An adsorbent is the most crucial element of the adsorption process. The one issue frequently related to the adsorption technique is the cost of the adsorbent utilized [29]. To eliminate this issue, cheaper adsorbents were discovered and established in numerous research papers. (Rafatullah et al. [100]) gathered 185 scattered research papers on low cost adsorbents and discussed it in a single review paper to prove the existence of cheap as well as effective adsorbents. Natural materials and even waste materials can be fashioned into an adsorbent for textile wastewater dye removal [4]. Some of the materials mentioned can completely remove dyestuff without a trace left from dye wastewater. The most crucial factor of an adsorbent is its adsorption capacity, the amount of adsorbate it can adsorb onto its surface. Another fundamental characteristic of a good adsorbent is its surface area [103]. The more porous an adsorbent, the higher the surface area of the adsorbent ensuring a high adsorption capacity [17]. Thirdly, a short adsorption period is also a desired trait of a good adsorbent. The time taken for the system to reach equilibrium should be short so that dye removal can be done in a short period of time. Fourthly, an adsorbent should be selected based on its diversity in removing a wide range of pollutants [32]. A good adsorbent should be able to function in varying dye concentrations, a wide range of pH as well as temperature. A list of low cost high efficiency adsorbents are listed along with its surface areas in Table 8. 5.1. Factors affecting adsorption The adsorption method works efficiently on an industrial scale as well as laboratory scale. The rate of adsorption depends on the parameters affecting the adsorption process such as the adsorbent dosage, the contact time between the adsorbate and the adsorbent, the dye concentration, the solution pH and the temperature of the solution [17,131,142]. Changes in any of the five parameters will affect the rate of adsorption. To ensure achievement of the desired rate of removal, optimum adsorption conditions should be set when conducting labscaled experiments. This can help develop as well as establish industrial-scaled dye removal treatments. Table 7 describes the five most 6.1. Activated carbon as an adsorbent These days, adsorption though activated carbon based adsorbents are more conventional as well as efficient compared to other adsorbents [3,32,138]. It is shown in Table 8 that activated carbons have a wide range of surface areas and its highest value is 2000 mg/g. Activated carbons can be produced from any material containing high levels of carbon in its composition. Desirable characteristics of activated carbon 4683 Rathilene Scarlet Red Acid Red 27 Methylene Blue Remazol Black B Direct Blue 2 Dead microbial Saccharomyces cerevisiae Isolated microbial Plouritus ostreatus Average success rate Algae degradation Immobilized Desmodesmus sp. Dried green algae Chlorella vulgaris Coagulated alginate taken from marine brown algae (Sargassum sp) 4684 A mixture of anthraquinone and azo dyes Acid Black 10 BX Green Domalan BL Acid Violet 109 Malachite Green Acid Red 151 and Orange II Wool dyeing effluent treatment through sequencing batch reactor Average success rate Enzyme degradation. Free and immobilized horseradish peroxidase Peroxidase extracted from post-harvest Lentil (Lens culinaris L.) stubble Horseradish peroxidase Average success rate Fungal cultures Immobilized Aspergillus niger fungal biosorbent Aspergillus flavus SA2 brown-rot fungi in the bio removal of azo dyes Decolourization with sequencing batch reactor system with 15 day old sludge Remazol Black 5, Remazol Brilliant Red 21 and Remazol Yellow RR Reactive Red 198 Methylene Blue Biological Adsorption by microbial biomass Spent immobilized rice straw biomass Average success rate Aerobic-anaerobic combination (conventional method) Real textile wastewater decolourized in a two-phase partitioning bioreactor Dye Method Table 6 Efficiency of various dye removal methods. Maximum dye adsorption occurred when the fungus adsorbent dosage was 15 g/L and contact time was 72 h at a dye concentration of 15 mg/L. To ensure maximum adsorption, the pH was set at 5.0 while the temperature of the solution was maintained at 32 °C. Agitation speed for the process is ideally 140 rpm. Best condition to remove dyes were found to be at a contact time of 8 days, dye concentration of 20 mg/L, pH of 5.6 and temperature of 30 °C. Experiment will produce better results when it is in shaking mode. Contact time was varied from 0 till 90 min. Dye concentration was varied from 5 to 40 mg/l. Enzyme concentration was varied from 0.735 to 4.41 units/ml. Hydrogen peroxide concentration was varied from 0.1 to 0.8 μl/l . pH was varied from 2 till 9. Highest dye removal through enzyme degradation occurred when the contact time is 60 min, dye concentration is 76 mg/L and when enzyme dosage was set at 2.26 U/mL onwards. Hydrogen peroxide concentration of 0.3 mM in 20 mM acetic acid or acetate buffer was considered ideal for this removal process along with centrifugation performed at 10 000 rpm for 2 min, pH value 4 and a temperature around 25 °C. Optimum treatment condition was when contact time is 15 min, dye concentration 30 mg/L, enzyme concentration 0.15 IU/mL, hydrogen peroxide concentration 0.4 mM, pH value 4, and temperature 24 °C. The Hytrel 8206 reactor along with the two-phase partitioning bioreactor (TPPB) were functioned simultaneously to obtain the best dye removal results where the pH was controlled from 4.5 to 7.5 and the reaction time was 23 h. Dye removal system was showing best results with initial dye concentration of about 20 mg/L. The system that produced best results was set to perform anaerobic activities for 16 h and aerobic activities for 4 h. Ideal pH for this method was 8. Only BOD and COD successfully removed at 95% and 85%. Maximum dye removal at contact time around 9 h at temperature around 20 °C. Maximum dye removal after 6 days contact time when dye concentration was set at 20 mg/L. Highest rate of dye removal when temperature is 35 °C and pH is 2. Successful dye removal until initial dye concentration reached 800 mg/L. Requires a contact time of at least 24 h. Batch studies were conducted and maximum dye removal was noticed when coagulant dosage is 40 mg/L, calcium dosage is 6 g/L, initial dye concentration is 200 mg/L and initial pH 4. Maximum dye removal at 1% adsorbent dosage, dye concentration of 300 mg/L, pH value 7 and at temperature 30 °C in 2 days. Ideal dye removal at contact time 30 min and temperature 25 °C. Highest percentage of dye removal observed when contact time is 9 days, dye concentration is 0.04 g/L and temperature is ambient. Decolourization was maximum when pH is in between 4 and 5. Conditions and results [6] [128] 85.2 86.1 67 82.6 90.1 (continued on next page) [13] [11] [108] [56] 88.6 94.7 [84] 87 80 [23] [71] 88 67 [123] 85 89.9 [8] [40] [12] [79] References 98.6 86 84 85 88 Maximum efficiency (%) V. Katheresan et al. Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 4685 Average success rate Methylene blue Advanced oxidation process with hydrogen peroxide and UV. Direct Blue 86 Average success rate Chemical Advanced oxidation process Advanced oxidation process with a combination of ozone and UV. COD and colour removal Reactive black 5 Mixed culture of pure 1E1 and pure C1 bacterial for dye removal. Advanced oxidation process with a combination of hydrogen peroxide, ozone and UV. Reactive red 198 Decolourization by pure bacteria Proteus mirabilis Brilliant green and Evans blue Acid red 151 Achromobacter xyloxidans and bacillus subtilis mixed bacterial consortium for COD reduction and colour removal Average success rate Pure and mixed culture Mixed fungal cultures of Pleurotus ostreatus (BWPH), Gloeophyllum odoratum (DCa), and Fusarium oxysporum (G1). Black B, Blue RR, Navy blue Red RR and Yellow RR Three isolated bacterial strains (Bacillus subtilis, Pseudomonas aeruginosa, and Psuedomonas putida) for dye degradation Acid Red-88, Direct Red-81, Disperse Orange-3 and Reactive Black-5 Mixture of Malachite green, Nigrosin and Basic fuchsin Phanerochaete chrysosporium fungi isolated from contaminated dye effluent sites Average success rate Microbial cultures such as mixed bacterial Acinetobacter sp., Citrobacter freundii and Klebsiella oxytoca mixed bacteria in dye and 4-nitroaniline degradation from textile dye wastewater Dye Method Table 6 (continued) Optimum dye removal observed when initial concentration of dye is 100 ppm, pH is 11 and reaction time is 35 min. Batch reactor was used for the experiment. Temperature should not be set above 40 °C for better results. About 62% reduction in COD was also noted. COD removal was 99% successful when optimum dye removal conditions were set. Aluminium Sulphate, Ferrous Chloride and Ferrous Sulphate are a necessity to ensure the succession of this experiment. Optimum conditions of dye removal were when 500 mg/L of chemicals were utilized, hydrogen peroxide concentration of 300 mg/L is added, pH value is set around 3 and when reaction time of 90 min were set. The experiment was conducted under shaking conditions in a batch reactor. A number of 8-watt UVC lamps were used to induce UV light radiation. Dye removal was tested with hydrogen peroxide of 1 Mmol, initial concentration of MB of 3, 5 and 10 mg/L, reaction time of 3.5, 4.5 and 10.5 min and UV irradiation intensity of 2400 μW/cm2. Rate of dye removal became higher as hydrogen peroxide concentration and UV light intensity became higher. Successfully removed Brilliant green at dye concentration of 0.06 g/L, Evans blue at dye concentration of 0.15 g/L and a mixture of both dyes at a concentration of 0.08 g/L with 96 h of contact time. Colour was best removed when contact time is around 20 h when dye concentration is 1 g/L, pH is between 6.5–7.5 and temperature in between 30–35 °C. Aerobic conditions proved to be best in this dye removal experiment. Shaking conditions were favoured more than stationary conditions. Ideal dye removal condition was found to be when pH is in between 4 till 10 and surrounding temperature is 28 °C. Contact time should be set to be 6 h at least and ideal dye concentration is 200 mg/L. Mixed culture produces better results than single culture. Bacterial mixed culture successfully removed 100 μmol/L of 4-nitroaniline with yeast extract at 5 g/L within 72 h under aerobic conditions. Dye concentrations were varied from 100 till 1000 μmol/L. Shaking conditions were adopted for this experiment. Ideal pH for the experiment was found to be 7 and the temperature was maintained at 35 °C Experiment was successful whereby the concentration of dye mixture with traces of glucose, sucrose and yeast extract was below 500 mg/l and contact time was above 4 days. The pH of the solution was adjusted to 7 and the temperature was maintained at 37 °C. To obtain high percentage of dye removal, centrifugation process of dye solution at 8000 rpm for 20 min should be done. Dye was removed from a 100 ml dye solution which was incubated with the bacteria for 7 days (contact time) under aerobic conditions. A shaker type incubator was used for maximum dye removal. Other conditions of the dye solution include an incubation speed of 8000 rpm, a temperature of 32 °C and pH of 7. Experiment was conducted in both shaking conditions and stationary at temperature 25 °C. Shaking conditions proved to produce better dye removal results. Dye removal occurred more rapidly in acidic conditions (pH 1–6). Conditions and results [101] 78.4 [110] 70 [18] 89.56 97.3 (continued on next page) [80] [16] 96 98 [52] 98 86.3 [27] 95 74.3 [99] [96] 82.9 81.6 [67] 92 76 References Maximum efficiency (%) V. Katheresan et al. Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 4686 Alizarin Yellow R Procion Red MX-5B Conductive-diamond electrochemical oxidation Reactive blue 19 Oxidation dye removal through combination of membrane-free up-flow biocatalyzed electrolysis reactor and aerobic bio-contact oxidation reactor Average success rate Oxidation Oxidation through sono, photo and sonophotocatalytic oxidation using visible light Acid orange 24 Fenton reaction through application of advanced photo-oxidation technique Direct Blue 71 Average success rate Fenton reaction Fenton reaction through oxidation Acid Red 14 Batik wastewater Electrochemical destruction with an electro catalytic reactor Fenton reaction using Taguchi orthogonal array design Remazol Brilliant Blue Textile wastewater Electrochemical destruction Electrochemical destruction with cylinder Ti/β-PbO2 electrode in an electro catalytic tube reactor Electrochemical destruction with in situ electro-generated active chlorine Dye Method Table 6 (continued) Sulfur-covered titanium dioxide also known as S-TiO2 nanoparticles were utilized to ensure the succession of this experiment. Best conditions for maximum dye removal through the sonophotocatalytic reaction are a catalyst dosage of 50 mg, sulfur weight of 5 wt%, initial dye concentration of 20 mg/L, pH value 3, weight of nanoparticle of 5 wt% and ultrasonic power of 100. Operating temperature of the experiment was maintained at 25 °C. The sonophotocatalytic process was found to remove dye particles better than the other processes. Reaction time for total dye degradation was 120 min. Maximum dye removal conditions were noted at reaction time 2 h when dye concentration was 100 mg/L. External power source of 0.5 V ensured high dye removal percentage. Close to 100% electron recovery in the cathode zone was noted. High dye removal was also due to a high loading rate of 780 g/m3d. Boron covered diamond anodes were used in this experiment for high dye removal. Ideal conditions for dye removal are when chloride concentration is 100 mg/dm3, current density is 10 mA/cm2, flow rate is 300 dm3/h and initial pH is 7. Maximum reaction time was observed to be approximately 240 min no matter what value of current density is applied. Electric charges of about 5 Ah/ dm3 is enough to remove high amounts of dye and COD. A batch reactor was used to conduct the experiment successfully. Ideal parameters for high percentage of dye removal include 3 mg/L (dosage of iron 2+), 100 mg/L (dye concentration), 3 (initial pH), 132 mg/L (hydrogen peroxide concentration) and 20–60 °C (temperature of the dye solution). Approximately 50.7% of COD was successfully removed from this experiment. Reaction time of 20 min is required to ensure high percentage of dye removal. Ideal conditions for high dye removal are a dye concentration of 20 mg/L, hydrogen peroxide concentration of 0.15 mmol, iron 2+ of 0.015 mmol, a pH value of 3.5 and temperature. Optimization was done using the Taguchi fractional factorial design. Volume of dye solution used in the experiment was 50 mL. Optimal conditions to achieve high dye removal were when ferrous sulphate dosage is 0.75 g/L, hydrogen peroxide concentration is 0.75 g/L, initial dye concentration is 3 ml/L, pH is 3 and reaction time is 40 min. There was significant reduction in COD level in treated dye solution. Synthesis of anode was done through the anodic electrodeposition method. Dye degradation was tested at hydraulic retention time 2 and 4 h, pH 6–9 as well as salt concentration of 3000 and 4000 mg/L. Ideal dye removal parameters are when direct current is 5.6 V, hydraulic retention time at 4 h, pH 6 and salt concentration 4000 mg/L. Electrode used was modified with titanium and lead dioxide. Dye degradation was most successful when the concentration of sodium chloride solution was 4000 mg/ L, the dye degradation time allowed was in between 50–60 min and pH was in between 5–10. The experiment was conducted in batch using a full-scale electro catalytic reactor. Ti/RuIrO2 electrode was designated as its anode while a stainless steel plate was designated as its cathode. An electrode gap of 30 mm was set. To find optimal conditions, the experiment was set up with parameters such as electrode concentration (2500–4000 mg/L), hydraulic retention time (30–180 min) and initial pH (3–9). Optimal conditions for treating batik wastewater was when direct current of 5 V was applied, hydraulic retention time was 120 min, mixing speed was set at 120 rpm, pH was 5 and salt concentration was 4000 mg/L. Conditions and results [89] 100 [37] 95 (continued on next page) [28] [30] 94.8 85 [68] 90 93.9 [113] 92.7 94 [41] [88] 70.38 88.8 [87] References 96 Maximum efficiency (%) V. Katheresan et al. Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 4687 Malachite green Chicago Sky Blue, Methyl Orange and Rhodamine B Ultraviolet irradiation through pulsed discharge plasma in water Average success rate Physical Adsorption Adsorption by treated sawdust Acid Blue 92, Acid Green 20, Acid Orange 7 and Acid Red 301 Ultraviolet irradiation using acrylic grafted nano membrane Acid red 4092 Reactive Blue 222, Remazol Black B, Reactive Blue 221 and Remazol Brilliant Blue R Semiconductor-assisted photochemical degradation Average success rate Ultraviolet irradiation Ultraviolet irradiation with zinc oxide nanoparticles Indigo Carmine Photochemical degradation with Calcium Oxide catalyst Methylene blue Acid yellow 19 Optimized ozonation Average success rate Photochemical Photochemical degradation with a combined system of titanium dioxide and UV. Acid Red 183 Nova cron super black G and Terasil red ww 3BS Dye Ozonation treatment Average success rate Ozonation Ozonation Process Method Table 6 (continued) Sawdust was treated by formaldehyde and sulphuric acid. It was found that sulphuric acid treated sawdust removes more dye than formaldehyde treated sawdust. Best conditions for highest dye removal by this process is when adsorbent dose is 0.4 g/100 ml, pH is in between 6 and 9 and temperature is around 26 °C. Dye removal is better done in a batch reactor or a stirred tank reactor. Experiments were conducted in a batch photo-reactor. Ideal parameters for maximum dye removal was noted as catalyst dosage of 0.2 g/L, dye concentration of 0.5 mg/L, irradiation time of 12 min, and a pH value of 5. Slight modifications were done to the polysulfone ultrafiltration membrane with the usage of acrylic acid. Ideal operating parameters for this experiment are an irradiation time of more than 30 min and pressure around 4 bars. Addition of about 80 mM of sodium sulfate in dye solution increases dye removal percentage. Dyes with lower molecular weights have a higher chance of getting completely removed. Highest rate of dye removal noticed when discharge operates in the spark–streamer mixed mode. Best conditions to ensure the succession of the experiment include an initial dye concentration of 0.01 g/L, a pH value that is acidic especially at 3.5, a reaction time higher than 100 min and a wavelength above 300 nm. Titanium dioxide was immobilized with polyvinyl alcohol to further enhance dye removal in this process. Ideal process parameters were found to be when initial dye concentration is 20 mg/L, light intensity of UV light at 4 W, liquid volumetric flow rate is 2 mL/min and wavelength of 254 nm. Reaction time for maximum dye removal was less than 20 h. Maximum dye removal was noted when parameters were calcium oxide particle size was in between 30 and 36 nm, concentration of calcium oxide was 0.12 g, dye concentration is 5.0 mg/100 mL, pH is 12 and temperature is in between 298 and 300 K. Best source of light for this process was visible light (8 W lamps). The experiment was carried out in an oxygenated UV coupled with zinc oxide environment. Optimization was done by factorial design to produce better dye removal results. Ideal parameters were recorded such as dye concentration of 50 mg/L at volume 100 ml, pH value 5.5 and required reaction time is approximately 60 min. The zinc oxide semiconductor produced better results than the titanium dioxide semiconductor. A batch reactor was utilized for the ozonation process. Ideal process parameters were when reaction time was 6 h, pH value was 9 and temperature was maintained at 35 °C. Volume of wastewater prepared for dye removal was 500 ml. Ideal dye removal parameters were found to be when contact time was 15 min, dye concentration was 50 mg dm−3, ozone dosage was 300 mg dm−3 and when the pH was in the acidic range. Central composite design was utilized to optimize typical ozonation process in dye removal. Favourable parameters for this experiment were initial concentration of the dye 20 mg/L, initial pH of the solution around 7.5, temperature of 40 °C and the ozone dosage of 400 mg/L. Conditions and results [65] 96.4 [127] [48] 99 99 [119] 95 99.8 (continued on next page) [46] [14] 99.9 98.3 [33] 100 99 [112] 99 94.5 [109] [135] References 97 90 90 Maximum efficiency (%) V. Katheresan et al. Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 Basic blue 41 Adsorption through nano porous silica 4688 Acid brown 348 Congo red and direct blue Irradiation by ultrasound exfoliated graphite Irradiation by acrylamide as well as starch based hydrogel and gamma Acidic, direct, disperse and reactive dyes 90 Dalton membrane in nano filtration Average success rate Reverse osmosis Acid red Nano filtration coupled with reverse osmosis Cibacron Yellow S-3R Acidic indigo carmine Average success rate Irradiation Irradiation with induced cationic hydrogels Average success rate Nano filtration or ultra-filtration Nano filtration using Hydracore50 membrane coupled with Electrochemical Process using Titanium and Platinum rods Basic Blue 9 Acid Orange 7 Purolite C145 Macroporous Polymeric Ion Exchangers Ion exchange by Lewatit MonoPlus MP 500 anion resins C.I. Acid Orange 7, C.I. Direct Blue 71 and C.I. Reactive Black 5 Cibacron Yellow FN-2R and Terasil Blue BGE-01 Coagulation/Flocculation using coagulants an anionic coagulant aid, alum, magnesium chloride and poly aluminium chloride Average success rate Ion exchange Ion exchange by Amberlite IRA 958 anion resins Disperse dye Coagulation/flocculation process using aluminium-based water treatment residuals Acid red 119 Congo Red Adsorption through bio-waste material such as ground nut shells charcoal and eichhornia charcoal Average success rate Coagulation and flocculation Coagulation/flocculation treatment using ferric chloride sludge from water treatment plant Dye Method Table 6 (continued) Crucial parameters to ensure the succession of the experiment were current density of 33 mA/cm2, a dye concentration of 0.1 g/L, a pH value of 3 and a salt (sodium chloride) concentration of 60 g/L Ideal parameters for high dye removal were noted as contact time of 2 h, dye concentration of 65 mg/L, feed temperature of 39 °C, operating pressure of 8 bar and pH of solution at 8.3. Ideal parameters include a contact time of 2 h, a dye concentration of 50 mg/L, a pressure of 12 bars and total dissolved solids concentration of 3000 mg/L. Studies on this topic were done using the batch adsorption technique. Ideal parameters for this experiment would be when contact time is 21 h, initial dye concentration is 120 mg/L, irradiation dose is 5.3 kGy and pH is 2.8. Maximum dye removal was achieved when contact time is 120 min, initial dye concentration of 40 mg/L, sorbent dosage is 2 g/L, pH is 1 and temperature is 40 °C. The optimal values for dye removal are a dye concentration of 100 mg/L, a solution pH in between 3–10, radiation dosage of 30–40 kGy and a temperature of 20–60 °C. The experiment is better done in shaking condition at 180 rpm in batches. Ideal parameters for this experiment were when anion dosage is 0.5 g, contact time is 3 h, dye concentration is 10 mg/L, pH is around 5 and at a temperature of 24 °C. Best conditions for the experiment were found to be when adsorption capacity is 1004.4 mg/g, anion dosage is 0.5 g, contact time is 3 h, dye concentration is 10 mg/L, pH is around 5 and at a temperature of 45 °C. The mode is experiment is batch adsorption. Tried and tested successful experiment parameters are when contact time is more than 5 h, initial dye concentration is 29.6 mg/L, initial solution pH is 12, resin dose is 40 g/L and temperature is 20 °C. The monolayer adsorption capacity of the cation was found to be 31.9846 mg/g. Process optimization was done through response surface methodology. Optimum parameters for dye removal are coagulant dosage of 236.68 mg, initial dye concentration of 65.91 mg/L and initial pH of 3.5. Modelling was done for this experiment through artificial neural networks. Ideal parameters for this experiment are aluminium dosage of 3 000 mg/L, initial dye concentration of 25 mg/L and initial pH value of 3. The jar test method was used to determine ideal process parameters. It was found that coagulant dosage of 1000 mg/L, dye concentration of 1.0 g/L and pH ranging from 3.8 till 5.2 are ideal for maximum dye removal. Ideal parameters for dye adsorption was at an adsorbent dose of 1.2 g, contact time of 60 min, dye concentration of 1 g/L, ionic strength of 0.05 M and temperature of 318 K. Maximum adsorption capacity of ground nut shells charcoal was found to be 117.6 mg/g while for eichhornia charcoal is was found to be 56.8 mg/g. When pH was in the acidic range, a higher dye removal was observed. Ideal parameters found that removed the highest amount of dye is contact time of 60 min, dye concentration of 50 mg/L, pH of 7 and temperature of 25 °C. Conditions and results [44] [136] 88 96.3 [74] 75 96.6 98 93.77 98 (continued on next page) [53] [2] [21] [115] 90 87.7 [106] 98.2 86.8 [120] [133] 87 85 [134] 88.3 93.6 [83] 96.53 99 [139] [66] 98 99 References Maximum efficiency (%) V. Katheresan et al. Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 97.1 [90] [64] 94 99.8 [10] 98.30 include its affinity with various compounds, its large surface area and its ability of be regenerated [20]. Known as the oldest and most efficient adsorbent, activated carbon can be derived from any carbonaceous materials such as coal. Coal based activated carbon have been used by numerous researches to successfully remove a wide variety of dye molecules from wastewater and is typically known as commercial activated carbon. Apart from dye molecules, activated carbon is known to remove heavy metals and other toxic pollutants as well [86,98]. Activated carbon is capable of removing any kind of dye and a number of pollutants present in wastewater [45]. The problem with coal based activated carbon is that coal itself is a fossil fuel and therefore an expansive non-renewable resource which soon might cease to exist. To overcome this, activated carbon nowadays is prepared from renewable resources like biomass, natural materials and even waste materials [100,105,117]. Besides being renewable, these alternatives are way cheaper than activated carbon prepared from non-renewable materials. Properties of activated carbon derived from different raw materials differ as well. Activated carbon can be produced by following two simple steps, first the selected carbonaceous raw material is carbonized in an inert surrounding at a temperature of 1000 °C then secondly, the carbonized material is activated with an appropriate chemical [4]. Activation of carbon can be done through one out of two methods, chemically or physically [57]. The difference between these two methods can be seen in Table 9. Synthesizing activated carbon from waste material will help reduce environmental waste. Not only is the environment being disposed of these unwanted waste materials, the cost of obtaining raw materials for activated carbon production would become less or sometimes none. The adsorption capacity of an activated carbon depends on the raw material used, its carbon content, and the method of treatment as well as treatment conditions. Activated carbon prepared from different raw materials will have different adsorption capacities and surface areas. Other factors affecting the adsorption capacity of an activated carbon are its pore structure as well as size, surface charge and surface chemistry [32,100]. An ideal activated carbon should possess characteristics such as a high surface area, has large pores and is a multipored structure. Microporous activated carbon is used to remove small molecules (smaller than 1 nm) while macro porous or mesoporous activated carbons are used to remove big molecules (bigger than 1 nm) from wastewater [69]. Activated carbon these days comes is numerous sizes such as blocks, fibres, granules, pellets and even in powdered form. Among the many forms of activated carbons, the powdered form activated carbon is the one conventionally used in dye removal due to their larger surface area than the other forms [105]. Adsorption onto activated carbon occurs with the aid of forces known as the van der Walls. Many studies exist to prove that dye removal through activated carbon adsorption is an ideal way to completely remove all types of dye particles. Usually, after continuous dye removal, adsorptive properties of the activated carbon will gradually become weak [133]. Activated carbon will not be able to adsorb dye molecules at the same capacity of fresh activated carbon as their pores will no longer be able to accommodate additional dye molecules. However, due to technology advancement, regeneration of activated carbon is possible through reactivation of activated carbon [141]. The downside of reactivating exhausted activated carbon is the loss of carbon and the decrease of adsorption capacity. It can be seen in Table 10 that activated carbon derived from low cost raw materials do have large surface areas and can efficiently remove dye molecules. Since the cost of obtaining alternative raw materials are low, the overall cost of the adsorption process is still cheap [122]. Anthrasol brown IBR Methyl orange Reverse osmosis Reverse osmosis through a thin film composite membrane module Average success rate Direct yellow Reverse osmosis through Polyamide Membrane Experiments were performed in batches varying in parameters such as contact time of 0.2 till 2.0 h, feed concentration of 75 to 450 ppm and operation temperature from 30 to 50 °C. It was found that good results are produced when the contact time is lower, when the feed concentration is low and when the temperature is low. Ideal parameters to be set for high dye removal are a dye concentration of 30 mg/ L, a feed concentration of 30 ppm, at pH value 4 and a temperature of 25 °C. The number of times the dye effluent passed through the membrane is 4. Optimal parameters to remove high percentage of dye is when the dye concentration is 100 mg/L, feed pressure is 400 psi, flow rate is higher than 2 L/ min, pH value is in between 2–4, salt concentration is 100 mg/L and when temperature is 25 °C. References Dye Method Table 6 (continued) Conditions and results Maximum efficiency (%) V. Katheresan et al. 6.2. Activated carbon bamboo as an adsorbent Abundantly found in the African, Asian and Latin American continents, bamboo is a kind of perennial grass-plant with a long life span. 4689 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. Table 7 Effect of different parameters on the adsorption process. Parameters Adsorbent dosage Contact time Dye concentration pH Temperature Description Effect - Measure of the amount of adsorbent used to adsorb dye particles. - Depends on the number of sorption sites available on the surface of the adsorbent. - Test can be done by preparing solutions with fixed dye concentration and pH but varying adsorbent dosage. - Measure of the amount of time the adsorbent and adsorbate is placed in contact with each other. - Test can be done by preparing solutions with a fixed adsorbent dosage, dye concentration and pH but allowing differing contact time between the adsorbent and adsorbate. - Measure of the amount of dye dissolved in water. - Dye particle adsorption depends on the vacant binding sites on the surface of the adsorbent. - Test can be done by preparing solutions with a fixed adsorbent dosage and pH with varying dye concentrations. - Measure of the acidity or alkalinity of a solution. - A solution with pH less than 7 is considered acidic while a solution with pH more than 7 is considered alkali. - Controls the degree of electrostatic charges transmitted by ionized dye molecules resulting in varying rate of adsorptions when the pH is changed. - Test can be done by preparing solutions with a fixed adsorbent dosage and dye concentration with varying pH. - Measure of the temperature of the solution when adsorption takes place. - Indicates the nature of adsorption whether it is endothermic or exothermic. - Test can be done by preparing solutions with a fixed adsorbent dosage, dye concentration and pH but heating the solution to varying temperatures. - Higher rate of adsorption if adsorbent dosage is high and vice versa. - Optimum rate of adsorption when adsorbent dosage is around than 10 g/L. - Higher rate of adsorption if contact time is long and vice versa. - If the adsorbent is efficient enough, optimum time required for complete dye removal is 3 h - Higher rate of adsorption if dye concentration is low and vice versa. - Highest rate of adsorption when dye concentration is around 0.1 g/L. - Low rate of adsorption when pH is low and vice versa. - Highest rate of adsorption if pH is around 6. - Low rate of adsorption if temperature is too low or too high. - Higher rate of adsorption if temperature is around 30 °C. carbonaceous mesoporous material with a large surface area as well as adsorption capacity. Compared to materials like treated rice husk, waste newspaper and sawdust, bamboo requires minimal processing to convert it into activated carbon. Preparation and regeneration of activated carbon bamboo is easy and safe. Bamboo activated carbon can potentially replace the usage of commercial activated carbon [50]. Commonly used for activities such as construction, furniture as well as handicraft making and paper production, bamboo have become one of the most sought after raw material these days [111]. Countries like Malaysia, India and Japan is known to largely produce and process bamboo plants resulting in huge amounts of bamboo waste being produced. This piqued the interest of researchers to develop a use for this waste hence bamboo waste was established as a raw material in the production of bioethanol. Next, it was found that waste bamboo can be used as an adsorbent to remove moisture as well as odours due to its absorptive characteristics which lead to the production of air fresheners, odour removers and water purifiers from bamboo [35]. Nowadays, bamboo is used in dye removal applications in the form of activated carbons as it can completely remove dyes and other pollutants like heavy metals and organic pollutants due to its unique composition. Utilizing bamboo waste as an adsorbent will not only help the nation dispose bamboo waste but also reduce the cost of adsorbent production for dye removal [57]. Among the various activated carbons listed in Table 10, bamboo is highlighted due to the fact that Malaysia is one of the leading producers of this plant in Asia [70]. Bamboo is easily assessable here in Malaysia, is cheap to acquire and is a naturally available non-hazardous material. Bamboo is known as a highly 7. Enzymes in dye removal 7.1. Free enzymes in dye removal Enzyme also known as biocatalyst is a cheap, efficient, regenerable and selective biological substance existing in liquid form [91]. Enzymes can work to specifically remove particular stubborn pollutants by converting them into products or through the precipitation process [47]. Biocatalysts are an upcoming technology utilized in various sectors for numerous applications. Enzymes became famous due to its easily accessibility, green chemistry and substrate specificity [31,59,108]. The main attraction of an enzyme is its environmental friendly and non-toxic nature along with its reusability factor. When an enzyme is utilized to adsorb dye molecules from wastewater, they are Table 8 List of adsorbents with their surface areas. Adsorbent Description Adsorption capacity (mg/ g) Reference Activated carbon Activated clay Bark Bentonite Cane pith Charred dolomite Chitosan Derived from any carbonaceous raw material. Dried up naturally occurring porous structure Outer hard layer of a plant or tree An aluminium phyllosilicate clay consisting of montmorillonite Spongy tissue available in sugar canes An anhydrous carbonate mineral consisting of calcium magnesium carbonate burned till char Treated chitin shells of shrimp or other crustaceans formed into a linear polysaccharide consisting of randomly distributed acetylated and deacetylated unit. Scraps of cotton disposed by cotton-making factories. Combustible sedimentary carbonaceous material obtained from below the earth surface. Dried partially decomposed organic materials commonly used as fertilizers. A protective skin around rice grains disposed before cooking. Disposed powder wood obtained from sawing factories. Coagulated colloidal silicic acid commonly used as a desiccant A commonly purged substance obtained in sugar industries. Strengthened cotton fibres. 500–2000 585 1119 1667 941.7 950 973.3 [24] [39] [81] [95] [61] [129] [137] 875 588 324 838 294.12 900 519 589 [81] [38] [42] [81] [51] [49] [73] [20] Cotton waste Natural coal Peat Rice husk Sawdust Silica gel Sugar industry mud Treated cotton 4690 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. effort. To overcome this issue, enzymes are immobilized instead of being left as free enzymes. For dye removing processes, enzymes are often immobilized onto an inert as well as insoluble material for resistance purposes. Enzyme immobilizing is practically the act of confining an enzyme onto a support system in order to stabilize it. For over a century, enzyme immobilization has been practiced through various applications such as diagnosis of disease, production of drug intermediates, and recovery of air, soil as well as water [26]. Whenever enzyme is required as part of a process, immobilization is always advised due to the perks it present. When an enzyme is immobilized, handling it becomes much easier as it becomes a stable substance immune to the physicochemical environment around it. This immobilized enzyme can be reused and has been proven to produce better separation results than free enzymes [36,117]. Enzyme immobilization is a straightforward flexible process that can be applied in all industrial operations as well as all types of reactors. Certain enzymes can be freeze-dried into powdered form known as lyophilized state. In this state, enzymes exhibit the same characteristics of immobilized enzymes [82]. Enzymes tend to behave like typical soluble enzymes once it has been dissolved in solutions and this enzyme cannot be reused. Apart from immobilization, enzymes have been further studied to areas like DNA technology, genomics, protein engineering, and proteomics but were found to pose unfavourable disadvantages such as its complicated techniques, high cost, short lifespan, and its inability to be regenerated. Enzyme immobilization possesses none of the said disadvantages thus can be said to be the best way to utilize an enzyme. There are certain factors that influences the immobilization process shown in Table 11. Enzyme immobilization have received substantial interest compared to soluble enzymes or other biological dye removal technologies only because of the benefits of this method. This method is a reliable dye removal method as it is cheap, stable, regenerable, easily assessable and extremely efficient [31]. The regenerable characteristic of the immobilized enzyme aids in reducing the cost of the overall enzyme degradation method. The cost of the enzyme degradation dye removal method is largely affected by the raw material used for enzyme extraction. Often, enzymes are extracted from animals, microbes or plant raw materials and their cost varies [26]. Cost of the method may also differ based on method of enzyme extraction, enzyme isolation, enzyme purification, chosen method of immobilization and finally the chemicals required for immobilization [36]. The method of immobilization and the type of enzyme used for immobilization determines the properties of an immobilized enzyme. Due to the accomplishments of immobilized enzymes, various methods of immobilizing an enzyme onto various surfaces have been developed in the past century [82]. To date, the enzyme immobilization Table 9 Difference between chemical and physical carbon activation methods. Activation time By-products Number of steps Requirement Steps Surrounding Temperature Washing Advantages End product Chemical activation Physical activation Short None 1 Carbon activation chemicals (H3PO4, KOH, K2CO3, NaOH, ZnCl2) and nitrogen 1. Raw material impregnated with chemicals 2. Heated under a flow of nitrogen gas (1 and 2 carried out simultaneously) Inert (nitrogen) Low (450-900 °C) Needed (presence of other chemicals that should be eliminated) - Less burnt activated carbon Long Non-porous char 2 Inert and oxidising gases (carbon dioxide and nitrogen) 1. Carbonization of raw material by pyrolysis process 2. Activation with either air, carbon dioxide, steam or a mixture of oxidising gases Inert (nitrogen) High (600-1200 °C) Not needed (no chemicals used for activation) - Mesoporous structure - Suitable for dye adsorption - Wider pore size Activated carbon (porous structure with large surface area) Table 10 List of activated carbon with their surface areas. Activated carbon Almond shell Apricot shell Bagasse Bamboo Cashew nut shell Commercial Corncob Granule Groundnut shell Hazelnut shell Pine sawdust Pinewood Plum kernel Sawdust Treated rice husk Walnut shell Waste newspaper Adsorption capacity (mg/ g) Surface area 1.33 4.11 391 454.2 476 980.3 1060 57.47 222.2 8.82 370.37 1176 904 183.8 290 3.53 390 783 783 1433 1896 984 650 943 1100 1114 793 1390 902 1162 516.3 2516 774 1740 Reference (m2 /g) [15] [15] [126] [50,70] [116,118] [9,62] [60] [94] [77] [15] [5] [125] [60] [76] [34] [15] [93] called bio adsorbents or biosorbents [26]. Biosorbents are an upcoming approach in dye removal that is being pursued by researchers nowadays [124]. It has the potential to be developed to remove dye on a large scale and can be categorised as an alternative adsorbent [43,85]. Enzymes can function in a wide range of pH and low temperatures. The biosorbent technology is still in the trial stage and more research is required before it can be established as a reliable adsorbent [4,25,29]. In Table 2, it can be seen that among the other listed biological dye removal methods, enzyme degradation (90.1% average success rate) is considered the best due to its multiple advantages. Besides that, this method only has a single disadvantage, an unreliable amount of enzyme production. This sole disadvantage of the enzyme degradation method is harmless compared to the disadvantages of the other existing biological dye removal methods. This disadvantage can be easily remedied through the usage of an exceptionally efficient raw material containing dye removing enzymes and undertaking an efficient mode of enzyme extraction. Table 11 Factors affecting immobilization of enzymes. Factor Effect Binding mode variation Affects the activity and stability of an enzyme Hydrophobic nature of enzyme gets stabilized Enzyme thermal stability is enhanced Enzyme activity decreases while enzyme stability increases Rate of reaction of the hydrophobic substrate is enhanced Large pore structure display high enzyme activity and vice versa Enzyme performance is improved Enzyme activity depends on the physical structure of the enzyme Retention of high enzyme activity Enzyme deactivation is prevented Carrier microenvironment Carrier multipoint attachment Constraints of diffusion Hydrophobic partition Nature of carrier (physically) Physical post-treatments Physical structure of enzyme (pore size) Presence of inhibitors or substrates Spacer arm of enzyme 7.2. Immobilized enzymes in dye removal Maintaining the structural stability of an enzyme requires some 4691 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. Fig. 5. Enzyme immobilization methods [26]. consequences. More enzyme immobilization techniques are being researched on a trial and error basis. Although many support systems have been researched, it cannot be said with certainty that one support system alone is ideal for all enzymes [26]. Nevertheless, it can be said with conviction from the numerous research conducted that enzymes are most stable in immobilized state. When enzymes are immobilized onto a solid surface, enzyme activities are confined to that particular surface where its concentration magnifies at least a thousand fold [82]. This explains its stability once it is immobilized onto a solid surface. The smaller the solid surface, the greater the catalytic efficiency and stability of the enzyme. Currently, nanoparticle research for enzyme immobilization is being studied. Immobilized enzyme in dye removal received considerable attention as well due to its efficiency [8]. Due to the usage of immobilized enzymes in various applications, interest for further research and enhancement of immobilization techniques are given importance. As mentioned before, biocatalysts are being introduced to various industrial applications. To keep up its demand, more studies should be conducted to improve aspects of it such as its activity, efficiency, regeneration and stability. It is hoped that further research will inaugurate novel applications for immobilized enzyme. technology has been modified to promote its compatibility with upcoming applications and its evolution continues [9]. When developing novel immobilization procedures, the factors that vouch for the feasibility of the method are the percentage of enzyme recovered and the stability of the procedure mainly [36]. Enzyme immobilization is a more environmental friendly procedure compared to other existing dye removal technologies as toxic or unstable chemicals are absent in this method. Enzyme immobilization can be achieved using one of the two existing fundamental methods, the chemical method or the physical method as shown in Fig. 5. The advantages and disadvantages of utilizing the various chemical and physical enzyme immobilization methods are shown in Table 12. Enzyme immobilization onto solid surfaces have been performed decades ago. This is mainly done to stabilize an enzyme by providing it with a solid support. The enzyme can then be utilized in deferring chemical or physical surroundings. In the year 1960, it was established that enzymes can be made stable by its own with the usage of a solid support through the crosslinking method [26,36]. In this method, a binding agent such as glutaradehyde known as the bifunctional chemical cross linker forms an amide connection between a NH2 compound on the enzyme surface and the binding agent. This act cross links the enzyme and the binding agent chemically making it a stable structure known as cross linked enzyme aggregates (CLEA) as shown in Fig. 6 [31,121]. Researchers Quiocho and Richards attempted crosslinking enzymes using binding agent glutaradehyde for X-ray diffraction studies in the year 1964. They received impressive results by which not only the enzyme was found to be completely stable, it was also found to be fully functioning in terms of catalytic activity [102]. Enzyme immobilization is a well-known technique to numerous industrialists and scientific researchers these days [91]. Among the various enzyme immobilization method, crosslinking appealed the most due to its effectiveness and compatibility with almost any type of enzyme. Crosslinking is also cheap and does not result in disastrous 7.3. Enzyme peroxidase in dye removal Degrading dye particles with exo enzymes such as peroxidase enzymes or phenol oxidases is an excellent method to resolve dye effluent issues. In the presence of hydrogen peroxide, peroxidase enzymes, a form of hemoprotein can catalyse reactions such as adsorption of dye molecules from dye effluents. Peroxidase enzymes are enzymes that can be extracted from animals, human, microorganisms as well as plants and this enzyme can be categorized as a biosorbents. Common sources of enzyme peroxidase are glycine max also known as soybean, horseradish, root vegetables and certain fungus [31]. Other kind of common peroxidases are lignin peroxidase and manganese peroxidase. 4692 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. Table 12 Various enzyme immobilization methods along with its advantages and disadvantages [124]. Method Chemical method Covalent Cross-linking Ionic Physical method Adsorption Entrapment Microencapsulation Description Advantages Disadvantages Enzyme is naturally or synthetically attached directly or through a spacer arm onto a solid surface through covalent bonding. Multiple covalent bonds are formed between the enzyme and the solid surface through the usage of multi-functional reagents. Similar process to physical adsorption method. The enzyme is bonded with the solid structure ionically. Minimum change in enzyme conformational. Fairly resistant structure. Affects the catalytic properties of enzymes. Harsh immobilization conditions. Strains the enzyme. Loss of enzyme as it diffuses into the solid surface. Minimum change in enzyme conformational. pH and temperature dependent process. Requires high maintenance. Enzyme is attached to a solid support directly by a non-covalent link. Optimization of adsorbent, concentration of enzyme, ionic strength, nature of the solvent, pH and temperature must be done in order to immobilize an enzyme. An enzyme is cross-linked to a polymer thoroughly by physical entrapment within the polymer lattice. Only allows penetration of appropriate sized substrates or products. Enzymes are immobilized within a permanent or nonpermanent spherical semi-permeable polymer membrane with controlled porosity. Simple method. Intense optimization required. Does not alter properties of enzyme. Less enzyme required. No chemical modification required. Numerous matrix shapes available. Straightforward. High catalytic efficiency. High enzyme concentration. Large surface area. Applicable only to a limited number of enzymes. Delicate. Enzyme leakage. Suitable to be used with only small sized products or substrates. Has flaws. Only works occasionally. Effective for dye removal processes. Straightforward method. Strong bonding. this area so its application at an industrial level should be further researched upon. Lignin peroxidase (LiP) as well as manganese peroxide (MnP) were first extracted from an organism called P. chrysosporium, a kind of fungus and are known to possess a similar reaction mechanisms to one another [9]. Non-phenolic aromatic compounds such as veratryl alcohol can be oxidised by catalysis of LiP. Oxidation of Mn2 + to Mn3 + can be accomplished by MnP where Mn3 + has the ability to oxidize various phenolic compounds while Mn2 + is required in order to complete the catalytic cycle of MnP [25,43,85]. There is prove in the form of researches papers that LiP and MnP from P. chrysosporium is an efficient dye particle and xenobiotic compounds degrading substance. Biosorbents function almost the same way regular adsorbent do, by accumulating and attaching roaming dye molecules from an adsorbate onto its surface through process a called reactive adsorption. There are existing research papers proving reactive adsorption is an efficient as well as cost-effective process in dye removal processes [117,138]. Peroxidase enzymes are a fairly novel enzymes used these days and it was found that immobilizing these enzymes onto a solid surface is more effective as it can function both in aqueous as well as organic solutions [36]. Immobilized enzyme peroxidase are better than ordinary soluble enzymes as they possess higher catalytic activities and is more stable operationally. Besides that, it has been found that the three dimensional structure of immobilized enzyme peroxidase is intact compared to other enzymes that have undergone immobilization resulting in structural damage [82]. So far, only laboratory level studies have been done on 7.4. Glycine max peroxidase in dye removal Glycine max is commonly known as soybean belonging to the class III secretory plant peroxidase family. The hull of glycine max approximately contains 37 kD of highly heterogeneous glycoprotein in the form of enzyme peroxidase merely 20 days after the seed sprouts [8]. Many countries are producers of soy milk and soy food products thus this raw material is easily available internationally for a cheap price [9]. Spotting an identity similarity of 57% with glycine max peroxidase, the horseradish peroxidase isoenzyme C (HRPC) is the most popular member of the same peroxidase family [54]. Due to possessing astounding characteristics like high thermal stability, high reactivity, and structural stability even in low pH, glycine max peroxidase has many substantial applications [107]. In a comparison study between glycine max peroxidase and HRPC, it was noticed that glycine max peroxidase will become inactive at a temperature of 90.5 °C while HRPC will become inactive at a much lower temperature at 81.5 °C [26]. Further studies showed that glycine max peroxidase has a higher affinity for haem than HRPC. Upon heating, glycine max peroxidase undergoes a loss of haem and can become irreversibly inactive. Even in low pH, optimally 2.4, glycine max peroxidase can function actively as usual without undergoing the loss of Fig. 6. Enzyme cross linking process. 4693 Journal of Environmental Chemical Engineering 6 (2018) 4676–4697 V. Katheresan et al. 9. Conclusion and recommendations haem whereas HRPC will become inactive due to the loss of haem [9]. As a result of their broad substrate specificity, peroxidases have a vast diversity of applications although there are limitations for large-scale utilization due to the environmental stability of an enzyme [47]. Glycine max peroxidase has a promising future in various industrial applications and is an excellent enzyme to remove dye molecules due to its phenomenal stability and catalytic characteristics. When mixed with hydrogen peroxide, glycine max peroxidase can oxidise a large range of organic or inorganic substances. As mentioned before, enzymes like enzyme peroxidase are more efficient when immobilized rather than left free [91]. The specificity of the enzyme will improve while the stability of the enzyme structure strengthens prolonging its activity. Immobilized enzymes have a longer life span than free enzymes [82]. This peroxidase is powerful enough to breakdown and remove dye particles from dye wastewater. Industrial wastewater treatment facilities have just begun exploring the potential of glycine max peroxidase as a biocatalyst for dye removal [8]. It is hoped that glycine max enzyme in dye removal will become an established process which can replace the conventional dye removal method most countries seem to prefer. Presence of dye effluents in the environmental water bodies is one of the causes of water pollution. To avoid this phenomenon, efficient dye removal techniques have to be utilized to treat dye effluents before release into the environment. This paper reviewed the efficiency of various dye removal methods biologically, chemically and physically. The idea was to make readers aware of its existence along with its efficiency (dye removal percentage) in removing dye particles from wastewater. The aim of this paper was to narrow down a single dye removal process which is perceived to be effective in completely removing dye. Releasing water with the least possible pollutants into the environment should be the aim of dye effluent treatment plants in Malaysia as well as around the world. Dye-utilizing industries have to be more responsible in releasing effluents as per the permissible standard set. Industries have to start exploring the reusability of treated dye wastewater as a water source for their processes. Since it is well known that the conventional method does not successfully remove all dye particles, this method should no longer be implemented in treatment plants. This review paper has discussed a number of biological, chemical and physical dye removal methods along with their efficiencies. The mentioned methods can be adopted to treat dye effluent so that the pollution in the water released from dye-utilizing industries can be drastically decreased. Most of the dye removal method listed managed to remove more than 80% of dye particles from wastewater while a few methods removed 90% of dye particles from wastewater. Chemical dye removal methods although extremely efficient should not be implemented in dye removal processes due to its harmful disadvantages (secondary pollution generation). Among all dye removal methods, adsorption (physical method) would be the best way to remove dye. The parameters affecting the rate of adsorption namely the adsorbent dosage, contact time, dye concentration, solution pH and temperature should be acknowledged as they are crucial to ensure the succession of the process. It should be noted that commercial activated carbon can be replaced by low cost adsorbents provided they are able to remove dye molecules at the same efficiency as commercial activated carbon and not just decolourize dye wastewater. Usage of biocatalysts such as enzymes is upcoming in various applications including dye removal. Biocatalysts are perceived to be effective but research on it is still in the developing stages. It is anticipated that combined adsorbent dye removal method will produce a more favourable result than a single adsorbent dye removal method. Rather than wasting money combining different dye removal methods to remove dye, it is better if a single method, adsorption, can be further improved. The adsorbent utilized for adsorption can be fashioned using a combination of activated carbon and peroxidase enzyme. This method will surely be very efficient as they are already efficient adsorbents on their own, cheap and best of all reusable time and again. It should be noted that real industrial dye wastewater may contain more than one dyestuff and a combined adsorbent may be able to eliminate these pollutants better than single adsorbents. Future researchers should further investigate combined adsorbents instead of stand-alone adsorbents. It has already been established that activated carbons are extraordinary adsorbents, so, in order to further improve dye removal with combined adsorbents, new biosorbents should be developed. Adsorbent selection should be done based on its easy availability, its cost and its renewability. Although it is repeatedly mentioned that the alternative adsorbents are of low cost, little effort have been made to mention the cost of the adsorbents. Future researchers should conduct more studies on this area to cover the existing gaps and make improvements on the adsorption method as well as the choice of adsorbent. Once more information is obtained, the possibility of utilizing these methods at industrial level should be considered. Researchers also should experiment on the adsorption process with real 8. Combined adsorbent in dye removal Certain literature suggests that using a combination of adsorbents can radically increase the efficiency of dye removal compared to a single adsorbent [59]. Other literatures suggest combining typical adsorbents (physical adsorbent) with a biocatalyst (biological adsorbent) will produce outstanding dye removal results [4,49]. Researchers suggest activated carbon is already an extremely efficient dye adsorbing material and combining it with an equally effective enzyme (biocatalyst) can perhaps further enhance dye removal [29,138]. Combined adsorbent may even be effective in removing a few hazardous substances at once. If the combined adsorbents do indeed complement each other, its efficiency in dye removal may surpass the highest recorded efficiency to date. Besides that, a combination of adsorbents will remove dye faster compared to single adsorbents. It is also perceived that improvements such as longer time of retention and lower cost can be achieved with combined adsorbent [69,141]. Low overall cost can be achieved using a combination of adsorbents due to the reusability factor of combined adsorbents. Individual adsorbents can only be used once hence its overall production cost is much higher than synthesis of combined adsorbents. An example of a combined adsorbent is immobilizing enzyme peroxidase onto activated carbon bamboo. This will stabilize the enzyme enabling enzyme recovery and reuse. Instead of synthesizing the adsorbent repeatedly, the same adsorbent can be reused until it is spent. This saves adsorbent production cost hence lowers the overall cost of the process. Unfortunately, information on this area of research is scarce resulting in doubts of this reactive adsorption mechanism. Researches are currently being done on this area but only on a small scale. Surely if combined adsorbents were used to remove dye from real industrial effluents, a higher dye decomposition rate can be achieved [43,107,132]. It is anticipated from this review that combined adsorbents will have a higher potential if not equal to single adsorbents to remove dye particles from dye wastewater. In future, industrialists should consider manufacturing combined adsorbents for wastewater treatment. It should be kept in mind that not only will the combined adsorbent be efficient in removing toxic particles but also economically feasible and made of easily assessable raw materials. 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