Comparative analysis of dye degradation methods: unveiling the most effective and environmentally sustainable approaches, a critical review

Fakhr Un Nisa; Khalida Naseem; Asad Aziz; Warda Hassan; Nimra Fatima; Jawayria Najeeb; Shafiq Ur Rehman; Awais Khalid; Mohammad Ehtisham Khan

doi:10.1515/revic-2024-0042

Article Open Access

Comparative analysis of dye degradation methods: unveiling the most effective and environmentally sustainable approaches, a critical review

Fakhr Un Nisa , Khalida Naseem , Asad Aziz , Warda Hassan , Nimra Fatima , Jawayria Najeeb , Shafiq Ur Rehman , Awais Khalid and Mohammad Ehtisham Khan

Published/Copyright: September 2, 2024

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From the journal Reviews in Inorganic Chemistry Volume 45 Issue 2

Abstract

The constant increase in population and as a result increase in industrial activities in many areas, such as textiles, cosmetics, leather, polymers, and food processing leads to the contamination of water sources with different dyes. Thus, the removal of dyes from contaminated water sources to make water reusable is the utmost requirement of the time in order to get environmental sustainability. The reason of removal is that many dyes and pollutants present in dyeing wastewater from industries have detrimental impacts on plants, wildlife, and humans. To lessen the negative effects of dye wastewater on the environment and living beings, it should be processed first to remove un-wanted components before being released in the water sources. However, due to some drawbacks of dye removal technologies, it is challenging to settle on a single solution that addresses the current dye effluent problem to make water clean. In the current work, we tried our best to elaborate different methods adopted for the treatment of dyes polluted wastewater with respect to their implementation along with drawbacks and advantages.

Keywords: water treatment; dye degradation; environmental impact; sustainable techniques; nanoparticles; pollution control

List of abbreviation

DO: dissolved oxygen
BOD: biological oxygen demand
COD: chemical oxygen demand
AOPs: advanced oxidation processes
EAOPs: electrochemical advanced oxidation processes
PES: polyether sulfone
PAN: polyacrylonitrile
TFC: thin-film composite
MO: methyl orange
RhB: rhodamine B
MB: methylene blue
CV: crystal violet
CR: Congo red
NF: nanofiltration
RO: reverse osmosis
GO: graphene oxide
LIBs: lithium-ion batteries
CNTs: carbon nanotubes
CNFs: carbon nanofibers
ECNFs: electro spun carbon nanofibers
VGCNFs: vapor-grown carbon nanofibers
NPs: nanoparticles
MG: malachite green

1 Introduction

The world is experiencing a growing freshwater problem due to the prompt increase in industrial development, global population, and climate change. All these factors substantially impact water quality. ¹ In addition, the prevalence of these dyes in watercourses will soon put aquatic life at risk. One of the adverse effects of dye availability in the native aquatic ecosystem is lowering the dissolved oxygen (DO) level in water induced by blocking the sunlight from the water system and inhibiting photosynthesis. Contrarily, dyes also result in a significant increase in the levels of water reservoirs, biological oxygen demand (BOD), and chemical oxygen demand (COD). ²

Dyes are organic substances that can adhere to cloth surfaces and provide color. ³ These dyes mostly come from two important sources such as manmade and natural. Natural sources of dyes contain plants, diverse pests, animals, and minerals while synthetic dyes are created artificially or are made utilizing variety of organic components. ⁴ Non-ionic, cationic, and anionic dyes have a unique chromophoric and auxochromic group. ⁵ The textile sector is the primary user of dyes. Along with this, dyes also find extensive application in the paper, plastics, rubber, concrete, and pharmaceutical industries. Knowing that about 10 % of the dyes used in industries are released into the surroundings which are very detrimental to the ecosystem is pretty upsetting. ⁶ Over than half of the dyestuffs currently present in the environment worldwide came from the textile industry which discharges the most of them (54 %). On second, high levels of dye wastes are reported to be created by a number of related activities in the coloring business (21 %), paper and pulp market (10 %), leather and tint production (8 %), and dye production industry (7 %). ⁷ Not only dyes but the inorganic chemical products released along with the dyes from the industries brings even higher negative impact on the environment. ⁸ To overcome or reduce the problems caused by these dyes and inorganic chemical products researchers have developed different methodologies. For the creation of techniques to lessen the severe toxic effects of contaminants, it is crucial to examine the detrimental effects of dye components and their derivatives. ⁹ Even while some of the dyes do not have much acute noxiousness however some of them especially azo dyes are known to cause cancer. Not only this but the reductive splitting of azo group (–N=N–) in azo dyes generates aromatic amines which are extremely poisonous, carcinogenic and even lethal. Most dyes contain common carcinogens like benzidine which must be handled prior to discharging into the environment. ¹⁰ The existence of dyes in aquatic bodies can lead to the generation of new molecules which are considerably more unsafe for the environment. Other environmental issue related to the existence of dyes in aquatic habitats is linked to excessive solar incorporation which causes the photosynthetic ability of phytoplankton to decline absorption. It has been observed that food can turn out to be polluted by dyes and other impurities contained in surface water. Current studies have shown that continued contact to dye contaminated water can have adverse effects on both animal and human tissues causing several problems in the intestinal and neurological systems. ¹¹

All of the approaches for removing dyes from water and sewage are described in the contemporary review study. The primary goal of this study is to offer a thorough account of the most recent research on the various techniques used to eliminate different dyes from industrial discharges. The organization of the dispersed knowledge on various dye contaminated water treatment systems is one of the key goals of this article’s publication. We believe that this review will be a helpful resource for newcomers and other researchers working to create technologies that effectively clean dye-contaminated waste waters.

2 Dyes removal technologies

One method cannot be used to treat all kinds of wastewater that holds dyes. Based on the types of dyes, toxins, and waste content, one technique may or may not be sufficient to treat dye-containing water. ¹² Though different dyes are widely used globally in numerous industries yet they come with significant environmental as well as medical concerns as they can result in many different diseases and abnormalities, some of them are given in Table 1. As there was no dye discharge restriction in the late 1990s, the first methods of water filtration used to remove dye were coagulation and deposition. ¹³ Owing to the accessibility of effective dye removal technology, certain changes were made following the acceptable setting of wastewater discharge regulations. ² Currently, a variety of ways for removing dye have been reported in numerous research journals appealing effective dye removal. Though, there are many operative dye removal methods but not all of them are effective or even practical to use because of their shortcomings. ¹⁴ There are mainly three categories of approaches for removing organic dyes from water which are chemical, physical, and biological. Different techniques are employed for their successful removal based on the nature, physical and chemical properties because of their extensive use in different sectors. ¹⁵

Table 1:

Applications and toxic effects of different kinds of dyes.

Sr. No	Class of dye	Dye	Applications	Toxicity	References
1	Acid	Methyl orange	Cosmetics, food, leather, nylon, ink for paper printing, silk and wool.	Carcinogenic (benign and malignant tumors)	16]
2	Basic	Basic orange 5	Medicine, ink, modified nylon, paper polyester.	Cytotoxic (benign and malignant tumors)	3]
3	Direct	Congo red	Cotton, leather, nylon, silk, paper.	Bladder cancer	17]
4	Disperse	Disperse blue 5	Acetate, acrylic fibers, cellulose, polyamide, polyester, cotton.	Allergenic (skin). Carcinogenic	18]
5	Reactive	Reactive blue 19	Cellulosic, nylon, silk, wool, cotton.	Dermatitis, allergic, conjunctivitis.	19]
6	Sulphur	Sulphur blue 11	Rayon, polyamide fibers, paper, leather, cotton, silk.	Carcinogenic, skin and eye irritation.	20]
7	Vat	Vat orange 15	Polyester cotton, rayon, wool, cellulosic fibers	Genotoxicity, mutagenicity, carcinogenic.	21]
8	Azo	Methylene blue	Cotton, acetate, rayon, cellulose, polyester, photography, additives in petroleum products	Bladder cancer, hepato carcinomas, chromosomal aberrations, affect soil fertility and plant growth.	16]

2.1 Chemical techniques for dye removal

Chemical techniques for dye removal from wastewater are essential in addressing environmental pollution from industrial activities particularly the textile sector. These methods includes some of widely used technologies such as coagulation-flocculation, electrochemical processes, ozonation, and advanced oxidation processes (AOPs). ²² These methods are employed due to their effectiveness in degrading and removing various dyes from waste water resulting in clean water. Though chemical methods have benefits such as time saving, efficient and frequently used procedures yet they could become more expensive due to the formation and deposition of the sludge. A lot of chemical substances and electrical power are typically used in chemical technology. ¹⁸ In addition, further pollution could be caused by the chemical remnant. A high oxidizing ability of sophisticated oxidation processes has recently given rise to new issues. Despite the efficiency of these procedures, their use in removal of dyes is discouraged because they involve the formation of harmful oxide mediators. ²³ While chemical techniques for dye removal offer significant benefits in terms of effectiveness and applicability, their limitations, including sludge production, high operational costs, and complexity, necessitate careful consideration. The choice of an appropriate dye removal method depends on a balance between these advantages and disadvantages, as well as specific wastewater characteristics, regulatory requirements, and economic factors. ¹⁷ Future research should aim to optimize these methods and explore hybrid solutions to enhance their sustainability and efficiency. Some of the most frequently utilized chemical methodologies are Coagulation-flocculation, electrochemical treatment, ozonation, advanced oxidation process, photo catalytic degradation, and chemical precipitation are examples of chemical procedures for dye removal. Some of them are further explained below.

2.1.1 Coagulation–flocculation method

Coagulation–flocculation is a water treatment process used to remove suspended particles, including dyes, from wastewater. This method involves two steps which are coagulation and flocculation. In the coagulation stage, different chemicals such as alum or ferric chloride are added in the contaminated water which act as coagulant. These coagulants get attached to the small dispersed particles to destabilize them and form aggregates of larger size. ²⁴ These flocs are then easier to separate from the water through sedimentation or filtration resulting in clearer, cleaner water. This whole mechanism is illustrated diagrammatically in Figure 1. Particulate collisions and floc growth are made possible by the methods of flocculation and coagulation, and precipitation then occurs as a result. Inability to finish the coagulation phase will cause the flocculation step to fail, which will cause the sedimentation operation to be unsuccessful. From submicron micro floc to noticeable colloidal matter, the particle size is increased during flocculation, a delicate mixing stage. ²⁵ The choice of coagulant is critical for the removal of toxins throughout the coagulation/flocculation mechanism. Coagulants can be distributed into a variety of inorganic and organic forms. For example, iron and aluminates salt were commonly used in the dealing of fabric runoff as inorganic coagulants. ²⁶ On the other hand, a hazardous inorganic coagulant produces a substantial amount of sludge that has a substantial negative impact on the pH of the treated wastewater. Because of their degradability, non-toxicity, diversity, and accessibility, polymeric macromolecules generated from plants, referred as organic coagulants, have drawn specific interest in the management of contaminated water. As a result, the use of conventional coagulants is dubious. ¹⁹ Coagulation-flocculation is a widely used method for dye removal in wastewater due to its cost-effectiveness, simplicity, and versatility, effectively removing a variety of dyes with rapid results. However, notable drawbacks associated with these techniques including the generation of significant sludge poses disposal challenges and additional costs. The use of chemical coagulants can introduce secondary pollutants. The effectiveness of process is highly dependent on the pH of water and ionic strength requiring careful monitoring and adjustment. ²⁰ Additionally, coagulation-flocculation may be less effective for certain low molecular weight or highly soluble dyes therefore other necessary supplemented treatments should be carried out. Continuous chemical consumption also incurs ongoing operational costs, which can be a limiting factor in some regions. Balancing these pros and cons is crucial for optimizing the method’s practical application. ²⁷

Figure 1:

Removal of wastewater contaminants as sludge by coagulation followed by flocculation.

Use of different coagulants against dyes contaminated wastewater and their removal percentages are given in Table 2.

Table 2:

Literature studies for the removal of dyes by means of coagulation and flocculation method.

Coagulants	Dyes	Removal (%)	References
Moringa oleifera seed extract	Reactive black 5	100	24]
Laterite soil	Acid orange 7	98.43 at pH 2	28]
Surjana seed powder Maize seed powder Chitosan	Congo red Congo red Congo red	98.0 at pH 4 94.5 89.4	17]
Potato starch	Solo phenyl blue dye	100	27]
Wtp sludge	Acid red and acid yellow	41.5	29]
Magnesium chloride	Malachite green	98.78 at pH 10.89	20]
Polyaluminium chloride and poly acrylamide	Cardboard color effluents	99 at pH 5	22]

2.1.2 Electrochemical treatment for the removal of dye

The electrochemical process for dye removal from industrial wastewater is an advanced treatment method that employs electrochemical reactions to degrade and remove dye contaminants. This technique encompasses various approaches including electrocoagulation and electrooxidation. In electrocoagulation, electrically charged particles called coagulants are generated in situ by dissolving metal electrodes (typically iron or aluminum) under an electric current. These coagulants destabilize and aggregate dye molecules, facilitating their removal through sedimentation or flotation. Electrooxidation involves direct oxidation of dyes at the electrode surface or the generation of oxidizing agents (e.g., hydroxyl radicals) that degrade the dyes. ³⁰ As a result of water oxidation across the electrodes significant amount of hydroxyl radicals is released during this process. These species are potent oxidizers that break down the organic material in wastewater accelerating the process of decomposition as represented in Figure 2. One of the most crucial aspect of this method is the choice of a suitable anode material as it directly monitors the formation of hydroxyl radicals. ³¹ Three steps follow after each other in the electro coagulation method to remove pollutants: (i) the oxidation of electrode in an electrolyte solution produces coagulants; (ii) the contraction of diffuse double layers and charge neutralization destabilizes pollutants and suspensions; and (iii) the accumulation of destabilized pollutants with coagulants. ³²

Figure 2:

Electrochemical oxidation of dye molecule due to in situ hydroxyl radicals.

The electrochemical process for dye removal from industrial wastewater offers several advantages and disadvantages. On the positive side, it is highly effective, capable of achieving high removal efficiencies for a wide range of dyes, including those resistant to conventional treatment methods. This method is also versatile and applicable to various types of waste water including both the synthetic and natural dyes polluted wastewater, and can be tailored to specific compositions and concentrations. Additionally, the absence of chemical additives simplifies the treatment process and reduces the generation of chemical sludge. However, electrochemical methods involve complex setups and operational challenges such as careful monitoring and control of parameters like current density and electrode maintenance. Energy consumption is another drawback, contributing to operational costs and potentially limiting scalability, particularly in regions with high electricity prices or unreliable power supply. Despite these challenges, the electrochemical process remains a promising option for dye removal in industrial wastewater treatment with its effectiveness and versatility outweighing its limitations in suitable contexts.

Palanisamy et al. ³² employed Al electrode and the electrocoagulation technique removed Reactive Red 2 with a 97 % dye removal rate. Salmani et al. ³³ utilized Iron (Fe) electrodes to remove Reactive Red 141 dye with a 99.88 % removal efficiency at a pH of 9.68 Yao et al. ³⁴ employed a Ce–PbO₂/ZrO₂ composite electrode in the electrochemical advanced oxidation technique to degrade acridine orange at pH 5. Khosravi et al. ³⁵ removed Reactive Red 198 using an Al electrode at a pH of 6.45 and an effectiveness of elimination of 91.3 % was observed. Mcyotto et al. ³⁶ used MgCl₂ for the removal of reactive dyes by chemical precipitation method and 90 % efficiency was found at pH 11.

Aqeel et al. ³⁷ removed Brilliant Green dye from wastewater by using Al electrode through electrocoagulation process and the removal efficiency was determined as 95.3 %. Sathishkumar et al. ³⁸ designed a titanium electrode coated in RuO₂–IrO₂ and utilized it to remove the Congo Red dye by electrochemical oxidation after biodecolorization with MN₁ (Pseudomonas stutzeri) and Acinetobacter baumannii MN₃. Vasconcelos et al. ³⁹ used boron incapacitated diamond electrode for the removal of Reactive Black 5 dye by electro Fenton route.

2.1.3 Ozonation

Ozonation falls in the category of chemical oxidation which is frequently utilized in alternative treatments as compared to the traditional methods. In chemical oxidation processes, the use of oxidizing chemicals such as potassium permanganate, ozone, chlorine and hydrogen peroxide for the treatment of dyes polluted wastewater is performed. Ozone is a dominant oxidizing agent due to which it is used for the remediation of pollutants and drinking water. ⁴⁰ The chromophore group with a carbon-based component and part of a ring (cyclic molecule), having double or single bond, are mostly present in the dye molecules. By using ozone, during ozonation, the double bonds are oxidized at the chromophores group of dye molecules. ⁴¹ Thus, one of the most desired solutions to decolorize dye effluent in modern years is ozonation. The ozonation method combined with the dye removal process is the most adopted one method. This is simple method and does not leave any toxic effluent in the sludge. Additionally, the positive aspect of this method is that the leftover ozone naturally turned into the oxygen. ⁴² Ozone interacts with aqueous compounds in two ways: directly through the action of molecules or indirectly through the breakdown of ozone into radicals and decomposition aided by basic pH began by hydroxyl radicals (OH^·). ⁴³ Figure 3 depicts the oxidation as well as reduction mechanism of reduction of pollutants by photo-ozonation. When ozone is used, reaction rates are twice as fast as they would be in H₂O₂/UV systems utilizing an equivalent oxidant dose. ⁴⁴ The primary drawback of this process is that it is a heterogeneous method with diffusion restrictions of a gaseous oxidizer within a liquid, which has an impact on the ensuing chemical oxidation of pollutants. ⁴⁵ Table 3 represents the potential effectiveness of ozonation process in the treatment of wastewater contaminated by numerous different dyes.

Figure 3:

Photo-reduction and photo-oxidation ozonation of pollutants.

Table 3:

Brief summary of various types of dye removal using ozone by oxidation process.

Dye	Ozone conc. (mg/L)	pH	Time (min)	Initial dye conc. (mg/L)	Removal efficiency (%)	References
Acid black 1	70	6	20	200	95.5	46]
Direct red 80	1,250	12	–	10	99	47]
Reactive red 239	20	7	20	5	100	48]
Acid red 14	–	7.10	25	1,500	93	49]
Crystal violet	2	6.8	60	50	78	50]
Direct black 22	5,000	11	30	–	55	51]
Reactive blue 19, reactive red 239, reactive yellow 176	20	7	60	–	60	52]
Direct red 81	–	11	27	2,000	61	53]
Methyl orange	109	9	–	100–500	96	16]
Reactive blue 194	178.8	5–12	40	50	100	21]
Alizarin red S	5,000	3–11	30	100–500	95	54]
Reactive blue 19, reactive red 239, reactive yellow 176	20	7	15	–	100	52]

Malakootian et al. ⁵⁵ used ozonation and Fenton’s procedure for the exclusion of Acid Red 337 and Reactive Orange 16 dye solutions. They observed that the removal percentage was close to 99 % in both cases. Similarly, Venkatesh et al. ⁵⁶ decomposed Reactive Black 5 dye by ozonation process followed by its anaerobic treatment with the removal percentage found as 94 %. Rodriguez et al. ⁴⁵ degraded Rhodamine G6 by oxidation process while using ozone as a source of oxygen. Values of dye removal was ranged from 95 to 99 % with varying the pH of the medium. Kamarehie and coworkers (2019) degraded the dye Alizarin Red by catalytic ozonation process using PAC/γ-Fe₂O₃ as a nano-catalyst in a batch investigation process, and attained efficient results.

2.1.4 Advanced oxidation processes

With the passage of time, the study and advancement of wastewater treatment techniques has focused more and more on advanced oxidation processes (AOPs) which are described as those techniques that use the hydroxyl radical (^·OH) for oxidation. Additional advanced oxidation techniques include radiation, photolysis, sonolysis, photo-catalysis, electrochemical oxidation techniques, and Fenton-based processes. ⁵⁷ Fenton’s reagent-based oxidation has emerged as a promising and alluring treatment approach for the efficient breakdown and color removal of dyes as well as the eradication of a significant number of toxic and organic contaminants. Using hydrogen peroxide and iron II ions in an acidic media, Fenton’s mechanism is a homogeneous catalytic oxidizing process that produces hydroxyl radicals. ⁵⁸ Those reactions produce natural radicals and begin further a series of chain reactions that involves the interaction with O₂ (creation of peroxy radicals) and the intermediates of the reaction. The next step is an additional oxidation process with newly produced oxidizing agents (^·OH, HO₂^·, and H₂O₂) until all organic pollutants are completely mineralized. ⁵⁹ The step adopted during advanced oxidation processes are described in form of Equations (1)–(3).

(1) RX + · + OH − → OH · + RX

(2) R · → OH · + RH + H 2 O

(3) PhX ( OH ) · → OH · + PhX

Here, RX and PhX stand for aliphatic and aromatic halogens, respectively. Electrochemical advanced oxidation processes (EAOPs) use electrolytically created hydroxyl radicals. ⁶⁰ EAOPs are environmentally friendly because the primary reagents used in all of these processes are the electrons which are a naturally clean species. ¹² Other benefits include their adaptability, greater effectiveness at removing pollutants, operational safety, and automation capability. ⁶¹ Additionally, the positive aspects of AOPs include their high efficiency in degrading a wide range of dyes, achieving near-complete mineralization of organic pollutants, and resulting in minimal secondary pollution. Their versatility allows them to be applied to different types of wastewater and pollutants, making them suitable for various industrial applications. However, the negative aspects include high operational costs due to the need for chemicals and energy, operational complexity requiring precise control of parameters, and the potential formation of harmful intermediate compounds during incomplete oxidation. Additionally, handling and storing chemicals like hydrogen peroxide demand stringent safety measures, and the maintenance of equipment such as UV lamps and catalysts adds to the operational challenges.

El Haddad et al. ⁵⁸ reported the 85 % elimination efficiency against the reactive yellow 84 dye using the Fenton reagent at pH 3. Similarly, Hassaan et al. ⁶² degraded the direct blue 86 dye by using ozone in conjunction with ultraviolet light with 98 % of the dye being removed at pH 11. Zazou et al. ⁶³ completely removed the methylene blue from wastewater by combining electrocoagulation with an improved electrochemical oxidation technique. Pacheco-Alvarez et al. ⁶⁴ was able to remove chocolate brown and eriochrome black dyes, and both entirely decolored at an acidic pH of 2.8–3.0 by coupling electro-oxidation, electro-Fenton, and photoelectro-Fenton. Different other researchers reported different methods for the treatment of dye present in wastewater and obtained effective results ⁶⁵ ^, ⁶⁶ under different processes conditions such as agitaion time, pH and temperature of the medium.

2.2 Physical methodologies of dye removal

Physical methods for dye removal from wastewater include adsorption, membrane filtration, and sedimentation, each with distinct mechanisms and advantages. Adsorption involves using materials like activated carbon, clay minerals, or biosorbents (such as agricultural waste, algae, or fungi) to attract and hold dye molecules from the water. ⁶⁷ These methods offer high efficiency and selectivity particularly with biosorbents that are renewable and cost-effective. Membrane filtration encompasses microfiltration, ultrafiltration, nanofiltration, and reverse osmosis. ⁶⁸ Nanofiltration is especially notable for its ability to remove small dye molecules and divalent ions while allowing monovalent ions to pass through making it suitable for partial desalination. Sedimentation, sometimes enhanced by coagulants, enables dye particles to settle out of the water under gravity, simplifying their removal.

On comparison of these methods, adsorption has been proved as highly effective one for a wide range of dyes removal and is relatively simple to implement. However, this method requires periodic replacement or regeneration of the adsorbent materials. Membrane filtration, including nanofiltration, provides precise separation and high-quality effluent but is prone to membrane fouling and requires significant maintenance and operational costs. Sedimentation is straightforward and cost-effective for large particles and suspended solids but is less effective for dissolved dyes and often needs to be combined with other methods to achieve comprehensive dye removal. Overall, the choice of method depends on the specific wastewater characteristics, desired effluent quality, and economic considerations. Some of these physical methods are discussed below.

2.2.1 Membrane filtration method

Membrane filtration is a physical separation process used to remove dyes and other contaminants from wastewater by passing the water through a semi-permeable membrane. This membrane acts as a barrier, selectively allowing water molecules to pass while retaining larger dye molecules, particles, and other impurities. The types of membrane filtration include microfiltration, ultrafiltration, nanofiltration, and reverse osmosis. Microfiltration, with pore sizes ranging from 0.1 to 10 μm, is primarily used for removing suspended solids, bacteria, and large colloidal particles, employing filter media made from materials like polypropylene and polyethersulfone (PES). ⁶⁹ Ultrafiltration, with pore sizes range from 0.01 to 0.1 µm, effectively removes viruses, proteins, and larger organic molecules, using different polymers such as polysulfone and polyacrylonitrile (PAN) as a ultra-filter. Nanofiltration, with pore sizes of 1–10 nm, is suitable for removing small organic molecules, divalent ions, and certain dyes, utilizing thin-film composite (TFC) materials. Reverse osmosis process with a membrane having pore size range from 0.1 to 1.0 nm can remove nearly all contaminants, including monovalent, divalent ions along with small organic molecules. ⁶⁷

The choice of membrane material significantly impacts filtration efficiency, chemical compatibility, and durability, with common materials including polymers like PES, PVDF, and ceramics. Membranes can be configured in various forms such as flat sheets, spiral wound, hollow fibers, and tubular modules, each offering different advantages in the form of surface area, packing density, and ease of cleaning. ⁶⁷ Operating conditions such as pressure, temperature, and flow rate influence the membrane filtration efficiency. Generally, higher pressure is required for tighter membranes like nanofiltration and reverse osmosis. Membrane fouling, caused by the accumulation of particles and organic matter on the membrane surface, poses a significant challenge. To avoid this, regular cleaning and maintenance protocols are ensured for long-term performance. These protocols also prevent reduced flux and membrane damage. Membrane filtration provides high-quality effluent. The ongoing operational costs, including energy consumption and membrane replacement, can be substantial to determine feasibility for specific applications. ⁷⁰

Particularly with reduced membrane pricing and increased membrane efficiency, wastewater separation/purification by membrane technology in terms of various dynamic factors (such as electrical, pressure and thermal) has gained considerable attention. ⁷¹ ^, ⁷² Membrane separation contributes to the efficient rejection of organics and minerals from the effluent in a direct membrane filtering system producing excellent permeate with an increased water recovery ratio. ⁷³ The direct membrane filtering system often requires a small footprint due to its high degree of compactness. Importantly, the direct membrane method uses less energy because it does not require a separate treatment process ⁷⁴ Furthermore, the forceful membrane filtration enriches the rejected organic material and nutrients at large concentrations, which can subsequently be post-digested to create renewable power (H₂, CH₄), or it can be changed to fertilizers. ⁷⁰ In order to endure workable long-term membrane performance, the membrane snarling control measures used in continuous membrane filtration are extremely important. ⁷² Membrane methods are commonly used to filter old dyeing solutions because of their ongoing use in technical processes. You can combine different membrane types with other dye removal methods or employ a variety of membrane types. Cascade systems, which combined reverse osmosis with ultrafiltration, are the most intriguing recently proposed treatment tools for dye removal from wastewater. ⁷⁵ The general filtration process of different dyes using a membrane is illustrated in Figure 4.

Figure 4:

Removal of dyes in contaminated wastewater by membrane filtration method.

Liu et al. ⁷⁶ used polyurethane froth membranes packed with humic acid-chitosan crosslinked gel to eliminate negatively charged methyl orange (MO), impartial Rhodamine B (RB), and impartially charged methylene blue (MB) dyes from wastewater. The improved separation of Congo red, direct red 23, reactive blue 2 and direct red 80, dyes and greater than 97 % of dye recovery after five cycles usage was observed in ultra-filtering membranes. ⁷⁷ Abdi et al. ⁷⁸ utilized a unique synthetic polyether sulfone nano-filtering membrane with enhanced properties by incorporating magnetic graphene oxide/metformin amalgam to eliminate the Direct Red 16 dye from water source. They observed that these membranes proved efficient for the removal of dyes from water medium. Different other researchers reported various membrane based techniques for the removal of toxic dyes and obtained good results. ⁷⁹ ^, ⁸⁰ Thus, Table 4 gives a brief summary of potential use of various membranes for the filtration of different dyes, time of filtration and removal efficiency.

Table 4:

Brief summary of many research that were implemented membrane filtration for dye removal.

Dye	Membrane used	Membrane operation	Time (h)	Initial dye conc. (mg/L)	Removal efficiency (%)	References
CV	Clay, flat sheet, pore size: 0.3 µm	Dead end membrane cell	–	100	100	81]
RhB	Flat sheet, polyether sulfone, pore diameter: 0.45	Vacuum mem brane filtration	50	5	98	82]
Blue corazol Dark blue	Polyether sulfone, polyethyleneimine graphene oxide polyethyleneimine, flat sheet, pore diameter: 0.2 µ	Dead end membrane cell	50	10	97.8	83]
MB	Polyvinylidene fluoride chitosan organo clay, flat sheet, pore size: 0.22 µ	Dead end membrane cell	3	1	85	84]
Direct blue 15	GN polymeric membrane	Cross flow membrane cell	–	10	85.43	85]
Reactive blue 2	Polyether sulfone, polyacrylonitrile	Cross flow membrane cell	–	50–2,000	100	86]
CV	Cellulose acetate	Cross flow membrane cell	0.5	10	99	87]
Direct red 16	Flat sheet polyether sulfone/magnetic graphene-based composite	Dead end membrane cell	2	30	99	78]
CV	Flat sheet Polyethyleneimine/SiO2	Dead end membrane cell	0.5	10	100	88]
CR MB Sunset yellow	Flat sheet Diethanolamine/poly-amide	Cross flow membrane cell	–	50 50 50	99.6 99.8 97.8	89]
Victoria blue Brilliant green CV	Hollow fiber Polyquaternium-10/poly vinyl alcohol/ Polypropylene	Cross flow membrane cell	2	100 100 100	99.8 99.8 99.2	90]
RhB CV	Hollow fiber Triethylene tetraamine/Poly ether sulfone	Cross flow membrane cell	2	100 50	99.8 98.4	91]
Brilliant green Victoria blue CR	Hollow fiber Polyelectrolytes/ Poly propylene	Cross flow membrane cell	100	50 50 50	99.8 99.6 99.4	92]
MB	Flat sheet poly sulfone/Zwitterionic monomer	Cross flow membrane cell	18	300	99.9	93]
Direct black 38 Xylenol orange Ponceau S	Flat sheet polyacrylonitrile/phosphorylated chitosan graphene oxide	Cross flow membrane cell	0.5	100 100 100	99.7 97.5 93.4	94]

2.2.2 Nanofiltration

An innovative improved membrane technique called nanofiltration (NF) has been used to remediate wastewater, especially for the removal of colors from the wastewater. ⁹⁵ Thus, nano-filtration has recently proved as potential separation technique to supersede or supplement some of the current separation methods. ⁹⁶ With pore size between 0.50 and 2.0 nm, these membranes efficiently eliminates the dyes. ⁹⁷ As a result, this method can eliminate different dye molecules through the electric and size repulsion process. ⁵ When NF is compared to the Ultra filtration and reverse osmosis, NF proves superior due to its greater flux permeability, high potential of retaining the multivalent salts, comparatively low expenditure, lower operating along with low maintenance expenses. ⁹⁸ For the purification of dyes like MV, MB, and Victoria Blue (VB), nano-filtration with cellulose nano crystals has shown to be a very successful method. ⁹⁹ NF has many benefits including a smaller osmotic pressure gradient, a higher saturate flux, the capacity to retain multivalent salts, and the capacity to remove organic substances with molecular weight ranging from 200 to 1,000 Da, such as dye and divalent salt. ¹⁰⁰ ^, ¹⁰¹ Additionally, NF membrane functional pressure is lower than RO membrane, which is about 2–40 bar. ¹⁰¹ Even if nanofiltration durability is inferior to RO, it is nevertheless viewed favorably since NF has lower running costs than RO; the greater the operative pressure, the higher the operating costs. ¹⁰²

Liu et al. ⁸⁹ explored the highly effective removal of neutral red, Congo red, and sunset yellow, dyes from the aqueous solution via nanofiltration using a diethanol amine-modified polyamide thin-film based hybrid membrane. These membranes were proved efficient for the removal of dyes from aqueous medium. Similarly, Long et al. ¹⁰³ prepared chitosan nano filtering membranes by using a film casting technique and observed that these membranes exhibit extremely high filtration potential for the efficient removal of BB dye. Qi et al. ¹⁰⁴ synthesized a polythyl enimine-modified novel positive charged nanofiltration membrane and evaluated its efficiency against Tropaeolin O, Victoria blue B, and semixylenol orange dyes with percentage removal values found as 98.3, 99.2, and 99 %, respectively.

Different other researchers also used NF technique for the removal of toxic dyes from aqueous medium while using membranes designed from different types of inorganic, organic and polymer materials. ⁹⁰ ^, ¹⁰⁵

2.2.3 Ion exchange method

One of the most standard method is the ion exchange procedure which proficiently removes the colored dyes from aqueous solutions by interacting with dyes having charge and functional groups on ion exchange adsorbent. In order to effectively separate the solutes from complex mixture by the resins, this procedure depends upon the exchange of ions. In this method, a fixed bed reactor cation exchangers or anion exchangers made of different polymers are used to isolate solutes with various surface charges. ⁵ ^, ¹⁰⁶ Ion-exchange resins are granular or beads made of polymers with a variation of functional groups that can bind ions with different charges. These resins can be either cations exchangers or anion exchanger and can remove cations of anions accordingly. Thus, anion exchange resin is not employed for anionic dyes due to comparable charge, while cation-exchange are not ideal for the elimination of reactive dyes from wastewater due to the dyes and resins having like charges. ¹⁰⁷ Ion exchanger containing anionic resin being used as adsorbent for the removal of cationic dyes from wastewater is illustrated in Figure 5. Ion exchange is a selective and efficient method for removing specific ionic dyes and contaminants from wastewater. It utilizes ion-exchange resins to rep\lace undesirable ions with more desirable ones. While offering high selectivity and efficiency, ion exchange requires periodic resin regeneration, incurring operational costs and generating waste brine solutions. Compared to the other physical methods like adsorption and membrane filtration, ion exchange stands out for its ability to target specific ions but may involve higher operational costs and environmental considerations due to resin regeneration.

Figure 5:

Treatment of wastewater by anionic resin.

Bayramoglu et al. ¹⁰⁸ detached two sepratedly dispersed dyes such as direct red and dispersion violet 28 from an aqueous solution by using a hydroxyl propyl methacrylate-co-ethyleneglycol dimethacrylate-co-(glycidylmetharylate) terpolymer resin that was modified with sulfonic acid groups. The resin’s maximum adsorption capacities for the DR-R and DV-28 were determined to be 86.1 and 179.6 mg/g, separately, and the desorbing percentage of dyes from the resin were found to be approximately 89.4 and 91.7 %, respectively. Various other researchers also reported the use of cation and anion exchange membranes for the effective removal of different dyes from aqueous medium. ¹⁰⁹ ^, ¹¹⁰ They attained good results in form of percentage removal values of dye from aqueous medium.

2.2.4 Adsorption

The phenomenon of adsorption of materials in form of gas or solid on the surface of a solid or fluid is identified as adsorption. The molecules (adsorbate) come in contact with the active sites present at the surface of the adsorbent and held on their surface. Any interaction between two phases, such as a liquid-liquid, gas-liquid, or liquid-solid interface, can experience the adsorption process. Adsorption can be used to purify water and is effective in a variety of physical, biological, and chemical processes. ¹¹¹ With the time, adsorption becomes the peak popular scheme for treating dyes contaminated wastewater because of its straightforward operation, low cost, and optimum outcome. ¹¹² Temperature based adsorption process simulates the interaction amid the adsorbents and adsorbates. Thus, it proves as a crucial parameter for the understanding of the adsorption processes. ¹¹³ The Langmuir isotherm is a hypothetical single layer adsorbed model that assumes each molecule is adsorbed on the surface of the adsorbent with each molecule occupy separate active site. These adsorbed molecules do not interact with each other and form a monolayer of the adsorbate molecules. A well-known model of multilayer adsorption is the Freundlich isotherm. It is hypothesized that soil or water molecules nonlinearly absorb adsorbates in form of multi-layered adsorption and surface of the adsorbent is assumed heterogeneous. ¹¹⁴

The adsorption of the dye molecules over the surface of adsorbents is primarily because of physical and chemical interactions. These interactions include van der Waals forces, electrostatic attraction, hydrogen bonding and in some cases covalent bonding. The high surface area and porosity of adsorbent materials such as activated carbon, zeolites, and certain nanomaterials provide numerous active sites for dye molecules to attach. ¹¹⁵ Additionally, the specific functional groups present on the surface of the adsorbents interact with dye molecules which result in enhancing the adsorption process. This makes adsorption an effective method for removing dyes from wastewater, as it concentrates the dye molecules on the adsorbent surface, facilitating their removal from the liquid phase.

The criteria of surface area, mechanical stability, porosity, and adsorption capacity should all be as large as feasible for an adsorbent to be efficient, along with the viability of other aspects like affordability, sustainability, ease of regeneration, and selectivity. ¹¹⁶ Currently, a wide variety of adsorbents are used in sewage disposal. These adsorbents can be in the form of polymers, organic and inorganic materials, household, industrial, and agricultural waste. ¹¹⁷ Some of them have been explained here briefly.

2.2.4.1 Industrial adsorbents

Industrial adsorbents are vital materials frequently utilized for removing contaminants from wastewater through adsorption processes. Among these, zeolites and clay minerals stand out as prominent industrial adsorbents for the adsorption of dyes from wastewater. Zeolites, crystalline aluminosilicate minerals, boast a porous structure and high surface area, making them effective in capturing dyes and other pollutants from wastewater. ¹¹⁸

Zeolites are often found in very porous, crystalline aluminum silicate forms in nature. They have the same ion exchange potential as clay and have a high dye adsorption capability. ¹¹⁹ These materials consist of a three-dimensional network of channels and cages. This structure provides zeolites with a large surface area and uniform pore size distribution, making them excellent adsorbents for various pollutants including dyes in wastewater treatment. In the context of dye removal, zeolites exhibit significant adsorption capacity due to their ion exchange properties and good surface properties. Dyes are typically organic compounds with chromophoric groups, which can interact with the surface of zeolites through electrostatic forces, hydrogen bonding, and Van der Waals interactions. These interactions enable the effective uptake of dyes onto the surface and within the pores of zeolite particles. ¹²⁰ Moreover, the selectivity of zeolites towards specific dyes can be tailored by modifying their surface properties through processes such as ion exchange or functionalization with organic or inorganic groups. This allows for the targeted removal of particular dye molecules from wastewater streams.

In addition to having a great ion-exchange ability, zeolites compound also have affordable pricing and comparatively high specific surface areas. Zeolites have thus been used extensively as adsorbents for the decontamination of water from the dyeing process. Natural zeolites come in a variety of forms, including clinoptilolite, laumontite, mordenite, chabazite, and analcime. ¹¹⁷ ^, ¹²¹ Zeolites have an ion replaceable surface that allows them to grip cations and/or anions by adsorption or ion exchange as its adsorption processes. Additionally, they have a large surface area, are inexpensive, abundant in nature, and have minimal toxicity. ¹²²

Their selective adsorption properties and thermal stability render them particularly suitable for dye removal applications in industries such as textiles and petrochemicals. Similarly, clay minerals like montmorillonite and kaolinite offer significant adsorption capacities due to their high cation exchange capacity and abundant availability in nature. ¹²³ These clay minerals can efficiently adsorb dyes from wastewater, contributing to the successful remediation of contaminated water sources ¹¹⁵ as generally represented in Figure 6.

Figure 6:

General mechanism of adsorption and desorption of pollutants using any adsorbent.

Thus, clay minerals are another class of naturally occurring materials widely used as adsorbents for the removal of dyes from wastewater. Clay minerals, such as kaolinite, montmorillonite, and bentonite, possess a layered structure with a high surface area and abundant surface functional groups, making them effective adsorbents for various contaminants, including dyes. The adsorption of dyes onto clay minerals occurs through a combination of mechanisms, including electrostatic interactions, ion exchange, surface complexation, and physical entrapment within the interlayer spaces of the clay structure. ¹²⁴ The polar nature of dye molecules facilitates their interaction with the polar surface of clay minerals, leading to adsorption onto the clay surface or incorporation into the interlayer spaces. ¹¹⁸

The adsorption capacity and efficiency of clay minerals for dye removal depend on several factors, including the mineral composition, surface area, pore structure, surface charge, pH, temperature, dye concentration, and contact time. ¹²⁵ Optimal conditions must be determined to maximize the adsorption performance of clay minerals in dye removal applications. One notable advantage of using clay minerals as adsorbents is their abundance in nature, low cost, and environmental compatibility. ¹²³ Additionally, clay minerals can be modified or functionalized to enhance their adsorption properties and selectivity for specific dye molecules.

Thus, their versatility and cost-effectiveness make them valuable tools in wastewater treatment processes. Both zeolites and clay minerals play critical roles as industrial adsorbents, offering effective solutions for the removal of dyes and other pollutants from wastewater. Thus, they contribute to environmental sustainability and water quality improvement efforts.

However, there are some limitations associated with the use of clay minerals for dye removal, including their relatively low adsorption capacity compared to the other adsorbents and potential for pore blockage or saturation over time. ¹²⁶ These challenges can be addressed through optimization of process parameters, development of hybrid adsorbent materials, and regeneration techniques to restore the adsorption capacity of spent clay adsorbents.

Moreover, activated carbon, alumina, and silica gel have also been used widely as industrial adsorbents. ¹¹¹

Natarajan and Bajaj ¹²⁵ observed that MB, an organic dye, was quickly adsorbed on graphene oxide (GO), a material synthesized from the used lithium-ion batteries (LIBs). Activated carbon organized with Enteromorpha prolifera by activated zinc chloride eliminate 59.88, 71.94, and 131.93 mg/g of Reactive Red, Reactive Blue and Reactive Blue from aqueous solution, respectively. ¹²⁷ Zhu et al. ¹²⁴ studied the adsorption mechanism of CR from aqueous solution on new multifunctional hybrid NiFe₂O₄/ZnO that was produced using hydrothermal synthesis and reported the good absorption efficiency of 221.73 mg/g of CR. Adsorption capacity of numerous adsorbents against a wide variety of dyes are given in Table 5.

Table 5:

Adsorption capabilities of clays, zeolites, and composites made of them that have been reported.

Adsorbent	Dye	Adsorption capacity (mg/g)	References
Magnesium phyllosilicates	Yellow GR Blue RN	1,343 1,286	128]
Montmorillonite	MB	641	129]
Zeolite with mesopore	CV	1,217	130]
Ordinary clay (Turkey)	Acid red 88	1,133	131]
Cellulose/clay composite hydrogel	MB	277	132]
Heterostructures made of porous clay and silica-zirconia	Acid blue 25	266	133]
Mesoporous zeolite	MB Basic fuchsin	548 238	130]
Kaolin based mesopore silica	MB	653	134]
Smectite rich natural clay	Basic yellow 28	77	135]
Montmorillonite	CV	746	136]
Magnesium phyllosilicates	Red RB	344	128]
Zeolite or chitosan composite	MB	199	137]

2.2.4.2 Biosorbents

Biosorbents are natural or modified materials derived from biological sources, such as agricultural residues, microorganisms, algae, or certain types of plants. These materials possess good adsorption properties due to the presence of different functional groups, such as hydroxyl, carboxyl, amino, and phenolic groups on their surface. ¹³⁸ Biosorbents offer a sustainable and eco-friendly approach for the removal of pollutants from wastewater due to their abundance, renewability, biodegradability, and low cost. They can efficiently remove dyes through mechanisms such as surface adsorption, ion exchange, complexation, and physical entrapment. ¹³⁹ The surface functional groups present on biosorbents interact with dye molecules, leading to their immobilization and removal from the aqueous phase. One of the key advantages of biosorbents is their high affinity and selectivity towards specific dye molecules, which can be attributed to the diverse chemical composition and surface properties of biological materials. Additionally, biosorbents can be tailored or modified through physical, chemical, or biological treatments to enhance their adsorption capacity and efficiency for dye removal.

Different biosorbents such as chitosan along with its composites, agriculture waste along with modified agriculture materials have been considered as efficient biosorbents for the removal of toxic dyes from aqueous medium.

Chitosan, a biopolymer derived from chitin, is renowned for its remarkable adsorption properties, making it a promising candidate for the removal of dyes from wastewater. ¹⁴⁰ Its popularity stems from its abundance, biodegradability, non-toxicity, and the presence of functional groups like amino and hydroxyl groups that facilitate dye adsorption through mechanisms like electrostatic attraction, hydrogen bonding, and surface complexation. ¹³⁸ Chitosan’s effectiveness as an adsorbent can be further enhanced by forming composites with other materials. These composites typically capitalize on the synergistic effects of chitosan and the second component, which could be another adsorbent, a nanomaterial, or a natural polymer. ¹⁴¹ The composites often exhibit improved adsorption capacity, selectivity, and mechanical strength compared to pure chitosan, expanding its applicability in dye removal. Chitosan-based composites have shown superior performance due to the combined advantages of chitosan and the secondary material; ¹⁴² their detailed insights are shown in Figure 7. For instance, combining chitosan with activated carbon, graphene oxide, clay minerals, or metal oxides can enhance its surface area, porosity, and surface chemistry, thereby increasing dye adsorption efficiency. ¹³⁹ Compared to other adsorption methods, chitosan-based composites offer several advantages. They exhibit high adsorption capacities, rapid kinetics, and excellent selectivity towards dyes, even in complex wastewater matrices. Moreover, they are cost-effective, environmentally friendly, and compatible with both batch and continuous-flow treatment systems. ¹³⁸ Zhang et al. ¹⁴¹ claim that the dodecyl trimethyl ammonium chloride (DTAC)/organic composite may adsorb up to 2,352.99 mg/g of acid orange seven.

Figure 7:

Chitosan and other materials supported adsorptive removal of dyes from wastewater.

Agricultural wastes are also often used as starting materials to create charcoal and biochar because they are inexpensive resources with high carbon concentrations. Firstly, agricultural waste is abundantly available globally, particularly in agricultural regions, making it easily accessible and cost-effective. ¹⁴³ This abundance ensures a sustainable and renewable source of adsorbents for wastewater treatment, aiding in addressing water pollution challenges. Secondly, due to its status as a by-product or residue of farming, agricultural waste is typically available at minimal or no cost. This makes it economically viable for wastewater treatment, especially in resource-limited settings. Thirdly, agricultural waste is composed of organic materials that are biodegradable and environmentally friendly. ¹⁴⁴ By repurposing agricultural waste as adsorbents, circular economy principles are promoted, contributing to waste reduction and environmental sustainability. ¹⁴⁵

Agricultural wastes have been identified by studies in the literature as a suitable source of raw ingredients for the fabrication of activated carbon with low ash content, high mechanical strength, and adsorption. ¹⁴⁶ Agricultural waste products are frequently difficult to dispose of and have little to no commercial benefit. Utilizing agricultural waste is quite important. The elimination of various colors from aqueous solutions using various agrarian waste products is being researched under various working circumstances such as wheat straw, ¹⁴⁷ bagasse, ¹⁴⁸ banana skin, ¹⁴⁹ walnut shell, ¹⁵⁰ olive powder, ¹⁵¹ mustard, linen, ¹⁵² waste tea, ¹⁵³ straw, ¹⁵⁴ oil palm trunk, ¹⁵⁵ guava (Psidium guajava) leaf powder, ¹⁴³ almond shell, ¹⁵⁶ orange peel ¹⁵⁷ and peanut hull. ¹⁴⁴ Because they are inexpensive or free, agricultural wastes are utilized as adsorbents to eliminate dyes. These wastes are produced in significant amounts as a result of the growing food sector and global population. ¹⁴⁶

Additionally, different functional groups present in the agricultural wastes such as carboxyl, alcohols, amine, amide, and phenols, promote the adsorption of dyes via different types of interactions. ¹⁵⁸ ^, ¹⁵⁹ Agricultural waste is a viable resource for green technologies since it is continuous and can be utilized to clean water and municipal wastewater. ¹⁶⁰ For the adsorption of dyes onto the numerous sites available in agricultural residues adsorbent, as listed in the Table 6, numerous research investigations have been conducted.

Table 6:

Different agricultural waste material as adsorbent to remove the dyes.

Agricultural waste	Dye	pH	Adsorption capacity (mg/g)	References
Coconut coir dust	MB	6.0	29.50	161]
Cucumis sativus	CV RhB	7.0	33.22 35.33	162]
Sesame scraps	Reactive red 141	1.1	27.55	163]
Wheat straw	CR	5.0	118.00	147]
Solanum tuberosum	Malachite green MB	7.0	33.30 52.60	164]
Corn stalk	Direct red 23	3.0	51.87	165]
Avocado integument	Basic red 2	7.0	102.45	166]
Banana faux stem	Reactive blue 5G	1.0	37.01	167]
Pine nut exterior,	MB	5.9	182.08	168]
Fe₃O₄-wheat straw	Basic blue 9	7.0	627.10	169]
Durian seed-KOH	Manmade dye	2.0	357.14	10]
Alfa grass	MB	12.0	200	170]

2.2.4.3 Nanomaterials as adsorbent

The fields of nanoscience and nanotechnology are currently expanding quickly and receiving special attention for the treatment of wastewater. ¹⁷¹ ^, ¹⁷² Nanomaterials as adsorbents represent a cutting-edge approach in wastewater treatment, offering unique advantages over conventional adsorbents. These materials are engineered at the nanoscale, typically with dimensions ranging from 1 to 100 nm, which impart them with exceptional surface area-to-volume ratios and surface reactivity. ¹⁷³ Nanomaterials exhibit remarkable adsorption capacities and efficiencies due to their high surface area, tunable surface chemistry, and tailored physicochemical properties. Nano adsorbents have a greater ability to bind pollutants, may act more quickly, and can successfully address wastewater. ¹⁷⁴ The Nano adsorbents have been distributed into many classes centered on their usefulness in the adsorption process. These include metallic and metallic oxide nanoparticles, nano structured, magnetic nanoparticles, and mixed oxides. ¹⁷⁵ In addition, nanoparticles of carbon, silicon, and polymers, as well as nano films, nano wires, nanotubes, and nano sheets are some other nanomaterials employed as adsorbents for the removal of contaminants from wastewater. ¹⁷¹ ^, ¹⁷⁶

Carbon nanotubes are made of graphene or graphite sheets that have been folded into tubular shapes with a nanometer to micro meter ranges in length and diameter. A hemisphere-shaped structure resembling a fullerene is used to cap each end of the tubing. These nanotubes are very hydrophobic, exhibit an unique sidewall curvature and have a pi-conjugative shape. ¹⁷⁷ Carbon nanotubes empty, layered structure provides more specific surface area and porosity resulting in higher adsorption potential. A fundamental component of nanostructures is surface functionalization which can be accomplished by irradiation, mechanical, and physicochemical, approaches. ¹⁷³ The morphology of carbon nanotube reported as an adsorbent for removal of toxic dyes is shown in Figure 8(a).

Figure 8:

Morphological representation of different nanoadsorbents as (a) carbon nanotube, (b) cellulosic nanofibers, and (c) stabilized nanoparticles.

Natarajan et al. ¹⁷⁸ investigated the selective binding of MB on the interface of the hydroxyl added TiO₂ nanotube. They employed a combination of MB and RhB dye and discovered that MB dye adhered to titanium nano tube surfaces more readily than RhB dye due to the presence of hydroxyl group in nanotubes. Due to the strong interaction between cationic MB dye and negatively charged, hydroxyl group-enriched titanium nano tube surfaces, about 87.7 % of the MB and 6.8 % of the RhB were adsorbed on the surface of TiO₂ nano tubes. Different CNTs, their adsorption capacity against various different dyes at specific pH values are given in Table 7.

Table 7:

Literature review of different CNTs material as adsorbent for the removal of dyes.

Carbon nano tube	Dye	Nature of dye	pH	Adsorption capacity (mg/g)	References
CoFe₂O₄-MWCNTs	MB	Cationic	10.0	11.95	179]
Magnetic/Chitosan/SiO₂/MWCNTs	Direct blue	Anionic	6.8	69.93	180]
MWCNTs/poly (1-glycidyl-3-methylimiazolium chloride)/ferro ferric oxide	Orange II	Anionic	6.2	68.03	181]
Glycine-βcyclodextrin–MWCNTs	MB MO	Cationic Anionic	8.0 6.0	19.50 18.95	182]
Magnetic/Chitosan/SiO₂/MWCNTs	Reactive blue 19	Anionic	2	106.38	180]
MWCNTs/chitosan/poly2-hydroxyethyl methacrylate	MO	Anionic	–	217.7	183]
MWCNTs/poly (propylene imine) dendrimer	Direct red 23	Anionic	3.0	464.73	184]
Gelatin/MWCNTs/iron oxide	MB Direct red	Cationic Anionic	– –	465.5 321.4	185]

Nanofiber is a type of fiber made from polymers that has a diameter ranging of 1–1,000 nm. Because of its large length-to-diameter and surface-to-volume ratios, nanofiber absorbents have a bigger surface area and more adsorption sites that are active. ¹⁸⁶ ^, ¹⁸⁷ The two main varieties of CNFs are electro spun CNFs (ECNFs) and vapor-grown CNFs (VGCNFs), with the latter being employed in the purification of wastewater. ¹⁸⁸ ^, ¹⁸⁹ Morphological representation of cellulosic nanofiber used as adsorbent is shown in Figure 8(b).

Thamer et al. ¹⁹⁰ studied the adsorption capacity between the surface functional groups of the O-ECNFs and MB through electrostatic interaction. They observed the increase in the adhering capability towards MB dye (170 mg g⁻¹) comparison to original ECNFs (32.5 mg g⁻¹) at 25 °C. Ibupoto et al. ¹⁹¹ demonstrated exceptional adsorption efficiency by totally discoloring the dye solution in only 60 min of contact period, with the adsorption isotherm suits the Langmuir isotherm model and having a q_max of 72.46 mg g⁻¹, which is particularly fit to the quasi 2nd order kinetic model.

Metal nanoparticles have also been reported as efficient adsorbents because of their high surface to volume ratio, strongly reactive sites, and regulated size. These particles are considered as the most preferred dye adsorbent across time. ¹⁹² Additionally, these particles have special physical and chemical features include optical properties, high chemical activity, conductance, magnetic, and catalytic potential. ¹⁹³ Green production of metal NPs, which is efficient, secure, simply accessible, non or less hazardous, sustainable, and free of fatal agents, use to get around the issues caused by chemical and physical synthesis. ¹⁹⁴ When contrasted to physical and chemical techniques, the advantages of biological treatment are widespread, straightforward, and ecological. Several microorganisms are typically utilized in aerobic or anaerobic conditions to decolorize the dyes polluted wastewater. ¹⁹⁵ Morphology of stabilized nanoparticle used as adsorbent is shown in Figure 8(c). However, severe external environmental requirements, such as dietary requirements, temperature, and pH are necessary for biological treatment. Furthermore, the bioreactor requires a specific quantity of time. ¹⁹⁶ Table 8 reflects the use of different NPs as adsorbent at different pH, their respective kinetic and isotherm models.

Table 8:

Different nanoparticles used for the removal of textile dyes from wastewater.

Adsorbent	Dye	pH	Adsorption capacity (mg/g)	Kinetic model	Isotherm model	References
ZnO NPs	Azo dye	6	40	Pseudo-second-order	Langmuir	197]
CuO-A nanoparticles	MB	10	95.5	Pseudo-second-order	Freundlich	198]
CeO₂ NPs	Sulfonate reactive red 198	3	60	Pseudo-second-order	Langmuir	199]
Fe₂O₃@SiO₂ nanoparticle	Acid blue 92	2	1.6	Pseudo-second-order	–	200]
Ho-CaWO4 nanoparticle	MB	2	103.9	Pseudo-second-order	Freundlich	201]
Cu-modified nanogoethite	Methylene blue	9	12.69	Pseudo-second-order	Langmuir	202]
Chitosan/Nano hydroxyapatite composite	Brilliant green	7	49.1	Pseudo-second-order	Langmuir	203]
Neodymium oxide (Nd₂O₃) nanoparticles	Acid blue 92	3	138.5	–	Freundlich	204]
Nanoparticles of Fe–Co–Mn supported by MgO	RhB	7	1,106	Pseudo-second-order	Langmuir	205]
P-γ-Fe₂O₃ NPs	Remazole black B	3	192.3	Pseudo-second-order	Freundlich	206]

3 Advantages and disadvantages of using physio-chemical methods

Physical methods, such as adsorption, filtration, and membrane separation, rely on physical separation mechanisms. Adsorption utilizes materials with high surface area to attract and trap dye molecules. This technique boasts high removal efficiency for various dyes and offers the potential for adsorbent regeneration. ²⁰⁷ However, selecting appropriate adsorbent materials and managing their disposal can add complexity. Filtration and membrane separation physically exclude dyes based on size or charge. ²⁷ These methods are simple to operate and generate minimal secondary waste, but their effectiveness can be limited by pore size and membrane fouling. ²⁰⁸ These techniques come with a number of disadvantages such as complex structures, high costs, ineffective color disposal, the creation of secondary substances, and the creation of enormous amounts of dirty sludge and the manufacturing of toxic waste byproducts. ²⁰⁹

Chemical methods, on the other hand, involve chemical reactions to degrade or transform dye molecules. Common techniques include oxidation, reduction, and ozonation. These methods can achieve complete dye destruction and are often effective for a broader range of dyes compared to physical methods. However, chemical processes often require precise control of reaction conditions, can generate hazardous byproducts, and may not be suitable for all dye types. ¹⁹⁵ Additionally, the cost of chemicals and the potential for incomplete reaction can be drawbacks.

The optimal choice between physical and chemical methods depends on several factors. For scenarios prioritizing cost-effectiveness and simplicity, adsorption with readily available materials like activated carbon might be preferred. ¹⁹⁶ Conversely, when complete dye destruction and applicability to a wide range of dyes are crucial, chemical oxidation might be a better option. Furthermore, environmental considerations are paramount. Physical methods generally offer a more sustainable approach by minimizing chemical consumption and waste generation. ²¹⁰

In conclusion, both physical and chemical methods offer viable options for dye removal from wastewater. Selecting the most appropriate technique requires careful consideration of factors like dye type, desired removal efficiency, operational complexity, and environmental impact. Future research should focus on developing cost-effective, sustainable methods that combine the advantages of both physical and chemical approaches, while minimizing their drawbacks, to achieve comprehensive dye removal and wastewater treatment. The advantages, disadvantages and characteristic features of the discussed physical techniques are summarized in Table 9.

Table 9:

The benefits and drawbacks of physio-chemical techniques employed in the manufacturing of textiles.

Technique	Main characteristics	Advantages	Disadvantages	References
Coagulation	Absorbing the contaminants and separating the generated products.	Simple, widely available, available in a wide variety of chemicals, effective for suspended particles, good dewatering capabilities, and much lower COD and BOD.	Sludge formation, increased chemical costs, a disposal issue, and physical-chemical control of the effluent (pH).	211]
Electrocoagulation	Emerging processes.	Less usage of chemicals, simple operation.	Greater energy costs, the need to replace electrodes, and the creation of disposal.	63], 212]
Oxidation	Application of an oxidant, such as Cl₂, ClO₂, H₂O₂, O₃or KMnO₄.	Quicker, more effective procedure. Complete chromophores group removal to achieve colourless dyes.	Sludge creation, higher material cost, higher energy utilization.	213], 214]
Membrane separation	Nondestructive separation semipermeable barrier.	Well suited to all dye types, efficient at removing COD, salinity	High operational costs (increased membrane costs), membrane obstruction, efficacy for high volume and pressure	215]
Ozonation	Use of ozone as oxidant.	When used in a gaseous condition, COD is completely eliminated.	Because of its short lifespan and high cost, ozone is not a cheap source of continuous supply.	57], 216]
Ion exchange (chelating resins), selective resins, mega porous resins, polymeric adsorbents, polymer-based mixed adsorbent.	Nondestructive.	Excellent for soluble dyes, with simple solvent recovery	Significant operational costs, ineffective at dye concentrations, and only useful for disperse dyes	107], 217]

4 Biological approaches for the removal of dyes

The procedure of biological cure is straightforward, affordable, and environmentally friendly. There are also many bacteria that are simple to keep going and demand little to no effort. ²¹⁸ Many kinds of microorganisms comprising yeast, bacteria, fungi and algae have a knack to mineralize and/or decolorize different dyes. ²¹⁹ ^, ²²⁰ Either pure culture or hybrid microbial culture can be used to treat colored wastewater. Owing to additive metabolic activities, it has been observed that heavily mixed microbial cultures can efficiently degrade dyes. ²²¹ Biological degradation can be directed under either aerobic or anaerobic circumstances. ²²² Dye decomposition is impacted by many microbial metabolic processes and development circumstances. ²²³

The degradation of dyes involves breaking down complex dye molecules into simpler, less harmful compounds through various chemical or biological processes. Chemical methods such as AOPs use oxidizing agents like ozone, hydrogen peroxide, or photocatalysts to generate reactive species that attack dye molecules breaking their bonds and converting them into non-toxic by-products. ²²⁴ Chemical methods involve use of chemical reductants which efficiently degrade the dye molecules. Biological degradation by utilizing the microorganisms such as bacteria, fungi, and algae, which produce enzymes that metabolize dyes, ultimately degrading them into carbon dioxide, water, and other harmless substances. ²²⁵ Additionally, the presence of nanoparticles in the adsorbent material can act as catalysts enhancing the degradation process by facilitating chemical reactions on the large surface area that break down dyes into non-toxic substances. These newly formed degraded products are environmentally friendly. These degradation processes are effective because they transform hazardous dye pollutants into harmless compounds reducing their impact on ecosystems. ²²⁶

The heterogeneous polysaccharides and lipids that make up the cell wall are made up of various functional groups, such as amino, phosphate, hydroxyl, carboxyl, and other charged groups. They may result in powerful forces of attraction between the dye and cell wall. ²²⁷

4.1 Degradation by fungi

Fungi can removed composite organic compounds via catalysis with external ligninolytic enzymes comprising laccase, manganese peroxidase and lignin peroxidase. ²²⁸ Fungi propose an capable system due to huge surface area and uncomplicated solid liquid partition. ²²⁹ Fungi also hold multiple processes for removal of organic and inorganic contaminants. ²³⁰ Fungi immobilization has been proposed as a technique for sustaining effective degrading biomass in the processes, and various immobilization techniques have been created that boost wastewater treatment efficiency. ²³¹ However, the lengthy hydraulic retention time necessary for proper decolorization is the constraint for the use of fungi to remove colors. Not only this but the retention of fungi in culture systems is another issue to take into account which makes it a less favorable choice for the researchers. ²³²

Intracellular and extracellular enzymes produced in large quantities by fungi have the potential to break down an extensive range of organic pollutants, including steroid compounds, dye emissions, organic waste, and poly aromatic hydrocarbons. Several researchers have documented how white-rot fungus are used to biodegrade azo colors. In this context, mycoremediation is a risk-free, inexpensive, and natural method of colour removal. ²³³ Shanmugam et al. ²³⁴ Trichoderma asperellum laccase activity transformed Malachite Green (MG) from benzaldehyde via the Mishler’s ketone route, resulting in the greatest biodegradation of MG. The reduction potential of different fungal strains against different dyes under different reaction conditions, and their mechanism is listed in Table 10.

Table 10:

Biological degradation of various commonly used textile dyes utilizing various fungus strains.

Fungal strain	Dye	pH	Time (h)	Removal (%)	Mechanism	References
Curvularia clavata NZ2	Congo red,	5	24	88–92	Reduction of azo bond	235]
Aspergillus niger	Direct blue 199	3	4	29.6	Biosorption	236]
Purified manganese peroxidase from Ganoderma lucidum IBL-05	Sandal red, Sandal-fix turq blue, Sandal foron blue, Sandal-fix black, Sandal- golden yellow.	4	12	87.5 82.1 89.4 95.7 83	Entrapment method	237]
Laccase from Peroneutypa scoparia	Triphenyl methane	6	6	75	Reduction of azo bond	238]
Activated carbon immobilized by Aspergillus niger	Reactive black Congo red Malachite green	5	72	98.2 84.6 82.6	– – –	239]
Laccase of Cerrena sp.	Malachite green	6	2.87	91.6	Reduction	240]
Thermomucor indicaeseudaticae	Azo anthraquinones dye mixture	6	24	79.26	Biosorption	241]
Aspergillus niger	Red azo	9	2	99.96	Breaking the dye complex bonds	242]

Among fungi, yeasts hold particular promise for dye removal due to a combination of advantageous traits. Firstly, their small size and rapid growth rate translate to a high biomass production per unit volume, allowing for efficient dye adsorption. Secondly, yeasts often possess a robust cell wall rich in binding sites for various dye molecules. ²⁴³ Additionally, their single-celled nature simplifies downstream processing after dye adsorption compared to filamentous fungi. Furthermore, some yeast species exhibit the unique ability to degrade or modify the adsorbed dyes, offering not just removal but potential detoxification as well. Finally, yeast strains can often be easily manipulated and optimized for enhanced dye removal capabilities, making them highly adaptable bioremediation tools. These combined advantages make yeasts stand out as frontrunners in the fungal fight against dye-contaminated wastewater. ²⁴⁴

Therefore, for the breakdown of textile colors, yeasts are superior to filamentous fungus and bacteria in a number of ways. For instance, they can withstand harsh settings and grow quickly. ²⁴⁵ Due to their superior attributes, they are usually employed by numerous researchers to investigate how yeasts decolorize and break down colours. A yeast strain has the ability to extract large quantities of different colours from wastewater. The biosorption and reductive breaking of the azo link are the main mechanisms for the breakdown of textile dyes utilizing yeast strains. ²⁴³ By means of an enzymatic breakdown process and biosorption, yeast removes aqueous dyestuff. Bio-adsorption, asymmetrical azo dye cleavage, and hydroxylation make up the typical mechanism of yeast-mediated dye degradation. The yeast cell wall and dye-binding properties play a vital role in biosorption, and the reduction and oxidation mechanisms play a part in the enzymatic breakdown of dye structure ²⁴⁴ as depicted in Figure 9.

Figure 9:

Bio-reduction of an azo dye is illustrated using a fungal cell.

The most popular yeasts for removing dyes from sewage include Issatchenkia sp., Saccharomyces cerevisiae, and Debaryomyces sp. ²⁴⁶ ^, ²⁴⁷ Kiayi et al. ²⁴⁸ used S. cerevisiae MTCC463 to illustrate the entire decolorization of azo Methyl Red (100 mg/L). Martorell et al. ²⁴⁹ studied the Trichosporon akiyoshidainum suspension-based decolorization of Reactive Blue-5 dye and claim that the existence of oxidase enzymes played a major part in the breakdown of reactive blue.

Tan et al. ²⁵⁰ used Candida tropicalis TL-F1 to study the bioremediation of Acid Brilliant Scarlet GR dye and observed that it could eliminate 97 % dye in just 24 h. Rovati et al. ²⁵¹ carried out the reduction of Reactive Blue 221, Reactive Yellow 84, Reactive Red 141, and Reactive Black 5, dyes by 61 yeast morph types extracted from diverse locations on 25 de Mayo/King George Island, Antarctica. They reported that 33 % of the yeast isolated among them demonstrated discernible activity for colour oxidation. Additionally, they stated that the isolates’ ligninolytic ability and existence of the laccase enzyme played a crucial part in the dye decomposition processes. The reduction potential of different yeasts strains against different dyes under different reaction conditions, and their mechanism is listed in Table 11.

Table 11:

Various studies on the biodegradation of widely used textile dyes via diverse yeast strains.

Yeast strain	Dye	pH	Time (hour)	Biosorption (mg/g)	Adsorption isotherm	References
S. cerevisiae	Acid blue 161	8.5	3	1.248	Langmuir, freundlich	252]
Yarrowia lipolytica 70,562	CV Brilliant green	7–8	–	56.497 65.359	Langmuir	253]
S. cerevisiae	Reactive red 120	4.75	0.9	99.97 (%)	Langmuir	254]
Brewery yeast	Reactive orange 16	3.0	48	0.56	Langmuir	255]
S. cerevisiae	Remazole orange RR	3.0	2.5	84.9 (%)	Langmuir	256]
Trichoderma lixii	Alizarin red quinizarine green	–	–	33.7 (%) 74.7 (%)	–	257]
Kluyveromces marxianus	Remazole black B	4.0	24	98 (%)	–	258]
S. cerevisiae	Orange 2 GL	2.5–8.5	5	55.4	Langmuir & freundlich	259]
Yeast treated peat	Crystal violet	–	–	17	Langmuir, freundlich,	260]
S. cerevisiae	Remazole blue	2.02	1	54.17	Langmuir	261]
Waste yeast from wine	Reactive red 239 Reactive black B direct blue 85	2.0	–	153 162.7 139.2	Langmuir	262]
S. cerevisiae	Astra zone blue	7.0	4	70	Langmuir	263]
Brewery yeast	MB Malachite green Safranin O	–	0.1	212 212 76.770	Langmuir freundlich redlich-peterson	264]
S. cerevisiae	Direct red 23	2.5	4	6.192	Langmuir, freundlich and temkin	265]
Yarrowia lipolytica	Crystal violet Brilliant green	7–8	4–20	56.497 65.359	Langmuir	253]
S. cerevisiae	Alizarin red	3.0	2	29.410	Langmuir	266]

4.2 Degradation by bacteria

Bacteria can be a good alternative for dye removal from wastewater due to their remarkable metabolic diversity and adaptability, which enable them to survive and thrive in various environmental conditions, including those present in industrial effluents. These microorganisms can degrade a wide range of dye compounds through their enzymatic systems, which include oxidoreductases and hydrolases capable of breaking down complex dye structures into less harmful substances. ²⁶⁷ Bacteria such as Pseudomonas, Bacillus, and Aeromonas species have shown effective dye removal capabilities due to their ability to perform both biosorption and biodegradation. ²⁶⁸ Additionally, bacteria can be cultivated rapidly and easily in bioreactors, offering scalability for large-scale applications. Their genetic tractability allows for the development of genetically engineered strains with enhanced dye-degrading abilities. Moreover, bacterial biomass can be regenerated and reused, reducing operational costs. The ability of bacteria to form biofilms also provides a stable and efficient system for continuous dye removal processes which makes them a versatile and efficient alternative for wastewater treatment. ²⁶⁹

Bacteria have revealed huge potential for dye degradation during both pure cultures and consortium settings. In contrast to single isolates, the bacterial consortia typically demonstrated greater percentage removal of dye. ²⁷⁰ By cleaving azo links under anaerobic environments, bacteria often decolorize azo dyes to create colorless aromatic amines. ²⁷¹ But because these aromatic amines are naturally mutagenic, toxic and carcinogenic, more degradation is needed to lessen their hazardous effects. In an aerobic biological system, bacteria subsequently breakdown the aromatic amines to innocuous chemicals. ²⁷⁰ ^, ²⁷²

Maqbool et al. ²⁷³ reported that after 180 h of incubation under static conditions, Pseudomonas aeruginosa ZM130 removed 100 mg/L of mixed reactive dyes (reactive red120, reactive orange 16, reactive black 5, and reactive yellow 2) with the removal rates of 76.6, 91.1, 98.7, 91.1 %, respectively. Deepti and Isha ²⁶⁸ used the soil-isolated Klebsiella sp. BI11 to decolorize synthetic culture media that included 100 mg/L of the anthraquinone dye (reactive blue 19). The isolated strain had a decolorization effectiveness of 95 %.

Shah ²⁶⁷ examined Pseudomonas sp. ability to decolorize and break down the dye Reactive Black using bioaugmentation. The bacteria were said to be able to decolorize up to 95 % of the starting dye concentration of 100 mg/L at pH 7, temperature of 40 °C, and a 24-h incubation time in fixed, non-aerated circumstances. Ayed et al. ²⁶⁹ studied bio-augmentation techniques to decolorize Reactive Violet 5 in dye-contaminated effluent by Staphylococcus aureus consortia. They claimed that bacteria could successfully eliminate 99 % of a dye solution containing 1,000 mg/L at temperature of 25 °C and a pH of 7.5 when the mixture was shaken. Other researchers also reported the use of various bacterial strains in the removal/degradation of toxic dyes present in wastewater. ²⁷⁴ ^, ²⁷⁵ ^, ²⁷⁶ ^, ²⁷⁷ The reduction potential of different bacterial strains against different dyes under different reaction conditions, and their degraded products are listed in Table 12.

Table 12:

Studies on various commonly utilized textile colors that biodegrade utilizing various bacterial strains.

Bacterial strain	Dye	Degraded product	pH	Removal (%)	References
SUK1 P. sp	Reactive red 2	2-Naphthol	6.2	80	278]
Lysinibacillus sp. KMK-A	Reactive orange M2R	3-Aminonaphthalene-1,5-(diol, hydroxyamino)-ethylidene	7	98	279]
Aeromonas hydrophila	Reactive black 5	Aromatic amines	7	76	280]
BD 15 strain of Micrococcus sp.	Malachite green	4-(Dimethylamine) benzophenone,	7.2	–	281]
Kocuria rosea MTCC 1532	Methyl orange	4-Amino sulfonic acid, N, N-dimethyl p-phenylenediamine	6.8	100	282]
Enterococcus gallinarum	Direct black 38	Benzidine, 4-aminobiphenyl (4-ABP)	–	63	283]
Bacillus megaterium, Micrococcus luteus Bacillus pumilus	Remazole blue	Anthraquinone, hydroxy and amino derivative	7	94	284]
Klebsiella sp. strain VN-31	Reactive yellow Reactive red 198 Direct blue 7	Aromatic amines	7	94	284]
Alcaligenes faecalis	Acid blue 193 Acid blue 194	4-amino-3-hydroxynaphthalene-1- sulfonic acid	7.4	80	285]
Lysinibacillus sp. RGS	Remazole red	1,3,5-Triazine	7	100	286]
Bacillus aryabhattai DC100	Coomassie bright blue Remazole brilliant blue	–	5–8	100	287]

4.3 Degradation of dyes by algae

Algae can be a good substitute for dye removal from wastewater due to their unique biological and environmental attributes. They possess a high surface area and contain various functional groups such as hydroxyl, carboxyl, and amine groups on their cell walls. These groups facilitate the adsorption of dye molecules by enhancing the processes like ion exchange, complexation, and adsorption. Algae, both microalgae and macroalgae, can thrive in diverse and often harsh environmental conditions, making them suitable for use in various wastewater settings. ²⁸⁸ They also contribute to bioremediation through photosynthesis, which not only aids in the removal of dyes but also in the reduction of other pollutants, such as heavy metals and excess nutrients. Additionally, algae can produce a range of extracellular enzymes capable of degrading complex dye molecules into less toxic forms. The cultivation of algae is relatively low-cost and sustainable as they require simple growth media. Additionally, these algae have the unique tendency to utilize the wastewater as a nutrient source thereby reducing overall treatment costs. ²⁸⁹ Algal biomass can be harvested and reused, and it has the added potential of being converted into value-added products like biofuels, fertilizers, and animal feed. These by-products further boost up the economic viability of using algae for wastewater treatment. Due to their widespread distribution in both freshwater and saltwater, algae are potential sustainable bio sorbents. ²⁰⁹

Algae’s great capacity for biosorption and bio coagulants can be ascribed to their substantial surface area and comparatively high binding affinity. ²⁹⁰ Algal kinds have superior cell-wall traits that are essential for biosorption, as well as complexion (which is supposedly to occur through the biosorption route) and electrostatic interaction. Phosphorus, hydroxyl, amino, and carboxylate functional groups allied to the algal cell surface are thought to play a substantial part in the removal of impurities from textile effluent. ²⁸⁸ Heat, pH, and the existence of functional groups like phosphate, carboxylate, hydroxyl, and amino are the key aspects influencing algal recovery of textile effluent. ²⁷⁰

Numerous algae strains have been thoroughly considered for their ability to degrade dyes, including Cosmarium sp., Chlorella pyrenoidosa, Nostoc linckia, Chlorella vulgaris, Phormidium sp., and Synechococcus sp. ²⁹¹ ^, ²⁹² In general, polysaccharides found in marine algae are abundant and have the ability to effectively bind with contaminants. ²⁹³ The further method of decolorization relies on the use of azo dyes by algae to produce water, CO₂, and biomass. ²⁹⁴ By using azo dyes, coloured dye solution is transformed into colourless solution. Chlorella species and Oscillatoria species may break chromophore linkages in the composition of azo dyes to produce colourless aromatic amines, and they can also assimilate these aromatic amine intermediary byproducts for development. ²⁸⁹

Chlorella pyrenoidosa, Fucus vesiculosus, and Spirulina maxima strains of chemically altered algae have just been shown to have improved bio adsorbent activity against Erichrome Black, RhB, and MB. ²⁹² Liang et al. ²⁹⁵ reported that the synthetic Synechococcus elongathus PCC7942 can significantly degrade dyes by removing Reactive blue 19, Acid red 18, Reactive red 11, Acid yellow 18, Reactive orange 5, Reactive blue 4, Reactive black 5, Acid red 27, and Indigo carmine. The reduction potential of different algal strains against different dyes under different reaction conditions such as pH, reaction completion time and percentage removal are listed in Table 13.

Table 13:

Numerous studies on the biodegradation of different commonly used textile dyes using different algal strain.

Algal strain	Dye	PH	Time (days)	Removal (%)	References
Chlorella pyrenoidosa	Methylene blue	7.2	15	75	296]
Haematococcus sp.	Congo red	7	5	98	297]
Spirogyra sp. and Oscillatoria sp.	Reactive blue Reactive red	7	14	94.44 92.77	298]
Chlorella Vulgaris Aphano capsaelachista	Disperse orange Reactive yellow	7	7	52.22 49.16	299]
H. oligotrichum	Basic fuchsin Methyl red	Static condition	7	92.44 53.23	300]
Oscillatoria limnetica	Basic fuchsin Methyl red	Static condition	7	90.23 50.18	300]
Chlorella vulgaris	Reactive black 5 Direct blue 71	5 8	–	100	291]

5 Conclusion and future direction

This study article analyzed and contrasted various dye degrading techniques, demonstrating their usefulness in tackling the expanding environmental issues brought on by dye pollution. Each technique, including physical approaches, biological therapies, photocatalysis, and sophisticated oxidation procedures, displayed distinct benefits and drawbacks. The study stresses how crucial it is to choose the best degrading method based on the precise type of dye and environmental setting. A thorough examination of these processes revealed that each had unique advantages and limits, making them ideal for specific dye kinds and environmental conditions. The incorporation of nanomaterial’s, biological agents, and new catalysts improved dye degradation efficiency significantly. However, while choosing a method, it is critical to consider aspects like as cost, scaling, and harmful by-products. Future study should concentrate on optimizing these procedures and investigating synergistic techniques. Implementing these novel solutions can help to decrease the environmental impact of dye contamination and open the way for a cleaner, more environmentally friendly future. In future, researchers should explore the integration of hybrid dye degradation techniques combining with the physical, chemical, and biological methods to enhance efficiency and sustainability of these processes. Development of advanced materials such as novel catalysts and reusable adsorbents is crucial for improving the efficiency of these technique. Biological entities such as bacteria, algae, fungi, and yeast should be evaluated under different reaction conditions in order to enhance their dye-degrading capabilities. While along with the advancement in nanotechnology, its role in dye removal requires further exploration. Assessing the environmental friendliness of the degraded products from these dye degradation reactions is essential to ensure that the by-products are non-toxic and do not pose any harm to ecosystems or human health. Considering cost factor and to compare the costs of different techniques will help to identify the most viable options. Additionally, developing regulatory frameworks and raising public awareness about dye pollution and sustainable solutions are crucial for sustainable environment.

Corresponding authors: Khalida Naseem, Department of Basic and Applied Chemistry, University of Central Punjab, Lahore, 54000, Pakistan; and Research Centre for Chemistry, National Research and Innovation Agency (BRIN), B.J Habibie Science and Technology Area, South Tangerang 15314, Indonesia, E-mail: khalidanaseem1@gmail.com; and Warda Hassan, Department of Chemistry, The Women University Multan, Multan, 60000, Pakistan, E-mail: warda.chem@wum.edu.pk

Research ethics: Not applicable.
Author contributions: Khalida Naseem (https://orcid.org/0000-0001-8329-5526) worked as the main supervisor during the writing and publication of the paper. Fakhr Un Nisa, Nimra Fatima, and Warda Hassan wrote the first draft of the review article. Asad Aziz, Jawayria Najeeb, and Shafiq Ur Rehman contributed to the pictorial diagrams, tables and finalizing the article. Awais Khalid and Mohammad Ehtisham Khan did the general analysis and proofread the article.
Competing interests: The authors have no relevant financial/non-financial conflict to disclose.
Research funding: Not applicable.
Data availability: Not applicable.

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Received: 2024-06-16

Accepted: 2024-07-22

Published Online: 2024-09-02

Published in Print: 2025-06-26

This work is licensed under the Creative Commons Attribution 4.0 International License.

Articles in the same Issue

https://doi.org/10.1515/revic-2024-0042

Keywords for this article

water treatment; dye degradation; environmental impact; sustainable techniques; nanoparticles; pollution control

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