Open Access Article
Ramat Onyeneoyiza Raji
ab,
Abdulrazaq Izuafa
*ad,
Helen Shnada Auta
ac,
Oluwafemi Adebayo Oyewole
a and
Olabisi Peter Abioye
a
aDepartment of Microbiology, Federal University of Technology, Minna, Niger State, Nigeria. E-mail: izuafa.abdulrazaq@fubk.edu.ng
bDepartment of Microbiology, Prince Abubakar Audu University, Anyigba, Kogi State, Nigeria
cAfrica Center of Excellence for Mycotoxin and Food Safety (ACEMFS), Federal University of Technology, Minna, Niger State, Nigeria
dDepartment of Biological Sciences, Federal University, Birnin Kebbi, Kebbi State, Nigeria
First published on 20th May 2026
Palm oil mill effluent (POME) is a highly contaminated wastewater resulting from palm oil processing, characterized by high levels of organic matter, suspended solids, oil and grease, and intense color. The improper release of untreated or inadequately treated POME leads to serious environmental issues, including water pollution, oxygen depletion in aquatic systems, and ecological harm. Traditional treatment methodologies, such as ponding systems, anaerobic digestion, and coagulation–flocculation, face numerous challenges like long treatment times, extensive land use, secondary sludge production, and inconsistent pollutant removal rates. Recently, nanotechnology has surfaced as an innovative treatment solution, with nanochitosan, a nanosized variant of the biopolymer chitosan, attracting attention for its large surface area, abundant amino groups, strong adsorption capacity, biodegradability, and environmental friendliness. This review examines synthesis techniques for nanochitosan (ionic gelation, microemulsion, precipitation), linking their structure–property relationships to pollutant removal mechanisms. A comparison between bulk and nanochitosan emphasizes how increased surface area and functional group richness enhance adsorption capability and treatment efficiency. The efficacy of nanochitosan in eliminating organic pollutants, suspended solids, oils, color compounds, and heavy metals from POME is highlighted. The integration of nanochitosan with conventional biological and physicochemical treatments is also examined to boost treatment performance and sustainability. Moreover, challenges related to large-scale applications, regeneration, economic factors, and possible environmental impacts are discussed. Overall, nanochitosan-based treatment systems show promising potential as sustainable, effective solutions for POME remediation, contributing to advancements in eco-friendly wastewater management technologies.
Among emerging materials, chitosan and its nanoscale derivatives have attracted sustained attention due to their bio-based origin, tunable molecular structure, and high density of reactive functional groups.9 Unlike conventional inorganic coagulants or purely biological systems, chitosan-based materials enable pollutant removal through well-defined physicochemical interactions, including electrostatic attraction, chelation, hydrogen bonding, and polymer bridging.9,10 This review critically evaluates the structure–property performance relationships of chitosan and nanochitosan in palm oil mill effluent (POME) treatment. It systematically links synthesis methods to pollutant removal mechanisms, compares the treatment performance of nanochitosan with bulk chitosan, and examines the role of nanochitosan in integrated treatment systems aimed at achieving regulatory compliance and supporting circular resource recovery.
The effluent contains exceptionally high levels of pollutants with Chemical Oxygen Demand (COD) values ranging from 44
000 to 100
000 mg L−1, and in some instances exceeding 80
000 mg L−1, Biochemical Oxygen Demand (BOD) between 25
000 and 66
000 mg L−1, and Total Suspended Solids (TSS) typically within 18
000 to 46
000 mg L−1.13 Beyond these primary organic pollutants, POME also contains residual oil, heavy metals, and substantial amounts of essential plant nutrients such as phosphorus, nitrogen, and potassium.17 Furthermore, it is rich in complex organic compounds, including carotene, pectin, tannin, phenolic compounds, and lignin.18 It is important to distinguish that some lower reported values for parameters like TSS (30–40 mg L−1), pH (7.5–8.9), BOD (20–300 mg L−1), and COD (30–200 mg L−1).19 Likely pertain to treated or partially treated POME, or effluent from specific mills operating under different processing conditions, rather than raw, high-strength POME.
The direct discharge of untreated POME into the environment results in severe ecological consequences. The high concentrations of COD, BOD, and heavy metals can devastate aquatic ecosystems, leading to oxygen depletion, interfering with photosynthesis, and causing tumors or mortality in aquatic organisms.17 On land, POME discharge increases soil acidity, negatively impacting nutrient availability for plants and facilitating the leaching of heavy metals into the soil, which in turn lead to clogging and waterlogging of soil pores, loss of agricultural land and eventual vegetation die-off.16 Beyond ecological damage, POME exposure can pose health risks to humans, including irritation, poisoning, gene mutations, and even cancer.19 Moreover, the common practice of storing POME in open lagoons contributes significantly to greenhouse gas (GHG) emissions, particularly methane (CH4) and carbon dioxide (CO2), which account for over 90% of GHG emissions from such systems.1
POME presents a complex challenge due to its dual nature: it is both a potent pollutant and a potential resource. While its high organic content and nutrient load contribute to its polluting properties, these very characteristics also represent opportunities for valorization, such as methane production for bioenergy or nutrient recovery for biofertilizers.17 This duality suggests that effective POME management should ideally transition from merely removing pollutants to actively recovering and utilizing these valuable resources. Such a shift from a “waste management” paradigm to “resource valorization” is crucial for achieving genuine sustainability in the palm oil industry, transforming an environmental liability into an economic asset. The inherent acidity of raw POME also poses a significant challenge for many biological treatment processes, which typically operate optimally under more neutral pH conditions. This necessitates that any proposed POME treatment technology must either demonstrate robustness in acidic environments or incorporate an initial pH adjustment step, which adds to the operational complexity and cost. This consideration is a critical design factor for any effective treatment methodology.
Moreover, the chemical heterogeneity of POME limits the effectiveness of single-mechanism treatment processes. While biological degradation can reduce readily biodegradable fractions, residual colour, turbidity, and metal-associated species frequently persist. This highlights the need for materials capable of interacting with pollutants across multiple length scales and chemical functionalities. The variability in Chemical Oxygen Demand (COD), Total Suspended Solids (TSS), and oil content in Palm Oil Mill Effluent (POME), constitutes the principal challenges in treatment efficacy and variability observed in reported efficiencies. This complexity underscores the need for flexible and multi-faceted treatment methodologies. Table 1 summarizes the typical physicochemical characteristics of raw palm oil mill effluent (POME) and compares them with relevant discharge limits.
| Parametera | Typical raw POME range | FEPA discharge limit (1991) | NESREA discharge limit (2011) | Unit |
|---|---|---|---|---|
| a Note: Biochemical Oxygen Demand (BOD), Chemical Oxygen Demand (COD), Total Suspended Solids (TSS), Total Nitrogen (N), Heavy metals (HMs), Temp (Temperature). | ||||
| pH | 3.5–5.0 | 6.0–9.0 | — | |
| Temperature | 80–90 | <40 | <40 | °C |
| Biochemical oxygen demand (BOD5) | 25 000–35 000 |
50 | 30 | mg L−1 |
| Chemical oxygen demand (COD) | 50 000–100 000 |
90 | 80 | mg L−1 |
| Total suspended solids (TSS) | 18 000–46 000 |
30 | 30 | mg L−1 |
| Total solids (TS) | 40 000–50 000 |
— | mg L−1 | |
| Total dissolved solids (TDS) | 30 000–40 000 |
2000 | 2000 | mg L−1 |
| Oil and grease | 2000–7000 | 10 | 10 | mg L−1 |
| Ammoniacal nitrogen | 20–50 | 20 | 20 | mg L−1 |
| Total phosphorus | 100–200 | 5 | 5 | mg L−1 |
Despite these perceived benefits, conventional methods, including open lagoon systems and mesophilic digesters, are fraught with significant limitations. Open lagoons are major contributors to greenhouse gas (GHG) emissions, with methane (CH4) and carbon dioxide (CO2) accounting for over 90% of the GHGs released from such systems.21 A critical failing is that the effluent discharged from these anaerobic ponds frequently does not meet the stringent government threshold limits, as observed in countries like Indonesia.17 Even post-conventional treatment, effluents often exceed limits (COD 1400 mg L−1, BOD5 800 mg L−1, turbidity 650 NTU) reported by.13 Furthermore, the consistency of treatment outcomes across different palm oil mills remains a challenge, partly because many studies on these methods are conducted under idealized laboratory conditions that do not always translate effectively to real-world operational variability.1
Mechanical and chemical methods for hydrocarbon removal, while available, often prove to be economically unviable due to their restricted applicability and high costs.17 For instance, electrocoagulation can achieve impressive removal efficiencies, such as 90% for TSS, 87% for COD, and 97% for BOD, but at an estimated operating cost of approximately 1.48 USD/m3.13
The inherent conflict between economic incentives and environmental compliance is a significant hurdle in POME treatment. The perceived “cost-effectiveness” of conventional, low-tech solutions like open lagoons often comes at the direct expense of meeting environmental regulations and mitigating climate change impacts. This situation underscores the necessity for a paradigm shift towards more environmentally sound technologies, even if their initial capital investment or operational costs appear higher.
In response to these persistent limitations, a variety of emerging treatment technologies is being actively explored. These include diverse chemical approaches such as coagulation, flocculation, adsorption, and electrochemical treatment, as well as advanced biotechnological methods like enhanced anaerobic/aerobic digestion, microalgae cultivation, phytoremediation, bioremediation, and mycoremediation.16 Membrane technologies are also gaining prominence as effective and potentially cost-efficient solutions for biogas purification and water reclamation from POME, offering a pathway to resource recovery.18 The fact that even after conventional biological treatment, POME effluent still exceeds discharge limits.17 Strongly indicates that a multi-stage or integrated treatment approach is often indispensable to achieve stringent discharge standards.
The limited performance of conventional biological treatments arises from their poor selectivity toward recalcitrant organic compounds, colloidal particles, and metal-associated species. Even after extended retention times, treated POME often exhibits elevated turbidity and residual organic load, necessitating additional post-treatment steps. Chemical and electrochemical polishing methods can enhance contaminant removal; however, their effectiveness is often offset by high reagent demand, secondary sludge formation, or limited compatibility with complex wastewater matrices.13,17
These constraints highlight a fundamental gap in conventional POME treatment: the absence of materials capable of simultaneously destabilizing colloids, binding dissolved organic species, and selectively capturing metal ions through well-defined physicochemical interactions. This limitation provides a strong rationale for exploring functional polymeric materials, such as chitosan, which offer tunable surface chemistry and multiple interaction pathways beyond those accessible through biological processes alone. Chitosan and nanochitosan, therefore, are likely to be most effective when employed as polishing steps or in conjunction with existing primary treatments, rather than as standalone solutions, to ensure full compliance and facilitate resource recovery.
The limitations of current processes for treating palm oil mill effluent (POME) reveal a disconnect between biological and chemical methods. Biological systems struggle with non-selective removal of complex components, while chemical treatments can lead to secondary pollution. This calls for research into multifunctional materials like nanochitosan that combine adsorption and coagulation. However, considerations around cost, scalability, and integration into existing systems must also be addressed.
Its physicochemical behavior is primarily governed by the degree of deacetylation, molecular weight, and functional group accessibility. The solubility of chitosan is generally enhanced with a higher degree of deacetylation (DDA) and a lower molecular weight (Mw).26 The DDA quantifies the percentage of D-glucosamine units present within the polymer structure,22 with high-purity chitosan potentially achieving a deacetylation degree of 99%.28
Under acidic conditions, protonation of amino groups confers a cationic character, enabling strong electrostatic interactions with negatively charged species.29 Chitosan's solubility behavior is directly linked to the protonation of its amino groups (–NH2) in acidic environments, converting them to positively charged –NH3+ groups.30 The pKa of the primary amine group is approximately 6.5.31 The abundance of these amino groups at the C2 position, along with hydroxyl (–OH) groups at the C3 and C6 positions, are critical to chitosan's powerful adsorption capacity, chemical reactivity, and its amenability to various chemical modifications.32
Chitosan can be obtained from various sources, predominantly from the exoskeletons of crustaceans such as crabs, shrimp, and snails.33 Alternatively, it can be derived from bacterial and fungal fermentation.28 Fungal sources offer distinct advantages, including independence from seasonal availability, more uniform particle size, lower molecular weight, and the absence of potential heavy metal contamination often associated with marine-derived sources.27 Despite its numerous beneficial properties, chitosan in its natural bulk form exhibits certain limitations. These include poor solubility, specific surface area (2–30 m2 g−1), a porous structure, and suboptimal mechanical properties, such as shrinkage and deformation upon drying.33
The ability to tailor chitosan's properties through its degree of deacetylation (DDA) and source is a significant advantage. The DDA directly influences the solubility of chitosan,33 with higher deacetylation and lower molecular weight generally leading to increased solubility.26 Furthermore, the choice of source, particularly fungal versus crustacean, can yield chitosan with different characteristics, such as particle size uniformity and molecular weight.27 This implies that the effectiveness of chitosan in POME treatment is not a static property but can be significantly optimized by precisely controlling its DDA and molecular weight during production, or by selecting specific sources. This capability allows for the development of highly customized chitosan variants tailored to the specific characteristics of POME or to achieve particular treatment goals, moving beyond a generic approach to wastewater remediation.
The presence of abundant amino and hydroxyl groups underpins chitosan's capacity for adsorption and coagulation–flocculation.34 However, bulk chitosan is limited by low specific surface area and restricted accessibility of active sites, which can constrain removal efficiency for dilute or strongly bound pollutants. Fig. 1 illustrates the chemical structure of chitosan and its major natural sources, highlighting its derivation from chitin and relevance for environmental applications.
Various synthesis routes, including ionic gelation, ultrasonication, and covalent cross-linking, enable control over particle size and surface charge. However, nanoscale modification also introduces challenges related to aggregation, stability, and reproducibility, underscoring the importance of rational material design.
The transformation of chitosan to its nanoscale form imparts significantly enhanced properties:
Increased surface area: this is a paramount advantage, directly leading to a substantially higher adsorption capacity for pollutants due to more available binding sites.40
Improved solubility and chemical reactivity: nanoscale modifications facilitate better solubility and increased chemical reactivity compared to bulk chitosan, broadening its applicability.33
Superior pollutant removal efficiency: nanochitosan consistently demonstrates superior performance in wastewater treatment. For example, it exhibits a turbidity removal efficiency of 75.4% and dealkalization of 58.3%, significantly outperforming bulk chitosan, which achieves only 35.4% and 11.1%, respectively, for these parameters.35
Higher adsorption rates: for heavy metals, nanochitosan exhibits faster adsorption rates and shorter equilibrium times, making the treatment process more efficient.40
Enhanced stability: chemical cross-linking, a common modification technique, can substantially increase the long-term stability of nanochitosan, addressing a key limitation of the bulk polymer.39
The transformation to nanoscale effectively acts as a performance multiplier for chitosan. While bulk chitosan faces limitations such as poor solubility, small surface area, and porous structure, nanochitosan synthesis directly addresses these shortcomings by increasing solubility and enhancing the ability to absorb metals.33 The direct comparison of performance, showing superior turbidity removal and dealkalization by nanochitosan over bulk chitosan,35 unequivocally establishes nanochitosan as a significantly more efficient material for POME treatment. This implies that future research and industrial applications should prioritize nanochitosan or its composites for achieving optimal pollutant removal.
A notable consideration in nanochitosan synthesis is the trade-off between simplicity and control. Techniques like ionic gelation and ultrasonication are appealing due to their straightforward nature and avoidance of harsh or expensive chemicals.35 However, more complex methods, such as covalent cross-linking, offer finer control over critical particle properties like size and stability.39 This control can be vital for addressing specific POME pollutant removal challenges. The selection of a synthesis method, therefore, depends on balancing factors such as cost, environmental footprint, and the precise performance characteristics required for a given POME treatment scenario. Hence, nanochitosan offers distinct functional advantages over bulk chitosan, particularly in terms of increased surface area and reactivity. Nevertheless, these advantages are mitigated by issues about synthesis variability, stability, and scalability, which are inadequately addressed in the existing literature.
Fig. 2 highlights method-dependent variations in particle size distribution, zeta potential, morphology, and stability. Ultrasonication yields polydisperse particles, ionic gelation produces highly charged but aggregation-prone nanoparticles, while emulsification and reverse micelle methods enable more uniform and stable nanostructures. Synthesis strategy governs nanochitosan performance and application suitability.
Table 2 summarizes common nanochitosan synthesis methods applied in POME treatment, including the chemicals used, particle size ranges, advantages, and associated limitations.
| Method | Chemicals used | Particle size (nm) | Advantages | Limitations |
|---|---|---|---|---|
| Ultrasonication | None | Variable | Simple and green process | Broad size distribution |
| Ionic gelation | Tripolyphosphate (TPP) | 100–500 | Mild reaction conditions | Risk of nanoparticle aggregation |
| Emulsification–crosslinking | Glutaraldehyde | 30–300 | Good particle size control | Toxic cross-linking agent |
| Reverse micelle | Surfactant, hexane | 50–200 | Uniform particle formation | Use of organic solvents |
Chitosan is recognized as a highly effective polymeric flocculant, demonstrating performance comparable to conventional inorganic coagulants like ferric salts, often achieving similar efficiencies with significantly reduced dosages.43 Its effectiveness is rooted in the protonation of its amino groups (–NH2) in acidic solutions, which renders chitosan positively charged (cationic). This cationic nature makes it highly attractive for binding to negatively charged surfaces through ionic or hydrogen bonding.32 For POME treatment, the coagulation process mediated by chitosan primarily involves a synergistic combination of charge neutralization and polymer bridging mechanisms.32,44 Furthermore, composite materials, such as chitosan-magnetite nanocomposites, exhibit enhanced performance. This is attributed to the synergistic effect of the cationic chitosan amino groups and the magnetite ions, which collectively lead to improved agglomeration, adsorption, and overall coagulation efficiency.32
Beyond merely achieving pollutant removal, chitosan's ability to reduce sludge generation offers a significant advantage. Optimizing chitosan-based coagulation–flocculation is noted to yield substantial environmental benefits by decreasing the reliance on toxic chemicals and minimizing the volume of sludge produced, thereby leading to less overall pollution.43 This contrasts sharply with conventional inorganic coagulants, which are known to generate large quantities of chemical sludge requiring costly and environmentally impactful disposal. Thus, the reduced sludge volume translates directly into lower disposal costs and a diminished environmental footprint associated with sludge management, positioning chitosan as a more holistic and environmentally sound solution for POME treatment.
Chitosan serves as an effective biomaterial for adsorption due to its abundant functional groups, predominantly hydroxyl (–OH) and amino (–NH2) groups.32 These groups provide numerous active sites that can interact chemically with various pollutants. Specifically, they can form complexes with metal ions through chelation, hydrogen bonding, or electrostatic attraction.27 The inherent adsorption capacity and selectivity of chitosan can be further enhanced through targeted chemical modifications that introduce additional functionalities into its basic polymeric structure.39
Nanochitosan distinguishes itself among nano-adsorbents due to its exceptionally large surface area, high adsorption capacity, and inherent environmental compatibility.39 For heavy metals, the primary adsorption mechanism involves electrostatic attraction between the positively charged amino groups on the nanochitosan surface and the negatively charged pollutant ions. Furthermore, the lone pair electrons on the nitrogen atoms within the amino and N-acetylamino groups can form dative bonds with transition metal ions, contributing to their effective removal from the aqueous solution with adsorption capacity for certain ions, such as lead, increases with pollutant concentration but decreases at higher pH values, where the surface charge of chitosan become more neutral, thereby reducing electrostatic attraction.47
At the molecular scale, the adsorption process facilitated by chitosan-derived materials is primarily influenced by the protonation-deprotonation dynamics of amino groups, where –NH2 groups become protonated to form –NH3+ in acidic environments (pKa ≈ 6.5), thereby establishing strong electrostatic attractions with anionic species. Simultaneously, the unprotonated amino and hydroxyl groups function as electron donors, engaging in coordination bonds with metal ions via chelation processes. These interactions are further augmented by hydrogen bonding and van der Waals forces, which collectively contribute to the overall adsorption mechanism.27,39 The empirical validation of these mechanisms is typically accomplished through a range of physicochemical characterization techniques. Fourier transform infrared spectroscopy (FTIR) is instrumental in identifying shifts in –NH and –OH stretching vibrations upon pollutant interaction, while zeta potential analysis elucidates alterations in surface charge in relation to pH and adsorption parameters. Furthermore, electron microscopy (SEM/TEM) offers valuable insights into morphological changes and particle dispersion, and Brunauer–Emmett–Teller (BET) analysis corroborates the significance of increased surface area in augmenting adsorption capacity.33,36 Nevertheless, it is crucial to acknowledge that such characterizations are generally performed under controlled laboratory conditions and may not adequately reflect the intricate, multicomponent interactions and competitive adsorption phenomena that occur in actual palm oil mill effluent (POME) systems, which can significantly impact adsorption efficiency and the predominance of specific mechanisms.
Moreover, elevated adsorption capacities observed in batch experiments may not necessarily correlate with continuous or large-scale applications due to limitations in mass transfer, particle aggregation, and fouling. These variables can considerably diminish the effective adsorption capacity in practical settings, thereby exacerbating the scalability issues addressed in this review.
The pH of POME, which is initially acidic (typically 3.4–5.2),13 is a critical parameter influencing the performance of both coagulation–flocculation and adsorption mechanisms. Chitosan's solubility and its cationic nature, essential for effective coagulation and flocculation, are highly dependent on pH, being soluble and protonated in acidic conditions but insoluble and more neutral at higher pH values.32 Similarly, nanochitosan's adsorption capacity for lead ions is highest at low pH due to strong electrostatic attraction, but it decreases as the pH rises and the surface charge becomes neutral.47 For instance, optimal conditions for ammonium ion (NH4+) adsorption by a chitosan-based material were identified at pH 5.5.40 This strong pH dependency implies that pH adjustment might be a necessary pre-treatment step to achieve optimal efficiency for chitosan and nanochitosan in POME treatment. Alternatively, specific chemical modifications of chitosan could be explored to enable effective performance across the wide pH range encountered in POME, adding a layer of operational complexity but also an avenue for process optimization. Fig. 3 illustrates the main mechanisms involved in the removal of pollutants from palm oil mill effluent (POME).
These functional groups facilitate pollutant removal through several mechanisms:
Electrostatic attraction: in acidic POME, the amine groups (–NH2) of chitosan become protonated to –NH3+, imparting a positive charge to the polymer.32 This cationic nature allows for strong electrostatic attraction with negatively charged pollutants, such as colloidal particles, organic acids, and certain heavy metal anions, leading to their effective removal through charge neutralization and subsequent agglomeration.47
Chelation and complexation: the lone pair electrons on the nitrogen atoms of the amino groups, and the oxygen atoms of the hydroxyl groups, enable chitosan to act as a ligand. This allows it to form stable complexes or chelates with various metal ions (e.g., lead, cadmium, copper, chromium), effectively sequestering them from the wastewater.27
Hydrogen bonding: the numerous hydroxyl groups can form hydrogen bonds with polar molecules present in POME, contributing to the adsorption of organic compounds.27
Polymer bridging: in the coagulation–flocculation process, the long polymeric chains of chitosan can extend into the solution and adsorb onto multiple particles, effectively “bridging” them together to form larger, more easily settleable flocs.32 While bulk chitosan possesses these functional groups, its relatively low specific surface area (2–30 m2 g−1) and porous structure limit the accessibility of these active sites for pollutant interaction.33 This inherent limitation significantly restricts its overall adsorption capacity.
The transformation of chitosan into nanochitosan dramatically enhances its performance by increasing the available surface area.40 Nanoparticles, by definition, have a significantly higher surface-to-volume ratio compared to their bulk counterparts. This increased surface area means more functional groups are exposed and accessible for interaction with pollutants, leading to:
Higher adsorption capacity: a larger number of active sites are available for binding, resulting in a greater quantity of pollutants adsorbed per unit mass of adsorbent.39 For example, nanochitosan-coated cotton fiber exhibited significantly higher Langmuir adsorption capacities for Cd(II), Pb(II), and Cr(VI) compared to plain cotton fiber.41
Faster adsorption kinetics: the shorter diffusion paths to the surface of nanoparticles allow for quicker pollutant uptake, leading to shorter equilibrium times and more rapid treatment processes.40 Nanochitosan-coated cotton fiber demonstrated a shorter half-time of adsorption and a greater initial adsorption rate.41
Improved turbidity and dealkalization efficiency: as demonstrated, nanochitosan significantly outperforms bulk chitosan in removing turbidity and facilitating dealkalization, directly attributable to its enhanced surface properties.35
The synergistic interplay between the inherent chemical functionality of chitosan (amino and hydroxyl groups) and the vastly increased physical accessibility provided by its nanoscale form is the cornerstone of its superior performance in POME treatment. This combination allows for highly efficient pollutant capture through both charge neutralization and direct adsorption mechanisms.
The elimination of pollutants utilizing chitosan-based materials is regulated by synergistic mechanisms, including electrostatic interactions, chelation, and polymer bridging. The efficacy of these mechanisms is significantly influenced by factors such as pH, surface chemistry, and the composition of wastewater. Moreover, the inherent complexity of real-world systems frequently restricts the attainment of optimal performance.
Nevertheless, these high efficiencies should be interpreted cautiously. Many studies, including the one above, are conducted under controlled pH and mixing conditions that may not reflect the variability of raw POME streams. In practice, fluctuations in pH, temperature, and pollutant composition can significantly influence coagulation performance, potentially reducing removal efficiency. The application of chitosan-magnetite nanocomposite particles has further enhanced treatment efficiency. These composites demonstrated superior parameter reductions at even lower dosages than chitosan alone. An optimum dosage of 250 mg L−1 of chitosan-magnetite particles at pH 6 resulted in turbidity, TSS, and COD reduction of 98.8%, 97.6%, and 62.5% respectively outperforming chitosan, which required 370 mg L−1 to achieve 97.7%, 91.7% and 42.70% reductions, with the improved performance attributed to the synergistic interactions between cationic chitosan amino groups and magnetite ions that enhances agglomeration, adsorption, and coagulation.32
For anaerobically digested POME (AAD-POME), coagulation solely by chitosan (2500 mg L−1) achieved maximum COD and TSS removal of 70.22% and 85.59%, respectively. Combining chitosan with hydrogen peroxide (H2O2), significantly enhanced performance, increasing COD removal to 82.82%, and TSS removal to 89.92%. The integration of chitosan with Fenton oxidation (FeSO4 and H2O2) resulted in 100% TSS removal and 73.08% COD removal.51 These results indicate that while chitosan alone is effective, its performance can be further optimized through combination with advanced oxidation processes.
Notwithstanding these benefits, the performance of raw palm oil mill effluent (POME) systems frequently exhibits greater inconsistency compared to pretreated wastewater. The existence of emulsified oils and greases can obstruct flocculation processes, while elevated ionic strength and the presence of competing ions diminish adsorption efficacy by occupying the binding sites available.52 Furthermore, the variability in the composition of raw POME from various processing mills generates unpredictability in treatment results and constrains the reproducibility of documented efficiencies.53 It is essential to acknowledge that the majority of existing research on the treatment of raw palm oil mill effluent (POME) predominantly relies on batch experimental methodologies, which may not adequately represent the continuous flow conditions typical of industrial settings. Key elements such as sludge management, material recovery, and regeneration especially concerning nanochitosan are infrequently explored within real effluent systems, yet they are vital for enhancing process scalability and ensuring economic feasibility. The inherent acidity of POME (pH 4.5) is particularly conducive to the coagulation action of chitosan and chitosan–magnetite composites. At this pH, chitosan–magnetite nanocomposite demonstrated excellent destabilization of POME, achieving over 99% turbidity reduction.32 Chitosan-based systems exhibit significant efficacy in reducing suspended solids and turbidity; however, the removal of chemical oxygen demand (COD) is characterized by greater variability and is frequently incomplete. This limitation is indicative of the existence of recalcitrant organic compounds within palm oil mill effluent (POME) that are not effectively eliminated through coagulation methods alone. Consequently, this underscores the necessity for the implementation of integrated treatment approaches.
Nanochitosan, in particular, demonstrates superior efficacy in heavy metal adsorption. Its small size and high surface area contribute to a high adsorption capacity and faster adsorption rates compared to bulk chitosan.40 The adsorption mechanism is primarily based on the electrostatic attraction between the positively charged amino groups on the nanochitosan surface and the negatively charged pollutant ions.39 The nitrogen lone pair electrons in the amino and N-acetylamino groups can also establish dative bonds with transition metal ions.47
Specific studies highlight the high removal efficiencies for various heavy metals:
Lead (Pb): nanochitosan nanoparticles have shown promising results for lead removal. Their positively charged surface at low pH facilitates adsorption through electrostatic attraction.36 An adsorption capacity of 192.3 mg g−1 for lead ions was reported at pH 6.1 with a contact time of 59.9 minutes.47 Nanochitosan-coated cotton fiber (NCCF) achieved a maximum Langmuir adsorption capacity of 6.40 mmol g−1 for Pb(II).41
Chromium (Cr): NCCF exhibited a maximum Langmuir adsorption capacity of 12.50 mmol g−1 for Cr(VI).41 Chitosan crosslinked with diethylenetriaminepentacetic acid or trimesic acid showed adsorption coefficients of 192.3 mg g−1 and 129.53 mg g−1 for Cr(VI) ions at optimal pH values.47
Cadmium (Cd): NCCF demonstrated a maximum Langmuir adsorption capacity of 4.76 mmol g−1 for Cd(II).41
Iron (Fe) and manganese (Mn): chitosan nanoparticles have been employed to eliminate Fe(II) and Mn(II) via adsorption, achieving capacities of 116.2 mg g−1 and 74.1 mg g−1, respectively.54 Another study documented remarkable efficiencies of 99.94% for Fe(II) and 80.85% for Mn(II) removal using nanochitosan.41
The enhanced performance of nanochitosan in heavy metal removal is a direct consequence of its nanoscale properties, which overcome the limitations of bulk chitosan's lower surface area and porosity. This makes nanochitosan a highly effective and environmentally friendly adsorbent for heavy metal pollution in POME. Despite these promising results, several limitations warrant consideration. Firstly, the efficacy of adsorption is significantly influenced by pH, with optimal removal generally achieved in acidic environments where chitosan becomes protonated as stated in Section 5.2. This pH dependency may require adjustments in actual palm oil mill effluent (POME) treatment processes, thereby complicating operations and elevating costs. Secondly, the majority of adsorption investigations are performed using single-metal systems or simplified matrices, which fail to incorporate the competitive adsorption phenomena prevalent in multicomponent wastewater like POME. Moreover, elevated adsorption capacities observed in batch experiments may not necessarily correlate with continuous or large-scale applications due to limitations in mass transfer, particle aggregation, and fouling. These variables can considerably diminish the effective adsorption capacity in practical settings, thereby exacerbating the scalability issues addressed in this review.
Chitosan and nanochitosan exhibit notable removal efficiencies when subjected to optimized conditions; however, their performance displays significant variability across different studies and tends to be less reliable within actual Palm Oil Mill Effluent (POME) systems, especially concerning Chemical Oxygen Demand (COD) removal. This variability highlights the disparity between laboratory findings and their practical implementation in real-world scenarios.
The pre-treatment of POME, chitosan-magnetite nanocomposite particles demonstrated better reductions in turbidity, TSS, and COD at a lower dosage (250 mg L−1) compared to chitosan alone (370 mg L−1). The nanocomposite achieved 98.8% turbidity, 97.6% TSS, and 62.5% COD reductions, whereas chitosan yielded 97.7% turbidity, 91.7% TSS, and 42.70% COD reductions.32 This indicates that the synergistic effect of the nanoscale modification, particularly with magnetic properties, significantly improves the efficiency of pollutant agglomeration, adsorption, and coagulation.
The nanoscale transformation of chitosan effectively acts as a performance multiplier,24 while bulk chitosan is limited by its poor solubility, small surface area, and porous structure. Nanochitosan synthesis directly addresses these shortcomings by increasing solubility and enhancing the ability to absorb pollutants.33,36 The direct comparative data on turbidity removal and dealkalization35 unequivocally establish nanochitosan as a more efficient material for POME treatment. This suggests that for optimal pollutant removal, future research and industrial applications should prioritize nanochitosan or its composite forms. Nonetheless, the benefits of nanochitosan's performance need to be weighed against the greater complexity of its synthesis, potential instability, and the difficulties associated with its recovery. As mentioned in Section 9, these aspects could restrict its practical use, even with enhanced removal efficiencies. Fig. 4 compares raw POME characteristics with regulatory discharge limits and illustrates the removal performance of bulk chitosan, chitosan–magnetite composites, and nanochitosan. It highlights both the severity of untreated POME and the improved treatment efficiency achieved with nanochitosan-based systems.
Reusability and regeneration are central to the practical viability of chitosan-based materials. Several studies have demonstrated that chitosan and nanochitosan can retain appreciable adsorption capacity over multiple regeneration cycles;36,39,55 however, progressive loss of activity is commonly observed due to surface fouling, partial deprotonation of amino groups, or structural degradation.36,56 These effects are particularly pronounced under complex wastewater conditions, where competitive adsorption and irreversible binding of organic matter can limit regeneration efficiency.
Scalability considerations are therefore closely linked to the stability and robustness of chitosan-based materials under repeated use rather than to production volume alone.57 Approaches such as chemical cross-linking, incorporation into composite matrices, and magnetic modification have shown promise in improving structural integrity and facilitating material recovery.58 Nevertheless, further optimization is required to balance enhanced stability with preservation of functional group accessibility, which remains critical for effective coagulation and adsorption.
Nanochitosan consistently demonstrates superior efficiency and kinetics compared to bulk chitosan, its practical benefits are mitigated by increased production complexity, difficulties in recovery, and ambiguous cost-effectiveness when produced at scale.
Integrated nanochitosan-based treatment systems offer several operational advantages, including reduced land requirements compared with large pond systems, lower greenhouse gas emissions associated with open lagoons, and improved opportunities for circular resource recovery, such as biogas, treated water, and nutrients. Additionally, sludge production can be 50–70% lower than that generated by conventional inorganic coagulants. These benefits position nanochitosan not merely as an auxiliary additive but as a key enabling technology for achieving regulatory compliance and resource-efficient POME management. The integration of nanochitosan with biological and advanced treatment methodologies presents the most promising avenue for the efficient remediation of palm oil mill effluent (POME), as it facilitates synergistic removal mechanisms. Nonetheless, the intricacy of the system and considerations of economic viability continue to pose significant challenges. Table 3 compares the operational benefits of nanochitosan-enhanced systems with conventional POME pond treatment, highlighting improvements in footprint, sludge generation, regulatory compliance, and resource recovery.
| Parameter | Conventional ponds | Nanochitosan-enhanced system | Improvement |
|---|---|---|---|
| Footprint | Large (months retention time) | Compact treatment units | 70–80% reduction |
| Sludge volume | High (inorganic coagulants) | Low sludge generation | 50–70% reduction |
| Regulatory compliance | Often fails discharge limits | Meets FEPA/NESREA standards | Improved compliance |
| Resource recovery | Limited | Biogas and nutrient recovery | Enhanced circular outputs |
These challenges underscore the importance of rational material design strategies, including controlled deacetylation, surface functionalization, and composite formation, to enhance stability, selectivity, and durability without compromising adsorption efficiency.
Advanced functionalization and derivatization: designing novel chitosan derivatives for specific applications is a priority.62 This includes modifying chitosan to improve its solubility across a wider pH range, enhancing its mechanical strength and stability, and increasing its selectivity for particular pollutants (e.g., specific heavy metals or recalcitrant organic compounds).33 Research into covalent cross-linking and graft copolymerization can create more robust and efficient materials.39
Sustainable production and green processing: continued focus on green extraction methods and eco-friendly processing techniques for both chitin and chitosan is essential.62 Exploring alternative, sustainable sources like fungal fermentation, which offer advantages such as seasonal independence and freedom from heavy metal contamination, should be prioritized.27
Mechanistic insights: deeper elucidation of the biological and chemical interactions between chitosan/nanochitosan and various POME pollutants will allow for more targeted and efficient material design.62 Understanding the precise mechanisms of degradation and stability will also inform storage and application strategies.59
Integration into smart biomaterials and hybrid systems: developing multifunctional systems by integrating chitosan/nanochitosan with other materials (e.g., magnetic nanoparticles, other polymers, or advanced oxidation processes) can create hybrid adsorbents with enhanced performance and easier separation capabilities.32 Combining chitosan coagulation with advanced oxidation processes (AOPs), for instance, has shown improved COD and TSS removal.51
Pilot-scale and industrial implementation studies: moving beyond laboratory conditions to conduct more pilot-scale and full-scale studies is crucial to validate performance, optimize operational parameters, and assess the long-term economic viability and scalability of chitosan-based POME treatment systems under real-world conditions.1
Standardization and regulation: the development of international quality standards for chitosan derivatives is imperative to ensure consistency, facilitate commercialization, and build confidence in their application in environmental remediation.62
The ongoing development and application of chitosan in both scientific and industrial sectors depend heavily on these further explorations. Chitosan-based materials hold immense potential to contribute significantly to environmental sustainability and improved wastewater management, particularly in industries like palm oil production. The advancements highlighted in current research underscore the dynamic and evolving landscape of chitosan science, promising more effective and sustainable solutions for complex industrial wastewater challenges.
Significant obstacles to widespread implementation encompass scalability, regeneration efficiency, economic feasibility, and environmental safety. This underscores the necessity for future research to emphasize system-level optimization, standardization, and empirical validation in practical contexts.
Beyond treatment efficiency, nanochitosan supports a more sustainable and circular approach to POME management. By improving effluent quality prior to downstream processing, it can enhance anaerobic digestion and biogas recovery while enabling nutrient recovery for potential reuse in agriculture. The use of chitosan derived from crustacean or fungal sources further contributes to waste valorisation and resource efficiency, as it allows for the conversion of waste materials into valuable products, thereby reducing environmental impact and promoting sustainability. These advantages point to the power of nanochitosan to transform POME management from a pollution-control challenge into an opportunity for resource recovery within a circular bioeconomy framework.
Despite these advances, large-scale industrial implementation still faces several challenges. Future research should focus on scalable and environmentally benign synthesis approaches, improved regeneration and reuse of nanochitosan materials, techno-economic comparisons with established treatment technologies, and comprehensive ecotoxicological assessments of potential nanoparticle release. Addressing these priorities will be essential for translating laboratory-scale success into practical, sustainable solutions for POME treatment and broader wastewater management applications. Hence, nanochitosan constitutes a promising, albeit not fully realized, approach for the treatment of palm oil mill effluent (POME), with its optimal efficacy likely residing in integrated systems rather than isolated applications. The successful implementation of this biopolymer is contingent upon addressing significant technical, economic, and environmental hurdles.
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