Application of Chitosan Nanoparticles in the Adsorption of Heavy Metals from Wastewater: A Concise Review

Ashok Kumar¹, Pawan Kumar², Sunil Chopra² and Anil Sindhu²

¹Department of Chemistry, RKSD College, Kaithal -136027, Haryana.

²Department of Biotechnology, DCR University of Science and Technology, Murthal -131039, Haryana.

*Corresponding Author E-mail: akumarrksd@gmail.com

ABSTRACT:

The biopolymer chitosan is a biodegradable, biocompatible polymer that has been scientifically proven to be an efficient organic compound for the adsorption of heavy metals from a variety of industrial wastewater. Heavy metals are toxic and can cause a variety of harmful health effects, even in low concentrations. Therefore, it is important to remove them from the wastewater to ensure the water is safe for consumption and other uses. Chitosan is a superior adsorbent because it contains functional groups like hydroxyl and amino. Nano-chitosan can be fabricated using various methods but modern nanotechnology research focuses on developing highly efficient and cost-effective green technology. The remarkable physicochemical features of nano-chitosan make it suited for usage in enhancing the durability and washability of textile supplies as well as giving them antibacterial capabilities.

KEYWORDS: Chitosan, Nanoparticles, Wastewater, Adsorption, Biopolymer.

INTRODUCTION:

Water that has been utilized or polluted by the anthropogenic activities of people is treated as wastewater¹. Wastewater treatment is crucial in order to face the water scarcity problem and protect humans and the ecosystem from hazardous and noxious elements found in wastewater^2,3. Potential remedies for the issue of inadequate water quantity and quality include wastewater treatment and reuse, which might effectively lower the levels of contaminants while still allowing for irrigation or recreational usage⁴. Reusing treated water might be one of the primary alternatives for increasing water resources, especially in arid places, as it is another renewable source of water^5-6. Treated wastewater has been discovered to be a more practical and environment-friendly alternative to using untreated wastewater⁷. There are certain hazardous substances in wastewater, including heavy metals (arsenic, cadmium, chromium, lead, etc.), pesticides, dyes, synthetic detergents, and pharmaceuticals which produce hazardous effects on general health^8-9. Due to their high cost or lack of environmental friendliness, the majority of commercially available water treatment materials are not widely used, especially in poor countries where resources are few¹⁰. Chitosan is one of the alternative options because of its easy availability, high adsorption capacity, biocompatibility, and lack of ecotoxicity^11-12. In addition, it possesses wide biological, and chemical applications due to its unique chemical, polycationic nature, and amino group presence^13-14. The second-most prevalent natural polymer in the world is chitosan polysaccharide, which is created when chitin biopolymer is N-deacetylated. The lower plant and animal kingdoms contain a variety of different living things that make chitin such as marine crustaceans and shellfish^15-17. It can be easily derived from chitin [poly (N-acetyl-1, 4-β-D-glucopyranosamine)], by deacetylation process¹⁸. The higher price of chitosan in comparison with that of synthetic polymers and ion exchange resins limited the utilization of large volumes of chitosan-based sorbents for liquid waste treatment at an industrial scale¹⁹. Although the interest in using chitosan-based materials for wastewaters treatment is sparked by chitosan's high affinity and chemically modified nanomaterials and composites with high selectivity to many metal ions²⁰. Nano-chitosan is unquestionably among the most effective ligands for binding a variety of metal ions, with the exception of alkali and alkali-earth metals, which lack free d- and f-orbitals⁴.

The treatment of heavy metals-contaminated water involves a number of remediation techniques, including physical and chemical remediation. The adsorption technique has received a lot of attention recently because of its great effectiveness, low cost, and lack of secondary contamination. Adsorption is thought to be the process by which molecules collect on a solid surface from a fluid^21-22. Recent years have seen a significant increase in interest in the use of widely available, low-cost industrial, agricultural, and home waste or byproducts as adsorbents to remove heavy metals from water bodies²³.

The main objective of the present review is to discuss the applications of chitosan nanoparticles in the removal of effluents from the wastewater.

Chitosan Nanoparticles:

Chitosan nanoparticles are made from a natural biopolymer chitosan i.e., derived from chitin (Figure 1), have been investigated for its potential use in wastewater treatment and other research fields due to its ability to remove contaminants from water^{24, 25}. Chitosan nanoparticles, which are particles with diameters in the nanometer range, have several unique properties such as their high surface area, biocompatibility, biodegradability, and ability to adsorb contaminants such as heavy metals, dyes, and organic compounds, make them a promising tool in the field of wastewater treatment^26-29. The preparation of chitosan nanoparticles involves the use of various techniques, including ionotropic gelation³⁰, emulsion crosslinking³¹, reverse micellar³², emulsification solvent diffusion³³ spay drying³⁴, nano precipitation³⁵, ultrasonication³⁶, microemulsion³⁷, and coacervation³⁸. These techniques allow for the control of the size and surface charge of the nanoparticles, which in turn can affect their properties and potential applications. Chitosan nanoparticles have been used to adsorb various toxic heavy metals in water due to their unique properties^39,40.

Figure 1. Natural sources and applications of chitosan (Jardine and Sayed, 2018)

Adsorption of heavy metals:

Chitosan nanoparticles have been shown to be effective in removing heavy metals from wastewater through adsorption⁴¹. The small size and high surface area of chitosan nanoparticles also contribute to their high adsorption capacity for heavy metals⁴². The adsorption mechanism of chitosan nanoparticles for heavy metals is mainly based on the electrostatic attraction between the positively charged amino groups on the surface of chitosan and the negatively charged pollutant ions²⁰. The positively and negatively charged conjugate adsorbed onto their surface, allowing for their removal from the water⁴³. In addition, the nitrogen lone pair electrons in the amino and N-acetylamino groups can establish dative bonds with transition metal ions⁴⁴ . Once the heavy metal ions have been adsorbed onto the surface of the chitosan nanoparticles, they can be separated from the wastewater by filtration or centrifugation³⁵. The heavy metal-loaded chitosan nanoparticles can then be regenerated or disposed of properly, depending on the specific application. Chitosan nanoparticles have been shown to effectively adsorb lead, cadmium, and copper ions from aqueous solutions.

Lead:

Chitosan nanoparticles have been investigated as a promising adsorbent for removing lead from water because it is a toxic heavy metal that can cause various health problems if it accumulates in the body⁴¹. The surface charge of chitosan nanoparticles is positively charged at low pH values, which facilitates the adsorption of lead ions through electrostatic attraction⁴⁶. The adsorption capacity of chitosan nanoparticles increases with an increase in the concentration of lead ions. However, at high pH values, the surface charge of chitosan nanoparticles becomes neutral, which reduces the adsorption capacity⁴⁷. The adsorption process of lead using chitosan nanoparticles can be influenced by the presence of other ions in the water⁴⁸. For instance, the presence of calcium and magnesium ions can reduce the adsorption of lead ions by chitosan nanoparticles due to competition for active sites⁴⁹. Therefore, it is essential to optimize the process conditions to achieve maximum adsorption efficiency. Several studies have reported high adsorption efficiency of chitosan nanoparticles for lead ions from aqueous solutions. A study reported an adsorption capacity of 192.3mg/g of chitosan nanoparticles for lead ions at a pH of 6.1 and a contact time of 59.9minutes⁵⁰.

Chromium (Cr):

For removing Cr(VI) ions from an aqueous solution, chitosan was crosslinked with diethylenetriaminepent acetic acid or trimesic acid. When compared to the former at an optimum pH of 3 and 2, the later crosslinking acid's adsorption coefficient was found to be greater at 192.3mg/g and 129.53mg/g⁵¹.

Cadmium (Cd):

Cd is an extremely toxic heavy metal which is primarily produced as a by-product of chemically treating copper, lead, and zinc ores⁵². It has found use in a variety of sectors, including metal refineries, printing, metal plating, and the manufacture of pigments, alloys, and batteries⁵³. Cd (II) cannot biodegrade in the environment like other heavy metals; hence can cause a variety of health problems in humans and animals even in low concentrations⁵⁴. Chitosan nanoparticles exhibits high surface area which enhances its adsorption capacity for cadmium. The amino and hydroxyl groups present on the surface of chitosan nanoparticles have a strong binding affinity for cadmium ions⁵⁵. The adsorption occurs through a complexation reaction, in which the cadmium ions form coordinate bonds with the functional groups on the chitosan nanoparticles⁵⁶.

Arsenic (Ar):

The negative effects on the environment and human health of Arsenic contamination in water are a major problem worldwide⁵⁷. The World Health Organization (WHO) has concluded that 10 parts per billion (ppb) is the upper limit for total arsenic in drinking water⁵⁸. Chitosan nanoparticles have shown promise as a potential method for the removal of arsenic from water. The positively charged surface of the chitosan nanoparticles attracts the negatively charged arsenic ions, allowing them to be adsorbed onto the surface of the nanoparticles⁵⁹. The adsorption process occurs through electrostatic attraction, surface complexation, chelation, and ion exchange mechanisms between the arsenic species and the amino and hydroxy groups present in chitosan nanoparticles⁶⁰.

Zinc (Zn):

Zinc is an essential trace element required for many biochemical processes in the human body⁶¹, however, excessive consumption of zinc may have hazardous effects⁶². The toxicity of zinc in water depends on the concentration and duration of exposure⁶³. In general, high concentrations of zinc in drinking water can cause gastrointestinal problems such as nausea, vomiting, and diarrhea⁶⁴. Chitosan nanoparticles have also been studied as a potential adsorbent for the removal of zinc metal ions from industrial wastewater and contaminated groundwater²⁷. The efficiency of zinc removal varies depending on the initial concentration of the zinc metal ions and the adsorbent dosage⁶⁵. At pH 7 and 25°C temperature, the maximum capacity of adsorption by chitosan macro and nano size particle was 196.07 and 370.37mg/g, respectively⁴⁰.

Optimization of adsorption conditions:

The adsorption capacity of chitosan nanoparticles can be optimized by adjusting parameters such as pH, contact time, temperature, and initial concentration of heavy metals in the wastewater⁶⁶. It is important to note that the pH of the solution can significantly affect the adsorption capacity of chitosan nanoparticles, as heavy metal ions tend to be more positively charged at lower pH levels, which can hinder their adsorption onto the negatively charged surface of chitosan²⁴.

CONCLUSION:

Chitosan nanoparticles have the potential to be a cost-effective and eco-friendly alternative to traditional water treatment methods, and its applications in wastewater treatment are an active area of research. Studies have shown that chitosan nanoparticles can be effective at removing a wide range of pollutants from water, including heavy metals, dyes, and organic compounds. They offer a more effective and sustainable alternative to traditional treatment methods. However, there are still some challenges that need to be addressed, such as the cost of production and the scalability of the process. Chitosan, however, has a number of drawbacks, including instability in acidic medium, low thermal stability, low mechanical strength, insufficient porosity, and insufficient surface area, which limit its potential application as an adsorbent in the water treatment. Overall, chitosan nanoparticles show great potential for the removal of heavy metals from water, and further research is needed to optimize their use for large-scale water treatment applications.

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Received on 29.03.2023                    Modified on 14.05.2023

Accepted on 27.07.2023                   ©AJRC All right reserved

Asian J. Research Chem. 2023; 16(5):389-393.

DOI: 10.52711/0974-4150.2023.00063