Enhanced biosorption of bisphenol A from wastewater using hydroxyapatite elaborated from fish scales and camel bone meal: A RSM@BBD optimization approach (2023)


Pollution is the main problem threatening the ecosystem, which the contamination of water by emerging pollutants is the main problem of the aquatic system [1,2]. Generally, these chemical compounds, such as dyes, pharmaceuticals, endocrine disruptors, pesticides, surfactants and personal care products, are difficult to eliminate in wastewater facilities because of their persistent and non-biodegradable character [3]. Bisphenol A (BPA) is one of the emerging contaminants classified as endocrine disruptors [4]. It has been used to produce polycarbonates, dyes, epoxy resins and other plastics and has also been used as an antioxidant, flame retardant and pesticide (fungicide) [5]. Although the Environmental Protection Agency (EPA) defines a pesticide as any chemical substance used to inhibit, destroy, suppress or mitigate any pest [6], the use of pesticides in modern agricultural practices to improve yields and meet food needs has become a matter of social responsibility [7]. These chemical substances kill specific target microorganisms. Moreover, they also affect the environmental medium, including surface and groundwater, soil, and atmosphere [8], polluting the natural ecosystem. Furthermore, pesticides may lead to several diseases such as cancer, neurological disorders, sterility and oxidative stress [9,10].

For this reason, the adsorption of BPA elements from aqueous media has attracted extensive interest. Various physical and chemical treatments, such as advanced oxidation process, photodegradation, filtration, coagulation, flocculation and adsorption, as well as biological treatments, such as activated sludge process and hygienic remediation, have been applied to remove these toxic substances from the aquatic system [11,12]. However, some limitations in applying these technologies bring the adsorption method for important purposes: simple, effective, and low cost [13]. In the last decade, many biomaterials such as clay, chitosan, date stone, and biochar have been used as adsorbents to eliminate pesticides from wastewater [14,15].

To reduce the technologies' cost, advanced research has been carried out to find low-cost materials with high adsorption performance. Due to its biocompatibility and availability, hydroxyapatite (HAP) is among the most widely used biomaterials as effective adsorbents to eliminate contaminants from water [16,17]. Moreover, HAP is a biocrystal constituted from phosphorus, hydrogen and calcium, under a chemical formula of Ca10(PO4)6(OH)2, a principal mineral material found in the bones of animals. According to the literature, various methods were applied for hydroxyapatite (HAP) synthesis [18], including wet chemical precipitation at low temperature [19], sol-gel method [20], emulsion and microemulsion [21], hydrothermal processes [22], pyrolysis and calcination [23]. Its extraction was from various biomaterials such as fish scales [24], eggshells [25], animal bones [26], Shells [27], etc. Nevertheless, these methods have disadvantages such as long reaction time, high chemical products consumption and impurities generation.

The treatment of BPA pesticides by membrane filtration [28], reverse osmosis [29], photocatalysis [30], advanced oxidation processes and adsorption [31,32] has been studied extensively. Adsorption is chosen because it is an efficient, fast and less expensive method compared to other processes [33].

This recent study aims to elaborate on natural HAP bioceramics from camel bone and fish scales in the scope of natural resources valorization, targeting a green circular economy. The reason for choosing these biomaterials is their high availability as a waste product. In addition, HAP is one of the excellent biosorbents because of its ion exchange capacity and reactive surface.

In this context, the present paper focuses on the extraction of hydroxyapatite from camel bone meal (CBM) and fish scales (FS) by an alkaline heat treatment process for use as a cost-effective biosorbent for removing the bisphenol A (BPA) pesticide from wastewater. First, the prepared biosorbents were characterized using SEM, EDS, FTIR, BET, TGA, DSC, and PZC. Then, a series of important parameters were studied, such as adsorbent dosage, pH effect, pesticide concentration, contact time, and temperature affecting the adsorption process. Finally, the adsorption mechanisms optimization of BPA on FS and CBM materials was performed using the response surface methodology coupled with the Box Behnken design (RSM-BBD).

Section snippets

Materials and chemical reagents

All chemical products used in this study were of analytical grade, Bisphenol A (C15H16O2), hydroxide sodium (NaOH), hydrochloric acid (HCl) and ethanol (CH3CH2OH) were provided from Sigma Aldrich Company-Casablanca (Morocco). Bisphenol A was dissolved in distilled water at a concentration of 100mg/L as stock solutions.

Preparation of adsorbents

In this work, fish scales and camel bone were sourced from the local market. Firstly, the collected biomaterials were rinsed with tap water and then distilled water to eliminate


The surface chemical functions present on the FS and CBM adsorbents are another essential aspect in determining the adsorption performance of these biomaterials. The FTIR spectra of FS and CBM are shown in Fig. 1. The typical bands of the HAP assigned to the hydroxyl and phosphate groups can be detected. Broadband characteristic of the water molecule adsorbed on the material surface is located at 3500 and 3290cm−1 for FS and CBM, respectively. The peaks at 2922 and 2852cm−1 in the FTIR


This recent research study demonstrated the viability of converting camel bone biowaste and fish scales into porous hydroxyapatite as an efficient adsorbent. For this purpose, hydroxyapatite was well developed from fish scales (FS) and camel bone meal (CBM) using the alkaline heat treatment method, as low coast technique of preparation. Hydroxyapatite has a high adsorption efficiency of emerging organic contaminants such as endocrine disruptors. This recent study used the hydroxyapatite

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Cited by (5)

  • A novel hydrogel beads based copper-doped Cerastoderma edule [emailprotected] biocomposite for highly fungicide sorption from aqueous medium

    2023, Chemosphere

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    A wide range of biomaterials was successfully used to absorb pesticides from wastewater (Jain et al., 2021). Including agricultural wastes (Aziz et al., 2021b), biomass (Komal et al., 2020), clays (Bueno et al., 2021), biochar (Brito et al., 2020), shrimp shells (Sabbagh et al., 2021), eggshells (Sen et al., 2021), camel bone (Aziz et al., 2022) etc. The adsorption process can be carried out in batch or continuous mode.

    The engineering of a novel biocomposite based on Cerastoderma edule shells doped with copper and alginate (Ce–[emailprotected]) forming hydrogel beads was used for batch and dynamic adsorption thiabendazole (TBZ) pesticide from water. The prepared biosorbent was analyzed by various characterization techniques such as scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller analysis (BET), and energy dispersive spectroscopy (EDS), thermogravimetric and differential analysis (TGA-DTA). The results of the TBZ batch biosorption by Ce–[emailprotected] composite showed that the Langmuir model was the most adequate to describe the adsorption process, with a maximum adsorption capacity value of 21.98mg/g. Moreover, the adsorption kinetics were adjusted by the pseudo-second-order model. The optimal conditions determined by the RSM approach coupled with the CCD design were 100ppm of initial TBZ concentration, a Ce–[emailprotected] beads dose of 6g/L and a contact time of 180min for maximum removal of 83.42%. On the other hand, the TBZ sorption on a fixed bed of Ce–[emailprotected] beads was effective at high column height, low effluent flow and low solution concentration. The Thomas model was best fitted to the kinetic data. This study shows the possibility of using this new hybrid biocomposite in the industrial sector to treat large effluent volumes.

  • Enhancement of bisphenol a removal from wastewater via the covalent functionalization of graphene oxide with short amine molecules

    2022, Case Studies in Chemical and Environmental Engineering

    Citation Excerpt :

    In the microbial treatment, BPA is utilized by microorganisms as a carbon source while in the enzymatic treatment, enzymes (e.g. peroxidases and laccases) act as biocatalysts and transform BPA into a polymeric component that might be removed from the treated wastewater via filtration or centrifugation [9]. In physical treatment, distillation [74], extraction, membrane-based separation [75], or/and adsorption [76] can be utilized to physically separate BPA from the contaminated waters. Although each of the above-mentioned processes has its own merits and limitations, the adsorption process is one of the most attractive methods due to its simplicity, flexibility, and potentially cost-effectiveness.

    Water pollution is a serious environmental problem worldwide. This problem is augmented by the shortages in fresh water supplies in several parts of the world. Thus, the effective treatment and reuse of polluted water is an inevitable necessity. One of the highly toxic water pollutants with potentially mutagenic and carcinogenic effects is bisphenol A (BPA). Accordingly, the adsorptive removal of BPA from wastewater samples using novel graphene-based materials has been investigated in this study. The results showed the ineffectiveness of the unmodified graphene oxide (GO) in removing BPA from the wastewater samples. The functionalization of GO with short organic amines (i.e., hexamethylenetetramine (HTMA), diethylenetriamine (DETA), and diethylamine (DEA)) boosted the BPA removal by several folds relative to GO and hydrazine-reduced GO. Additionally, the amine structure affected the performance of the amine-modified GO adsorbents. The most effective adsorbent was found to be the one modified with DEA (GO-DEA) followed by GO-DETA. The maximum adsorption capacity (qmax) of BPA on GO-DETA and GO-DEA were 258.6 and 334.4 mg/g respectively, relative to 16.2 and 87.0 mg/g in the case of the unmodified GO and the hydrazine-reduced GO (i.e., rGO), respectively. The results of the adsorption kinetics revealed that BPA adsorption on GO-DETA is much faster than its adsorption on GO-DEA. The adsorption kinetics for both adsorbents were best fitted using the Avrami model with adsorption rate constant of 0.0149 (GO-DETA) and 0.0033 min−0.47 (GO-DEA). Although variations in BPA adsorption capacity were observed with changing the pH of the wastewater, the lowest BPA adsorption was encountered at pH 10 for all the graphene-based materials synthesized in this study. The characterization of the synthesized adsorbents revealed that BPA adsorption is not correlated with the surface area/porosity of the adsorbents. It is also not correlated with the degree of GO deoxygenation or nitrogen content alone. The most plausible adsorption mechanisms are π−π stacking interaction and hydrogen bonding. The findings reported in this study reveal the potential of GO functionalization with short organic amines in significantly boosting the adsorptive removal of phenolic pollutants from wastewater.

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