1. Introduction
Tetracycline (TC) is one of the most widely used antibiotics for treating different bacterial infections in humans and animals [
1]. However, excessive usage of TC causes antibiotic-resistant pathogens to emerge, leading to profound environmental and health implications when discharged into aquatic systems. Tetracyclines have been categorized as one of the emerging pollutants because of their occurrence in aquatic ecosystems [
2]. Due to growing concerns over increased TC and other antibiotic concentrations in wastewater, removing them from wastewater before disposal is creating a greater challenge. Raw domestic and industrial wastewater often contains TC concentrations varying from 100 ppb to 20 ppm [
3,
4]. Therefore, it is essential to establish a cost-effective and efficient approach for removing antibiotics before discharging wastewater into aquatic habitats. Traditional sewage treatment plants are found to be inadequate to treat the pharmaceuticals in aquatic ecosystems [
5]. Hence, various advanced wastewater treatment, methods such as chemical decomposition, biological treatment, photocatalysis, electrochemical oxidation, ozonation, advanced oxidation [
6], and adsorption [
7,
8], have emerged. Adsorption is one of the most widely used methods due to its simplicity and affordability. Numerous studies have explored the efficacy of biochar, carbon nanotubes, zeolites, activated carbon, and clay minerals in the adsorption of diverse contaminants, including pharmaceutical compounds [
9]. However, these adsorbents are expensive and face availability issues for large-scale applications. In order to address this issue, waste products from agriculture [
10] and industry [
7] are being used as substitutes for conventional adsorbents to it more feasible for the adsorption process to eliminate diverse pollutants in water and wastewater [
11,
12].
GGBS is a major byproduct of iron production that is primarily used in the construction industry [
13], and a significant portion of it ends up as environmental waste [
14]. GGBS primarily consists of calcium, silicon, iron, aluminum, and manganese oxides [
15]. GGBS has been effectively applied for the removal of numerous contaminants, such as dye, heavy metal ions, and a few emerging contaminants, because of its ion-exchange capacity and alkalinity [
16,
17]. Further, its availability, cost-effectiveness, lack of toxicity, and ease of modification make it a desirable adsorbent. GGBS is also employed for the remediation of diverse organic contaminants within an aqueous milieu, including ECs [
18,
19,
20]. Gupta et al. (2006) studied the use of raw steel slag waste to remove 2,4-dichloro phenoxyaceticacid (2,4-D) [
18]. The findings indicated that the utilization of raw steel slag as an adsorbent is not efficacious, due to its lower surface area. Bhuyan et al. (2022) examined the alkaline activation of blast furnace slag for the removal of methylene blue (MB) [
19]. It had a surface area of 83 m
2/g after alkaline treatment, giving it a removal efficiency of 74% at 5 ppm concentration of MB. Saood et al. (2022) compared two different steel factory slags and tested them for the removal of Eriochrome black T (EBT) [
16]. It was shown that the slags had a good affinity for the EBT dye, with an adsorption capacity of 100% for a dye concentration of 20 ppm at pH 2. Further, Zubair et al. (2022) examined the synthesis of a biochar-steel dust composite for treating phosphate [
21]. The adsorption capacity of the composite material was 175 mg/g at pH 4 for 100 ppm phosphate. The important role that steel dust plays in the adsorption process has been clearly shown in these studies. This suggests that steel slag could be a good adsorbent for effectively cleaning up pollutants in water [
21]. Therefore, the utilization of GGBS can be regarded as an effective strategy for promoting and attaining a circular economy [
22]. This is primarily attributed to its ability to offer alternative applications or pathways within the life cycle of this industrial waste source. By doing so, GGBS aids in waste reduction and contributes to the advancement of sustainable development. This is achieved through the process of modification, which involves enhancing the value of waste materials, as well as the significant enhancement of surface area and porosity through the upcycling process. GGBS may be seen as offering further benefits to waste materials that would otherwise pose challenges, facilitating their transformation into more valuable resources [
23].
Over the last decade, various statistical and machine learning-based prediction models have emerged to evaluate the effects of process parameters on the objective function for process optimization. Response Surface Methodology (RSM) based on rotatability is one of the most popular classical statistical tools among researchers for studying the second-order interaction effects and evaluating individual parameter effects on the process. The CCD and BBD are commonly utilized techniques in RSM [
24]. Traditional optimization approaches need a higher number of runs and are time-demanding, but RSM has the ability to predict process parameters in a limited number of runs while employing minimal resources [
24,
25]. BBD-based RSM models facilitate optimal settings and provide better accuracy with a smaller number of runs. For large-scale optimization, machine learning approaches such as artificial neural network (ANN) and random forest (RF) have been increasingly adopted by researchers. The utilization of ANN and RF represents an advanced and robust approach to efficient predictions. ANN possesses the ability to autonomously learn and operate even with inadequate information and spread data over the complete network. The ANN can also predict experimental variations in a wide range of applications [
26]. Traditional techniques of regression and classification may be improved by RF combining hundreds of decision trees. RF can identify correlations between variables in a small dataset as well as offering regular observation of processes and tolerance for many input variables [
27]. Elijah et al., (2021) carried out a study in which ANN and RF were employed to explore the adsorption of EBT dye using a modified clay [
28]. Geyikc, (2012) constructed models in the form of RSM and ANN to examine the effectiveness of red mud as an adsorbent for extracting lead that has leached from industrial waste [
29]. Ahmadi Azqhandi et al. (2017) investigated the modeling of RBF-NN, RF, and RSM to study the adsorption of Brilliant Green on ZnS-NP-AC adsorbent [
30]. Their findings suggested RF as the most appropriate model to determine the adsorption capacity. The results demonstrated that these models offered high accuracy in predicting the adsorption capacity. Hence, these models prove to be efficient for optimizing the process parameters in the adsorption process.
In recent years, Oxalate-based adsorbents have been applied to treat a wide variety of waterborne contaminants. They are immensely beneficial due to their biodegradability, cost-effectiveness, non-toxicity, and global availability [
31]. These adsorbents are extensively employed for the treatment of various metal ions, including nickel, cobalt, lead, and zinc, from aqueous environments and industrial effluents [
32]. The oxalate-treated slag has been utilized for treating lead (Pb), cadmium (Cd), and cobalt (Co) [
32,
33]. However, to the best of the author’s knowledge, there have been no studies on the utilization of oxalate-treated GGBS for the removal of any organic contaminants. Moreover, it is worth noting that the modeling and comparison of TC adsorption parameters using RSM, ANN, and RF techniques are yet to be explored. Therefore, this study focuses on the synthesis of oxalate modified GGBS for the removal of TC and characterizing the adsorbent via FTIR, XRD SEM, XPS, BET, and DLS. Further, the mutual and individual effects of adsorption parameters, such as initial solution pH, stirring speed, and contact time, on the removal efficiency of TC are determined by deploying BBD-based RSM, ANN, and RF models. This study also investigates the kinetics and isotherm models along with thermodynamics to evaluate the adsorption mechanism involved in TC removal. In summary, this study would yield valuable and meaningful contributions to the broader academic community working on non-conventional adsorbents for treating different aquatic pollutants.
2. Materials and Methods
2.1. Chemicals
The oxalic acid, sodium hydroxide, sodium hydroxide (NaOH), tetracycline hydrochloride, Hydrochloric acid (HCl) and Ground granulated blast furnace slag (GGBS) are procured from Fisher Scientific, FINAR Limited, Alfa Aesar chemicals, and Nature and Greens Pvt. Ltd. (Jamnagar, India). All experimental investigations are conducted using Millipore water.
2.2. Preparation of Adsorbent
A total of 5 g of GGBS powder was dissolved in 40 mL of a 1 M oxalic acid solution. The resulting mixture underwent stirring for 90 min. Subsequently, 10 mL of a 3 M NaOH solution was added dropwise to the mixture, which continued to be stirred on a hot plate set to 80 °C. Once a brown precipitate emergence was observed, the precipitate was then put into a water bath maintained at 80 °C and allowed to undergo crystallization for 12 h, promoting improved crystalline structure. Then, the resulting precipitate was subjected to vacuum filtration, then rinsed with deionized water until a neutral pH of 7 was attained. The washed precipitate was then dried overnight in an oven operating at 80 °C. After drying completely, the powder was kept in an airtight vial until it was needed for adsorption studies [
32,
33].
2.3. Characterization Details
Analysis of XRD was conducted to determine the crystal phase of the adsorbents using a PANalytical X’pert PRO X-ray diffractometer. The measurements were conducted utilizing a copper K-alpha (k = 1.541) source, employing a nickel filter. The scanning procedure was carried out within the angular range of 5–80°, with a step size of 0.0167° and a scan rate of 0.0301°/s. To characterize the surface of the adsorbent, a JIB-4700 F FE-SEM instrument manufactured by JEOL, Akishima, Japan, was utilized for SEM. FTIR spectroscopy employing an FTIR-Bruker a-T model was employed within the spectral range of 4000 to 500 cm−1. The determination of the specific surface area (SSA) of the adsorbents was carried out using the BET (Brunauer, Emmett, and Teller) method, employing a Quantachrome Nova 2200 (Boynton Beach, FL, USA) surface area analyzer. The adsorption and desorption isotherms were obtained by degassing the samples at 150 °C for three hours prior to analysis. The XPS analysis of the synthesized adsorbents was conducted using a Krato axis Ultra Spectrometer manufactured by Shimadzu Corporation (Kyoto, Japan). The measurements were performed using an Al-K source operating at an energy level of 1489.5 eV, with an emission current of 10 mA and an emission voltage of 15 kilovolts (kV). The concentration of TC was measured using a PG Instruments Ltd. (Lutterworth, UK), India T90 + UV-vis spectrometer. To determine the PZC and particle size, a Nanotrac wave II DLS analyzer was used in conjunction with water measurements at 26 °C. Before measuring the zeta potential, the POC was determined by modulating the pH of the solution from 2 to 12 with NaOH and HCl while stirring continuously for 12 h.
2.4. Batch Experiment Details
This study aimed to examine the adsorption of TC on GGBS-Ox through a series of batch experiments. All experiments involved 50 mL of aqueous TC solution at 25 ± 3 °C. Experiments were performed to assess the optimal dosage of adsorbent between 10 mg and 100 mg, as well as the optimal concentration of TC between 20 ppm and 100 ppm, and the contact time was 180 min. Following each adsorption experiment, 1 mL of samples were subjected to filtration and subsequent centrifugation at a speed of 6000 revolutions per minute for 10 min, until complete settling of adsorbent was achieved. A UV-visible spectrophotometer operating at a specified wavelength of 358 nm was used to determine the concentration of TC. The pH of the solution was adjusted with NaOH or HCl solution (0.1 M). All experiments are performed three times, and the average of the results is used in these analyses. The error in percent removal obtained was less than ±2% in all cases. Additionally, the removal efficacy of TC for BBD was established through three repeated trials conducted under ideal conditions. The efficiency of TC removal (%) and the adsorption capacity of TC was determined using the following equations:
In the above equations, Co denotes the initial concentration of TC (ppm), while Ct signifies the TC concentration at a particular time. Qe represents the adsorption capacity (mg/g), V corresponds to the volume of the solution (L), and W denotes the mass of the adsorbent (g).
2.5. Response Surface Methodology
The RSM-based BBD reveals the extent of the correlation between the selected adsorption parameters. The primary objective of this investigation is to model the adsorption of TC from an aqueous solution into GGBS-Ox. The Design-Expert software, version 11, was utilized. Based on the preliminary experiment, the BBD experiment is conducted using independent adsorption factors, such as (A) pH, (B) contact time, and (C) stirring speed, with percent removal efficiency as the response (Y). Each independent parameter was subdivided into three levels (−1, 0, and 1), allowing the model creation of an experimental design with 17 investigative runs and five replications at the central level, as shown in
Table 1. The following is a second-order quadratic model that establishes the correlation between specific input factors and the performance of TC adsorption.
where
Y is the efficiency of TC adsorption,
Xi denotes the variables under consideration, and (
β0,
βi,
βii, and
βij) denote the model terms, which represent the intercept, quadratic, linear, and interaction effects, respectively. Analysis of variance (ANOVA) was performed to determine the relevance and adequacy of the postulated model using the Design-Expert program. The multiple regression parameters were calculated, such as the coefficient of determination R
2, adjusted R
2,
p-value, and lack-of-fit.
2.6. Artificial Neural Network
An ANN is a computational model that draws inspiration from the structure and functioning of the human brain and nervous system. To identify non-linear relationships between variables that cannot be stated mathematically, ANN is a trustworthy and reliable validation methodology [
34]. ANN consists of several interconnected neurons that flow as shown in
Figure S1a. The precise number of neurons can be determined through an iterative process. In this study, the data obtained from BBD and other experiments are used to train and test the ANN modal. The input data consists of initial pH, time (min), and stirring speed, with the output variable as removal (%). The data set is divided into training (75%) and testing data (25%) set for modal input [
35]. In this case, three hidden layers are considered, with 15 neurons in each layer. The model uses the Kernel initializer as normal in the hidden and output layers. The rectified linear activation function (ReLU) and linear activation function are employed in hidden and output layers, respectively.
2.7. Random Forest
RF is a combination of the regression trees method and a large set of classifications. RF takes data samples from the input data and constructs a decision tree, followed by a voting procedure for each predicted parameter and a determination of the highest-voted predicted result, as shown in
Figure S1b [
36]. In this study, the data obtained from BBD and preliminary experiments on the RF model are trained and tested. The data set is divided into training (70%) and testing data (30%) for modal input. The model consists of 15 trees taken after an iterative process. The inputs consist of the initial pH, contact time (min), and stirring speed (rpm). The output is the removal (%).
4. Conclusions
The present investigation demonstrated the successful synthesis of GGBS-Ox and its subsequent application for the removal of TC from an aqueous solution. The prepared adsorbent underwent characterization through various techniques including FTIR, XRD, SEM, DLS, and XPS. The preliminary adsorption studies showed the higher removal of TC (68%) at an optimum adsorbent and pollutant dosage of 50 mg and 20 ppm, respectively. RSM incorporating BBD, ANN, and RF were successfully employed to evaluate the influence of three chosen independent variables, such as pH, stirring speed, and time, on the adsorption process. Statistical tools such as R2, RMSE, and MEA were employed to evaluate the models. All models show that pH plays a key role in the adsorption process, and there is minimal effect from time and stirring speed. The RSM-based BBD was determined to be reliable (R2 = 0.98) in predicting the percentage removal of TC compared to RF (R2 = 0.98) and RSM (R2 = 0.95). The kinetic and isotherm data suggested that the adsorption of TC was predominantly controlled by the pseudo-second order adsorption mechanism (R2 = 0.99) and Langmuir model (R2 = 0.98), indicating faster and monolayer adsorption. Thermodynamic study indicates that the adsorption is endothermic and spontaneous in nature. The studies show that the GGBS-Ox can be applied for the adsorption of TC due to its efficiency, availability, reusability, and cost-effectiveness.