1. Introduction
Polycyclic aromatic hydrocarbons (PAHs) are hazardous organic micropollutants that are colorless or pale-yellow and widely present in the ecosystem. Chemically, these micropollutants consist of two or more fused benzene rings [
1]. All PAHs, both low and high molecular weight, are stable and resistant to biodegradation [
2]. These compounds are generated by both anthropogenic (industrial discharge, waste incineration, and biomass burning) and natural sources (natural oil seeps, forest fires, and volcanic eruptions). PAHs can cause cancer (i.e., lung, bladder, and skin cancer) in human beings and also severe health problems in aquatic life by inhalation and ingestion even in very low concentrations (ng/L–μg/L) [
1,
3]. The United States Environmental Protection Agency (USEPA) has categorized 16 PAHs as priority micropollutants because of their mutagenic and carcinogenic effects [
4]. Produced water (PW) is also one of the largest anthropogenic sources that contains a considerable amount of PAHs [
2,
5]. PW is a byproduct of oil and gas industries, which is generated during the oil and gas extraction process. Many studies have confirmed that acute and chronic toxicity of PW is mainly because of PAHs, phenols, and high amounts of COD [
6]. Globally, the production of PW increases day by day, and its production has been reported to have reached up to 250 million barrels per day [
7]. Moreover, almost 40% of PW is directly discharged into water bodies without any treatment [
6]. The direct discharge of untreated PW into the environment contaminates surface and groundwater. Several treatment methods, such as volatilization, combined microfiltration and biological processes, chlorination, biochar adsorption, ozonation, electrodialysis, reverse osmosis, electrocoagulation, ion exchange, membrane-based technology, and conventional phase separation, have been employed for the treatment of PW [
8,
9]. Although more than 90% of organic pollutants removal from PW was attained by electrocoagulation, it is not cost-effective, produces a large amount of sludge, and consumes more energy [
10]. Membrane-based technologies are efficient for PW treatment; however, these technologies have several problems such as membrane fouling, high energy consumption, and the lack of potential to degrade refractory organic pollutants [
11]. Combined microfiltration and biological process reported almost 65% of COD removal from oilfield wastewater; however, it is also a time-consuming process [
12]. More than 50% removal of total dissolved solids from PW was obtained by electrodialysis, but it utilized a large amount of energy to accomplish the treatment [
13]. Constructed wetland is an efficient method for organic matter removal from PW, but its maintenance cost is very high [
14]. Moreover, most of the techniques are very expensive. In many cases, they just transfer organic pollutants from one phase to another and cannot remove dissolved organic contaminants from PW. Some of the available technologies produce toxic byproducts that limit their practical use [
15]. Therefore, it is imperative to explore economic and ecotechnological solutions for PAH reduction from PW.
Different materials/chemicals such as zeolites, metal oxides, and nanoparticles have been applied for the remediation of contaminants from water and wastewater [
16]. In recent years, ferrate (VI) (Fe (VI)) with high valent iron (VI) has gained attention due to its high oxidation/reduction potential [
17,
18,
19]. The Fe (VI) oxidation method is a promising technique due to its environment-friendly nature, low cost, and high efficiency for organic pollutant removal [
20]. Surprisingly, Fe (VI) acts as a coagulant, disinfectant, and oxidizer at the same time. Fe (VI) is considered as one of the most efficient oxidants for the treatment of wastewater due to its strong oxidizing power [
3]. The redox potential of the Fe (VI) ion in both acidic and neutral environments is higher than many other oxidizing agents, as shown in
Table 1, making it a favorable oxidant for the treatment of wastewater [
21]. In an acidic environment, Fe (VI)’s electrode potential is 2.20 V, and, in an alkaline medium, it is 0.72 V. However, the Fe (VI) cations’ structure can be modified by adjusting the pH value to control the oxidation activity, so as to achieve high selectivity [
22]. Fe (VI) is a robust multifunctional oxidizer with a tetrahedral structure (FeO
42−). Fe (VI) is converted into Fe
3+ and Fe(OH)
3 during disinfection and oxidation processes and acts as coagulant and oxidizer, as shown in Equations (1) and (2). Fe (VI) produces molecular oxygen during spontaneous oxidation, as shown in Equation (3) [
23]. The reactivity of Fe (VI) with refractory organic and inorganic pollutants shows its usefulness for the removal of pollutants from industrial effluents [
19,
21].
Response surface methodology (RSM) using Design-Expert software is a powerful statistical and mathematical tool that is commonly used for the systematic design and analysis of experiments. It provides optimization and validation of a system based on its statistical modeling. RSM is far better than the conventional one-factor-at-a-time optimization technique because it helps to reduce the vast amount of laboratory experimental work. Traditional methods are complicated, time-consuming, and expensive for multivariable experiments [
24]. Moreover, the influence of multiple variables on responses during the optimization process can be studied in RSM [
25]. It also addresses the interaction between different independent variables and can be practiced in multivariable analyses for the optimization of functional variables [
24].
Various researchers have studied the application of Fe (VI) for remediation of different organic pollutants in several types of wastewater, such as municipal wastewater secondary effluent [
18], oil sands process-affected water [
26], fracturing wastewater [
27], dyeing effluent [
28], textile wastewater [
29], coking wastewater [
30], and tannery wastewater [
31]. In addition, a few studies have explored the potential of Fe (VI) for the removal of just one or two PAHs from synthetic wastewater rather than from real wastewater, especially PW [
22,
30,
32]. Guan et al. [
22] investigated the separate removal of only three PAHs, i.e., phenanthrene, pyrene and naphthalene, from synthetic water using Fe (VI) oxidation. Li et al. [
30] studied the potential of Fe (VI) for the removal of just one PAH (phenanthrene) in coking wastewater. Similarly, Tan et al. [
32] evaluated the potential of Fe (VI) just for one PAH, i.e., phenanthrene removal in synthetic wastewater. Each PAH has different characteristics based on its number of benzene rings; each PAH may react differently against Fe (VI) oxidation. More studies are required to investigate the potential of Fe (VI) for combination of PAHs, especially priority PAHs in aqueous media, so that consistent performance is achieved. It appears from literature that, so far, no study has explored the application of Fe (VI) oxidation for 15 PAHs and COD removal from PW. Secondly, integrated optimization of 15 PAHs and COD removal using RSM is also yet to be explored. Therefore, understanding of the performance of Fe (VI) for combined PAH removal is important to fill the gap in the previous studies. The objectives of this study are (i) to evaluate the potential of Fe (VI) for PAHs and COD removal from PW and (ii) to optimize the independent parameters viz., Fe (VI) concentration, pH, and contact time using RSM.