Elsevier

Chemical Engineering Journal

Volume 334, 15 February 2018, Pages 1502-1517
Chemical Engineering Journal

Review
Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants

https://doi.org/10.1016/j.cej.2017.11.059Get rights and content

Highlights

  • Sulfate radical-based AOPs have some advantages compared with radical dotOH-based methods.

  • Sulfate radical-based AOPs are efficient for degrading organic pollutants.

  • Various activation methods and mechanisms for PS and PMS were summarized.

  • Their application for degrading emerging contaminants was reviewed.

Abstract

Sulfate radical-based advanced oxidation processes (AOPs) have been received increasing attention in recent years due to their high capability and adaptability for the degradation of emerging contaminants. Persulfate (PS, S2O82−) and peroxymonosulfate (PMS, HSO5) can be activated by thermal, alkaline, ultraviolet light, activated carbon, transition metal (such as Fe0, Fe2+, Cu2+, Co2+, Ag+), ultrasound and hydrogen peroxide to form sulfate radical (SO4radical dot), which is strong oxidant and capable of effectively degrading emerging pollutants. Sulfate radical-based AOPs have a series of advantages in comparison with radical dotOH-based methods, for example: higher oxidation potential, higher selectivity and efficiency to oxidize pollutants containing unsaturated bonds or aromatic ring, wider pH range. Therefore, sulfate radicals are capable of removing the emerging contaminants more efficiently. In this review paper, various methods for the activation of PS and PMS were introduced, including, thermal, alkaline, radiation, transition metal ions and metal oxide, carbonaceous-based materials activation and so on; and their possible activation mechanisms were discussed. In addition, the application of activated PS and PMS for the degradation of emerging contaminants and the influencing factors were summarized. Finally, the concluding remarks and perspectives are made for future study on the activation of PS and PMS. This review can provide an overview for the activation and application of PS and PMS for the degradation of emerging contaminants, as well as for the deep understanding of the activation mechanisms of PS and PMS by various methods.

Introduction

The environmental pollution caused by the emerging contaminants has received extensive attention in recent years [1], [2]. Many emerging contaminants are toxic, persistent and non-biodegrade, such as pharmaceuticals and personal care products (PPCPs), endocrine-disrupting chemicals (EDCs), and other recalcitrant organic compounds. It is thus necessary to develop the new technologies for the degradation of emerging contaminants in the environment.

For the groundwater remediation, the common technology is to pump and treat [3]. This method is expensive and time-consuming. Injecting the specific microorganism into the groundwater is effective in some cases for the in situ remediation of groundwater such as the dechlorinating-culture for the removal of chlorinated organic pollutants [4]. But the specific microorganism capable of degrading various emerging contaminants is not always available. Moreover, the condition in some cases for bioremediation is harsh, such as anaerobic condition. For the soil remediation and wastewater treatment, microbial degradation is considered to be the main technology. But some emerging pollutants are resistant to biodegradation [1], [5], [6], which resulted in the incomplete removal of emerging contaminants. Therefore, advanced oxidation processes (AOPS) have been proposed to treat the emerging contaminants in the environment.

The conventional AOPs exhibited good performance in the removal of emerging contaminants, and their mechanisms are mainly dependent on the hydroxyl radical [7], [8]. Hydroxyl radical (OHradical dot) is a non-selective strong oxidant with the redox potential of 2.8 V, which can destruct the structure of organic compounds and even mineralize them to some extent [9]. Recently, sulfate radicals (SO4radical dot)-based technology has received increasing attention [10]. In comparison to hydroxyl radical, sulfate radicals possess equal or even higher redox potential (2.5–3.1 V) based on the activation methods [11]. In addition, sulfate radical has higher selectivity and longer half-life than hydroxyl radical in certain cases [12]. Therefore, sulfate radical could be expected to show similar or better capacity in degrading the emerging contaminants.

Sulfate radical-based AOPs have been widely investigated in recent years, which can be reflected by the increasing number of published papers on the activation and application of PS and PMS, which are depicted in Fig. 1, based on the database of Web of Science. It is clear that the studies on the sulfate radical-based decontamination technology increased rapidly in recent years

The objective of this review paper was to analyze, summarize and compare the various activation methods of PS and PMS and the application of sulfate radicals-based AOPs for the removal of emerging contaminants. The possible activation mechanisms were discussed, the kinetics for the degradation of emerging contaminants was analyzed to provide a broad overview of sulfate radical-based decontamination technology. Finally, the concluding remarks and perspectives for future research were made.

Section snippets

Chemistry of PS and PMS

PS is colorless or white crystal, and has high stability. It can be easily dissolved in water, with the solubility of 730 g L−1 [13]. The water solution of PS is acidic. It has symmetrical structure, the distance of Osingle bondO bond is 1.497 Å, and its bond energy is 140 kJ/mol [14], [15]. The common PS used in the experiments is sodium PS (Na2S2O8) and potassium PS (K2S2O8).

Peroxymonosulfate is white solid powder. It is stable when pH is less than 6 or pH is 12. When pH is 9, it showed the poorest

The activation methods, mechanisms and applications

PS and PMS can be activated by a variety of methods, such as heat, UV, alkaline, metal ions and activated carbon [19]. The redox potential of sulfate radical produced through the activation of PS and PMS depended on the activation methods.

Remediation of polluted soil and wastewater by PS and PMS

Many studies on the removal of organic contaminants in water and soil have been conducted towards the practical application of PS and PMS. However, up to now most studies were only conducted in laboratory and in batch experiment. A few studies have been conducted in situ, which are presented and discussed as follows.

Bandala et al. investigated the treatment of the soil washing wastewater by Co2+/permoxymonosulfate/ultraviolet system [178]. The initial concentration of COD (chemical oxidation

Concluding remarks and perspectives

The reaction rate of PS and PMS are low when they directly react with the organic contaminants. Thus, activation is necessary for PS and PMS when treating the organic contaminants. The redox potential of sulfate radicals varied with the activated methods. Sulfate radicals have similar or even higher redox potential than hydroxyl radicals, and higher redox potential than chlorine radicals, superoxide radicals, carbonate radicals and perhydroxyl radicals. Fig. 5 depicts the formation of sulfate

Acknowledgements

This research was supported by the National Natural Science Foundation of China (51338005), the Program for Changjiang Scholars and Innovative Research Team in University (IRT-13026) and China Postdoctoral Science Foundation (2017M610920).

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