Heterogeneous iron-based catalysts have drawn increasing attention in the advanced oxidation of persulfates due to their abundance in nature, the lack of secondary pollution to the environment, and their low cost over the last a few years. In this paper, the latest progress in the research on the activation of persulfate by heterogeneous iron-based catalysts is reviewed from two aspects, in terms of synthesized catalysts (Fe0, Fe2O3, Fe3O4, FeOOH) and natural iron ore catalysts (pyrite, magnetite, hematite, siderite, goethite, ferrohydrite, ilmenite and lepidocrocite) focusing on efforts made to improve the performance of catalysts. The advantages and disadvantages of the synthesized catalysts and natural iron ore were summarized. Particular interests were paid to the activation mechanisms in the catalyst/PS/pollutant system for removal of organic pollutants. Future research challenges in the context of field application were also discussed.

Due to the complicated transport and reactive behavior of organic contamination in groundwater, the development of mathematical models to aid field remediation planning and implementation attracts increasing attentions. In this study, the approach coupling response surface methodology (RSM), artificial neural networks (ANN), and kinetic models was implemented to model the degradation effects of nano-zero-valent iron (nZVI) activated persulfate (PS) systems on benzene, a common organic pollutant in groundwater. The proposed model was applied to optimize the process parameters in order to help predict the effects of multiple factors on benzene degradation rate. Meanwhile, the chemical oxidation kinetics was developed based on batch experiments under the optimized reaction conditions to predict the temporal degradation of benzene. The results indicated that benzene (0.25 mmol) would be theoretically completely oxidized in 1.45 mM PS with the PS/nZVI molar ratio of 4:1 at pH 3.9°C and 21.9 C. The RSM model predicted well the effects of the four factors on benzene degradation rate (R2 = 0.948), and the ANN with a hidden layer structure of [8-8] performed better compared to the RSM (R2 = 0.980). In addition, the involved benzene degradation systems fit well with the Type-2 and Type-3 pseudo-second order (PSO) kinetic models with R2 > 0.999. It suggested that the proposed statistical and kinetic-based modeling approach is promising support for predicting the chemical oxidation performance of organic contaminants in groundwater under the influence of multiple factors.

The removal of p-nitrophenol (PNP) from wastewater was evaluated by the activated persulfate process using different materials - carbon xerogels (XG), carbon nanotubes (CNT), and activated carbon (AC) -, and also using such materials doped with nitrogen (XGM, CNTM and ACM). These carbon materials were impregnated with 2 wt.% of iron and tested in the oxidative process to assess the influence of their textural and surface chemical properties. The carbon-based materials\' properties influence the efficiencies of the adsorption and oxidative processes; in adsorption, the materials with higher specific surface areas (SBET), i.e. AC (824 m2/g) and Fe/AC (807 m2/g), have shown to be the most promising (having achieved a PNP removal of about 20%); on the other hand, in the activated persulfate process the carbon or iron-containing carbon materials with the highest mesoporous areas (Smeso) were the preferential ones - XG and Fe/XG, respectively - reaching removals of 47.3% and 75.7% for PNP and 44.9 and 63.3% for TOC, respectively. Moreover, the presence of nitrogen groups on the samples\' surface benefits both processes, being found that PNP degradation and mineralization increase with the nitrogen content. The stability of the best materials (XGM and Fe/XGM) was evaluated during four cycles, being noticed that while XGM lost catalytic activity, the Fe/XGM sample remained stable without leaching of iron. The quantification of intermediate compounds formed during persulfate oxidation was performed, and only oxalic acid was detected, in addition to PNP, being that their contribution to the TOC measured was higher than 99%. Experiments carried out in the presence of radical scavengers proved that only the sulfate radical is present under the acidic conditions used. Complete PNP oxidation and TOC removal of ∼96% were reached for the activated persulfate process, proving to be more attractive than the Fenton one.

The standard method for estimating the chemical oxygen demand (COD) of water bodies uses dichromate as the main oxidant, a chemical agent whose use has been restricted in the European Union since 2017. This method is hazardous, time-consuming, and burdensome to adapt to on-site measurements. As an alternative and following the current trends of sustainable and green chemistry, a method using the less toxic reagent sodium persulfate as the oxidizing agent has been developed. In this method an excess of persulfate, activated through heating in an alkaline solution, oxidizes the chemically degradable organic fraction through a 2-step radical mechanism. The remaining persulfate is evaluated by chemiluminescence (CL) using luminol and a portable charge-coupled device (CCD) camera. The method provided quantitative recoveries and a sample throughput of >60 samples h-1. It was validated in river water samples by comparison of COD estimations with the standard dichromate method (R = 0.973, p < 0.05) and with a UV-Vis permanganate-based method (R = 0.9998, p < 0.05), the latter being also used for drinking waters. The proposed method is a sustainable and green alternative to the previous used methods. Overall, the method using activated persulfate is suitable for use as COD quantitation/screening tool in surface waters. Considering that its main components are portable, it can be ultimately adapted for in situ analysis at the point of need.

Controlled release materials (CRMs) are an emerging oxidant delivery technique for in-situ chemical oxidation (ISCO) that solve the problems of contaminant rebound, backflow and wake during groundwater remediation. CRMs were fabricated using ordered mesoporous manganese oxide (O-MnOx) and sodium persulfate (Na2S2O8) as active components, for the removal of antibiotic pollutants from groundwater. In both static and dynamic groundwater environments, persulfate can first be activated by O-MnOx within CRMs to form sulfate radicals and hydroxyl radicals, with these radicals subsequently dissolving out from the CRMs and degrading tetracycline (TC). Due to their excellent persulfate activation performance and good stability, the constructed CRMs could effectively degrade TC in both static and dynamic simulated groundwater systems over a long period (>21 days). The TC removal rate reached >80 %. Changing the added content of O-MnOx and persulfate could effectively regulate the performance of the CRMs during TC degradation in groundwater. The process and products of TC degradation in the dynamic groundwater system were the same as in the static groundwater system. Due to the strong oxidizing properties of sulfate radicals and hydroxyl radicals, TC molecules were completely mineralized within the groundwater systems, resulting in only trace levels of degradation products being detectable, with low- or non-toxicity. Therefore, the CRMs constructed in this study exhibited good potential for practical application in the remediation of organic pollutants from both static and dynamic groundwater environments.

Ultrasound coupled with activated persulfate can synergistically degrade aqueous organic contaminants. Here, in situ electron paramagnetic resonance spin trapping was used to compare radicals produced by ultrasonically activated persulfate (US-PS) and its individual technologies, ultrasound alone (US) and heat-activated persulfate (PS), with respect to temperature. Radicals were trapped using 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, to form detectable nitroxide adducts. Using initial rates of radical adduct formation, and compared to US and PS, US-PS at 40 and 50 °C resulted in the largest synergistic production of radicals. Radicals generated from US were reasonably consistent from 40 to 70 °C, indicating that temperature had little effect on cavitational bubble collapse over this range. However, synergy indexes calculated from initial rates showed that ultrasonic activation of persulfate at the bubble interface changes with temperature. From these results, we speculate that higher temperatures enhance persulfate uptake into cavitation bubbles via nanodroplet injection. DMPO-OH was the predominant adduct detected for all conditions. However, competition modeling and spin trapping in the presence of nitrobenzene and atrazine probes showed that SO4•- predominated. Therefore, the DMPO-OH signal is derived from SO4•- trapping with subsequent DMPO-SO4- hydrolysis to DMPO-OH. Spin trapping is effective in quantifying total radical adduct formation but limited in measuring primary radical speciation in this case.

In this research, a novel iron based bimetallic nanoparticles (Fe-Ni) supported on activated carbon (AC) were synthesized and employed as an activator of persulfate in polycyclic aromatic hydrocarbons (PAHs) polluted sites remediation. AC-supported Fe-Ni activator was prepared according to two-step reduction method: the liquid phase reduction and H2- reduction under high temperature (600 °C), which was defined as Fe-Ni/AC. Characterizations using micropore physisorption analyzer, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HR-TEM) showed that the synthetic material had large specific surface area, nano-size and carbon-encapsulated metal particles, moreover, the lattice fringes of metals were clearly defined. The PAH compound types and their concentrations were determined by gas chromatography mass spectrometry (GC-MS) with SIM mode, the method detection limit (MDL) was estimated to about 0.21 μg/kg for PAHs, and the average recovery of PAHs was 96.3%. Mechanisms of PAH oxidation degradation with the reaction system of Fe-Ni/AC activated persulfate were discussed, the results showed that short-life free radicals, such as SO4-·, OH·, and OOH· were generated simultaneously, which acted as strong oxidizing radicals, resulting in the oxidation and almost complete opening of the PAH rings.

Coupling ultrasound with other remediation technologies has potential to result in synergistic degradation of contaminants. In this work, we evaluated synergisms from adding high-power ultrasound (20 kHz; 250 W) to activated persulfate over a range of bulk temperatures (20-60 °C). We studied the aqueous degradation kinetics of three polycyclic aromatic hydrocarbons (PAHs: naphthalene, phenanthrene, and fluoranthene) treated by ultrasound-alone, heat-activated persulfate, and combined ultrasonically-activated persulfate (US-PS). At 20 °C, observed US-PS rate constants strongly correlated with Wilke-Chang diffusion coefficients. This correlation indicates PAH molecules diffuse to the bubble-water interface prior to reaction with sulfate radicals (SO4-) generated at the interface. At higher temperatures, observed US-PS rate constants appear to be a more complicated function of temperature and diffusion coefficients. Synergy indexes for PAHs with fast diffusion coefficients were greatest at 20 °C. Fluoranthene, the largest and most hydrophobic PAH, had a maximum synergy index at 30 °C; it benefited from additional thermal persulfate activation in bulk solution. Fluoranthene synergy indexes, however, decreased above 30 °C and became antagonistic at 60 °C. Electron paramagnetic resonance (EPR) spin trapping was used to quantify hydroxyl radical (OH) produced from acoustic cavitation in the absence of persulfate. These data showed consistent OH production from 20 to 60 °C, indicating PAH antagonisms at 60 °C were not due to lower bubble collapse temperatures. Instead, the results suggest that PAH antagonisms are caused by increased radical-radical recombination as bulk temperature increases. In effort to develop an efficient, combined remediation technology, this work suggests bulk temperatures between 20 and 40 °C maximize US-PS synergisms.

In this study, the magnetic fraction (MF) of a low-grade titanium ore (TO) was successfully used as an alternative Fe2+ source in five reuse cycles, in combination with persulfate (PS) and simulated sunlight (SSL) for the degradation of ciprofloxacin (CIP). The best response of the CIP initial concentration, irradiation time, and doses of MF and PS to degrade completely this pollutant were determined based on an experimental design. However, the individual application of MF, PS, or SSL fails to achieve this goal at the optimal experimental condition. Furthermore, the MF-PS-SSL system showed a higher production of sulfate radicals and a concentration of dissolved Fe2+ ions compared with data obtained for the MF-PS system. The best performance attained by the former system is due to the synergy produced between the photo-generated electrons, and the reaction of PS with the Fe2+ ions leached gradually from the MF, which increased sulfate radical production. After five reuse cycles of the MF, the oxidation system showed a CIP degradation of 100% in 100 min, no residual content of PS, a CIP mineralization of 6%, a marginal increase in the biodegradability (BOD5/COD ratio), a MF loss of 7.5%, and a twofold increase in toxicity; however, this parameter was lower than the effective concentration at 50% inhibition (EC50). The substitution of MF with an iron salt decreased the degradation efficiency of the antibiotic by 14%, probably owing to the immediate excess of Fe2+ in the solution, which can be oxidized to Fe3+ ions, and as a consequence of this, the production rate of the sulfate radical was also reduced.

In situ chemical oxidations are known to remediate PAH contaminations in groundwater and soils. In this study, batch-scale oxidations aim to compare the PAC (polycyclic aromatic compound) degradation of three oxidation processes traditionally applied for soil treatment: permanganate, heat-activated persulfate (60 °C) and Fenton-like activated by magnetite, to results obtained with ferrates (FeVI). Widely studied for water treatments, ferrates are efficient on a wide range of pollutants with the advantage of producing nontoxic ferric sludge after reaction. However, fewer works focus on their action on soil, especially on semi-industrial grade ferrates (compatible with field application). Oxidations were carried out on sand spiked with dense non-aqueous phase liquid (DNAPL) sampled in the groundwater of a former coking plant. Conventional 16 US-EPA PAHs and polar PACs were monitored, especially potential oxygenated by-products that can be more harmful than parent-PAHs. After seven reaction days, only the Fenton-like showed limited degradation. Highest efficiencies were obtained for heat-activated persulfate with no O-PAC ketones formed. Permanganate gave important degradation, but ketones were generated in large amount. The tested ferrates not only gave slightly lower yields due to their auto-decomposition but also induced O-PAC ketone production, suggesting a reactional pathway dominated by oxidoreductive electron transfer, rather than a radical one.