Impact of Water Saturation on the Fate and Mobility of Antibiotics in Reactive Porous Geomedia.

Understanding contaminant transport through unsaturated porous media is a considerable challenge, given the complex interplay of nonlinear physical and biogeochemical processes driven by variations in water saturation. In this study, we tackled this challenge through a series of column experiments involving fine (100-300 µm) and coarse (1.0-1.4 mm) sand particles coated with birnessite (MnO2) under variable saturation degrees. Dynamic flow experiments in sand columns revealed that desaturation altered the ability of MnO2 in removing tetracycline (TTC), a redox-active antibiotic, yet the effect depends on the sand type and then on the saturation degree. Moderate saturation degrees in fine-grained sand columns promoted fractional and preferential water flow which favored a more acidic pH and increased dissolved oxygen levels. These conditions enhanced TTC removal, despite the reduced physical accessibility of reactive phases. In contrast, lower saturation degrees in coarse-grained sand columns induced stronger flow heterogeneity with a very small fraction of the water content participating in flow. The mobility behavior of all the columns was predicted using transport models that consider TTC adsorption and transformation, as well as dual porosity under variable water saturation degrees. This research offers valuable insights into predicting the fate and transport of redox-active contaminants in unsaturated soils and subsurface environments.

Redox-Driven Formation of Mn(III) in Ice.

Redox-driven reactions involving Mn(II) species adsorbed at Mn(IV) oxide surfaces can release Mn(III) in the form of dissolved Mn(III)-ligand species in natural waters. Using pyrophosphate (PP) as a model ligand, we show that freezing accelerates and enhances Mn(III) formation in the form of Mn(III)-PP complexes. This freeze-promoted reaction is explained by the concentration of Mn(IV) oxides and solutes (Mn(II), Na+, and Cl-) into the minute fractions of liquid water locked between ice (micro)crystals - the Liquid Intergrain Boundary (LIB). Time-resolved freezing experiments at -20 °C showed that Mn(III) yields were greatest at low salt (NaCl) content. In contrast, high salt content promoted Mn(III) formation through chloride complexation, although yields became lower as the cryosalt mineral hydrohalite (NaCl·2H2O) dehydrated the LIB by drawing water into its structure. Consecutive freeze-thaw cycles also showed that dissolved Mn(III) concentrations increased within the very first few minutes of each freezing event. Because each thaw event released unreacted PP previously locked in ice, each sequential freeze-thaw cycle increased Mn(III) yields, until ∼80% of the Mn was converted to Mn(III). This was achieved after only seven cycles. Finally, temperature-resolved freezing experiments down to -50 °C showed that the LIB produced the greatest quantities of Mn(III) at -10 °C, where the volumes were greater. Reactivity was however sustained in ice formed below the eutectic (-21.3 °C), down to -50 °C. We suspect that this sustained reactivity was driven by persistent forms of supercooled water, such as Mn(IV) oxide-bound thin water films. By demonstrating the freeze-driven production of Mn(III) by comproportionation of dissolved Mn(II) and Mn(IV) oxide, this study highlights the potentially important roles these reactions could play in the production of pools of Mn(III) in natural water and sediments of mid- and high-latitudes environments exposed to freeze-thaw episodes.

Efficient PFAS removal from contaminated soils through combined washing and adsorption in soil effluents.

This study investigates soil washing as a viable strategy to remove poly- and perfluoroalkyl substances (PFAS) from contaminated soils using various washing agents including water, methanol, ethanol, and cyclodextrin ((2-Hydroxypropyl)-ß-cyclodextrin HPCD)). Water was less effective (removing only 30 % of PFAS), especially for long-chain hydrophobic PFAS. Methanol (50 % v/v) or HPCD (10 mg g-1 soil) achieved > 95 % PFAS removal regardless of PFAS type, soil size fraction (0-400 µm or 400-800 µm), or experimental setups (batch or column, at liquid/solid (L/S) = 1). Column optimization studies revealed improved efficiency at L/S = 10 with diluted washing solutions, where HPCD exhibited rapid PFAS mobilization even at lower concentrations (1 mg mL-1). We then applied a first-order decay model to effectively predict PFAS breakthrough curves and mobilization within soil columns. Subsequent treatment of wash effluents by activated carbon and biochar effectively reduced PFAS concentrations below detection limits. The performance of both soil washing and subsequent adsorption was found to depend strongly on the specific characteristics of PFAS compounds. These findings highlight the significant potential of methanol and HPCD in soil washing and the effectiveness of integrated soil washing and adsorption for optimizing PFAS removal.

How mineral induced antibiotic transformation products impact bacterial growth and denitrification activity.

The abiotic transformations of quinolones and tetracyclines facilitated by redox-active minerals has been studied extensively, however limited information is available regarding the antimicrobial activity and toxicity of their resultant transformation products. In this study, we first investigated the mechanisms underlying the transformation of two commonly used antibiotics, ciprofloxacin (CIP) and tetracycline (TC), by the ubiquitous redox soil mineral, birnessite (MnO2). Subsequently, we evaluated the impact of these transformation products on both the growth and activity of the environmental denitrifier Pseudomonas veronii. Following the reaction with birnessite, four transformation products for CIP and five for TC were identified. Remarkably, the antibacterial activity of both CIP and TC was lost upon the formation of transformation products during their interaction with birnessite. This loss of antimicrobial efficacy was associated with specific chemical transformations, such as the opening of the piperazine ring for CIP and hydroxylation and demethylation for TC. Interestingly, denitrifying activity, quantified in terms of nitrate reduction rates, remained unaffected by both CIP and TC at low concentrations that did not impact bacterial growth. However, under certain conditions, specifically at low concentrations of CIP, the second step of denitrification-nitrite reduction-was hindered, leading to the accumulation of nitrite. Our findings highlight that the transformation products induced by the mineral-mediated reactions of CIP or TC lose the initial antibacterial activity observed in the parent compounds. This research contributes valuable insights into the intricate interplay between antibiotics, redox-active minerals, and microbial activity in environmental systems.

Microscale Chaotic Mixing as a Driver for Chemical Reactions in Porous Media.

Mixing-induced reactions play a key role in a large range of biogeochemical and contaminant transport processes in the subsurface. Fluid flow through porous media was recently shown to exhibit chaotic mixing dynamics at the pore scale, enhancing microscale concentration gradients and controlling mixing rates. While this phenomenon is likely ubiquitous in environmental systems, it is not known how it affects chemical reactions. Here, we use refractive index matching and laser-induced fluorescence imaging of a bimolecular redox reaction to investigate the consequence of pore scale chaotic mixing on the reaction rates. The overestimation of measured reaction rates by the classical macrodispersion model highlights the persistence of incomplete mixing on the pore scale. We show that the reaction product formation is controlled by microscale chaotic mixing, which induces an exponential increase of the mixing interface and of the reaction rates. We derive a reactive transport model that captures experimental results and predicts that chaotic mixing has a first order control on reaction rates across a large range of time scales and Péclet and Damköhler numbers. These findings provide a new framework for understanding, assessing, and predicting mixing-induced reactions and their role on the fate and mobility of environmental compounds in natural porous media.

Unveiling the oxidation mechanism of persistent organic contaminants via visible light-induced dye-sensitized reaction by red mud suspension with peroxymonosulfate.

A dye-sensitized photocatalysis system was developed for degrading persistent organic contaminants using solid waste (i.e., red mud, RM) and peroxymonosulfate (PMS) under visible light. Complete degradation of acid orange 7 (AO7) was achieved in RM suspension with PMS, where the co-existence of amorphous FeO(OH)/α-Fe2O3 was the key factor for PMS activation. The experimental results obtained from photochemical and electrochemical observations confirmed the enhanced PMS activation due to the Fe-OH phase in RM. DFT calculations verified the acceleration of PMS activation due to the high adsorption energy of PMS on FeO(OH) and low energy barrier for generating reactive radicals. Compared to the control experiment without AO7 showing almost no degradation of other organic contaminants (phenol, bisphenol A, 4-chlorophenol, 4-nitrophenol, and benzoic acid), photo-sensitized AO7* enhanced electron transfer in the FeIII/FeII cycle, dramatically enhancing the degradation of organic contaminants via radical (•OH, SO4•-, and O2•-) and non-radical (dye*+ and 1O2) pathways. Therefore, the novel finding of this study can provide new insights for unique PMS activation by heterogeneous Fe(III) containing solid wastes and highlight the importance of sensitized dye on the interaction of PMS with Fe charge carrier for the photo-oxidation of organic contaminants under visible light.

Nalidixic Acid and Fe(II)/Cu(II) Coadsorption at Goethite and Akaganéite Surfaces.

Interactions between aqueous Fe(II) and solid Fe(III) oxy(hydr)oxide surfaces play determining roles in the fate of organic contaminants in nature. In this study, the adsorption of nalidixic acid (NA), a representative redox-inactive quinolone antibiotic, on synthetic goethite (α-FeOOH) and akaganéite (ß-FeOOH) was examined under varying conditions of pH and cation type and concentration, by means of adsorption experiments, attenuated total reflectance-Fourier transform infrared spectroscopy, surface complexation modeling (SCM), and powder X-ray diffraction. Batch adsorption experiments showed that Fe(II) had marginal effects on NA adsorption onto akaganéite but enhanced NA adsorption on goethite. This enhancement is attributed to the formation of goethite-Fe(II)-NA ternary complexes, without the need for heterogeneous Fe(II)-Fe(III) electron transfer at low Fe(II) loadings (2 Fe/nm2), as confirmed by SCM. However, higher Fe(II) loadings required a goethite-magnetite composite in the SCM to explain Fe(II)-driven recrystallization and its impact on NA binding. The use of a surface ternary complex by SCM was supported further in experiments involving Cu(II), a prevalent environmental metal incapable of transforming Fe(III) oxy(hydr)oxides, which was observed to enhance NA loadings on goethite. However, Cu(II)-NA aqueous complexation and potential Cu(OH)2 precipitates counteracted the formation of ternary surface complexes, leading to decreased NA loadings on akaganéite. These results have direct implications for the fate of organic contaminants, especially those at oxic-anoxic boundaries.

Retention and transport of PFOA and its fluorinated substitute, GenX, through water-saturated soil columns.

Perfluoro-2-propoxypropanoic acid (GenX) has emerged as a substitute for perfluorooctanoic acid (PFOA) especially since PFOA was listed among the persistent organic pollutants (POPs) by the Stockholm Convention in 2019. However, limited knowledge exists regarding the behavior and mobility of GenX in natural soils hindering the prediction of its environmental fate. This study investigated the mobility and retention of GenX and PFOA in soils under batch and water-saturated flow-through conditions. Batch experiments revealed that GenX has a lower binding affinity to soil than longer-chained PFOA, potentially threatening groundwater resources. Unlike metal-oxides/minerals (ferrihydrite, gibbsite and manganese dioxide), biochar (BC) and activated carbon (AC) amendments significantly enhanced the sorption of both GenX and PFOA in soil. Sorption data on minerals and carbonaceous materials implied that for shorter-chained GenX, the predominant mode of sorption was through electrostatic (ionic) interactions, while for longer-chained PFOA, hydrophobic interactions became progressively more important with increasing chain length. The dynamic flow experiments demonstrated that these soil amendments enhanced the retention of both compounds, thereby decreasing their mobility. Simultaneous injection of both compounds into columns pre-loaded with either PFOA or GenX increased their retardation. GenX sorption was more affected by pre-sorbed PFOA compared to the minimal impact of pre-loaded GenX on PFOA sorption. A newly developed reactive transport model, which incorporates a two-site sorption model and accounts for kinetic-limited processes, accurately predicted the sorption and transport of both compounds in single and binary contamination systems. These findings have important implications for predicting and assessing the fate and mobility of per- and polyfluoroalkyl substances (PFAS) in soils and groundwaters.

Mineral Nanoparticle Aggregation Alters Contaminant Transport under Flow.

Iron oxyhydroxide nanoparticle reactivity has been widely investigated, yet little is still known on how particle aggregation controls the mobility and transport of environmental compounds. Here, we examine how aggregates of goethite (α-FeOOH) nanoparticle deposited on 100-300 µm quartz particles (GagCS) alter the transport of two emerging contaminants and two naturally occurring inorganic ligands-silicates and phosphates. Bromide tracer experiments showed no water fractionation into mobile and immobile water zones in an individual goethite-coated sand (GCS) column, whereas around 10% of the total water was immobile in a GagCS column. Reactive compounds were, in contrast, considerably more mobile and affected by diffusion-limited processes. A new simulation approach coupling the mobile-immobile equation with surface complexation reactions to surface reactive sites suggests that ∼90% of the binding sites were likely within the intra-aggregate zones, and that the mass transfer between mobile and immobile fractions was the rate-limited step. The diffusion-controlled processes also affected synergetic and competitive binding, which have otherwise been observed for organic and inorganic compounds at goethite surfaces. These results thereby call for more attention on transport studies, where tracer or conservative tests are often used to describe the reactive transport of environmentally relevant molecules.

Aging and reactivity assessment of nanoscale zerovalent iron in groundwater systems.

In this study, changes in the reactivity of nanoscale zerovalent iron (NZVI) in five different groundwater (GW) systems under anoxic and oxic conditions were examined over a wide range of aging time (0 - 60 d). p-nitrophenol (p-NP) was used as a redox-sensitive probe, whereas nalidixic acid (NA), a typical antibiotic found in the natural environment, was used as a sorbing compound. Investigation of the p-NP reduction in pure water systems showed that NZVI lost 41% and 98% of its reductive activity under anoxic and oxic conditions after 60 d, while enhancement of its reactivity was observed after short-term aging in GW (1 - 5 d), followed by a further decline. This behavior has been ascribed to the formation of secondary Fe(II)-bearing phases, including magnetite and green rust, resulting from NZVI aging in GW. Adsorption experiments revealed that GW-anoxic-aged NZVI samples exhibited a good affinity toward NA, and a greater NA adsorption (∼27 µmol g - 1) than that of pristine NZVI (∼2 µmol g - 1) at alkaline pH values. Surface complexation modeling showed that the enhanced adsorption of NA onto secondary minerals can be attributed to the Fe(II)-NA surface complexation. This considerable change in the reductive ability and the adsorption capacity of NZVI arising from groundwater corrosion calls for greater attention to be paid in assessment studies, where NZVI is injected for long-term remediation in groundwater.

Fate and Transport of Pharmaceuticals in Iron and Manganese Binary Oxide Coated Sand Columns.

Predicting the fate and transport of pharmaceuticals in terrestrial environments requires knowledge of their interactions with complex mineral assemblages. To advance knowledge along this front, we examined the reactivity of pipemidic acid (PIP), a typical quinolone antibiotic, with quartz particles coated with a mixture of manganese oxide (MnO2) and goethite (α-FeOOH) under static and dynamic flow conditions. Batch and dynamic column experiments showed that PIP binding to MnO2 proceeded through a heterogeneous redox reaction, while binding to goethite was not redox-reactive. Mixed columns of aggregated goethite-manganese particles however enhanced redox reactivity because (i) goethite facilitated the transport of dissolved Mn(II) ion and increased the retention of PIP oxidation products, and (ii) MnO2 was protected from passivation. This mobility behavior was predicted using transport models accounting for adsorption and transformation kinetics of PIP on both goethite and MnO2. This work sheds new light on reactivity changes of mixtures of Fe and Mn oxides under flow-through conditions and will have important implications in predicting the fate and transport of redox-active organic compounds as well as development of new geomedia filters for environmental remediation.

Fate and transport of tetracycline and ciprofloxacin and impact on nitrate reduction activity in coastal sediments from the Seine Estuary, France.

Fluoroquinolones and tetracyclines are frequently detected antibiotics in aquatic sediments. In this study, the transport of ciprofloxacin (CIP) and tetracycline (TET) was investigated in sediments from the Seine Estuary (France), under nitrate reducing conditions. Dynamic flow experiments showed that although TET and CIP strongly interacted with the sediment components through adsorption and (bio)-chemical transformation, they kept their antimicrobial activities. Less nitrate reduction was observed during the first period of breakthrough, while TET and CIP were absent in the column effluent. Batch experiments with freeze-dried vs fresh sediments showed that adsorption and abiotic degradation are the major removal processes, while microbe-driven transformation is of less importance. Whereas TET is to a large extent chemically transformed and little adsorbed in the sediment, CIP was less transformed and more adsorbed, most likely due to the great reactivity of TET with redox-active mineral surfaces. Our findings show the strong capacity of natural sediment to retain and transform antibiotics, while still maintaining their antimicrobial activity or inhibitory effect of nitrate reducing activity.

Alteration of birnessite reactivity in dynamic anoxic/oxic environments.

Although the oxidative capacity of manganese oxides has been widely investigated, potential changes of the surface reactivity in dynamic anoxic/oxic environments have been often overlooked. In this study, we showed that the reactivity of layer structured manganese oxide (birnessite) was highly sensitive to variable redox conditions within environmentally relevant ranges of pH (4.0 - 8.0), ionic strength (0-100 mM NaCl) and Mn(II)/MnO2 molar ratio (0-0.58) using ofloxacine (OFL), a typical antibiotic, as a target contaminant. In oxic conditions, OFL removal was enhanced relative to anoxic environments under alkaline conditions. Surface-catalyzed oxidation of Mn(II) enabled the formation of more reactive Mn(III) sites for OFL oxidation. However, an increase in Mn(II)/MnO2 molar ratio suppressed MnO2 reactivity, probably because of competitive binding between Mn(II) and OFL and/or modification in MnO2 surface charge. Monovalent cations (e.g., Na+) may compensate the charge deficiency caused by the presence of Mn(III), and affect the aggregation of MnO2 particles, particularly under oxic conditions. An enhancement in the removal efficiency of OFL was then confirmed in the dynamic two-step anoxic/oxic process, which emulates oscillating redox conditions in environmental settings. These findings call for a thorough examination of the reactivity changes at environmental mineral surfaces (e.g., MnO2) in natural systems that may be subjected to alternation between anaerobic and oxygenated conditions.

Transformation mechanisms of iopamidol by iron/sulfite systems: Involvement of multiple reactive species and efficiency in real water.

Although the ability of iron/sulfite system for decontamination purposes has been investigated, the complex reactive species generated and the underlying transformation mechanisms remain elusive. Here, we have comprehensively examined the transformation of iopamidol (IPM), a representative of iodinated X-ray contrast media, by iron catalyzed sulfite oxidation process under different water chemistry conditions. Multiple reactive intermediates including Fe(IV), SO4•-, and SO5•- were identified by conducting a series of experiments. Eight transformation products were detected by mass spectrometry analysis, and correlation with the nature of involved reactive species has been made. Further, the transformation pathways including amide hydrolysis, deiodination, amino and hydroxyl groups oxidation were proposed. Interestingly, these transformation products could be removed through adsorption to iron precipitates formed via pH adjustment. Combining Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, we revealed an effective way to reduce the amount of transformation products in the treated solutions. Since the iron/sulfite process appears to be less sensitive to natural organic matter, it exhibited very good efficiency for IPM removal in real water samples, even with a high organic carbon loading. These findings may have strong implications in the development of novel oxidation process based on the sulfite/iron systems for wastewater treatment.

Interactions of Anti-Inflammatory and Antibiotic Drugs at Mineral Surfaces Can Control Environmental Fate and Transport.

Various pharmaceutical compounds often coexist in contaminated soils, yet little is known about how their interactions impact their mobility. We here show that two typical antibiotic and anti-inflammatory agents (nalidixic acid (NA) and niflumic acid (NFA)) commonly form dimers at several representative soil- and sediment-building minerals of contrasting composition and structure. Cobinding occurs in the form of a NFA-NA dimer stabilized by hydrogen bonding and van der Waals interactions. Using dynamic column experiments containing goethite-coated sand, we then demonstrated that presorbed NA effectively captured the otherwise weakly binding NFA from solution. Simultaneously injecting NA and NFA to presorbed NA enhanced even further both NA and NFA loadings, thereby altering their transport under flow-through conditions. We also showed that environmental level amounts of natural organic matter can reduce the overall retention in column experiments, yet it does not suppress dimer formation. These environmentally relevant scenarios can be predicted using a new transport model that accounts for kinetics and cobinding reactions of NFA onto NA bound to goethite through metal-bonded, hydrogen-bonded, and outer-sphere complexes. These findings have important implications on assessing the fate of coexisting pharmaceutical compounds under dynamic flow conditions in contaminated soils.

Fenton oxidation for soil remediation: A critical review of observations in historically contaminated soils.

Fenton-based treatments have received tremendous attention in recent decades as viable strategies for soil decontamination. Historically contaminated soils are characterized by particular contamination types, pollution composition patterns, soil constituents, and complex soil-pollutant interactions arising due to long-term pollutant aging. These major pitfalls dictate the remediation efficiency in a significantly different way in soils with a history of contamination than that in a spiked soil. It becomes, therefore, highly challenging to treat historically contaminated soils. Despite the immense amount of collected research data in these soils, to our knowledge, no comprehensive review of this topic has been published. This article is intended to provide a critical review of the applications, limitations, and implications of various Fenton-based processes exclusively in these soils. These processes are differentiated on the basis of experimental conditions, reaction chemistry, efficiency, and impacts on soil biota. These processes are critically evaluated to illustrate the promising techniques with a brief description of related challenges and their potential solutions. Moreover, coupling Fenton oxidation with other remediation techniques such as bioremediation, chemical reduction, and soil washing has also been discussed. The last part of this review describes the effects of these processes onto soil quality and native biota, and how they can be addressed. It is also highly demanding to identify the processes which are not likely to evolve in practice either due to their poor efficiency, treatment cost, or environmental impacts. Future critical research directions have been identified to promote research for the upscaling of this technique for real field application.

Silicate surface coverage controls quinolone transport in saturated porous media.

Although silicates are the most common anions in aquatic systems, little is known on the roles they play on the transport of emerging contaminants, such as antibiotics. Using dynamic column experiments, we revealed the controls of Si loadings on goethite (α-FeOOH) coated sands on the transport of a widely used quinolone antibiotic, here focusing on Nalidixic Acid (NA). We find that dynamic flow-through conditions (Darcy velocities of 2.98 cm/h and 14.92 cm/h) sustain monomeric Si species with loadings of up to ~ 0.8 Si/nm2 but that oligomeric species can form at the goethite surfaces under static (batch, no-flow conditions). While these monomeric species occupy no more than ~ 22% of the reactive OH groups on goethite, they can effectively suppress NA binding, and therefore enhance NA mobility in dynamic conditions. NA can also bind on goethite when it is simultaneously injected with high concentrations of Si (2000 µM), yet it becomes progressively replaced by Si over time. Combining kinetics and surface complexation modeling, we present a new transport model to account for the stepwise polymerization of Si on goethite and NA transport. Our findings show that dissolved Si, common to natural surface waters, can play a determining role on the surface speciation and transport of antibiotics in the environment.

Competitive Carboxylate-Silicate Binding at Iron Oxyhydroxide Surfaces.

Dissolved silicate ions in wet and dry soils can determine the fate of organic contaminants via competitive binding. While fundamental surface science studies have advanced knowledge of binding in competitive systems, little is still known about the ranges of solution conditions, the time dependence, and the molecular processes controlling competitive silicate-organic binding on minerals. Here we address these issues by describing the competitive adsorption of dissolved silicate and of phthalic acid (PA), a model carboxylate-bearing organic contaminant, onto goethite, a representative natural iron oxyhydroxide nanomineral. Using surface complexation thermodynamic modeling of batch adsorption data and chemometric analyses of vibrational spectra, we find that silicate concentrations representative of natural waters (50-1000 µM) can displace PA bound at goethite surfaces. Below pH ∼8, where PA binds, every bound Si atom removes ∼0.3 PA molecule by competing with reactive singly coordinated hydroxo groups (-OH) on goethite. Long-term (30 days) reaction time and a high silicate concentration (1000 µM) favored silicate polymer formation, and increased silicate while decreasing PA loadings. The multisite complexation model predicted PA and silicate binding in terms of the competition for -OH groups without involving PA/silicate interactions, and in terms of a lowering of outer-Helmholtz potentials of the goethite surface by these anions. The model predicted that silicate binding lowered loadings of PA species, and whose two carboxylate groups are hydrogen- (HB) and metal-bonded (MB) with goethite. Vibrational spectra of dried samples revealed that the loss of water favored greater proportions of MB over HB species, and these coexisted with predominantly monomeric silicate species. These findings underscored the need to develop models for a wider range of organic contaminants in soils exposed to silicate species and undergoing wet-dry cycles.

A Review of Manganese(III) (Oxyhydr)Oxides Use in Advanced Oxidation Processes.

The key role of trivalent manganese (Mn(III)) species in promoting sulfate radical-based advanced oxidation processes (SR-AOPs) has recently attracted increasing attention. This review provides a comprehensive summary of Mn(III) (oxyhydr)oxide-based catalysts used to activate peroxymonosulfate (PMS) and peroxydisulfate (PDS) in water. The crystal structures of different Mn(III) (oxyhydr)oxides (such as α-Mn2O3, γ-MnOOH, and Mn3O4) are first introduced. Then the impact of the catalyst structure and composition on the activation mechanisms are discussed, as well as the effects of solution pH and inorganic ions. In the Mn(III) (oxyhydr)oxide activated SR-AOPs systems, the activation mechanisms of PMS and PDS are different. For example, both radical (such as sulfate and hydroxyl radical) and non-radical (singlet oxygen) were generated by Mn(III) (oxyhydr)oxide activated PMS. In comparison, the activation of PDS by α-Mn2O3 and γ-MnOOH preferred to form the singlet oxygen and catalyst surface activated complex to remove the organic pollutants. Finally, research gaps are discussed to suggest future directions in context of applying radical-based advanced oxidation in wastewater treatment processes.