Anti-respiratory syncytial virus and anti-herpes simplex virus activity of chemically engineered sulfated fucans from Cystoseira indica.

Seaweed polysaccharides, particularly sulfated ones, exhibited potent antiviral activity against a wide variety of enveloped viruses, such as herpes simplex virus and respiratory viruses. Different mechanisms of action were suggested, which may range from preventing infection to intracellular antiviral activity, at different stages of the viral cycle. Herein, we generated two chemically engineered sulfated fucans (C303 and C304) from Cystoseira indica by an amalgamated extraction-sulfation procedure using chlorosulfonic acid-pyridine/N,N-dimethylformamide and sulfur trioxide-pyridine/N,N-dimethylformamide reagents, respectively. These compounds exhibited activity against HSV-1 and RSV with 50 % inhibitory concentration values in the range of 0.75-2.5 µg/mL and low cytotoxicity at concentrations up to 500 µg/mL. The antiviral activities of chemically sulfated fucans (C303 and C304) were higher than the water (C301) and CaCl2 extracted (C302) polysaccharides. Compound C303 had a (1,3)-linked fucan backbone and was branched. Sulfates were present at positions C-2, C-4, and C-2,4 of Fucp, and C-6 of Galp residues of this polymer. Compound C304 had a comparable structure but with more sulfates at C-4 of Fucp residue. Both C303 and C304 were potent antiviral candidates, acting in a dose-dependent manner on the adsorption and other intracellular stages of HSV-1 and RSV replication, in vitro.

Microwave-assisted synthesis of highly sulfated mannuronate glycans as potential inhibitors against SARS-CoV-2.

Algae-based marine carbohydrate drugs are typically decorated with negative ion groups such as carboxylate and sulfate groups. However, the precise synthesis of highly sulfated alginates is challenging, thus impeding their structure-activity relationship studies. Herein we achieve a microwave-assisted synthesis of a range of highly sulfated mannuronate glycans with up to 17 sulfation sites by overcoming the incomplete sulfation due to the electrostatic repulsion of crowded polyanionic groups. Although the partially sulfated tetrasaccharide had the highest affinity for the receptor binding domain (RBD) of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) Omicron variant, the fully sulfated octasaccharide showed the most potent interference with the binding of the RBD to angiotensin-converting enzyme 2 (ACE2) and Vero E6 cells, indicating that the sulfated oligosaccharides might inhibit the RBD binding to ACE2 in a length-dependent manner.

Comparative study of the removal of sulfate by UASB in light and dark environment.

At present, the application of sewage treatment technologies is restricted by high sulfate concentrations. In the present work, the sulfate removal was biologically treated using an upflow anaerobic sludge blanket (UASB) in the absence/presence of light. First, the start-up of UASB for the sulfate removal was studied in terms of COD degradation, sulfate removal, and effluent pH. Second, the impacts of different operation parameters (i.e., COD/SO42- ratio, temperature and illumination time) on the UASB performance were explored. Third, the properties of sludge derived from the UASB at different time were analyzed. Results show that after 28 days of start-up, the COD removal efficiencies in both the photoreactor and non-photoreactor could reach a range of 85-90% while such reactors could achieve > 90% of sulfate being removed. Besides, higher illumination time could facilitate the removal of pollutants in the photoreactor. To sum up, the present study can provide technical support for the clean removal of sulfate from wastewater using photoreactors.

Carbothermal synthesis of sulfurized nano zero-valent iron from sulfate-reducing bacteria biomass for mercury removal: The first application of biomass sulfur source.

The development of low-cost, highly efficient adsorbent materials is of significant importance for environmental remediation. In this study, a novel material, sulfurized nano zero-valent iron loaded biomass carbon (S-nZVI/BC), was successfully synthesized by a simple manufacturing process. The preparation of S-nZVI/BC does not require the use of expensive and hazardous chemicals. Instead, residual sludge, a solid waste product, is used as feedstock. The sludge is rich in Sulfate-Reducing Bacteria (SRB), which can provide carbon and sulfur sources for the synthesis of S-nZVI/BC. It was observed that S-nZVI particles formed in situ were dispersed within BC and covered by it. Additionally, S-nZVI/BC inherited the large specific surface area and porosity of BC. The adsorption capacity of S-nZVI/BC can reach 857.55 mg g-1 Hg (II) during the remediation of mercury-polluted water. This research offers new perspectives for developing composites in terms of the low cost and harmlessness of raw materials.

Direct Determination of Absolute Radical Quantum Yields in Hydroxyl and Sulfate Radical-Based Treatment Processes.

The absolute radical quantum yield (Φ) is a critical parameter to evaluate the efficiency of radical-based processes in engineered water treatment. However, measuring Φ is fraught with challenges, as current quantification methods lack selectivity, specificity, and anti-interference capabilities, resulting in significant error propagation. Herein, we report a direct and reliable time-resolved technique to determine Φ at pH 7.0 for commonly used radical precursors in advanced oxidation processes. For H2O2 and peroxydisulfate (PDS), the values of Φ•OH and ΦSO4•- at 266 nm were measured to be 1.10 ± 0.01 and 1.46 ± 0.05, respectively. For peroxymonosulfate (PMS), we developed a new approach to determine Φ•OHPMS with terephthalic acid as a trap-and-trigger probe in the nonsteady state system. For the first time, the Φ•OHPMS value was measured to be 0.56 by the direct method, which is stoichiometrically equal to ΦSO4•-PMS (0.57 ± 0.02). Additionally, radical formation mechanisms were elucidated by density functional theory (DFT) calculations. The theoretical results showed that the highest occupied molecular orbitals of the radical precursors are O-O antibonding orbitals, facilitating the destabilization of the peroxy bond for radical formation. Electronic structures of these precursors were compared, aiming to rationalize the tendency of the Φ values we observed. Overall, this time-resolved technique with specific probes can be used as a reliable tool to determine Φ, serving as a scientific basis for the accurate performance evaluation of diverse radical-based treatment processes.

Denigrins H-L: Sulfated Derivatives of Denigrins D and E from a New Zealand Dictyodendrilla c.f. dendyi Marine Sponge.

Five new sulfated arylpyrrole and arylpyrrolone alkaloids, denigrins H-L (1-5), along with two known compounds, dictyodendrin B and denigrin G, were isolated from an extract of a New Zealand Dictyodendrilla c.f. dendyi marine sponge. Denigrins H-L represent the first examples of sulfated denigrins, with denigrins H and I (1-2), as derivatives of denigrin D, containing a pyrrolone core, and denigrins J-L (3-5), as derivatives of denigrin E (6), containing a pyrrole core. Their structures were elucidated by interpretation of 1D and 2D NMR spectroscopic data, ESI, and HR-ESI-MS spectrometric data, as well as comparison with literature data. Compounds 1-5, along with six known compounds previously isolated from the same extract, showed minimal cytotoxicity against the HeLa cervical cancer cell line.

Marine-Derived Sulfated Glycans Inhibit the Interaction of Heparin with Adhesion Proteins of Mycoplasma pneumoniae.

Mycoplasma pneumoniae, a notable pathogen behind respiratory infections, employs specialized proteins to adhere to the respiratory epithelium, an essential process for initiating infection. The role of glycosaminoglycans, especially heparan sulfate, is critical in facilitating pathogen-host interactions, presenting a strategic target for therapeutic intervention. In this study, we assembled a glycan library comprising heparin, its oligosaccharide derivatives, and a variety of marine-derived sulfated glycans to screen the potential inhibitors for the pathogen-host interactions. By using Surface Plasmon Resonance spectroscopy, we evaluated the library's efficacy in inhibiting the interaction between M. pneumoniae adhesion proteins and heparin. Our findings offer a promising avenue for developing novel therapeutic strategies against M. pneumoniae infections.

Oxidation effects on Microcystis aeruginosa inactivation through various reactive oxygen species: Degradation efficiency, mechanisms, and physiological properties.

The study investigated the inactivation of Microcystis aeruginosa using a combined approach involving thermally activated peroxyacetic acid (Heat/PAA) and thermally activated persulfate (Heat/PDS). The Heat/PDS algal inactivation process conforms to first-order reaction kinetics. Both hydroxyl radical (•OH) and sulfate radical (SO4-•) significantly impact the disruption of cell integrity, with SO4-• assuming a predominant role. PAA appears to activate organic radicals (RO•), hydroxyl (•OH), and a minimal amount of singlet oxygen (1O2). A thorough analysis underscores persulfate's superior ability to disrupt algal cell membranes. Additionally, SO4-• can convert small-molecule proteins into aromatic hydrocarbons, accelerating cell lysis. PAA can accelerate cell death by diffusing into the cell membrane and triggering advanced oxidative reactions within the cell. This study validates the effectiveness of the thermally activated persulfate process and the thermally activated peroxyacetic acid as strategies for algae inactivation.

Selective degradation of endogenous organic metabolites in acidified fresh human urine using sulphate radical-based advanced oxidation.

The human urine metabolome is complex, containing a wide range of organic metabolites that affect treatment of urine collected in resource-oriented sanitation systems. In this study, an advanced oxidation process involving heat-activated peroxydisulphate was used to selectively oxidise organic metabolites in urine over urea and chloride. Initial experiments evaluated optimal conditions (peroxydisulphate dose, temperature, time, pH) for activation of peroxydisulphate in unconcentrated, non-hydrolysed synthetic urine and real urine acidified to pH 3.0. Subsequent experiments determined the fate of 268 endogenous organic metabolites (OMs) and removal of COD from unconcentrated and concentrated real urine (80-90% mass reduced by evaporation). The results revealed >90% activation of 60 mM peroxydisulphate in real unconcentrated urine heated to 90 °C for 1 h, resulting in 43% ΣOMs degradation, 22% COD removal and 56% total organic carbon removal, while >94% of total nitrogen and >97% of urea in real unconcentrated urine were recovered. The mechanism of urea degradation was identified to be chemical hydrolysis to ammonia, with the rate constant for this reaction determined to be 1.9 × 10-6 s-1 at pH 3.0 and 90 °C. Treating concentrated real urine resulted in similar removal of COD, ΣOMs degradation and total nitrogen loss as observed for unconcentrated urine, but with significantly higher chloride oxidation and chemical hydrolysis of urea. Targeted metabolomic analysis revealed that peroxydisulphate treatment degraded 157 organic metabolites in urine, of which 67 metabolites were degraded by >80%. The rate constant for the reaction of sulphate radicals with oxidisable endogenous organic metabolites in urine was estimated to exceed 108 M-1 s-1. These metabolites were preferentially oxidised over chloride and urea in acidified, non-hydrolysed urine treated with peroxydisulphate. Overall, the findings support the development of emerging urine recycling technologies, including alkaline/acid dehydration and reverse osmosis, where the presence of endogenous organic urine metabolites significantly influences treatment parameters such as energy demand and product purity.

Insights into the transformation of natural organic matter during UV/peroxydisulfate treatment by FT-ICR MS and machine learning: Non-negligible formation of organosulfates.

Natural organic matter (NOM) is a major sink of radicals in advanced oxidation processes (AOPs) and understanding the transformation of NOM is important in water treatment. By using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in conjunction with machine learning, we comprehensively investigated the reactivity and transformation of NOM, and the formation of organosulfates during the UV/peroxydisulfate (PDS) process. After 60 min UV/PDS treatment, the CHO formula number and dissolved organic carbon concentration significantly decreased by 83.4 % and 74.8 %, respectively. Concurrently, the CHOS formula number increased substantially from 0.7 % to 20.5 %. Machine learning identifies DBE and AImod as the critical characteristics determining the reactivity of NOM during UV/PDS treatment. Furthermore, linkage analysis suggests that decarboxylation and dealkylation reactions are dominant transformation pathways, while the additions of SO3 and SO4 are also non-negligible. According to SHAP analysis, the m/z, number of oxygens, DBE and O/C of NOM were positively correlated with the formation of organosulfates in UV/PDS process. 92 organosulfates were screened out by precursor ion scan of HPLC-MS/MS and verified by UPLC-Q-TOF-MS, among which, 7 organosufates were quantified by authentic standards with the highest concentrations ranging from 2.1 to 203.0 ng L‒1. In addition, the cytotoxicity of NOM to Chinese Hamster Ovary (CHO) cells increased by 13.8 % after 30 min UV/PDS treatment, likely responsible for the formation of organosulfates. This is the first study to employ FT-ICR MS combined with machine learning to identify the dominant NOM properties affecting its reactivity and confirmed the formation of organosulfates from sulfate radical oxidation of NOM.

Biogenic sulfur recovery from sulfate-laden antibiotic production wastewater using a single-chamber up-flow bioelectrochemical reactor.

The high-concentration sulfate (SO42-) in the antibiotic production wastewater hinders the anerobic methanogenic process and also proposes possible environmental risk. In this study, a novel single-chamber up-flow anaerobic bioelectrochemical reactor (UBER) was designed to realize simultaneous SO42- removal and elemental sulfur (S0) recovery. With the carbon felt, the cathode was installed underneath and the anode above to meet the different biological niches for sulfate reducing bacteria (SRB) and sulfur oxidizing bacteria (SOB). The bio-anode UBER (B-UBER) demonstrated a much higher average SO42- removal rate (SRR) of 113.2 ± 5.7 mg SO42--S L-1 d-1 coupled with a S0 production rate (SPR) of 54.4 ± 5.8 mg S0-S L-1 d-1 at the optimal voltage of 0.8 V than that in the abio-anode UBER (control reactor) (SRR = 86.6 ± 13.4 mg SO42--S L-1 d-1; SPR = 25.5 ± 9.7 mg S0-S L-1 d-1) under long-term operation. A large amount of biogenic S0 (about 72.2 mg g-1 VSS) was recovered in the B-UBER. The bio-anode, dominated by Thiovirga (SOB genus) and Acinetobacter (electrochemically active bacteria genus), exhibited a higher current density, lower overpotential, and lower internal resistance. C-type cytochromes mainly served as the crucial electron transfer mediator for both direct and indirect electron transfer, so that significantly increasing electron transfer capacity and biogenic S0 recovery. The reaction pathways of the sulfur transformation in the B-UBER were hypothesized that SRB utilized acetate as the main electron donor for SO42- reduction in the cathode zone and SOB transferred electrons to the anode or oxygen to produce biogenic S0 in the anode zone. This study proved a new pathway for biogenic S0 recovery and sulfate removal from sulfate-laden antibiotic production wastewater using a well-designed single-chamber bioelectrochemical reactor.

Alleviative effects of sulfated polysaccharide from Ishige Okamurae against DSS-induced ulcerative colitis via inhibiting inflammation and modulating gut microbiota.

A water-soluble polysaccharide from the brown alga Ishige Okamurae, designated IOP-0, was obtained by preparative anion-exchange and size-exclusion chromatography. Chemical and spectroscopic investigations revealed that IOP-0 was a sulfated fucoidan with a backbone primarily composed of 3-linked and 4-linked-L-fucose with sulfate groups at C-2/C-4 of the 3-linked-L-fucose. The protective effect of IOP-0 on ulcerative colitis was evaluated in this work. The results showed that IOP-0 could significantly alleviate the symptoms of ulcerative colitis by preventing weight loss, preserving the structure of intestinal tissues, and ameliorating the dysregulation of inflammatory cytokines (TNF-α, IL-6, and IL-10). Meanwhile, IOP-0 protected the colonic mucosal barrier by promoting the tight junction protein ZO-1 and occludin expression. In addition, IOP-0 was able to maintain intestinal homeostasis and improve intestinal function by regulating the gut microbiota and their metabolites, such as short-chain fatty acids (SCFAs). These results suggest that IOP-0 might be a potential dietary supplement for the prevention and treatment of ulcerative colitis.

Unveiling activation mechanism of persulfate by homologous hemp-derived biochar catalysts for enhanced tetracycline wastewater remediation.

Advancements in biochar activating persulfate advanced oxidation processes (PS-AOP), have gained significant attention. However, the understanding of biochar-based catalysts in activating PS remains limited. Herein, biochar (BC) and N-doped biochar (NBC) were synthesized from hemp for activating PS to treat tetracycline (TC) wastewater and analyzed their mechanisms separately. Surprisingly, N-doped in biochar leads to a change in the activation mechanism of PS. The BC-PS system operates mainly through a radical pathway, advantageous for treating soil organic pollution (68%) with pH adaptability (less than 10% variation). Nevertheless, the NBC-PS system primarily employs an electron transfer non-radical pathway, demonstrating stability (only 7% performance degradation over four cycles) and enhanced resistance to anionic interference (less than 10% variation) in organic wastewater treatment. This study provides a technical reference and theoretical foundation for enhancing biochar activation of PS in the removal of organic pollutants from aquatic and terrestrial environments.

Divergent redistribution behavior of divalent metal cations associated with Fe(II)-mediated jarosite phase transformation.

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).

Modeling subsurface contaminant transport from a former open-pit uranium mine in fractured granites (La Ribière, France): Reducing uncertainties with geophysics.

The long-term management of tailings from former uranium (U) mines requires an in-depth understanding of the hydrogeological processes and water flow paths. In France, most of the legacy U mines are located in fractured crystalline (plutonic) rocks, where the intrinsic subsurface heterogeneity adds to the uncertainties about the former extraction and milling activities and the state of the mine when production was ceased. U ores were mainly processed by sulfuric acid leaching, leading to high-sulfate-content mill tailings now contained in several tailing storage facilities (TSFs). The La Ribière site, located in western central France, is a former open-pit and underground U mine, closed in 1992 and used to store mill tailings. This site is being used as a test case to establish a workflow in order to explain and predict water flow and subsurface contaminant transport. A conceptual model of water flow and sulfate transport, at the scale of the La Ribière watershed, is first developed based on available information and hydrogeochemical monitoring. Recent geophysical investigations allows refining this model. Electrical Resistivity Tomography (ERT) proves to be efficient at localizing the extent of the highly conductive sulfate plume inherited from the U-mill tailings, but also at imaging the weathering profile. Magnetic Resonance Sounding (MRS), despite the limited signal intensity due to the low porosity in crystalline rocks, gives some insight into the porosity values, the depth of the fractured layer and the location of the low-porosity ore-processing muds. Based on this conceptual model, a 3D flow and non-reactive transport model with the METIS code is developed and calibrated. This model allows predicting the evolution of the sulfate plume, but will also be used in future investigations, to build reactive transport models with simplified hydrogeology for U and other reactive contaminants.

Sulfated Polysaccharide-Based Nanocarrier Drives Microenvironment-Mediated Cerebral Neurovascular Remodeling for Ischemic Stroke Treatment.

Stroke is a leading cause of global mortality and severe disability. However, current strategies used for treating ischemic stroke lack specific targeting capabilities, exhibit poor immune escape ability, and have limited drug release control. Herein, we developed an ROS-responsive nanocarrier for targeted delivery of the neuroprotective agent rapamycin (RAPA) to mitigate ischemic brain damage. The nanocarrier consisted of a sulfated chitosan (SCS) polymer core modified with a ROS-responsive boronic ester enveloped by a red blood cell membrane shell incorporating a stroke homing peptide. When encountering high levels of intracellular ROS in ischemic brain tissues, the release of SCS combined with RAPA from nanoparticle disintegration facilitates effective microglia polarization and, in turn, maintains blood-brain barrier integrity, reduces cerebral infarction, and promotes cerebral neurovascular remodeling in a mouse stroke model involving transient middle cerebral artery occlusion (tMCAO). This work offers a promising strategy to treat ischemic stroke therapy.

Biological evaluation of sulfonate and sulfate analogues of lithocholic acid: A bioisosterism-guided approach towards the discovery of potential sialyltransferase inhibitors for antimetastatic study.

The naturally occurring bile acid lithocholic acid (LCA) has been a crucial core structure for many non-sugar-containing sialyltranferase (ST) inhibitors documented in literature. With the aim of elucidating the impact of the terminal carboxyl acid substituent of LCA on its ST inhibition, in this present study, we report the (bio)isosteric replacement-based design and synthesis of sulfonate and sulfate analogues of LCA. Among these compounds, the sulfate analogue SPP-002 was found to selectively inhibit N-glycan sialylation by at least an order of magnitude, indicating a substantial improvement in both potency and selectivity when compared to the unmodified parent bile acid. Molecular docking analysis supported the stronger binding of the synthetic analogue in the enzyme active site. Treatment with SPP-002 also hampered the migration, adhesion, and invasion of MDA-MB-231 cells in vitro by suppressing the expression of signaling proteins involved in the cancer metastasis-associated integrin/FAK/paxillin pathway. In totality, these findings offer not only a novel structural scaffold but also valuable insights for the future development of more potent and selective ST inhibitors with potential therapeutic effects against tumor cancer metastasis.

Conductometric investigation of nano MnSO4 association parameters and complex formation with glycylglycine in aqueous and methanol-water mixtures: Thermodynamic parameters and potential applications.

This study aimed to investigate the ion pair association values and association parameters of nano MnSO4 in water and methanol-water mixtures (20 % and 40 % methanol by mass percentage) at varying temperatures (298.15, 303.15, 308.15, and 313.15 K) using the conductometric technique. Additionally, the parameters for complex formation between nano MnSO4 and glycylglycine as a ligand were determined. The focus was on elucidating the thermodynamic formation parameters for the nano Mn2+-glycylglycine interaction, with particular emphasis on comparing the 1: 1 and 1: 2 (M: L) complexes to understand the complexation behavior more comprehensively. The results indicated that the complexation process was spontaneous, as evidenced by negative ΔGf (formation free energy change) values, which increased with temperature, highlighting the enhanced spontaneity of the process. The findings provide valuable insights into designing new materials and procedures by enhancing our understanding of the complexation behavior of nano MnSO4 with ligands like glycylglycine, thus contributing to advancements in various applications such as chemical synthesis, medicines, and environmental remediation. By elucidating the thermodynamic aspects of these interactions, the study aimed to provide valuable information that could be utilized in practical applications and further research endeavors.

Highly efficient targeted adsorption and catalytic degradation of ciprofloxacin by a novel molecularly imprinted bimetallic MOFs catalyst for persulfate activation.

Given the presence of emerging pollutants at low concentrations in water bodies, which are inevitably affected by background substances during the removal process. In this study, we synthesized molecularly imprinted catalysts (Cu/Ni-MOFs@MIP) based on bimetallic metal-organic frameworks for the targeted degradation of ciprofloxacin (CIP) in advanced oxidation processes (AOPs). The electrostatic interaction and functional group binding of CIP with specific recognition sites on Cu/Ni-MOFs@MIP produced excellent selective recognition (Qmax was 14.82 mg g-1), which enabled the active radicals to approach and remove the contaminants faster. Electron paramagnetic resonance (EPR) analysis and quenching experiments revealed the coexistence of ∙OH, SO42-, and 1O2, with ∙OH dominating the system. Based on experimental and theoretical calculations, the reaction sites of CIP were predicted and the possible degradation pathways and mechanisms of Cu/Ni-MOFs@MIP/PMS systems were proposed. This study opens up a new platform for the targeted removal of target pollutants in AOPs.

Kinetics and mechanism analysis of advanced oxidation degradation of PFOA/PFOS by UV/Fe3+ and persulfate: A DFT study.

UV/Fe3+ and persulfate are two promising advanced oxidative degradation systems for in situ remediation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), yet a lack of comprehensive understanding of the degradation mechanisms. For the first time, we used density functional theory (DFT) to calculate the entire reaction pathways of the degradation of PFOA/PFOS in water by UV/Fe3+ and persulfate. In addition, we have deeply explored the different attack pathways driven by •OH and SO4-•, and found that SO4-• determines PFOA/PFOS to obtain PFOA/PFOS free radicals through single electron transfer to initiate the degradation reaction, while •OH determines the speed of PFOA/PFOS degradation reaction. Both degradation reactions were thermodynamically advantageous and kinetically feasible under calculated conditions. Based on the thermodynamic data, persulfate was found to be more favorable for the advanced oxidative degradation of Perfluorinated compounds (PFCs). Moreover, for SO4-• and •OH co-existing in the persulfate system, pH will affect the presence and concentration of these two types of free radicals, and low pH is not necessary for the degradation of PFOA/PFOS in the persulfate system. These results can considerably advance our understanding of the PFOA/PFOS degradation process in advanced oxidation processes (AOPs), which is driven by •OH and SO4-•. This study provides a DFT calculation process for the mechanism calculation of advanced oxidation degradation of other types of PFCs pollutants, hoping to elucidate the future development of PFCs removal. Further research should focus on determining the advanced oxidation degradation pathways of other types of PFCs, to support the development of computational studies on the advanced oxidation degradation of PFCs.