Understanding Variations in Ferrate Detection through the ABTS Method in the Presence of Electron-Rich Organic Compounds.

The chromogenic reaction between 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and ferrate [Fe(VI)] has long been utilized for Fe(VI) content measurement. However, the presence of electron-rich organic compounds has been found to significantly impact Fe(VI) detection using the ABTS method, leading to relative errors ranging from ∼88 to 100%. Reducing substances consumed ABTS•+ and resulted in underestimated Fe(VI) levels. Moreover, the oxidation of electron-rich organics containing hydroxyl groups by Fe(VI) could generate a phenoxyl radical (Ph•), promoting the transformation of Fe(VI) → Fe(V) → Fe(IV). The in situ formation of Fe(IV) can then contribute to ABTS oxidation, altering the ABTS•+:Fe(VI) stoichiometry from 1:1 to 2:1. To overcome these challenges, we introduced Mn(II) as an activator and 3,3',5,5'-tetramethylbenzidine (TMB) as a chromogenic agent for Fe(VI) detection. This Mn(II)/TMB method enables rapid completion of the chromogenic reaction within 2 s, with a low detection limit of approximately 4 nM and a wide detection range (0.01-10 µM). Importantly, the Mn(II)/TMB method exhibits superior resistance to reductive interference and effectively eliminates the impact of phenoxyl-radical-mediated intermediate valence iron transfer processes associated with electron-rich organic compounds. Furthermore, this method is resilient to particle interference and demonstrates practical applicability in authentic waters.

Anthracite Releases Aromatic Carbons and Reacts with Chlorine to Form Disinfection Byproducts in Drinking Water Production.

Anthracite is globally used as a filter material for water purification. Herein, it was found that up to 15 disinfection byproducts (DBPs) were formed in the chlorination of anthracite-filtered pure water, while the levels of DBPs were below the detection limit in the chlorination of zeolite-, quartz sand-, and porcelain sandstone-filtered pure water. In new-anthracite-filtered water, the levels of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and ammonia nitrogen (NH3-N) ranged from 266.3 to 305.4 µg/L, 37 to 61 µg/L, and 8.6 to 17.1 µg/L, respectively. In aged anthracite (collected from a filter at a DWTP after one year of operation) filtered water, the levels of the above substances ranged from 475.1 to 597.5 µg/L, 62.1 to 125.6 µg/L, and 14 to 28.9 µg/L, respectively. Anthracite would release dissolved substances into filtered water, and aged anthracite releases more substances than new anthracite. The released organics were partly (around 5%) composed by the µg/L level of toxic and carcinogenic aromatic carbons including pyridine, paraxylene, benzene, naphthalene, and phenanthrene, while over 95% of the released organics could not be identified. Organic carbon may be torn off from the carbon skeleton structure of anthracite due to hydrodynamic force in the water filtration process.

Highly Efficient Utilization of Ferrate(VI) Oxidation Capacity Initiated by Mn(II) for Contaminant Oxidation: Role of Manganese Species.

Manganese ion [Mn(II)] is a background constituent existing in natural waters. Herein, it was found that only 59% of bisphenol A (BPA), 47% of bisphenol F (BPF), 65% of acetaminophen (AAP), and 49% of 4-tert-butylphenol (4-tBP) were oxidized by 20 µM of Fe(VI), while 97% of BPA, 95% of BPF, 96% of AAP, and 94% of 4-tBP could be oxidized by the Fe(VI)/Mn(II) system [20 µM Fe(VI)/20 µM Mn(II)] at pH 7.0. Further investigations showed that bisphenol S (BPS) was highly reactive with reactive iron species (RFeS) but was sluggish with reactive manganese species (RMnS). By using BPS and methyl phenyl sulfoxide (PMSO) as the probe compounds, it was found that reactive iron species contributed primarily for BPA oxidation at low Mn(II)/Fe(VI) molar ratios (below 0.1), while reactive manganese species [Mn(VII)/Mn(III)] contributed increasingly for BPA oxidation with the elevation of the Mn(II)/Fe(VI) molar ratio (from 0.1 to 3.0). In the interaction of Mn(II) and Fe(VI), the transfer of oxidation capacity from Fe(VI) to Mn(III), including the formation of Mn(VII) and the inhibition of Fe(VI) self-decay, improved the amount of electron equivalents per Fe(VI) for BPA oxidation. UV-vis spectra and dominant transformation product analysis further revealed the evolution of iron and manganese species at different Mn(II)/Fe(VI) molar ratios.

Occurrence of Iodophenols in Aquatic Environments and the Deiodination of Organic Iodine with Ferrate(VI).

Toxic and odorous iodophenols are commonly identified as disinfection by-products (DBPs) in drinking water. Herein, ng/L levels of iodophenols were identified in river water, wastewater treatment plant effluent, and medical wastewater, with the simultaneous identification of µg/L to mg/L levels of iodide (I-) and total organic iodine (TOI). Oxidation experiment suggested that the I-, TOI, and iodophenols could be oxidized by ferrate [Fe(VI)], and more than 97% of TOI had been transformed into stable and nontoxic IO3-. Fe(VI) initially cleaved the C-I bond of iodophenols and led to the deiodination of iodophenols. The resulted I- was swiftly oxidized into HOI and IO3-, with the intermediate phenolic products be further oxidized into lower molecular weight products. The Gibbs free energy change (ΔG) of the overall reaction was negative, indicating that the deiodination of iodophenols by Fe(VI) was spontaneous. In the disinfection of iodine-containing river water, ng/L levels of iodophenols and chloro-iodophenols formed in the reaction with NaClO/NH2Cl, while Fe(VI) preoxidation was effective for inhibiting the formation of iodinated DBPs. Fe(VI) exhibited multiple functions for oxidizing organic iodine, abating their acute toxicity/cytotoxicity and controlling the formation of iodinated DBPs for the treatment of iodide/organic iodine-containing waters.

Enhanced Radical Generation in an Ultraviolet/Chlorine System through the Addition of TiO2.

Ultraviolet (UV)/chlorine draws increasing attention for the abatement of recalcitrant organic pollutants. Herein, it was found that TiO2 would significantly promote the degradation of dimethyl phthalate (DMP) in the UV/chlorine system (from 19 to 84%). Hydroxyl radicals (HO•) and chlorine radicals (Cl•) were the dominant reactive species for DMP degradation in the UV/chlorine/TiO2 system. Chlorine decayed much faster in UV/chlorine/TiO2 compared with UV/chlorine, which is possibly because photogenerated electrons (ecb-) and superoxide radicals (O2•-) have high reactivity with chlorine. As a result, the recombination of photogenerated holes (hvb+) and ecb- was inhibited and the accumulation of HO• and Cl• was facilitated. A kinetic model was established to simulate the reaction process, and it was found that the concentrations of HO• and Cl• were several times to dozens of times higher in UV/chlorine/TiO2 than that in UV/chlorine. The contributions of HO• and Cl• to DMP degradation were 70.3 and 29.7% by model simulation, respectively, and were close to the probe experiment result. In the UV/chlorine/TiO2 system, the degradation of DMP did not follow pseudo-first-order kinetics but the degradation of benzoate fitted well with pseudo-first-order kinetics. This phenomenon was elucidated by the structure of the pollutant and TiO2 and further tested by calculating the adsorption energy (Eads)/binding energy (Eb) with density functional theory. Due to faster decay of chlorine, lower amounts of disinfection byproducts formed in UV/chlorine/TiO2 compared with UV/chlorine. Adding TiO2 into the UV/chlorine system can promote the degradation of recalcitrant organic pollutants in an aqueous environment.

Ferrate Oxidation of Phenolic Compounds in Iodine-Containing Water: Control of Iodinated Aromatic Products.

Highly toxic iodinated products would form in oxidation and disinfection of iodine-containing water. Variation of iodinated aromatic products in ferrate [Fe(VI)] oxidation of phenolic compounds (phenol, bisphenol A (BPA), and p-hydroxybenzoic acid (p-HBA)) in iodine-containing water was investigated. At pH 5.0, oxidation of phenolic compounds was inhibited by competitive reaction of ferrate with I-, and no formation of iodinated aromatic products was detected. Almost all I- was converted into nontoxic IO3-. At pH 7.0, 8.0, and 9.0, HOI formed in ferrate oxidation of I- and further reacted with phenols, with the formation of iodinated aromatic products. Mass spectrometry analysis showed that both kinds and contents of iodinated aromatic products were raised with the increase in solution pH and the content of I-, and these iodinated aromatic products were further oxidized by ferrate. Ferrate deprived iodine from iodinated aromatic products and transferred highly toxic organic iodine into nontoxic IO3-. An electron-donating substituent (alkyl) increased the reactivity of phenol with ferrate and HOI and facilitated ferrate oxidation of iodinated phenols. An electron-drawing substituent (carboxyl) decreased the reactivity of phenol with ferrate and HOI and hindered the further oxidation of iodinated aromatic products. A kinetic model about the variation of phenol, BPA, and p-HBA in reaction with ferrate in iodine-containing water was developed, and the oxidation profile of phenolic compounds could be satisfactorily predicted at various iodide concentrations.

Enhanced Permanganate Oxidation of Sulfamethoxazole and Removal of Dissolved Organics with Biochar: Formation of Highly Oxidative Manganese Intermediate Species and in Situ Activation of Biochar.

Sulfamethoxazole (SMX) is a broad-spectrum antibiotic and was largely used in breeding industry. The reaction rate of SMX with KMnO4 is slow, and the adsorption efficiency of biochar for SMX was inferior (less than 11% in 30 min). By adding biochar powder into SMX solution with the addition of permanganate, the oxidation ratio of SMX surged to 97% in 30 min, and over 58% of the total organic carbon (TOC) was simultaneously removed. KMnO4 interacted with biochar and resulted in the formation of highly oxidative intermediate manganese species, which transformed SMX into hydrolysis products, oxygen-transfer products, and self-coupling products. Brunauer-Emmett-Teller (BET) analysis showed that surface area, total pore volume, and micropore volume of biochar increased by 32.1%, 36.4%, and 80.6%, respectively, after reaction process. This in situ activation of biochar with KMnO4 enhanced its adsorption capacity and led to great improvement of TOC removal. Besides KMnO4 oxidation, biochar also enhanced TOC removal in Mn(III) oxidation (KMnO4+ bisulfite) and ozonization of SMX. Considering that KMnO4 could react with biochar and result in the formation of intermediate manganese species, while biochar can be simultaneously activated and exhibit high capacity for organic adsorption, the combination of biochar with the chemical/advanced oxidation could be a promising process for the removal of environmental pollutants.

Impact of Phosphate on Ferrate Oxidation of Organic Compounds: An Underestimated Oxidant.

Ferrate (K2FeO4) is a powerful oxidant and up to 3 mol of electrons could be captured by 1 mol of ferrate in the theoretical conversion of Fe(VI)-Fe(V)-Fe(IV)-Fe(III). However, it is reported that the utilization efficiency of the ferrate oxidation capacity is quite low because of the rapid autodecomposition of intermediate iron species, which negatively influences the potential of ferrate on organic pollutants control. We accidentally found that for the ferrate oxidation of carbamazepine (CBZ), bisphenol S (BPS), diclofenac (DCF), and ciprofloxacin (CIP), the determined reaction rate constants were 1.7-2.4 times lower in phosphate buffer than those in borate buffer at pH 8.0. For the reaction of ferrate with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) at pH 7.0, the determined reaction stoichiometries were 1:1.04 in 100 mM phosphate buffer, 1:1.18 in 10 mM phosphate buffer, and 1:1.93 in 10 mM borate buffer, respectively. The oxidation ability of ferrate seems depressed in phosphate buffer. A kinetic model involving the oxidation of ABTS by Fe(VI), Fe(V) and Fe(IV) species was developed and fitted the ABTS•+ formation kinetics well under different buffer conditions. The results showed that phosphate exhibited little influence on the oxidation ability of Fe(VI) and Fe(IV) species, but decreased the specific rate constants of ABTS with Fe(V) species by 1-2 orders of magnitude, resulting in the outcompeting of Fe(V) autodecomposition pathway. The complexation between phosphate anions and Fe(V) species may account for the inhibition effect of phosphate buffer. Considering that many studies regarding ferrate oxidation were carried out in phosphate buffer, the actual oxidation ability of ferrate may be underestimated.

[Effects of Shoutai Pill Containing Serum on Bioactivity Behavior of Trophoblast Cells of Spontaneous Abortion Patients].

OBJECTIVE: To explore the effect of Shoutai Pill (STP) containing serum on bioactivity behaviors of trophoblast cells in spontaneous abortion (SA) patients such as cell proliferation, invasion, migration and secretion. METHODS: Trophoblast cells in artificial abortion in normal pregnancy and SA patients were isolated and cultured in vitro, which were then treated with STP containing serum at various concentrations (5%, 10%, 20%, respectively). Blank serum was taken as the normal control group and dydrogesterone containing serum as the dydrogesterone control group. The proliferation, cycle distribution, invasion and migration capacity, and beta human chorionic gonadotropin (p-HCG) level were detected by methyl thiazolyl tetrazolium (MTT) colorimetry, flow cytometry (FCM), Transwell experiments, and ELISA, respectively. RESULTS: Compared with the normal control group, the activity of cell proliferation obviously decreased, ratios of apoptotic cells (SubGO/G1) and G2/M phase were obviously elevated, S phase cell ratio was obviously reduced (all P < 0.05). Transwell experiments indicated invasion and migration capacity obviously decreased, secreted beta-HCG level were obviously reduced after 72-h intervention (P < 0.05). Compared with the SA group, the activity of cell proliferation obviously increased, ratios of apoptotic cells and G2/M phase were obviously reduced, S phase cell ratio was obviously elevated, invasion and migration capacity were obviously enhanced, secreted beta-HCG level were obviously elevated after 72-h intervention in the dydrogesterone control group and each STP containing serum group (all P < 0.05). The activity of trophoblastic cell proliferation, S phase cell ratio, invasion and migration capacity, and secreted beta-HCG level were strengthened along with increased STP containing serum. Besides, the effects of 20% STP containing serum group were significantly superior to those of the dydrogesterone control group (P < 0.05). CONCLUSION: STP containing serum could dose-dependently enhance the proliferative activity of trophoblastic cells, invasion and migration capacity, secretion of beta-HCG, and reduce the apoptosis of trophoblast cells, which might be one of mechanisms for STP preventing and treating SA.

High efficiency removal of organic and inorganic iodine with ferrate[Fe(VI)] through oxidation and adsorption.

I- is a halogen species existing in natural waters, and the transformation of organic and inorganic iodine in natural and artificial processes would impact the quality of drinking water. Herein, it was found that Fe(VI) could oxidize organic and inorganic iodine to IO3-and simultaneously remove the resulted IO3- through Fe(III) particles. For the river water, wastewater treatment plant (WWTP) effluent, and shale gas wastewater treated by 5 mg/L of Fe(VI) (as Fe), around 63 %, 55 % and 71 % of total iodine (total-I) had been removed within 10 min, respectively. Fe(VI) was superior to coagulants in removing organic and inorganic iodine from the source water. Adsorption kinetic analysis suggested that the equilibrium adsorption amount of I- and IO3- were 11 and 10.1 µg/mg, respectively, and the maximum adsorption capacity of IO3- by Fe(VI) resulted Fe(III) particles was as high as 514.7 µg/mg. The heterogeneous transformation of Fe(VI) into Fe(III) effectively improved the interaction probability of IO3- with iron species. Density functional theory (DFT) calculation suggested that the IO3- was mainly adsorbed in the cavity (between the γ-FeOOH shell and γ-Fe2O3 core) of Fe(III) particles through electrostatic adsorption, van der Waals force and hydrogen bond. Fe(VI) treatment is effective for inhibiting the formation of iodinated disinfection by-products in chlor(am)inated source water.

Effects of Acupuncture on Endometrium and Pregnancy Outcomes in Patients with Polycystic Ovarian Syndrome Undergoing in vitro Fertilization-Embryo Transfer: A Randomized Clinical Trial.

OBJECTIVE: To observe the effect of acupuncture on endometrium and pregnancy outcomes in patients with polycystic ovary syndrome (PCOS) infertility undergoing in vitro fertilization-embryo transfer (IVF-ET). METHODS: Eighty-three patients were randomly assigned to observation group (40 cases) and control group (43 cases) according to the random numbers generated by SPSS software. The patients of the two groups received GnRH agonist long protocol as a routine treatment. In the observation group, acupuncture was given at two acupoint groups for 30 min once every other day. Group 1 included Guanyuan (CV 4), Qihai (CV 6), Zhongji (CV 3), bilateral acupoints Zigong (EX-CA1). Group 2 included Mingmen (GV 4), Yaoyangguan (GV 3), bilateral Shenshu (BL 23) and Ciliao (BL 32). The two groups of acupoints were used alternately. The whole needling process was performed at the time of ovulation induction until the transplantation day and consisted of 3 courses, while the control group did not receive acupuncture interventions. The Gn dosage and Gn stimulation time, endometrial thickness and type (A, B, and C), serum oestradiol (E2) and progesterone (P) levels on the day of injection of human chorionic gonadotropin (hCG), clinical pregnancy rate, as well as live birth rate were observed. Adverse reactions were also be recorded. All patients were followed up for the pregnant rate 14 days after IVF-ET and live birth rate after pregnancy. All adverse reactions (AEs) of acupuncture were recorded during the trial. RESULTS: The Gn dosage and Gn stimulation time in the observation group were lower in the observation group than in the control group (P<0.01). The proportion of type A endometrium in the observation group were higher than that in the control group (P<0.05). The serum E2 and P levels on the day of hCG injection was lower and the clinical pregnancy rate was higher in the observation group compared to those in the control group (P<0.05). There was no serious AEs during this trial. CONCLUSION: Acupuncture can improve the proportion of type A endometrium, regulate the levels of serum E2 and P on the day of hCG injection, and improve the pregnancy rate in patients with PCOS infertility undergoing IVF-ET.

Formation of iodinated aromatic DBPs at different molar ratios of chlorine and nitrogen in iodide-containing water.

Variations in iodinated aromatic disinfection byproducts (DBPs) in the presence of I- and organic compounds as a function of reaction time in different molar ratios (MRs) of HOCl:NH3-N were investigated. Up to 17 kinds of iodinated aromatic DBPs were identified in the breakpoint chlorination of iodide (I-)/organic (phenol, bisphenol S (BPS) and p-nitrophenol (p-NP)) systems, and the possible pathways for the formation of iodinated aromatic DBPs were proposed. The reaction pathways include HOCl/HOI electrophilic substitution and oxidation, while the dominant iodinated DBPs were quantified. In the I-/phenol system (pH = 7.0), the sum of the concentrations of four iodinated aliphatic DBPs ranged from 0.32 to 1.04 µM (triiodomethane (TIM), dichloroiodomethane (DCIM), diiodochloromethane (DICM) and monoiodoacetic acid (MIAA)), while the concentration of 4-iodophenol ranged from 2.99 to 12.87 µM. The concentration of iodinated aromatic DBPs remained stable with an MR = 1:1. When the MR was 6:1, iodinated aromatic DBPs decreased with increasing reaction time, in which the main disinfectant in the system was active chlorine. This study proposed the formation mechanism of iodinated aromatic DBPs during the breakpoint chlorination of iodide-containing water. These results can be used to control the formation of hazardous iodinated aromatic DBPs in the disinfection of iodine containing water.

The position of the posterolateral bundle femoral tunnel during arthroscopic double-bundle anterior cruciate ligament reconstruction: a cadaveric study.

PURPOSE: The purpose was to find a simple guideline to help establish accurate positioning of the posterolateral bundle (PLB) femoral bone tunnel during double-bundle anterior cruciate ligament reconstruction by measuring the distance between the center of the PLB femoral footprint to the shallow and the deep articular cartilage borders of the lateral wall of the intercondylar notch. METHODS: The femoral insertions of the anteromedial bundle and PLB of the anterior cruciate ligament were dissected in 22 male cadaveric knees, aged 25 to 45 years. By use of the intercondylar notch as the landmark, the distances between the center of the PLB femoral footprint and the shallow and the deep articular cartilage borders of the lateral wall of the intercondylar notch were measured with the knees flexed at 90°. The measured data (mean ± standard deviation) were evaluated and compared. RESULTS: The center of the PLB was positioned 8.60 ± 1.52 mm and 8.65 ± 1.54 mm from the shallow and the deep cartilage borders of the lateral wall of the intercondylar notch, respectively (P = .95). The distance between the center of the PLB footprint to the low cartilage border of the lateral intercondylar wall was 5.05 ± 0.76 mm. CONCLUSIONS: The findings suggest that the position of the center of the PLB femoral footprint is at the middle of the line joining the shallow and the deep borders of the femoral cartilage. CLINICAL RELEVANCE: Surgeons can use our results as a guideline and use the PLB footprint remnant as a reference at the same time to locate the femoral PLB tunnel in a simple, easy, and repeatable way.

[Preliminary report on lateral ulnar collateral ligament reconstruction or repair for treatment of posterolateral rotatory instability of elbow].

OBJECTIVE: To explore the preliminary results of lateral ulnar collateral ligament (LUCL) reconstruction or repair for posterolateral rotatory instability (PLRI) of elbow. METHODS: Between December 2006 and September 2010, 9 consecutive patients (9 elbows) undergoing surgical reconstruction or repair of LUCL for the treatment of elbow PLRI were studied. Surgical reconstruction of LUCL was performed with a tendon graft in 6 elbows and reattachment of LUCL to humerus in 3. The mean patient age was 28 years (range: 17 - 48). All patients had a previous history of elbow injury. Among them, 6 had a history of elbow dislocation. The average duration of symptoms was 10.7 months (range: 5 days - 30 months). The outcomes were graded with respects to objective and subjective stability, pain and range of motion as defined by Nestor. RESULTS: All patients were followed up. The mean follow-up period was 20 months (range: 4 - 49). Postoperatively, no patient had residual instability or a positive pivot shift test in elbow. Their outcomes were graded as excellent (n = 6), good (n = 2) and fair (n = 1). Subjective assessment revealed that all were satisfied with their surgical outcomes. CONCLUSION: An accurate recognition of PLRI of elbow is important for its appropriate management. Tendon graft is recommended for the reconstruction of LUCL. Surgical ligament reconstruction or repair is the preferred treatment option for restoring normal functions and elbow stability. Further studies are warranted because of a limited number of patients in the present study.

Chlorination decreases acute toxicity of iodophenols through the formation of iodate and chlorinated aliphatic disinfection byproducts.

Highly toxic iodinated phenolic by-products were frequently detected in the oxidative treatment and disinfection of iodine-containing water. Herein, it was found that three model iodinated phenolic disinfection byproducts (DBPs), 2-iodophenol, 4-iodophenol and 2,4,6-triiodophenol, were reactive with HOCl, and the reaction rate constants (at pH 7.0 and 25℃) were 1.86 ×102, 1.62 ×102 and 7.5 ×101 M-1s-1, respectively. When HOCl was in excess (HOCl/iodophenol = 40/1, [iodophenol]0 = 20 µM), acute toxicity of water sample containing iodophenols could be largely eliminated (> 85%), with the conversion of iodophenols into stable and non-toxic iodate (IO3-) and iodinated and chlorinated aliphatic DBPs. Besides IO3-, seven kinds of aromatic intermediate products including iodophenols, chloroiodophenols, iodoquinones, chloroiodoquinones, chloroquinones, chlorophenols, and coupling products were detected. C-I bond of iodophenols was cleaved in the reaction and the resulted aromatic products were further transformed into chlorinated aliphatic DBPs [trichloromethane (TCM), trichloroacetic acid (TCAA), dichloroacetic acid (DCAA), and chloral hydrate (CH)] (mg/L level) and iodinated trihalomethanes (µg/L level). HOCl was effective for converting iodophenols into IO3- and less toxic chlorinated aliphatic DBPs. Considering that chlorine was widely used as disinfectant, transformation and toxicity alteration of emerging DBPs during chlorination/booster chlorination warrant further investigations.

Effect of ferrate pre-oxidation on algae-laden water ultrafiltration: Attenuating membrane fouling and decreasing formation potential of disinfection byproducts.

Effect of ferrate [Fe(VI)] pre-oxidation on improving FeCl3/ultrafiltration (UF) of algae-laden source water was investigated. Fe(VI) disrupted algae cells and the in situ formed ferric (hydr)oxides aggregated with cell debris. Particle size and zeta potential of algae increased by 20% and 55% on average, respectively, after treatment with 0.02 mM of Fe(VI). These variations facilitated the formation of algae-ferric floc. Fe(VI) degraded algal extracellular organic matter into lower molecular weight products (fulvic-like and humic-like substances). Membrane flux, reversible membrane resistance (Rr) and irreversible membrane resistance (Rir) were improved by 51%, 61%, and 52% in Fe(VI) (0.02 mM)/FeCl3/UF treatment group compared with FeCl3/UF treatment after three filtration cycles. Fe(VI)/FeCl3/UF removed more than 10% ~ 34% of the dissolved organic compounds (DOC) and 6% ~ 17% of the total nitrogen (TN) compared with FeCl3/UF. Due to the enhanced removal of DOC and TN, formation potential of 12 kinds of carbonaceous-disinfection byproducts (C-DBPs) and 7 kinds of nitrogenous-disinfection byproducts (N-DBPs) decreased by 32.5% and 22.5%, respectively. Fe(VI) pre-oxidant was effective for alleviating membrane fouling and reducing formation potential of DBPs in algal laden water treatment.

Ferrate self-decomposition in water is also a self-activation process: Role of Fe(V) species and enhancement with Fe(III) in methyl phenyl sulfoxide oxidation by excess ferrate.

To reveal the role of ferrate self-decomposition and the fates of intermediate iron species [Fe(V)/Fe(IV) species] during ferrate oxidation, the reaction between ferrate and methyl phenyl sulfoxide (PMSO) at pH 7.0 was investigated as a model system in this study. Interestingly, the apparent second-order rate constants (kapp) between ferrate and PMSO was found to increase with ferrate dosage in the condition of excess ferrate in borate buffer. This ferrate dosage effect was diminished greatly in the condition of excess PMSO where ferrate self-decomposition was lessened largely, or counterbalanced by adding a strong complexing ligand (e.g. pyrophosphate) to sequester Fe(V) oxidation, demonstrating that the Fe(V) species derived from ferrate self-decomposition plays an important role in PMSO oxidation. A mechanistic kinetics model involving the ferrate self-decomposition and PMSO oxidation by Fe(VI), Fe(V) and Fe(IV) species was then developed and validated. The modeling results show that up to 99% of the PMSO oxidation was contributed by the ferrate self-decomposition resultant Fe(V) species in borate buffer, revealing that ferrate self-decomposition is also a self-activation process. The direct Fe(VI) oxidation of PMSO was impervious to presence of phosphate or Fe(III), while the Fe(V) oxidation pathway was strongly inhibited by phosphate complexation or enhanced with Fe(III). Similar ferrate dosage effect and its counterbalance by pyrophosphate as well as the Fe(III) enhancement were also observed in ferrate oxidation of micropollutants like carbamazepine, diclofenac and sulfamethoxazole, implying the general role of Fe(V) and promising Fe(III) enhancement during ferrate oxidation of micropollutants.

Straw biochar enhanced removal of heavy metal by ferrate.

This study demonstrated that As(III) was appreciably removed by ferrate in the presence of straw biochar. Removal efficiency of As in ferrate/biochar system was over 91%, increased by 34% compared with ferrate alone ([biochar]0 = 10 mg/L, [ferrate]0 = 6 mg/L, [As(III)]0 = 200 µg/L). In the reaction process, As(III) was oxidized to As(V) mainly by ferrate, while ferrate was reduced into ferric (hydr)oxides and coated on the biochar. Biochar was oxidized in the reaction and its surface area, pore volume and the amount of Lewis acid functional groups were substantially improved, which provided interaction sites for As adsorption. Analysis of hydrodynamic diameter and zeta potential revealed that biochar interacted with the ferrate resulted ferric oxides and enlarged the Fe-C-As particle/floc, which promoted their settlement and thus the liquid-solid separation of As. As(V) was adsorbed on the surface of biochar and ferric (hydr)oxides through hydrogen bond, electrostatic attraction and As-(OFe) bond. Ferrate/biochar was not only effective for As removal, but removed 73.31% of As, 50.38% of Cd, and 75.27% of Tl when these hazardous species synchronously existed in polluted water (initial content: As, 100 µg/L; Cd, 50 µg/L; Tl, 1 µg/L). The combination of ferrate with biochar has potential for the remediation of hazardous species polluted water.

Heterogeneous catalytic ozonation of atrazine with Mn-loaded and Fe-loaded biochar.

After reaction with permanganate or ferrate, the resulted Mn-loaded and Fe-loaded biochar (MnOx/biochar and FeOx/biochar) exhibited excellent catalytic ozonation activity. O3 (2.5 mg/L) eliminated 48% of atrazine (ATZ, 5 µM) within 30 min at pH 7.0, while under identical conditions, ozonation efficiency of ATZ increased to 83% and 100% in MnOx/biochar and FeOx/biochar (20 mg/L) heterogeneous catalytic systems, respectively. Radical scavenger experiment and electron paramagnetic resonance (EPR) analysis confirmed that hydroxyl radical (•OH) was the dominant oxidant. Total Lewis acid sites on MnOx/biochar and FeOx/biochar were 3.5 and 4.1 times of that on the raw biochar, which induced enhanced adsorption of O3 and its subsequent decomposition into •OH. Electron transfer via redox pairs on MnOx/biochar and FeOx/biochar was observed by cyclic voltammetry scans, which also functioned in the improved catalytic capacity. Degradation pathways of ATZ in MnOx/biochar and FeOx/biochar ozonation systems were proposed, with 34.6% and 44.8% of dechlorination effect accomplished within 30 min of reaction, which was improved by 4.1 and 5.3 times compared to pure ozonation. After 12-hour treatment, acute toxicity of ATZ oxidation products was reduced from 38.3% of pure ozonation system to 14.5% and 6.3% of activated ozonation systems with MnOx/biochar and FeOx/biochar, respectively. Mn-loaded biochar and Fe-loaded biochar have great potential for heterogeneous catalytic ozonation of polluted water.

Overlooked enhancement of chloride ion on the transformation of reactive species in peroxymonosulfate/Fe(II)/NH2OH system.

Though hydroxylamine (NH2OH) is effective for accelerating pollutants degradation in Fenton and Fenton-like systems, the effect of anions simultaneously introduced by the hydroxylamine salts have always been ignored. Herein, effect of two commonly used hydroxylamine salts, hydroxylamine hydrochloride (NH2OH·HCl) and hydroxylamine sulfate [(NH2OH)2·H2SO4], for the degradation of dimethyl phthalate (DMP) in peroxymonosulfate (PMS)/Fe(II) system was comparatively investigated. Degradation efficiency of DMP with NH2OH·HCl was 1.6 times of that with same dosages of (NH2OH)2·H2SO4. SO4·-, Fe(IV) and ·OH formed in the PMS/Fe(II)/NH2OH system, but ·OH was the major species for DMP degradation. Addition of Cl- significantly improved the production of ·OH and Cl·, and the exposure dose of ·OH (CT·OH) was more than 10 times that of CTCl· as the concentration of Cl- increased to 1 mM. Calculations based on branching ratios of Cl· and ·OH indicated that the reactions of Cl- with SO4·- and Cl· with H2O were not the only production sources of ·OH in the system. Further experiments with methyl phenyl sulfoxide (PMSO) as the probe indicated that Cl- would facilitate the shift of reactive species from Fe(IV) to radicals (SO4·- or ·OH) in the system. Both hydroxylation and nitration intermediate products were detected in the oxidation of DMP. Cl- promoted the formation of hydroxylation intermediates and reduced the formation of nitration intermediates. This study revealed for the first time that Cl- could shift reactive species from Fe(IV) to radicals in PMS/Fe(II) system, raising attention to the influence of the coexisting anions (especially Cl-) for pollutants oxidation in iron-related oxidation processes.