Potassium Ferrate Research Articles

Sludge reduction and microbial community structure in an anaerobic/anoxic/oxic process coupled with potassium ferrate disintegration

An anaerobic/anoxic/oxic (AAO) wastewater treatment system combining with a potassium ferrate (K2FeO4) oxidation side-stream reactor (SSR) was proposed for sludge reduction. Batch experiments showed that optimal K2FeO4 dosage and reaction time for sludge disintegration was 100mg/g suspended solids (SS) and 24h, respectively. Subsequently, an AAO-SSR and a conventional AAO were operated in parallel to investigate effects of K2FeO4 oxidation on process performance, sludge characteristics and microbial community structures. The AAO-SSR process operated under the optimized condition achieved efficient COD and NH4+-N removal, and reduced sludge by 47.5% with observed yield coefficient of 0.21gSS/g COD. K2FeO4 addition broke sludge particles, increased dissolved organic matters in the mixed liquor, and improved sludge dewaterability. Illumina-MiSeq sequencing results showed that K2FeO4 oxidation in the AAO-SSR decreased microbial richness and diversity, enriched slow growers (Dechloromonas), anaerobic fermentative bacteria (Azospira) and Fe(III)-reducing bacteria (Ferribacterium), but limited the growth of phosphate-accumulating organisms.

Transformation of substituted anilines by ferrate(VI): Kinetics, pathways, and effect of dissolved organic matter

This study showed that substituted anilines of environmental concerns could be appreciably degraded by potassium ferrate (K2FeO4) in the pH range of 6–10 with apparent second-order rate constants (kapp) varying from 0.32 to 36,500M−1s−1. The pH-dependence rate curves were well fitted via a kinetic model, which involved the formation of intermediates between Fe(VI) and substituted anilines. The plausible degradation pathways were proposed including the generation of aniline radical cations and their further oxidation to nitrobenzene compounds or dimerization to azobenzene compounds. Humic acid (HA) significantly reduced the transformation rates of substituted anilines with Fe(VI) even though considering the effect of oxidant consumption. This suppression effect likely resulted from the reaction between HA and the aniline radical cation, where the aniline radical cation was turned back to parent compound. Meanwhile, it was found that HA also had an impact on the formation kinetics of oxidation products. The effectiveness of Fe(VI) for degradation of substituted anilines in natural water was evaluated, where background matrix constituents could affect both the kinetics of contaminants degradation and products formation, similar to the case of HA. These results have advanced the understanding of Fe(VI) chemistry involved in water and wastewater treatment.

Effect of ferrate on green algae removal.

Green algae Cladophora aegagropila, present in cooling water of thermal power plants, causes many problems and complications, especially during summer. However, algae and its metabolites are rarely eliminated by common removal methods. In this work, the elimination efficiency of electrochemically prepared potassium ferrate(VI) on algae from cooling water was investigated. The influence of experimental parameters, such as Fe(VI) dosage, application time, pH of the system, temperature and hydrodynamics of the solution on removal efficiency, was optimized. This study demonstrates that algae C. aegagropila can be effectively removed from cooling water by ferrate. Application of ferrate(VI) at the optimized dosage and under the suitable conditions (temperature, pH) leads to 100% removal of green algae Cladophora from the system. Environmentally friendly reduction products (Fe(III)) and coagulation properties favour the application of ferrate for the treatment of water contaminated with studied microorganisms compared to other methods such as chlorination and use of permanganate, where harmful products are produced.

Trials of Treating Decentralized Domestic Sewage from a Residential Area by Potassium Ferrate(VI)

The present study aims to investigate the performance of potassium ferrate(VI) in treating decentralized domestic sewage from a rural scattered residential area. Major results were that around 90% of total phosphorus (TP) and 40% of chemical oxygen demand (COD) could be reduced when 25 mg L−1 of ferrate(VI) was applied. The removal of ammonia and total nitrogen (NH3–N and TN) was also monitored. However, the nitrogen removal during the chemical dosing was rather low. Big fluctuations of removal rates were observed against shock pollutants concentrations. Considering its strong ability in removing emerging organic pollutants and P, ferrate(VI) is competitive in the treatment of decentralized domestic sewage as an advanced treatment unit following some traditional treatment units.

Degradation of anti-inflammatory drug diclofenac in sewage water

Abstract In recent years, interest in the presence of chemical and biological pollutants (drugs, pesticides, heavy metals etc.) in sewage water has been permanently increasing and, at the same time, significant effort to eliminate them has been shown. The aim of this work was to investigate the influence of ferrates activity on the decomposition of the drug diclofenac (DCF), which is commonly present in sewage water. The main task is to follow the effect of potassium ferrate dosage on DCF degradation and to evaluate the most effective ferrates concentration in solution. Subsequently, real samples of waste water containing a significant amount of various micro‑pollutants were treated by the same amount of ferrates as laboratory samples. High-performance liquid chromatography (HPLC) was used for the sample analysis. Ferrates removal effectiveness was determined by comparing the chromatographic peak areas of residual DCF in the treated samples. Removal efficiency of diclofenac is proportional to the concentration of potassium ferrate in the treated solutions.

Impacts of potassium ferrate(VI) on the growth and organic matter accumulation, production, and structural changes in the cyanobacterium Microcystis aeruginosa.

Cyanobacterial blooms generated by nutrient addition into aquatic systems pose serious risks to ecosystems and human health. Though there are established chemical, physical, and biological means of eradication, more efficient and environmentally friendly measures are desired. This study investigates the effect of potassium ferrate(VI) on the growth and intracellular and extracellular organic matter accumulations of the cyanobacterium Microcystis aeruginosa. Cultures were inoculated with three separate concentrations of potassium ferrate(VI) (3, 15, 30mgL-1) and monitored by measuring chlorophyll-a (Chl-a) and intracellular/extracellular dissolved organic carbon. Results show that ferrate(VI) addition effectively removed the microalgae from the medium, as indicated by the reduction of Chl-a. Organic matter accumulation of the microalgae was also affected by ferrate(VI) treatment; fluorescence EEM spectra show details of changing intracellular dissolved organic matter (IDOM) and extracellular dissolved organic matter (EDOM). A new peak appeared in the EDOM indicating altered humic and proteinaceous compounds. This study demonstrates that ferrate(VI) is a potential treatment for the water contaminated with the toxic microalgae M. aeruginosa.

Degradation of chloramphenicol by potassium ferrate (VI) oxidation: kinetics and products

The oxidation of chloramphenicol (CAP) by potassium ferrate (VI) in test solution was studied in this paper. A series of jar tests were performed at bench scale with pH of 5-9 and molar ratio [VI/CAP] of 16.3:1-81.6:1. Results showed that raising VI dose could improve the treatment performance and the influence of solution pH was significant. VI is more reactive in neutral conditions, presenting the highest removal efficiency of CAP. The rate law for the oxidation of CAP by VI was first order with respect to each reactant, yielding an overall second-order reaction. Furthermore, five oxidation products were observed during CAP oxidation by VI. Results revealed that VI attacked the amide group of CAP, leading to the cleavage of the group, while benzene ring remained intact.

Comparison of coagulation, ozone and ferrate treatment processes for color, COD and toxicity removal from complex textile wastewater.

In this study, the comparative performance of coagulation, ozone, coagulation + ozone + coagulation and potassium ferrate processes to remove chemical oxygen demand (COD), color, and toxicity from a highly polluted textile wastewater were evaluated. Experimental results showed that ferrate alone had no effect on COD, color and toxicity removal. Whereas, in combination with FeSO4, it has shown the highest removal efficiency of 96.5%, 83% and 75% for respective parameters at the optimal dose of 40 mgL-1 + 3 ml FeSO4 (1 M) in comparison with other processes. A seed germination test using seeds of Spinach (Spinacia oleracea) also indicated that ferrate was more effective in removing toxicity from contaminated textile wastewater. Potassium ferrate also produces less sludge with maximum contaminant removal, thereby making the process more economically feasible. Fourier transform infrared spectroscopy (FTIR) analysis also shows the cleavage of the chromophore group and degradation of textile wastewater during chemical and oxidation treatment processes.

Effect of Combined Freeze-Thaw and Ferrate(VI) Treatments on Escherichia coli in Phosphate-Buffered Saline

AbstractThe study examined the individual and combined effects of potassium ferrate(VI) and freeze-thaw treatment for the inactivation of Escherichia coli (E. coli) in a phosphate buffered saline (...

Ferrrate(VI) and freeze-thaw treatment for oxidation of hormones and inactivation of fecal coliforms in sludge.

This study examined the individual and combined effects of potassium ferrate(VI) additions and freeze-thaw conditioning for the treatment and dewatering of wastewater sludge in cold climates, with particular focus on the inactivation of fecal coliforms and oxidation of estrogens, androgens, and progestogens. The first phase of the study evaluated the effects of potassium ferrate(VI) pre-treatment followed by freeze-thaw at -20 °C using a low (0.5 g/L) and high (5.0 g/L) dose of potassium ferrate(VI). The results showed that pre-treatment of anaerobically digested sludge with 5 g/L of potassium ferrate(VI) reduced the concentration of fecal coliforms in the sludge cake to below 100 MPN/g DS. The second phase evaluated the ability of ferrate(VI) to oxidise selected hormones in sludge. Anaerobically digested sludge samples were spiked with 10 different hormones: estrone (E1), 17α-estradiol, 17β-estradiol (E2), estriol (E3), 17α-ethinylestradiol (EE2), equilin, mestranol, testosterone, norethindrone and norgestrel in two groups of low (3-75 ng/mL) and high (12-300 ng/L) concentration ranges of hormones. The samples were treated with either 0.5 or 1.0 g/L of potassium ferrate(VI), and hormone concentrations were measured again after treatment. Potassium ferrate(VI) additions as low as 1.0 g/L reduced the concentration of estrogens in sludge. Potassium ferrate(VI) additions of 0.5 and 1.0 g/L were less effective at reducing the concentrations of androgens and progestogens. Increasing ferrate(VI) dose would likely result in more substantial decreases in the concentrations of fecal coliforms and hormones. The results of this study indicate that the combined use of freeze-thaw and ferrate(VI) has the potential to provide a complete sludge treatment solution in cold regions.

SONO-OXIDATIVE PRE-TREATMENT OF WASTE ACTIVATED SLUDGE BEFORE ANAEROBIC BIODEGRADATION

Abstract The effects of sonication, potassium ferrate (K2FeO4) oxidation and their simultaneous combination (called pre-treatment) on chemical properties and anaerobic digestion of waste activated sludge (WAS) were investigated and compared comprehensively. Based on chemical parameters, the optimum operating conditions were found to be 0.3 g K2FeO4/g total solids (TS) dosage for 2-h individual K2FeO4 oxidation, 0.50 W/mL ultrasonic power density for 10-min individual sonication and, lastly, the combination of 2.5-min sonication at 0.75 W/mL ultrasonic power density with 2-h chemical oxidation at 0.3 g K2FeO4/g TS dosage for sono-oxidative pre-treatment. The disintegration efficiencies of these methods under the optimized conditions were in the following descending order: 37.8% for sono-oxidative pre-treatment > 26.3% for sonication > 13.1% for K2FeO4 oxidation. The influences of these methods on anaerobic biodegradability were tested with the biochemical methane potential assay. It was seen that the cumulative methane production increased by 9.2% in the K2FeO4 oxidation reactor, 15.8% in the sonicated reactor and 18.6% in the reactor with sono-oxidative pre-treatment, compared to the control (untreated) reactor.

Oxidation of L-alanine by Potassium Ferrate (VI) in Alkaline Media-Kinetics and Mechanism Study

Oxidation of L-alanine by Potassium Ferrate (VI) in Alkaline Media-Kinetics and Mechanism Study

Removal of pharmaceuticals by a potassium ferrate(vi) material: from practical implementation to reactivity prediction

A ferrate(vi) material was used to treat a hospital effluent. Experimental measurements and calculations of the first ionization energies of pharmaceuticals were correlated to explain the oxidation selectivity of ferrate.

Decolorization of reactive orange 16 via ferrate(VI) oxidation assisted by sonication

The decolorization of azo dye C.I. reactive orange 16 (RO 16) via ferrate(VI) and sono-ferrate(VI) methods, which is the combination of the ferrate(VI) oxidation method with sonication, has been achieved in the present study. The influences of some important operating parameters, which are the initial pH, the concentration of potassium ferrate(VI) (K$_{2}$FeO$_{4})$ and the RO 16 dye, and ultrasonic density (for only the sono-ferrate(VI) method), on the color removal have been investigated. The optimum conditions have been determined as pH = 7 and [K$_{2}$FeO$_{4}$] = 50 mg L$^{-1}$ for the individual ferrate(VI) oxidation method and pH = 7 and [K$_{2}$FeO$_{4}$] = 50 mg L$^{-1}$ by direct sonication at 0.50 W mL$^{-1}$ ultrasonic density and 20 kHz fixed frequency for the sono-ferrate(VI) method. The color removal efficiencies were 85% by ferrate(VI) method and 91% by sono-ferrate(VI) method. Kinetic studies were also performed for the decolorization of RO 16 under the optimized conditions at room temperature. It was seen that the oxidative decolorization of RO 16 via the sono-ferrate(VI) method happened more rapidly because of the production of OH$^{\bullet }$ radical through sonication compared to the individual ferrate(VI) method.

In situ chemical oxidation of BTEX and MTBE by ferrate: pH dependence and stability

Gasoline spills from underground storage tanks are a worldwide environmental problem. BTEX and MtBE are the compounds of gasoline that present the highest degree of migration due to their chemical properties, and are therefore able to impact groundwater reservoirs. In situ chemical oxidation (ISCO) is an emerging technology for groundwater remediation. Several compounds such as permanganate and hydrogen peroxide among others have been used as oxidants, a strong impact of pH on the relative stabilities and reduction potentials having been in each case determined. This paper presents a study of stability and degradation of BTEX and MtBE at different pH ranges of a novel oxidant for ISCO, potassium ferrate (K2FeO4). To carry out this study, BTEX and MtBE solutions were prepared in different phosphate buffers (pH 5,8; 7; 9; 10 and 11) in concentration ratio of (FeO4−2)/(BTEX+MtBE)=100:1. Each solution was analyzed at different times by gas chromatography with photoionization and tandem mass spectrometer detector. The results show a higher degree of degradation at pH 7 for Benzene and Toluene, and at pH 9 for Ethyl benzene and Xylenes, while MtBE proved recalcitrant to degradation by ferrate. The most favorable pH for stability of FeO4−2 solution was confirmed in 9–10.

Evaluation of the properties of potassium ferrate used for water purification by luminescence bioassay

Characteristics of four natural water samples from urban and rural areas and the efficiency of a new purifying agent, potassium ferrate K2FeO4, were studied by bacterial luminescence bioassay for 30 minutes. It was revealed that two samples of water from the urban areas are toxic, while the other two samples (one from urban and one from rural environment) are nontoxic. Numerous data obtained on the increase in toxicity index with time allow reasonable conclusions to be made about the chemical nature of substances present in the test water samples. Toxic natural water samples were likely to contain heavy metals and were well purified using potassium ferrate, including via their adsorption. In nontoxic natural water samples, toxic complexes with organic compounds present in water could form at the addition of potassium ferrate. The obtained data call for further studying the properties of potassium ferrate complexes with organic compounds. Bacterial luminescence bioassay is a promising method for the rapid assessment of properties of various water sources (their integral toxicity and presumable chemical composition) and new reagents for their purification (effective concentrations, bactericidal properties, and mechanisms of interacting with heavy metals and organic substances in water).

Positive and negative electrospray ionization analyses of the organic fractions in raw and oxidized oil sands process-affected water

This work investigated the oxidative transformation of the organic species in oil sands process-affected water (OSPW) using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) in both negative and positive electrospray ionization (ESI) modes. This is the first time to apply FTICR-MS to investigate species transformation in OSPW treatments by ferrate (VI), UV/H2O2, and molecular ozone, and also this is the first preliminary study to use positive ESI to investigate organic species in addition to naphthenic acids (NAs) in these treatment processes. The oxidation processes with potassium ferrate (VI), UV/H2O2, and ozone transformed the distribution profiles of Ox, OxSy, and OxNy organic fractions (i.e., species containing oxygen, sulfur, and nitrogen, with x, y specifying the oxygen number and sulfur/nitrogen number, respectively), with OxSy distribution profiles showing the most sensitive responses to the oxidation extent and can be used as a signature fraction to evaluate the oxidation effectiveness. Negative mode UPLC-TOF-MS confirmed the transformation pattern of Ox species observed with FTICR-MS, but positive mode UPLC-TOF-MS results showed severe discrepancies with FTICR-MS results and should be subjected for future further investigation, regarding the relatively low mass resolution of UPLC-TOF-MS. The investigation of the transformation patterns of different organic species using two ionization modes was a preliminary study to enhance the understanding of the efficiency, selectivity, and mechanism of different oxidation processes in OSPW remediation for both NAs and non-NA species.

Oxidation of benzyl alcohol by K2FeO4 to benzaldehyde over zeolites

A novel and green procedure for benzaldehyde synthesis by potassium ferrate oxidation of benzyl alcohol employing zeolite catalysts was studied. The prepared oxidant was characterized by SEM and XRD. The catalytic activity of various solid catalysts was studied using benzyl alcohol as a model compound. USY was found to be a very efficient catalyst for this particular oxidation process. Benzaldehyde yields up to 96.0% could be obtained at the following optimal conditions: 0.2 mL of benzyl alcohol, 4 mmol of K2FeO4, 0.5 g of USY zeolite; 20 mL of cyclohexene, 0.3 mL of acetic acid (36 wt %), 30°C temperature, 4 h reaction time.

Mechanism of thermal decomposition of K2FeO4 and BaFeO4: A review

This paper presents thermal decomposition of potassium ferrate(VI) (K2FeO4) and barium ferrate(VI) (BaFeO4) in air and nitrogen atmosphere. Mossbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe V and Fe IV as intermediate iron species using the applied techniques are given. Thermal decomposition of K2FeO4 involved Fe V, Fe IV, and K3FeO3 as intermediate species while BaFeO3 (i.e. Fe IV) was the only intermediate species during the decomposition of BaFeO4. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K2FeO4 and BaFeO4 under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.

Individual and Combined Effects of Freeze-Thaw and Ferrate(VI) Oxidation for the Treatment and Dewatering of Wastewater Sludges

The study examined the individual and combined effects of potassium ferrate(VI) additions and freeze-thaw conditioning for the treatment and dewatering of sludge samples. The first part of the experiments, using primary sludge, compared potassium ferrate(VI) additions prior to freeze-thaw treatment (pretreatment) versus potassium ferrate(VI) additions following freeze-thaw treatment (posttreatment). A low dose (LD) of 1.0 g/L and a high dose (HD) of 10.0 g/L of potassium ferrate(VI) were evaluated along with a freezing temperature of −20 °C and freezing periods of 1, 8 and 15 days. Following the designated freezing period, the samples were removed from the freezer and thawed at room temperature for 12 h. The second part of the study, using anaerobically digested sludge, evaluated the effects of potassium ferrate(VI) pretreatment, using LD = 0.5 g/L and HD = 5.0 g/L, and used simulated drainage beds to separate meltwater from the sludge cake during the thawing period. The study demonstrated that stand-alone freeze-thaw can reduce faecal coliform by >3-log after being frozen for only 1 day, and pretreatment with potassium ferrate(VI) can be used to improve the effects of freeze-thaw on faecal coliform inactivation in sludge. Furthermore, the drainability of the sludge following freeze-thaw was not significantly deteriorated when potassium ferrate(VI) was added to the sludge prior to freezing, despite greater than fourfold increases in the concentrations of soluble proteins and soluble carbohydrates. The meltwater collected during the sludge thawing was approximately 85 % of the initial sludge volume. When 5 g/L of potassium ferrate(VI) was added to the sludge prior to freezing, the meltwater collected had <0.28 MPN/mL faecal coliform, the turbidity was <10 NTU and the pH was 9.1. Pretreatment with potassium ferrate(VI) also reduced the concentration of faecal coliform in the sludge cake, suggesting that freeze-thaw coupled with potassium ferrate(VI) additions can be used to stabilise sludge and reduce sludge volume.