Roles of MnO2 Colloids and Mn(III) during the Oxidation of Organic Contaminants by Permanganate.

Although intermediate manganese species can be generated during the reactions of permanganate (Mn(VII)) with organic pollutants in water, the role of the in situ generated MnO2 colloids in the Mn(VII) oxidation process remained controversial and the contribution of Mn(III) was largely neglected. This study showed that the apparent second-order rate constants (kapp) of Mn(VII) oxidation of methyl phenyl sulfoxide and carbamazepine remained constant with time. However, the degradation of four selected phenolic contaminants by Mn(VII) exhibited an autoaccelerating trend and a linear trend at pH 3.0-6.0 and pH 7.0-9.0, respectively. Multiple lines of evidence revealed that the occurrence of the autoaccelerating trend in the Mn(VII) oxidation process was ascribed to the oxidation of the phenolic organics by MnO2 colloids. The influence of pyrophosphate on the oxidation of different organic contaminants by MnO2 colloids suggests that Mn(III) was also responsible for the autoaccelerating oxidation of organic contaminants by Mn(VII) under specific reaction conditions. The kinetic models revealed that the overall contributions of MnO2 colloids and Mn(III) ranged within 6.6-67.9% during the autoaccelerating oxidation of phenolic contaminants by Mn(VII). These findings advance the understanding of the roles of MnO2 colloids and Mn(III) in the Mn(VII) oxidation process.

Naproxen as a Turn-On Chemiluminescent Probe for Real-Time Quantification of Sulfate Radicals.

Current techniques for identifying and quantifying sulfate radicals (SO4·-) in SO4·--based advanced oxidation processes (SR-AOPs) are unsatisfactory due to their low selectivity, poor reliability, and limited feasibility for real-time quantification. In this study, naproxen (NAP) was employed as a turn-on luminescent probe for real-time quantification of SO4·- in SR-AOPs. The chemiluminescence(CL) yield (ΦCL) of the reaction of NAP with SO4·- was first determined to be 1.49 × 10-5 E mol-1 with the bisulfite activation by cerium(IV) [Ce(IV)/BS] process. Then, the maximum peak concentrations of SO4·- in the Ce(IV)/BS-NAP process was quantified to be ∼10-11 M based on the derived equation. Since ΦCL of the reaction of NAP with SO4·- was much greater than that with other reactive oxidizing species (ROS), the developed CL method worked well in selective quantification of SO4·- in various SR-AOPs (e.g., the activation of peroxymonosulfate and persulfate by iron processes). Finally, the electron transfer from NAP to SO4·- was proposed to be the critical step for CL production. This work provides a novel CL method for real-time quantification of SO4·-, which facilitates the development of SR-AOPs and their application in water and wastewater treatment.

Simultaneous Sequestration of Humic Acid-Complexed Pb(II), Zn(II), Cd(II), and As(V) by Sulfidated Zero-Valent Iron: Performance and Stability of Sequestration Products.

Heavy metal(loid)s (HMs) such as Pb(II), Zn(II), Cd(II), and As(V) are ubiquitously present in co-contaminated soil and shallow groundwater, where the humic acid (HA)-rich environments can significantly influence their sequestration. In this study, sulfidated zero-valent iron (S-ZVI) was found to be able to simultaneously sequestrate these HA-complexed HMs. Specially, the HA-complexed Pb(II), Zn(II), Cd(II), and As(V) could be completely removed by S-ZVI within 60 min, while only 35-50% of them could be sequestrated within 72 h by unsulfidated ZVI. Interestingly, different from the S-ZVI corrosion behavior, the kinetics of HM sequestration by S-ZVI consisted of an initial slow reaction stage (or a lag phase) and then a fairly rapid reaction process. Characterization results indicated that forming metal sulfides controlled the HM sequestration at the first stage, whereas the enhanced ZVI corrosion and thus-improved adsorption and/or coprecipitation by iron hydroxides governed the second stage. Both metal-oxygen and metal-sulfur bonds in the solid phase could be confirmed by X-ray photoelectron spectroscopy and extended X-ray absorption fine structure analysis. Moreover, the transformation of S species from SO42-, SO32-, and S22- to S2- under reducing conditions could allow the sequestrated HMs to remain stable over a long period.

Mechanistic Insights into the Markedly Decreased Oxidation Capacity of the Fe(II)/S2O82- Process with Increasing pH.

The poor oxidation capacity of the Fe(II)/S2O82- [Fe(II)/PDS] system at pH > 3.0 has limited its wide application in water treatment. To unravel the underlying mechanism, this study systematically evaluated the possible influencing factors over the pH range of 1.0-8.0 and developed a mathematical model to quantify these effects. Results showed that ∼82% of the generated Fe(IV) could be used for pollutant degradation at pH 1.0, whereas negligible Fe(IV) contribution was observed at pH 7.5. This dramatic decline of Fe(IV) contribution with increasing pH dominantly accounted for the pH-dependent performance of the Fe(II)/PDS process. Unexpectedly, Fe(II) could consume ∼80% of the generated SO4•- non-productively under both acidic and near-neutral conditions, while the larger formation of Fe(III) precipitates at high pH inhibited the SO4•- contribution mildly. Moreover, the strong Fe(II) scavenging effect was difficult to be compensated for by slowing down the Fe(II) dosing rate. The competition of dissolved oxygen with PDS for Fe(II) was insignificant at pH ≤ 7.5, where the second-order rate constants for reactions of Fe(II) with oxygen were much lower than or comparable to that between Fe(II) and PDS. These findings could advance our understanding of the chemistry and application of the Fe(II)/PDS process.

Influence of Pyrophosphate on the Generation of Soluble Mn(III) from Reactions Involving Mn Oxides and Mn(VII).

The detection of soluble Mn(III) is typically accomplished using strong complexing agents to trap Mn(III), but the generation of soluble Mn(III) induced by strong complexing agents has seldom been considered. In this study, pyrophosphate (PP), a nonredox active ligand, was chosen as a typical Mn(III) chelating reagent to study the influence of ligands on soluble Mn(III) formation in reactions involving Mn oxides and Mn(VII). The presence of excess PP induced the generation of soluble Mn(III)-PP from α- and δ-MnO2 and led to the conproportionation reaction of α-, ß-, δ-, or colloidal MnO2 with Mn(II) at pH 7.0. Compared to MnO2 minerals, colloidal MnO2 showed much higher reactivity toward Mn(II) in the presence of PP and the conproportionation rate of colloidal MnO2 with Mn(II) elevated with increasing PP dosage and decreasing pH. The generation of Mn(III) was not observed in MnO4-/S2O32- or MnO4-/NH3OH+ system without PP while the introduction of excess PP induced the generation of Mn(III)-PP. Thermodynamic calculation results were consistent with the experimental observations. These findings not only provide evidence for the unsuitability of using strong ligands in quantification of soluble Mn(III) in manganese-involved redox reactions, but also advance the understanding of soluble Mn(III) generation in aquatic environment.

Overlooked Role of Sulfur-Centered Radicals During Bromate Reduction by Sulfite.

In this work, the kinetics and mechanisms of the reductive removal of BrO3- by sulfite in air atmosphere were determined. BrO3- could be effectively reduced by sulfite at pHini 3.0-6.0, and the reduction rate of BrO3- increased with decreasing pH. The coexisting organic contaminants with electron-rich moieties could be degraded, accompanied with BrO3- reduction by sulfite. The reaction stoichiometries of -Δ[sulfite]/Δ[bromate] were determined to be 3.33 and 15.63 in the absence and presence of O2, respectively. Many lines of evidence verified that the main reactions in the BrO3-/sulfite system in air atmosphere included the reduction of BrO3- to HOBr and its further reduction to Br-, as well as the oxidation of H2SO3 by BrO3- to form SO3·- and its further transformation to SO4·-. Moreover, SO4·- rather than HOBr was determined to be the major active oxidant in the BrO3-/sulfite system. SO3·- played a key role in the over-stoichiometric sulfite consumption because of its rapid reaction with dissolved oxygen. However, the formed SO3·- was further oxidized by BrO3- in the N2 atmosphere. BrO3- reduction by sulfite is an alternative for controlling BrO3- in water treatment because it was effective in real water at pHini ≤ 6.0.

Can multiple harvests of plants improve nitrogen removal from the point-bar soil of lake?

Point bar areas around lakes can provide ecological service functions. For example, plants growing on point bars absorb and remove nutrients from the soil and water. However, if the point-bar plants are unregulated, in the fall and winter, plant debris will decompose, releasing nutrients that then enter the water body and cause eutrophication. Therefore, any harvesting should be managed. But how to harvest plants and how often to harvest them, and there is little research on these. In this study, the point bar at Qingcaosha Reservoir was used to study the effects of three plant harvesting modes (M1: unharvested; M2: one harvest in the fall; and M3: one harvest in summer and one in the fall) on the removal of nitrogen (N) from point-bar soil. The largest amount of N was removed by the plants when the M3 mode was used (26.93 g/m2). However, the M2 mode removed the most N from the soil during the plant growth season (81.62 g/m2), which implied that the nitrification and denitrification effects of soil microorganisms make the largest contribution to N removal from this point-bar soil. The nitrification and denitrification activity of microorganisms was higher for M2 than for M1 and M3 in the following year. Additionally, summer harvesting (M3) had a negative effect on nitrification efficiency in the current season because anaerobic bacteria in the soil significantly increased and nitrifying bacteria significantly decreased after harvesting. However, after a period of recovery, the number of microbial nitrifiers increased again and nitrification activity rose in the following year. The reduction in oxygen supply after harvesting may be the main reason for low nitrification in the current season, but it was beneficial to nitrification and denitrification in the following year because there was luxuriant plant growth. Therefore, when considering both the current season and the following year, harvesting should not be too frequent and one harvest in the fall (M2) led to the largest removal of N from the soil.

Weak magnetic field accelerates chromate removal by zero-valent iron.

Weak magnetic field (WMF) was employed to improve the removal of Cr(VI) by zero-valent iron (ZVI) for the first time. The removal rate of Cr(VI) was elevated by a factor of 1.12-5.89 due to the application of a WMF, and the WMF-induced improvement was more remarkable at higher Cr(VI) concentration and higher pH. Fe2+ was not detected until Cr(VI) was exhausted, and there was a positive correlation between the WMF-induced promotion factor of Cr(VI) removal rate and that of Fe2+ release rate in the absence of Cr(VI) at pH4.0-5.5. These phenomena imply that ZVI corrosion with Fe2+ release was the limiting step in the process of Cr(VI) removal. The superimposed WMF had negligible influence on the apparent activation energy of Cr(VI) removal by ZVI, indicating that WMF accelerated Cr(VI) removal by ZVI but did not change the mechanism. The passive layer formed with WMF was much more porous than without WMF, thereby facilitating mass transport. Therefore, WMF could accelerate ZVI corrosion and alleviate the detrimental effects of the passive layer, resulting in more rapid removal of Cr(VI) by ZVI. Exploiting the magnetic memory of ZVI, a two-stage process consisting of a small reactor with WMF for ZVI magnetization and a large reactor for removing contaminants by magnetized ZVI can be employed as a new method of ZVI-mediated remediation.

Reinvestigation of the role of humic acid in the oxidation of phenols by permanganate.

Humic acid (HA) affects the oxidation of phenolic compounds by permanganate, but the role of HA in the oxidation of phenols by permanganate is far from clear. The mechanisms by which HA influences the oxidation of phenols by permanganate at pH 5.0-9.0 were systematically examined in this study. The presence of HA enhanced the oxidation of phenolic compounds by permanganate at pH ≤7.0, with greater enhancement at lower pH values. The presence of HA facilitated the in situ formation of MnO2, implying the importance of reductive moieties of HA in this reaction. This was supported by the finding that HA preoxidized by ozone showed enhancements in the oxidation of phenols by permanganate at pH 5.0-6.0 smaller than those seen with pristine HA. The good correlation between HA-induced improvement in the oxidation rates of phenols by permanganate and those by preformed colloidal MnO2 at pH 5.0 confirmed that contribution of MnO2 formed in situ for the oxidation of phenols under this condition. The differences in the influence of Na2S2O3 and HA on the oxidation of phenol by permanganate revealed the fact that the continuous generation of fresh MnO2 and stabilization of the MnO2 formed in situ by HA were crucial for the HA-induced enhancement of the oxidation of phenols by permanganate at pH ≤7.0. The consumption of permanganate by HA and the poor oxidation ability of in situ-generated MnO2 under alkaline conditions resulted in the slightly negative effect of HA on the degradation rates of phenols by permanganate at pH >7.0.

Ruthenium nanoparticles supported on CeO2 for catalytic permanganate oxidation of butylparaben.

This study developed a heterogeneous catalytic permanganate oxidation system with ceria supported ruthenium, Ru/CeO2 (0.8‰ as Ru), as catalyst for the first time. The catalytic performance of Ru/CeO2 toward butylparaben (BP) oxidation by permanganate was strongly dependent on its dosage, pH, permanganate concentration and temperature. The presence of 1.0 g L(-1) Ru/CeO2 increased the oxidation rate of BP by permanganate at pH 4.0-8.0 by 3-96 times. The increase in Ru/CeO2 dosage led to a progressive enhancement in the oxidation rate of BP by permanganate at neutral pH. The XANES analysis revealed that (1) Ru was deposited on the surface of CeO2 as Ru(III); (2) Ru(III) was oxidized by permanganate to its higher oxidation state Ru(VI) and Ru(VII), which acted as the co-oxidants in BP oxidation; (3) Ru(VI) and Ru(VII) were reduced by BP to its initial state of Ru(III). Therefore, Ru/CeO2 acted as an electron shuttle in catalytic permanganate oxidation process. LC-MS/MS analysis implied that BP was initially attacked by permanganate or Ru(VI) and Ru(VII) at the aromatic ring, leading to the formation of various hydroxyl-substituted and ring-opening products. Ru/CeO2 could maintain its catalytic activity during the six successive runs. In conclusion, catalyzing permanganate oxidation with Ru/CeO2 is a promising technology for degrading phenolic pollutants in water treatment.

Synergistic effects of nano-sized titanium dioxide and zinc on the photosynthetic capacity and survival of Anabaena sp.

Anabaena sp. was used to examine the toxicity of exposure to a nano-TiO2 suspension, Zn2+ solution, and mixtures of nano-TiO2 and Zn2+ suspensions. Typical chlorophyll fluorescence parameters, including effective quantum yield, photosynthetic efficiency and maximal electron transport rate, were measured by a pulse-amplitude modulated fluorometer. Nano-TiO2 particles exhibited no significant toxicity at concentrations lower than 10.0 mg/L. The 96 h concentration for the 50% maximal effect (EC50) of Zn2+ alone to Anabaena sp. was 0.38 ± 0.004 mg/L. The presence of nano-TiO2 at low concentrations (<1.0 mg/L) significantly enhanced the toxicity of Zn2+ and consequently reduced the EC50 value to 0.29 ± 0.003 mg/L. However, the toxicity of the Zn2+/TiO2 system decreased with increasing nano-TiO2 concentration because of the substantial adsorption of Zn2+ by nano-TiO2. The toxicity curve of the Zn2+/TiO2 system as a function of incremental nano-TiO2 concentrations was parabolic. The toxicity significantly increased at the initial stage, reached its maximum, and then decreased with increasing nano-TiO2 concentration. Hydrodynamic sizes, concentration of nano-TiO2 and Zn2+ loaded nano-TiO2 were the main parameters for synergistic toxicity.

Pre-oxidation with KMnO4 changes extra-cellular organic matter's secretion characteristics to improve algal removal by coagulation with a low dosage of polyaluminium chloride.

Microcystis aeruginosa was used to study the effect of KMnO4 pre-oxidation on algal removal through coagulation with polyaluminium chloride (PAC). KMnO4 pre-oxidation improved the coagulation efficiency of algal at a low dosage of PAC. The optimal KMnO4 feeding period was in the stationary growth phase of Microcystis aeruginosa. KMnO4 traumatized the algal cells and stimulated cellular release of organic matter, contributing to the pool of extra-cellular organic matter (EOM). KMnO4 also decomposed EOM, especially small molecular weight EOM. Lower concentrations of KMnO4, such as 2 mg/L, induced algae cells to produce moderate amounts of new EOM with molecular weights of 11, 280, and 1500 kDa. These relatively large molecules combined easily with PAC, promoting coagulation and removal of algae. High concentrations of KMnO4 lysed algae cells and produced much high-molecular-weight EOM that did not enhance flocculation by PAC at lower dosages.

Enhanced immobilization of lead, cadmium, and arsenic in smelter-contaminated soil by sulfidated zero-valent iron.

Soils contaminated with multiple heavy metal(loid)s (HMs) such as lead (Pb), cadmium (Cd), and arsenic (As) are of great concern in many countries. In this study, taking three lead-zinc smelter soils, the performance of sulfidated zero-valent iron (S-ZVI) toward Pb, Cd, and As immobilization was systemically investigated. Results showed that more than 88% of water-extractable Pb and Cd could be immobilized and transformed into reducible, oxidizable, and/or reducible forms by S-ZVI within 3 h, whereas only 3-56% of them could be immobilized by unsulfidated ZVI even after 72 h. Meanwhile, the phytoavailability of the tested HMs could be effectively reduced by 79% after S-ZVI amendment. More importantly, anoxic/oxic incubation tests revealed that the dissolved concentrations of HMs were much lower in S-ZVI-treated soils than in the untreated or unmodified ZVI-treated soils. Speciation analysis further suggested that unmodified ZVI seemed to reduce the long-term soil stability by changing the residual HMs species to mild-acid soluble and/or reducible ones. In contrast, S-ZVI could effectively alleviate the remobilization of HMs under the changeover of soil redox environments. All these findings indicate that S-ZVI may be a promising amendment for the immobilization of Pb, Cd, and As in smelter-contaminated soil.

Green polyaspartic acid as a novel permanganate activator for enhanced degradation of organic contaminants: Role of reactive Mn(III) species.

Attention has been long focused on enhancing permanganate (Mn(VII)) oxidation capacity for eliminating organic contaminants via generating active manganese intermediates (AMnIs). Nevertheless, limited consideration has been given to the unnecessary consumption of Mn(VII) due to the spontaneous disproportionation of AMnIs during their formation. In this work, we innovatively introduced green polyaspartic acid (PASP) as both reducing and chelating agents to activate Mn(VII) to enhance the oxidation capacity and utilization efficiency of Mn(VII). Multiple lines of evidence suggest that Mn(III), existing as Mn(III)-PASP complex, was generated and dominated the degradation of bisphenol A (BPA) in the Mn(VII)/PASP system. The stabilized Mn(III) species enabled Mn(VII) utilization efficiency in the Mn(VII)/PASP system to be higher than that in Mn(VII) alone. Moreover, the electrophilic Mn(III) species was verified to mainly attack the inclusive benzene ring and isopropyl group to realize BPA oxidation and its toxicity reduction in the Mn(VII)/PASP system. In addition, the Mn(VII)/PASP system showed the potential for selectively oxidizing organic contaminants bearing phenol and aniline moieties in real waters without interference from most of coexisting water matrices. This work brightens an overlooked route to both high oxidation capacity and efficient Mn(VII) utilization in the Mn(VII)-based oxidation processes.

Preparation and application of amino functionalized mesoporous nanofiber membrane via electrospinning for adsorption of Cr3+ from aqueous solution.

Novel amino (-NH2) functionalized mesoporous polyvinyl pyrrolidone (PVP)/SiO2 composite nanofiber membranes were fabricated by a one-step electrospinning method using poly (vinyl alcohol) and tetraethyl orthosilicate (TEOS) mixed with cationic surfactant, cetyltrimethyl ammonium bromide (CTAB) as the structure directing agent. Ureidopropyltriethoxysilane was used for functionalization of the internal pore surfaces. The membranes were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), element analyzer and N2 adsorption-desorption isotherms. The nanofiber diameters, average pore diameters and surface areas were 100-700 nm, 2.86 nm and 873.62 m2/g, respectively. These mesoporous membranes functionalized with -NH2 groups exhibited very high adsorptions properties based on the adsorption of Cr3+ from an aqueous solution. Equilibrium adsorption was achieved after approximately 20 min and more than 97% of chromium ions in the solution were removed. The membrane could be regenerated through acidification.

[Investigation of the Performance of Organic Contaminant Degradation by Fe2+/PDS Under Environmentally Relevant pH Conditions].

Peroxydisulfate (PDS) activation by Fe2+ has proven to be a promising method to abate emerging organic contaminants by generating reactive oxidation species. Nevertheless, this process may only achieve good decontamination performance under acidic conditions, which has markedly limited its application in real practice. To address this issue, we comprehensively investigated the performance of the Fe2+/PDS process toward some probe contaminants at different pH levels and explored the potential change in reactive oxidative species and the influence of oxygen. Both SO4-· and Fe(Ⅳ) were identified to be involved in the Fe2+/PDS process, and the types of these oxidative species did not change with varying pH values. Although dissolved oxygen could compete with PDS for Fe2+, especially at high pH values, this competition process was not the major reason for the declined performance of the Fe2+/PDS process, since 37.6%-100% of PDS could also be activated with the presence of oxygen. Instead, the overdosing of Fe2+could greatly inhibit carbamazepine removal, indicating that the nonproductive consumption of reactive oxidants by Fe2+should account for the declined performance of Fe2+/PDS under environmentally relevant pH conditions. Accordingly, the feasibility of applying zero-valent iron and sulfidated zero-valent iron was further evaluated, and the formation of corrosion products was characterized using X-ray absorption fine structure spectroscopy. All these findings will improve our understanding about the Fe2+/PDS process and thus facilitate its application.

Abiotic reductive removal of organic contaminants catalyzed by carbon materials: A short review.

Since the observation that carbon materials can facilitate electron transfer between reactants, there is growing literature on the abiotic reductive removal of organic contaminants catalyzed by them. Most of the interest in these processes arises from the participation of carbon materials in the natural transformation of contaminants and the possibility of developing new strategies for environmental treatment and remediation. The combinations of various carbon materials and reductants have been investigated for the reduction of nitro-organic compounds, halogenated organics, and azo dyes. The reduction rates of a certain compound in carbon-reductant systems vary with the surface properties of carbon materials, although there are controversial conclusions on the properties governing the catalytic performance. This review scrutinizes the contributions of quinone moieties, electron conductivity, and other carbon properties to the activity of carbon materials. It also discusses the contaminant-dependent reduction pathways, that is, electron transfer through conductive carbon and intermediates formed during the reaction, along with possibly additional activation of contaminant molecules by carbon. Moreover, modification strategies to improve the catalytic activity for reduction are summarized. Future research needs are proposed to advance the understanding of reaction mechanisms and improve the practical utility of carbon material for water treatment. PRACTITIONER POINTS: Reduction rates of contaminants in carbon-reductant systems and modification strategies for carbon materials are summarized. Mechanisms for the catalytic activity of carbon materials are discussed. Research needs for new insights into carbon-catalyzed reduction are proposed.

Enhanced Oxidation of Organic Contaminants by Mn(VII)/CaSO3 Under Environmentally Relevant Conditions: Performance and Mechanisms.

Although permanganate activation by sodium sulfite (Mn(VII)/Na2SO3) has shown great potential for rapid abatement of organic contaminants, the limited reactivity under alkaline conditions and undesirable Mn residual may prevent its widespread application. To solve these challenges, calcium sulfite (CaSO3) was employed as a slow-release source of SO32-/HSO3- (S(IV)) to activate Mn(VII) in this study. It was found that the application of CaSO3 solid could extend the effective working pH range of Mn(VII)/S(IV) from ≤7.0 to ≤9.0. Moreover, due to the enhanced precipitation of MnO2 with the presence of Ca2+, very low Mn residual (<0.05 mg/L) was achieved in Mn(VII)/CaSO3 system. Mn(VII)/CaSO3 system is a unique two-stage oxidation process in terms of reaction kinetics and reactive oxidants. Specifically, Mn(VII) was rapidly consumed and reactive Mn intermediates (e.g., Mn(VI), Mn(V)), SO4•-, and HO• were produced in the first stage. However, the second stage was governed by the interaction between MnO2 and S(IV), with SO4•- and HO• serving as the dominant reactive oxidants. Taking advantage of an automatic titrator, excess S(IV) was found to greatly quench the generated radicals, whereas it did not cause a significant consumption of reactive Mn species. All these results improved our understanding of the Mn(VII)/S(IV) process and could thus facilitate its application.

Efficient degradation of lube oil by a mixed bacterial consortium.

A laboratory study was performed to assess the biodegradation of lube oil in bio-reactor with 304# stainless steel as a biofilm carrier. Among 164 oil degrading bacterial cultures isolated from oil contaminated soil samples, Commaonas acidovorans Pxl, Bacillus sp. Px2, Pseudomonas sp. Px3 were selected to prepare a mixed consortium for the study based on the efficiency of lube oil utilization. The percentage of oil degraded by the mixed bacterial consortium decreased slightly from 99% to 97.2% as the concentration of lube oil was increased from 2000 to 10,000 mg/L. The degradation of TDOC (total dissolved organic carbon) showed a similar tendency compared with lube oil removal, which indicated that the intermediates in degradation process hardly accumulated. Selected mixed bacterial consortium showed their edge compared to activated sludge. Scanning electron microscopy (SEM) photos showed that biofilms on stainless steel were robust and with a dimensional framework constructed by EPS (extracellular polymeric substances), which could promote the biodegradation of hydrocarbons. The increase of biofilm followed first-order kinetics with rate of 0.216 microg glucose/(cm2-day) in logarithm phase. With analysis of Fourier transform infrared spectroscopy (FT-IR) and gas chromatography-mass spectrometry (GC-MS) combined with removal of lube oil and TDOC, mixed bacterial consortium could degrade benzene and its derivatives, aromatic ring organic matters with a percentage over 97%.

Influence of [sulfite]/[Fe(VI)] molar ratio on the active oxidants generation in Fe(VI)/sulfite process.

Although several groups have made efforts to study micropollutants degradation by Fe(VI)/sulfite process, the mechanism is far from clear and warrants further investigation. Herein, the degradation kinetics and mechanism of selected micropollutants by sulfite (SO32-)-activated Fe(VI) oxidation were systematically investigated. The oxidation rates of enrofloxacin (ENR) and phenol in Fe(VI)/sulfite process ranged from 0.151 s-1 to 6.18 s-1 at pH 6.5 and 8.0. Sulfite applied in multiple-addition mode improved the degradation efficiency of micropollutants with electron-rich moieties compared to the single-addition mode. Based on results of the quenching experiments and kinetic simulation, Fe(V) was identified as the predominant active oxidant at [SO32-]/[Fe(VI)] molar ratio of 0.1 to 0.3. However, both Fe(V) and SO4-/OH contributed to micropollutants oxidation at [SO32-]/[Fe(VI)] molar ratio ≥ 0.4 and their contributions were strongly dependent on the properties of micropollutants. The different degradation products of ENR in Fe(VI)/sulfite process at different sulfite dosages further supported the contribution of different active oxidants at different [SO32-]/[Fe(VI)] molar ratios. The toxicity of the reaction products of ENR towards Vibrio qinghaiensis sp.-Q67 decreased dramatically after Fe(VI)/sulfite treatment. The results of this work may promote the application of sulfite-activated Fe(VI) oxidation in water treatment.