The effect of particle size of silica, as catalyst binder, on the chemical and mechanical properties of iron based FT catalyst was studied in this work. The samples were characterized using XRD, BET, TEM, FT-IR, and H...The effect of particle size of silica, as catalyst binder, on the chemical and mechanical properties of iron based FT catalyst was studied in this work. The samples were characterized using XRD, BET, TEM, FT-IR, and H2-TPR, re- spectively. The attrition resistance and the FT activity were tested. Si-8-Si-15 catalysts prepared with 8-15 nm silica sol show good attrition resistance （attrition loss 〈 4%）, especially Si-13 with an attrition loss of 1.89%. He- matite appeared in XRD patterns when silica sol above 15 nm is used. TEM micrographs show that no obvious SiO2 particles appear when silica sol particle with size less than 8 nm was used, but SiO2 particles coated with small ferrihydrite particles appear when silica sol above 8 nm was used. Si-O-Si vibration peak in FT-IR spectra increases with increasing silica sol size. Samples prepared with silica sol show good stability of FT reactions, and the average molecular weight of FT products increases with the increase of SiO2 particle.展开更多
Biotransformation of 6:2 fluorotelomer sulfonate(6:2 FTS)by two species of white-rot fungi,Pleurotus ostreatus(P.ostreatus)and Trametopsis cervina(T.cervina),was investigated in a sulfurrich medium designed to stimula...Biotransformation of 6:2 fluorotelomer sulfonate(6:2 FTS)by two species of white-rot fungi,Pleurotus ostreatus(P.ostreatus)and Trametopsis cervina(T.cervina),was investigated in a sulfurrich medium designed to stimulate production of lignin-degrading enzymes.Degradation of 6:2 FTS was observed by T.cervina over the study period of 30 d,but not by P.ostreatus.Biotransformation rates were comparable to those found in other studies investigating mixed culture degradation in nonsulfur limiting media,with approximately 50 mol%of applied 6:2 FTS removed after 30 d.Stable transformation products were short-chain perfluorocarboxylic acids(PFCAs),including PFHxA(2.27 mol%),PFPeA(0.24 mol%),and PFBA(0.28 mol%).The main intermediate products include 5:2 sFTOH(16.3 mol%)and 5:3 FTCA(2.99 mol%),while 6:2 FTCA,6:2 FTuCA,and 5:2 ketone were also identified at low levels.Approximately 60 mol%of detected products were assigned to the major pathway to 5:2 ketone,and 40 mol%were assigned to the minor pathway to 5:3 FTCA.The overall molar balance was found to decrease to 75 mol%by Day 30,however,was closed to near 95 mol%with a theoretical estimation for the volatile intermediates in the headspace,5:2 ketone and 5:2 sFTOH.The different capabilities of the two white-rot fungal species for 6:2 FTS biotransformation in sulfur-rich media suggest that the enzyme processes of T.cervina to de-sulfonate 6:2 FTS may be unrelated to sulfur metabolism.展开更多
The 6：2 FTS was the substitute for perfluorooctane sulfonate（PFOS） in the chrome plating industry in Japan. Electrochemical oxidation of 6：2 FTS was investigated in this study. The degradabilities of PFOS and 6：2...The 6：2 FTS was the substitute for perfluorooctane sulfonate（PFOS） in the chrome plating industry in Japan. Electrochemical oxidation of 6：2 FTS was investigated in this study. The degradabilities of PFOS and 6：2 FTS were tested on the Ti/SnO2–Sb2O5–Bi2O3anode. The effects of current density,potential,and supporting electrolyte on the degradation of 6：2 FTS were evaluated. Experimental results showed that 6：2 FTS was more easily degraded than PFOS on the Ti/SnO2–Sb2O5–Bi2O3anode. At a low current density of 1.42 mA/cm2,6：2 FTS was not degraded on Ti/SnO2–Sb2O5–Bi2O3,while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm2. The degradation of 6：2 FTS at current density of 6.80 mA/cm2 followed pseudo first-order kinetics with the rate constant of 0.074 hr-1. The anodic potential played an important role in the degradation of 6：2 FTS,and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO2–Sb2O5–Bi2O3was contaminated after electrolysis at constant potential of 3 V,while the fouling phenomenon was not observed at 5 V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer（UPLC–MS/MS） were shorter chain perfluorocarboxylic acids. The 6：2 FTS was first attacked by hydroxyl radical,and then formed perfluorinated carboxylates,which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.展开更多
Per-and polyfluoroalkyl substances(PFAS)are found ubiquitously in wastewater treatment plants(WWTPs)due to their multiple sources in industry and consumer products.In Australia,limited spatial data are available on PF...Per-and polyfluoroalkyl substances(PFAS)are found ubiquitously in wastewater treatment plants(WWTPs)due to their multiple sources in industry and consumer products.In Australia,limited spatial data are available on PFAS levels inWWTPs influent,while no temporal data have been reported.The aim of this study was to investigate the occurrence and temporal trend of PFAS in the influent of two large WWTPs in Australia(WWTP A and B)over a four-year period.Daily influent samples were collected over one week at different seasons from 2014 to 2017.Eleven perfluoroalkyl acids(PFAA)(i.e.seven perfluoroalkyl carboxylic acids(PFCAs)and four perfluoroalkyl sulfonic acids(PFSA))were detected with mean S11PFAA concentrations of 57±3.3e94±17 ng/L at WWTP A,and 31±6.1e142±73 ng/L at WWTP B.The highest mean concentrations were observed for perfluorohexanoate(PFHxA)(20±2 ng/L)in WWTP A,and perfluorooctane sulfonate(PFOS)(17±13 ng/L)in WWTP B.The precursor 6:2 fluorotelomer sulfonate was detected over five sampling periods from Aug 2016 to Oct 2017,with mean concentrations of 37±18e138±51 ng/L for WWTP A and 8.8±4.5e29±5.1 ng/L for WWTP B.Higher concentration of 6:2 FTS(1.8e11 folds)than those of PFOA and PFOS in WWTP A indicate a likely substitution of C8 PFAA by fluorotelomer-based PFAS in this catchment.Temporal trends(annual and seasonal)in per-capita mass load were observed for some PFAA,increasing for PFPeA,PFHxA,PFHpA,PFNA,and PFHxS,while decreasing for PFBS and PFOS in either WWTPs.Notably,elevated levels of PFOS in October 2017 were observed at both WWTPs with the highest per capita mass load of up to 67 mg/day/inhabitant.For some PFAS release trends,longer sampling periods would be required to achieve acceptable statistical power.展开更多
Perfluorooctane sulfonate（PFOS） had wide applications,such as in the electroplating industry,but its use was restricted in 2009 by the Stockholm Convention,due to its environmental persistence and potential hazards....Perfluorooctane sulfonate（PFOS） had wide applications,such as in the electroplating industry,but its use was restricted in 2009 by the Stockholm Convention,due to its environmental persistence and potential hazards.As the most common PFOS alternative,lH,lH,2H,2H-perfluorooctane sulfonic acid（6：2FTS） and its salts have been increasingly used.However,little is known about its photochemical decomposition.This paper reports the ferric ion-induced efficient decomposition and defluorination of 6：2FTS under 254 nm ultraviolet（UV） irradiation;the underlying mechanisms were also investigated.In the presence of 100 ｜imol/L ferric ion and at pH 3.0,the first-order decomposition rate constant of 6：2FTS（10 mg/L） was 1.59/hr,which was 6 times higher than for direct UV photolysis.The effects of the ferric ion concentration and the solution pH on the 6：2FTS photodecomposition were investigated and the optimal reaction conditions were determined.In addition to fluoride and sulfate ions,shorter-chain PFCAs（C2-C7） were detected as major intermediates.The addition of hydrogen peroxide or oxalic acid accelerated the decomposition of 6：2FTS under UV irradiation,but not its defluorination,indicating that hydroxyl radicals can directly react with 6：2FTS but not with the shorter-chain PFCAs.Accordingly,a mechanism for 6：2FTS photochemical decomposition in the presence of ferric ion was proposed,which comprises two reaction pathways.First,hydroxyl radicals can directly attack 6：2FTS,leading to C- C bond cleavage.Alternatively,6：2FTS coordinates with ferric ion to form Fe（III）-6：2FTS complexes,which can undergo ligand-to-metal charge transfer under UV irradiation,causing C-S bond cleavage.展开更多
基金financial support from Shenhua Group and Zhejiang University of Technology is highly acknowledged for the catalyst test
文摘The effect of particle size of silica, as catalyst binder, on the chemical and mechanical properties of iron based FT catalyst was studied in this work. The samples were characterized using XRD, BET, TEM, FT-IR, and H2-TPR, re- spectively. The attrition resistance and the FT activity were tested. Si-8-Si-15 catalysts prepared with 8-15 nm silica sol show good attrition resistance （attrition loss 〈 4%）, especially Si-13 with an attrition loss of 1.89%. He- matite appeared in XRD patterns when silica sol above 15 nm is used. TEM micrographs show that no obvious SiO2 particles appear when silica sol particle with size less than 8 nm was used, but SiO2 particles coated with small ferrihydrite particles appear when silica sol above 8 nm was used. Si-O-Si vibration peak in FT-IR spectra increases with increasing silica sol size. Samples prepared with silica sol show good stability of FT reactions, and the average molecular weight of FT products increases with the increase of SiO2 particle.
基金support by the Center for Air and Aquatic Resources Engineering and Sciences(CAARES)at Clarkson University and thank the employees at the Center of Forest Mycology Research(CFMR)in Madison,WI,for providing all cultures used in this research.
文摘Biotransformation of 6:2 fluorotelomer sulfonate(6:2 FTS)by two species of white-rot fungi,Pleurotus ostreatus(P.ostreatus)and Trametopsis cervina(T.cervina),was investigated in a sulfurrich medium designed to stimulate production of lignin-degrading enzymes.Degradation of 6:2 FTS was observed by T.cervina over the study period of 30 d,but not by P.ostreatus.Biotransformation rates were comparable to those found in other studies investigating mixed culture degradation in nonsulfur limiting media,with approximately 50 mol%of applied 6:2 FTS removed after 30 d.Stable transformation products were short-chain perfluorocarboxylic acids(PFCAs),including PFHxA(2.27 mol%),PFPeA(0.24 mol%),and PFBA(0.28 mol%).The main intermediate products include 5:2 sFTOH(16.3 mol%)and 5:3 FTCA(2.99 mol%),while 6:2 FTCA,6:2 FTuCA,and 5:2 ketone were also identified at low levels.Approximately 60 mol%of detected products were assigned to the major pathway to 5:2 ketone,and 40 mol%were assigned to the minor pathway to 5:3 FTCA.The overall molar balance was found to decrease to 75 mol%by Day 30,however,was closed to near 95 mol%with a theoretical estimation for the volatile intermediates in the headspace,5:2 ketone and 5:2 sFTOH.The different capabilities of the two white-rot fungal species for 6:2 FTS biotransformation in sulfur-rich media suggest that the enzyme processes of T.cervina to de-sulfonate 6:2 FTS may be unrelated to sulfur metabolism.
基金supported by the National Natural Science Foundation of China (No.21307036)the National High-Tech Research and Development Program of China (No.2013AA062705)the National Key Scientific and Technological Project for Water Pollution Control and Management (Nos.2012ZX07206-002,2012ZX07206-003)
文摘The 6：2 FTS was the substitute for perfluorooctane sulfonate（PFOS） in the chrome plating industry in Japan. Electrochemical oxidation of 6：2 FTS was investigated in this study. The degradabilities of PFOS and 6：2 FTS were tested on the Ti/SnO2–Sb2O5–Bi2O3anode. The effects of current density,potential,and supporting electrolyte on the degradation of 6：2 FTS were evaluated. Experimental results showed that 6：2 FTS was more easily degraded than PFOS on the Ti/SnO2–Sb2O5–Bi2O3anode. At a low current density of 1.42 mA/cm2,6：2 FTS was not degraded on Ti/SnO2–Sb2O5–Bi2O3,while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm2. The degradation of 6：2 FTS at current density of 6.80 mA/cm2 followed pseudo first-order kinetics with the rate constant of 0.074 hr-1. The anodic potential played an important role in the degradation of 6：2 FTS,and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO2–Sb2O5–Bi2O3was contaminated after electrolysis at constant potential of 3 V,while the fouling phenomenon was not observed at 5 V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer（UPLC–MS/MS） were shorter chain perfluorocarboxylic acids. The 6：2 FTS was first attacked by hydroxyl radical,and then formed perfluorinated carboxylates,which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.
基金The authors would like to thank Sharon Grant,Jake O'Brien,Ben Tscharke and Rachel Mackie for organizing sample collection and providing data.Hue T.Nguyen is also grateful to Christine M.Baduel for LC/MS-MS analytical training.Hue T.Nguyen is supported by an Australian Award Scholarship granted by Australian Department of Foreign Affairs and Trade.Jochen F.Mueller is funded by a UQ Fellowship.
文摘Per-and polyfluoroalkyl substances(PFAS)are found ubiquitously in wastewater treatment plants(WWTPs)due to their multiple sources in industry and consumer products.In Australia,limited spatial data are available on PFAS levels inWWTPs influent,while no temporal data have been reported.The aim of this study was to investigate the occurrence and temporal trend of PFAS in the influent of two large WWTPs in Australia(WWTP A and B)over a four-year period.Daily influent samples were collected over one week at different seasons from 2014 to 2017.Eleven perfluoroalkyl acids(PFAA)(i.e.seven perfluoroalkyl carboxylic acids(PFCAs)and four perfluoroalkyl sulfonic acids(PFSA))were detected with mean S11PFAA concentrations of 57±3.3e94±17 ng/L at WWTP A,and 31±6.1e142±73 ng/L at WWTP B.The highest mean concentrations were observed for perfluorohexanoate(PFHxA)(20±2 ng/L)in WWTP A,and perfluorooctane sulfonate(PFOS)(17±13 ng/L)in WWTP B.The precursor 6:2 fluorotelomer sulfonate was detected over five sampling periods from Aug 2016 to Oct 2017,with mean concentrations of 37±18e138±51 ng/L for WWTP A and 8.8±4.5e29±5.1 ng/L for WWTP B.Higher concentration of 6:2 FTS(1.8e11 folds)than those of PFOA and PFOS in WWTP A indicate a likely substitution of C8 PFAA by fluorotelomer-based PFAS in this catchment.Temporal trends(annual and seasonal)in per-capita mass load were observed for some PFAA,increasing for PFPeA,PFHxA,PFHpA,PFNA,and PFHxS,while decreasing for PFBS and PFOS in either WWTPs.Notably,elevated levels of PFOS in October 2017 were observed at both WWTPs with the highest per capita mass load of up to 67 mg/day/inhabitant.For some PFAS release trends,longer sampling periods would be required to achieve acceptable statistical power.
基金supported by the National Natural Science Foundation of China(Nos.21221004,21177071)the National Basic Research Program of China(No.2013CB632403)the Collaborative Innovation Center for Regional Environmental Quality
文摘Perfluorooctane sulfonate（PFOS） had wide applications,such as in the electroplating industry,but its use was restricted in 2009 by the Stockholm Convention,due to its environmental persistence and potential hazards.As the most common PFOS alternative,lH,lH,2H,2H-perfluorooctane sulfonic acid（6：2FTS） and its salts have been increasingly used.However,little is known about its photochemical decomposition.This paper reports the ferric ion-induced efficient decomposition and defluorination of 6：2FTS under 254 nm ultraviolet（UV） irradiation;the underlying mechanisms were also investigated.In the presence of 100 ｜imol/L ferric ion and at pH 3.0,the first-order decomposition rate constant of 6：2FTS（10 mg/L） was 1.59/hr,which was 6 times higher than for direct UV photolysis.The effects of the ferric ion concentration and the solution pH on the 6：2FTS photodecomposition were investigated and the optimal reaction conditions were determined.In addition to fluoride and sulfate ions,shorter-chain PFCAs（C2-C7） were detected as major intermediates.The addition of hydrogen peroxide or oxalic acid accelerated the decomposition of 6：2FTS under UV irradiation,but not its defluorination,indicating that hydroxyl radicals can directly react with 6：2FTS but not with the shorter-chain PFCAs.Accordingly,a mechanism for 6：2FTS photochemical decomposition in the presence of ferric ion was proposed,which comprises two reaction pathways.First,hydroxyl radicals can directly attack 6：2FTS,leading to C- C bond cleavage.Alternatively,6：2FTS coordinates with ferric ion to form Fe（III）-6：2FTS complexes,which can undergo ligand-to-metal charge transfer under UV irradiation,causing C-S bond cleavage.
