Persistent perfluorinated organic compounds, such as perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are used in a variety of industrial applications. They are very stable in the environment, distribute...Persistent perfluorinated organic compounds, such as perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are used in a variety of industrial applications. They are very stable in the environment, distribute widely in the global environment and in wild life, and are detected in human sera. Our searches have detected ppt levels of PFOS and PFOA in the surface water of Japan and China; their levels are generally more than ten times higher in city areas. Neither PFOS nor PFOA is removed by the purification process of city water. Both PFOS and PFOA are detected in sera of all the people of Japan and China (about 1000 times as high as those in surface water), and their concentrations are increasing in both countries, especially in China. PFOS and PFOA primarily distribute to the liver and cause the liver toxicity. They also cause developmental toxicity. PFOS which is not genotoxic in a variety of assay system including our in vivo comet assay, induced tumors of the liver, thyroid and mammary gland of rats. PFOA which is weakly carcinogenic is not mutagenic in many studies including our in vivo comet assay.展开更多
Fluorochemicals(FCs)are oxidatively recalcitrant,environmentally persistent,and resistant to most conventional treatment technologies.FCs have unique physiochemical properties derived from fluorine which is the most e...Fluorochemicals(FCs)are oxidatively recalcitrant,environmentally persistent,and resistant to most conventional treatment technologies.FCs have unique physiochemical properties derived from fluorine which is the most electronegative element.Perfluorooctanesulfonate(PFOS),and perfluorooctanoate(PFOA)have been detected globally in the hydrosphere,atmosphere and biosphere.Reducing treatment technologies such as reverses osmosis,nano-filtration and activated carbon can remove FCs from water.However,incineration of the concentrated waste is required for complete FC destruction.Recently,a number of alternative technologies for FC decomposition have been reported.The FC degradation technologies span a wide range of chemical processes including direct photolysis,photocatalytic oxidation,photochemical oxidation,photochemical reduction,thermally-induced reduction,and sonochemical pyrolysis.This paper reviews these FC degradation technologies in terms of kinetics,mechanism,energetic cost,and applicability.The optimal PFOS/PFOA treatment method is strongly dependent upon the FC concentration,background organic and metal concentration,and available degradation time.展开更多
The photodegradation of persistent and bioaccumulative perftuorooctanoic acid (PFOA) in water by 185 nm vacuum ultraviolet (VUV) light was examined to develop an effective technology to deal with PFOA pollution. P...The photodegradation of persistent and bioaccumulative perftuorooctanoic acid (PFOA) in water by 185 nm vacuum ultraviolet (VUV) light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids (PFCAs), that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.展开更多
Environmentally persistent and bioaccumulative perfluorooctanic acid (PFOA) was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol/L Fe(Ⅲ), 80% of PFOA with i...Environmentally persistent and bioaccumulative perfluorooctanic acid (PFOA) was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol/L Fe(Ⅲ), 80% of PFOA with initial concentration of 48μmol/L (20 mg/L) was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe(Ⅲ) initiated degradation of PFOA irradiated with 254 nm UV light.展开更多
Perfluorooctanoic acid(PFOA)is a widespread synthetic persistent organic pollutant that may enrich along the food chain and affect the growth,development,reproduction,and lipid metabolism of aquatic organisms,particul...Perfluorooctanoic acid(PFOA)is a widespread synthetic persistent organic pollutant that may enrich along the food chain and affect the growth,development,reproduction,and lipid metabolism of aquatic organisms,particularly the benthic organisms.How-ever,the toxic effects of PFOA on the half-smooth tongue sole Cynoglossus semilaevis,a commercial benthic fish in China,have rarely been reported.Because juvenile fish are sensitive to environmental pollutants,in the present study,histological assessment and tran-scriptome sequencing were performed to determine the short-term impact of PFOA on juvenile half-smooth tongue soles.Histologi-cal analysis showed that PFOA exposure caused hepatocyte rupture,intestinal villi breakage,increased goblet cell count,and brain ab-normal.Transcriptome results showed that some interesting signaling pathways,such as glycolysis/gluconeogenesis,PPAR signaling pathway and GABAergic synapse signaling pathway,were enriched after PFOA exposure.In addition,some metabolic,immune and neural genes were differentially expressed,which including ependymin,hbb1-like and gad 1,and they were up-regulated after 14 days of exposure.Transcriptome results also indicated that half-smooth tongue sole might improve energy metabolism in response to PFOA toxicity after 7 days of exposure.These findings provide a basis for studying the ecological effects of PFOA on marine benthic fishes.展开更多
Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amount of hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is...Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amount of hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is equal to 1750. The substitution extent, defined by the number of substituting units in a chain, for the four FPVA samples was in the range of 0.5-5 perfluorooctanoyl groups per chain. The FPVA samples with the highest substitution extent still had good solubility in water. It was shown by experimental measurement at 30.0 +/- 0.1 degreesC that the surface tension of the aqueous solution of the highest substituted FPVA decreased to 16.6 mN/m at a higher concentration, e.g. about 0.1 g/mL. Obviously, macromolecules of FPVA exhibit a very strong tendency to adsorb at the air-water interface, because the hydrophobic perfluorooctanoyl groups in FPVA have a very high surface activity as they are in small molecular fluorinated surfactants. The chain conformation of such a model polymer adsorbed on the air-water interface was also discussed.展开更多
Surfactant doped polyaniline was synthesized in the aqueous solution of aniline and anionic surfactant of perfluorooctanoic acid (PFO) by chemical synthesis using potassium peroxy disulphate as an oxidant by varying t...Surfactant doped polyaniline was synthesized in the aqueous solution of aniline and anionic surfactant of perfluorooctanoic acid (PFO) by chemical synthesis using potassium peroxy disulphate as an oxidant by varying the aniline to surfactant ratio. The solubility of the chemically prepared surfactant doped polyaniline (PANI) was ascertained and it showed good solubility in dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, acetonitrile, ethanol, aceticacid, trichloroethylene, dichloromethane, tetrahydrofuran, ethylacetate, diethylether, toluene, chloroform and sparingly soluble in n-hexane and water. The prepared polymers were characterized by fourier transform infrared spectroscopy (FTIR), UV-visible, X-ray diffraction (XRD), cyclic voltammetric (CV), EIS and scanning electron microscopy (SEM). The analysis of UV-visible and FTIR showed that aniline has been polymerized to PANI in its conducting emeraldine form. FTIR spectra showed that the peaks at 1670, 3315 and 1400 cm-1 corresponded to PFO. FTIR spectra showed that amine peak observed at 1593 cm-1 was shifted to lower wave number due to the interaction between PANI and the surfactant. SEM analysis showed that the variation in morphology of doped PANI was predominantly dependent on the concentration of the surfactant. Elemental analysis was done by energy dispersive spectroscopic (EDAX) which shows the presence of C, N, O, S and F. XRD pattern showed that the formation of nanosized (18 nm) and crystalline polymer. CV studies of the synthesized polymer exhibited good adherent behavior on electrode surface. It exhibited three oxidation peaks at approximately 0.283 V, 0.541 V and 0.989 V and two reduction peaks at 0.1421 and 0.3854 V. Electrical conductivity of PFO doped PANI was studied by impedance spectroscopic method.展开更多
Aqueous perfluorooctanoic acid(PFOA)elimination has raised significant concerns due to its persistence and bioaccumulation.Althoughβ-PbO_(2)plate anodes have shown efficient mineralization of PFOA,it remains unclear ...Aqueous perfluorooctanoic acid(PFOA)elimination has raised significant concerns due to its persistence and bioaccumulation.Althoughβ-PbO_(2)plate anodes have shown efficient mineralization of PFOA,it remains unclear whether PFOA can be effectively degraded usingβ-PbO_(2)reactive electrochemical membrane(REM).Herein,we assessed the performance of Ti/SnO_(2)-Sb/La-PbO_(2)REM for PFOA removal and proposed a possible degradation mechanism.At a current density of 10 mA/cm2and a membrane flux of 8500(liters per square meter per hour,LMH),the degradation efficiency of 10 mg/L PFOA was merely8.8%,whereas the degradation efficiency of 0.1 mg/L PFOA increased to 96.6%.Although the porous structure of theβ-PbO_(2)REM provided numerous electroactive sites for PFOA,the generated oxygen bubbles in the pores could block the pore channels and adsorb PFOA molecules.These hindered the protonation process and significantly impeded the degradation of high-concentration PFOA.Quenching experiments indicated that·OH played dominant role in PFOA degradation.The electrical energy per order to remove 0.1 mg/L PFOA was merely 0.74 Wh/L,which was almost an order of magnitude lower than that of other anode materials.This study presents fresh opportunities for the electrochemical degradation of low-concentration PFOA usingβ-PbO_(2)REM.展开更多
There is an urgent need for developing cost-effective methods for the treatment of perfluorooctanoic acid(PFOA)due to its global emergence and potential risks.In this study,taking surface-defective BiOCl as an example...There is an urgent need for developing cost-effective methods for the treatment of perfluorooctanoic acid(PFOA)due to its global emergence and potential risks.In this study,taking surface-defective BiOCl as an example,a strategy of surface oxygen vacancy modulation was used to promote the photocatalytic defluorination efficiency of PFOA under simulated sunlight irradiation.The defective BiOCl was fabricated by a fast microwave solvothermal method,which was found to induce more surface oxygen vacancies than conventional solvothermal and precipitation methods.As a result,the asprepared BiOCl showed significantly enhanced defluorination efficiency,which was 2.7 and33.8 times higher than that of BiOCl fabricated by conventional solvothermal and precipitation methods,respectively.Mechanistic studies indicated that the defluorination of PFOA follows a direct hole(h^+)oxidation pathway with the aid of·OH,while the oxygen vacancies not only promote charge separation but also facilitate the intimate contact between the photocatalyst surface and PFOA by coordinating with its terminal carboxylate group in a bidentate or bridging mode.This work will provide a general strategy of oxygen vacancy modulation by microwave-assisted methods for efficient photocatalytic defluorination of PFOA in the environment using sunlight as the energy source.展开更多
Microwave-hydrothermal treatment of persis- tent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S2O2-) has been found effective. However, applications of this process to effectively re...Microwave-hydrothermal treatment of persis- tent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S2O2-) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects ofpH (pH= 2.5, 6.6, 8.8, and 10.5), chloride concentra- tions (0.01-0.15 mol.L-1), and temperature (60℃, 90℃, and 130℃) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol.L^-1 at 90℃ and 0.06mol.L^-1 at 60℃, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.展开更多
Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO.) due to its stable chemical structure and the high electronegativi...Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO.) due to its stable chemical structure and the high electronegativity of fluorine. Photocatalytic reduction of PFOA with β-Ga2O3 in anoxic aqueous solution was investigated for the first time, and the results showed that the photoinduced electron (ecb) coming from the β-Ga2O3 conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, CnF2n+1COOH, 1 ≤ n ≤ 6) were the dominant products. Furthermore, the concentration of F- was measured by the IC technique and defluorination efficiency was calculated. After 3 hr, the photocatalytic degradation efficiency was 98.8% and defluorination efficiency was 31.6% in the presence of thiosulfate and bubbling N2. The degradation reaction followed first-order kinetics (k = 0.0239 min-1, t1/2 = 0.48 hr). PFCAs (CnF2n+xCOOH, 1 ≤ n≤ 7) were detected and measured by LC-MS and LC-MS/MS methods. It was deduced that the probable photocatalytic degradation mechanism involves ec-b attacking the carboxyl of CnF2n+1COOH, resulting in decarboxylation and the generation of CnFzn+1. The produced CnF2n+1 reacted with H2O, forming CnF2n+1OH, then CnF2n+1OH underwent HF loss and hydrolysis to form CnF2,+1COOH.展开更多
Bismuth-based material has been broadly studied due to their potential applications in various areas,especially used as promising photocatalysts for the removal of persistent organic pollutants(POPs) and several appro...Bismuth-based material has been broadly studied due to their potential applications in various areas,especially used as promising photocatalysts for the removal of persistent organic pollutants(POPs) and several approaches have been adopted to tailor their features.Herein,the bismuth-based photocatalysts(BiOCl,BiPO4,BiOPO4/BiOCl) were synthesized by hydrothermal method and advanced characterization techniques(XRD,SEM,EDS elemental mapping,Raman and UV-vis DRS) were employed to analyze their morphology,crystal structure,and purity of the prepared photocatalysts.These synthesized photocatalysts offered a praiseworthy activity as compared to commercial TiO2(P25) for the degradation of model pollutant perfluorooctanoic acid(PFOA) under 254 nm UV light.It was interesting to observe that all synthesized photocatalysts show significant degradation of PFOA and their photocatalytic activity follows the order:bismuth-based catalysts> TiO2(P25)> without catalyst.Bismuth-based catalysts degraded the PFOA by almost 99.99% within 45 min while this degradation efficiency was 66.05% with TiO2 under the same reaction condition.Our work shows that the bismuth-based photocatalysts are promising in PFOA treatment.展开更多
When wood-based activated carbon was tailored with quaternary ammonium/epoxide(QAE) forming compounds(QAE-AC), this tailoring dramatically improved the carbon's effectiveness for removing perfluorooctanoic acid(PF...When wood-based activated carbon was tailored with quaternary ammonium/epoxide(QAE) forming compounds(QAE-AC), this tailoring dramatically improved the carbon's effectiveness for removing perfluorooctanoic acid(PFOA) from groundwater. With favorable tailoring, QAE-AC removed PFOA from groundwater for 118,000 bed volumes before halfbreakthrough in rapid small scale column tests, while the influent PFOA concentration was 200 ng/L. The tailoring involved pre-dosing QAE at an array of proportions onto this carbon, and then monitoring bed life for PFOA removal. When pre-dosing with 1 mL QAE, this PFOA bed life reached an interim peak, whereas bed life was less following 3 mL QAE pre-dosing, then PFOA bed life exhibited a steady rise for yet subsequently higher QAE pre-dosing levels. Large-scale atomistic modelling was used herein to provide new insight into the mechanism of PFOA removal by QAE-AC. Based on experimental results and modelling, the authors perceived that the QAE's epoxide functionalities cross-linked with phenolics that were present along the activated carbon's graphene edge sites, in a manner that created mesopores within macroporous regions or created micropores within mesopores regions. Also, the QAE could react with hydroxyls outside of these pore, including the hydroxyls of both graphene edge sites and other QAE molecules. This latter reaction formed new pore-like structures that were external to the activated carbon grains. Adsorption of PFOA could occur via either charge balance between negatively charged PFOA with positively charged QAE, or by van der Waals forces between PFOA's fluoro-carbon tail and the graphene or QAE carbon surfaces.展开更多
Nanophotocatalysts have shown great potential for degrading poly-and perfluorinated substances(PFAS).In light of the fact that most of these catalysts were studied in pure water,this study was designed to elucidate ef...Nanophotocatalysts have shown great potential for degrading poly-and perfluorinated substances(PFAS).In light of the fact that most of these catalysts were studied in pure water,this study was designed to elucidate effects from common environmental factors on decomposing and defluorinating perfluorooctanoic acid(PFOA)by In2O3 nanoparticles.Results from this work demonstrated that among the seven parameters,pH,sulfate,chloride,H2O2,In2O3 dose,NOM and O2,the first four had statistically significant negative effects on PFOA degradation.Since PFOA is a strong acid,the best condition leading to the highest PFOA removal was identified for two pH ranges.When pH was between 4 and 8,the optimal condition was:pH=4.2;sulfate=5.00 mg/L;chloride=20.43 mg/L;H2O2=0 mmol/L.Under this condition,PFOA decomposition and defluorination were 55.22 and 23.56%,respectively.When pH was between 2 and 6,the optimal condition was:pH=2;sulfate=5.00 mg/L;chloride=27.31 mg/L;H2O2=0 mmol/L.With this condition,the modeled PFOA decomposition was 97.59%with a defluorination of approximately 100%.These predicted results were all confirmed by experimental data.Thus,In2O3 nanoparticles can be used for degrading PFOA in aqueous solutions.This approach works best when the target contaminated water contains low concentrations of NOM,sulfate and chloride and at a low pH.展开更多
The distribution of polyfluoroalkyl compounds(PFCs)in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied.The PFCs quantified included C_(4)-C_(8) perfluorinated...The distribution of polyfluoroalkyl compounds(PFCs)in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied.The PFCs quantified included C_(4)-C_(8) perfluorinated sulfonates(PFSAs),6∶2 fluorotelomer sulfonate(6∶2 FTS),C_(6) and C_(8) perfluorinated sulfinates(PFSiAs),C_(4)-C_(12) perfluorinated carboxylic acids(PFCAs),perfluoro-3,7-dimethyl-octanoic acid(3,7m_(2)-PFOA),perfluorooctane sulfonamide(FOSA),and n-ethyl perfluroctane sulfonamidoethanol(EtFOSE).PFCs were mostly distributed in the dissolved phase,where perfluorooctanoic acid(PFOA)dominated with 2.9–12.5 ng/L.In the suspended particulate matter FOSA and perfluorooctane sulfonate(PFOS)showed the highest concentrations(4.0 ng/L and 2.3 ng/L,respectively).The total flux ofΣPFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate phase.This indicates that the river Elbe acts as a source of PFCs into the North Sea.However,the concentrations of perfluorobutane sulfonate(PFBS)and perfluorobutanoic acid(PFBA)in the North Sea were higher than that in the river Elbe,thus an alternative source must exist for these compounds.展开更多
Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and p...Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and polyfluoroalkyl substances(PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time.The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10^(6) ng/g, and <MDL(method detection limit) to 5.3 × 10^(3) ng/g,respectively.Generally, the levels of PFOA in raw materials were higher than in products,implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps.By tracking a company’s polytetrafluoroethylene(PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10^(6) to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued.High concentrations of HFPO-TrA(2.7 × 10^(5) to 8.2 × 10^(5) ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.展开更多
Perfluorooctanoic acid(PFOA)is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in...Perfluorooctanoic acid(PFOA)is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85℃ under UV light(201–600 nm).The limited degree of decomposition at 25℃ was due to low quantum yield,which was increased by a factor of 12 at 85℃.Under the imposed conditions,the defluorination ratio increased from 8% at 25℃ to 50% at85℃ in 60 min.Production of perfluorinated carboxylic acids(PFCAs,C7–C5),PFCAs(C4–C3)and TFA(trifluoroacetic acid,C2)accelerated and attained a maximum within 30 to 90 min at 85℃.However,these reactions did not occur at 25℃ despite extended irradiation to180 min.PFOA was decomposed in a step-wise process by surrendering one CF2unit.In each cyclical process,increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals.The energy consumption for removing eachμmol of PFOA was reduced from 82.5 k J at 25℃ to 10.9 k J at 85℃ using photolysis.Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.展开更多
Poly-and perfluoroalkyl substances(PFASs)are important environmental contaminants globally and in the early 2000s they were shown to be ubiquitous contaminants in Arctic wildlife.Previous reviews by Butt et al.and Let...Poly-and perfluoroalkyl substances(PFASs)are important environmental contaminants globally and in the early 2000s they were shown to be ubiquitous contaminants in Arctic wildlife.Previous reviews by Butt et al.and Letcher et al.have covered studies on levels and trends of PFASs in the Arctic that were available to 2009.The purpose of this review is to focus on more recent work,generally published between 2009 and 2018,with emphasis on PFASs of emerging concern such as perfluoroalkyl carboxylates(PFCAs)and short-chain perfluoroalkyl sulfonates(PFSAs)and their precursors.Atmospheric measurements over the period 2006e2014 have shown that fluorotelomer alcohols(FTOHs)as well as perfluorobutanoic acid(PFBA)and perfluoroctanoic acid(PFOA)are the most prominent PFASs in the arctic atmosphere,all with increasing concentrations at Alert although PFOA concentrations declined at the Zeppelin Station(Svalbard).Results from ice cores show generally increasing deposition of PFCAs on the Devon Ice cap in the Canadian arctic while declining fluxes were found in a glacier on Svalbard.An extensive dataset exists for long-term trends of long-chain PFCAs that have been reported in Arctic biota with some datasets including archived samples from the 1970s and 1980s.Trends in PFCAs over time vary among the same species across the North American Arctic,East and West Greenland,and Svalbard.Most long term time series show a decline from higher concentrations in the early 2000s.However there have been recent(post 2010)increasing trends of PFCAs in ringed seals in the Canadian Arctic,East Greenland polar bears and in arctic foxes in Svalbard.Annual biological sampling is helping to determine these relatively short term changes.Rising levels of some PFCAs have been explained by continued emissions of long-chain PFCAs and/or their precursors and inflows to the Arctic Ocean,especially from the North Atlantic.While the effectiveness of biological sampling for temporal trends in long-chain PFCAs and PFSAs has been demonstrated,this does not apply to the C4eC8ePFCAs,perfluorobutane sulfonamide(FBSA),or perfluorobutane sulfonate(PFBS)which are generally present at low concentrations in biota.In addition to air sampling,sampling abiotic media such as glacial cores,and annual sampling of lake waters and seawater would appear to be the best approaches for investigating trends in the less bioaccumulative PFASs.展开更多
Heterogeneous photocatalysis has gained substantial research interest in treating per-and polyfluoroalkyl substances(PFAS)-contaminated water.However,sluggish degradation kinetics and low defluorination efficiency com...Heterogeneous photocatalysis has gained substantial research interest in treating per-and polyfluoroalkyl substances(PFAS)-contaminated water.However,sluggish degradation kinetics and low defluorination efficiency compromise their practical applications.Here,we report a superior photocatalyst,defected Bi_(3)O(OH)(PO_(4))_(2),which could effectively degrade typical PFAS,perfluorooctanoic acid(PFOA),with high defluorination efficiency.The UV light irradiation could in situ generate oxygen vacancies on Bi_(3)O(OH)(PO_(4))_(2) through oxidation of the lattice hydroxyls,which further promotes the formation of Lewis acidic coordinately unsaturated bismuth sites.Then,the Lewis acidic sites couple with the proximal surface hydroxyls to constitute the surface frustrated Lewis pairs(SFLPs).With the in-depth spectroscopic analysis,we revealed that the photo-induced SFLPs act as collection centers to effectively adsorb PFOA and endow accessible pathways to transfer photogenerated holes to PFOA rapidly.Consequently,activation of the terminal carboxyl,a ratelimiting step for PFOA decomposition,could be easily achieved over the defected Bi_(3)O(OH)(PO_(4))_(2) photocatalyst.These results suggest that SFLPs exhibit great potential in developing highly efficient photocatalysts to degrade persistent organic pollutants.展开更多
文摘Persistent perfluorinated organic compounds, such as perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are used in a variety of industrial applications. They are very stable in the environment, distribute widely in the global environment and in wild life, and are detected in human sera. Our searches have detected ppt levels of PFOS and PFOA in the surface water of Japan and China; their levels are generally more than ten times higher in city areas. Neither PFOS nor PFOA is removed by the purification process of city water. Both PFOS and PFOA are detected in sera of all the people of Japan and China (about 1000 times as high as those in surface water), and their concentrations are increasing in both countries, especially in China. PFOS and PFOA primarily distribute to the liver and cause the liver toxicity. They also cause developmental toxicity. PFOS which is not genotoxic in a variety of assay system including our in vivo comet assay, induced tumors of the liver, thyroid and mammary gland of rats. PFOA which is weakly carcinogenic is not mutagenic in many studies including our in vivo comet assay.
文摘Fluorochemicals(FCs)are oxidatively recalcitrant,environmentally persistent,and resistant to most conventional treatment technologies.FCs have unique physiochemical properties derived from fluorine which is the most electronegative element.Perfluorooctanesulfonate(PFOS),and perfluorooctanoate(PFOA)have been detected globally in the hydrosphere,atmosphere and biosphere.Reducing treatment technologies such as reverses osmosis,nano-filtration and activated carbon can remove FCs from water.However,incineration of the concentrated waste is required for complete FC destruction.Recently,a number of alternative technologies for FC decomposition have been reported.The FC degradation technologies span a wide range of chemical processes including direct photolysis,photocatalytic oxidation,photochemical oxidation,photochemical reduction,thermally-induced reduction,and sonochemical pyrolysis.This paper reviews these FC degradation technologies in terms of kinetics,mechanism,energetic cost,and applicability.The optimal PFOS/PFOA treatment method is strongly dependent upon the FC concentration,background organic and metal concentration,and available degradation time.
基金Project supported by the National Natural Science Foundation of China (No. 20577026) the New Century Excellent Talents in University (No. NCET-04-0090).
文摘The photodegradation of persistent and bioaccumulative perftuorooctanoic acid (PFOA) in water by 185 nm vacuum ultraviolet (VUV) light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids (PFCAs), that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.
文摘Environmentally persistent and bioaccumulative perfluorooctanic acid (PFOA) was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol/L Fe(Ⅲ), 80% of PFOA with initial concentration of 48μmol/L (20 mg/L) was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe(Ⅲ) initiated degradation of PFOA irradiated with 254 nm UV light.
基金supported by the National Key R&D Program(No.2018YFD0900301-03)the MNR Key Laboratory of Marine Eco-Environmental Science and Technology,China(No.MEEST-2021-04).
文摘Perfluorooctanoic acid(PFOA)is a widespread synthetic persistent organic pollutant that may enrich along the food chain and affect the growth,development,reproduction,and lipid metabolism of aquatic organisms,particularly the benthic organisms.How-ever,the toxic effects of PFOA on the half-smooth tongue sole Cynoglossus semilaevis,a commercial benthic fish in China,have rarely been reported.Because juvenile fish are sensitive to environmental pollutants,in the present study,histological assessment and tran-scriptome sequencing were performed to determine the short-term impact of PFOA on juvenile half-smooth tongue soles.Histologi-cal analysis showed that PFOA exposure caused hepatocyte rupture,intestinal villi breakage,increased goblet cell count,and brain ab-normal.Transcriptome results showed that some interesting signaling pathways,such as glycolysis/gluconeogenesis,PPAR signaling pathway and GABAergic synapse signaling pathway,were enriched after PFOA exposure.In addition,some metabolic,immune and neural genes were differentially expressed,which including ependymin,hbb1-like and gad 1,and they were up-regulated after 14 days of exposure.Transcriptome results also indicated that half-smooth tongue sole might improve energy metabolism in response to PFOA toxicity after 7 days of exposure.These findings provide a basis for studying the ecological effects of PFOA on marine benthic fishes.
基金The project was supported by the National Natural Science Foundation of China (No.29774016).
文摘Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amount of hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is equal to 1750. The substitution extent, defined by the number of substituting units in a chain, for the four FPVA samples was in the range of 0.5-5 perfluorooctanoyl groups per chain. The FPVA samples with the highest substitution extent still had good solubility in water. It was shown by experimental measurement at 30.0 +/- 0.1 degreesC that the surface tension of the aqueous solution of the highest substituted FPVA decreased to 16.6 mN/m at a higher concentration, e.g. about 0.1 g/mL. Obviously, macromolecules of FPVA exhibit a very strong tendency to adsorb at the air-water interface, because the hydrophobic perfluorooctanoyl groups in FPVA have a very high surface activity as they are in small molecular fluorinated surfactants. The chain conformation of such a model polymer adsorbed on the air-water interface was also discussed.
文摘Surfactant doped polyaniline was synthesized in the aqueous solution of aniline and anionic surfactant of perfluorooctanoic acid (PFO) by chemical synthesis using potassium peroxy disulphate as an oxidant by varying the aniline to surfactant ratio. The solubility of the chemically prepared surfactant doped polyaniline (PANI) was ascertained and it showed good solubility in dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, acetonitrile, ethanol, aceticacid, trichloroethylene, dichloromethane, tetrahydrofuran, ethylacetate, diethylether, toluene, chloroform and sparingly soluble in n-hexane and water. The prepared polymers were characterized by fourier transform infrared spectroscopy (FTIR), UV-visible, X-ray diffraction (XRD), cyclic voltammetric (CV), EIS and scanning electron microscopy (SEM). The analysis of UV-visible and FTIR showed that aniline has been polymerized to PANI in its conducting emeraldine form. FTIR spectra showed that the peaks at 1670, 3315 and 1400 cm-1 corresponded to PFO. FTIR spectra showed that amine peak observed at 1593 cm-1 was shifted to lower wave number due to the interaction between PANI and the surfactant. SEM analysis showed that the variation in morphology of doped PANI was predominantly dependent on the concentration of the surfactant. Elemental analysis was done by energy dispersive spectroscopic (EDAX) which shows the presence of C, N, O, S and F. XRD pattern showed that the formation of nanosized (18 nm) and crystalline polymer. CV studies of the synthesized polymer exhibited good adherent behavior on electrode surface. It exhibited three oxidation peaks at approximately 0.283 V, 0.541 V and 0.989 V and two reduction peaks at 0.1421 and 0.3854 V. Electrical conductivity of PFO doped PANI was studied by impedance spectroscopic method.
基金financially supported by the National Key Research and Development Program(No.2022YFE0135700)the National Natural Science Foundation of China(Nos.52000028,52370076 and 51978658)+1 种基金the Fundamental Research Funds for the Central Universities(No.2023MS063)Australian Research Council(No.G180200015)。
文摘Aqueous perfluorooctanoic acid(PFOA)elimination has raised significant concerns due to its persistence and bioaccumulation.Althoughβ-PbO_(2)plate anodes have shown efficient mineralization of PFOA,it remains unclear whether PFOA can be effectively degraded usingβ-PbO_(2)reactive electrochemical membrane(REM).Herein,we assessed the performance of Ti/SnO_(2)-Sb/La-PbO_(2)REM for PFOA removal and proposed a possible degradation mechanism.At a current density of 10 mA/cm2and a membrane flux of 8500(liters per square meter per hour,LMH),the degradation efficiency of 10 mg/L PFOA was merely8.8%,whereas the degradation efficiency of 0.1 mg/L PFOA increased to 96.6%.Although the porous structure of theβ-PbO_(2)REM provided numerous electroactive sites for PFOA,the generated oxygen bubbles in the pores could block the pore channels and adsorb PFOA molecules.These hindered the protonation process and significantly impeded the degradation of high-concentration PFOA.Quenching experiments indicated that·OH played dominant role in PFOA degradation.The electrical energy per order to remove 0.1 mg/L PFOA was merely 0.74 Wh/L,which was almost an order of magnitude lower than that of other anode materials.This study presents fresh opportunities for the electrochemical degradation of low-concentration PFOA usingβ-PbO_(2)REM.
基金supported by the National Natural Science Foundation of China (Nos. 21607028, 41425015 and 41573086)the Research Grant Council of Hong Kong Special Administrative Region (SAR) Government (No. GRF14100115)+3 种基金Science and Technology Project of Guangdong Province, China (No. 2017A050506049)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No. 2017BT01Z032)Innovation Team Project of Guangdong Provincial Department of Education (No. 2017KCXTD012)Leading Scientific, Technical and Innovation Talents of Guangdong Special Support Program (No. 2016TX03Z094)
文摘There is an urgent need for developing cost-effective methods for the treatment of perfluorooctanoic acid(PFOA)due to its global emergence and potential risks.In this study,taking surface-defective BiOCl as an example,a strategy of surface oxygen vacancy modulation was used to promote the photocatalytic defluorination efficiency of PFOA under simulated sunlight irradiation.The defective BiOCl was fabricated by a fast microwave solvothermal method,which was found to induce more surface oxygen vacancies than conventional solvothermal and precipitation methods.As a result,the asprepared BiOCl showed significantly enhanced defluorination efficiency,which was 2.7 and33.8 times higher than that of BiOCl fabricated by conventional solvothermal and precipitation methods,respectively.Mechanistic studies indicated that the defluorination of PFOA follows a direct hole(h^+)oxidation pathway with the aid of·OH,while the oxygen vacancies not only promote charge separation but also facilitate the intimate contact between the photocatalyst surface and PFOA by coordinating with its terminal carboxylate group in a bidentate or bridging mode.This work will provide a general strategy of oxygen vacancy modulation by microwave-assisted methods for efficient photocatalytic defluorination of PFOA in the environment using sunlight as the energy source.
文摘Microwave-hydrothermal treatment of persis- tent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S2O2-) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects ofpH (pH= 2.5, 6.6, 8.8, and 10.5), chloride concentra- tions (0.01-0.15 mol.L-1), and temperature (60℃, 90℃, and 130℃) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol.L^-1 at 90℃ and 0.06mol.L^-1 at 60℃, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.
基金supported by the National Natural Science Foundation of China (No. 20907026)the High Level Talent Research Foundation of Qindao Technological University (No:C-10-210)
文摘Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO.) due to its stable chemical structure and the high electronegativity of fluorine. Photocatalytic reduction of PFOA with β-Ga2O3 in anoxic aqueous solution was investigated for the first time, and the results showed that the photoinduced electron (ecb) coming from the β-Ga2O3 conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, CnF2n+1COOH, 1 ≤ n ≤ 6) were the dominant products. Furthermore, the concentration of F- was measured by the IC technique and defluorination efficiency was calculated. After 3 hr, the photocatalytic degradation efficiency was 98.8% and defluorination efficiency was 31.6% in the presence of thiosulfate and bubbling N2. The degradation reaction followed first-order kinetics (k = 0.0239 min-1, t1/2 = 0.48 hr). PFCAs (CnF2n+xCOOH, 1 ≤ n≤ 7) were detected and measured by LC-MS and LC-MS/MS methods. It was deduced that the probable photocatalytic degradation mechanism involves ec-b attacking the carboxyl of CnF2n+1COOH, resulting in decarboxylation and the generation of CnFzn+1. The produced CnF2n+1 reacted with H2O, forming CnF2n+1OH, then CnF2n+1OH underwent HF loss and hydrolysis to form CnF2,+1COOH.
基金financial support from Ministry of Science and Technology of the People’s Republic of China (Nos.2016YFE0112200 and 2016YFC0202700)National Natural Science Foundation of China (Nos.21507011,21677037 and 21607027)Natural Science Foundation of Shanghai (Nos. 19ZR1471200,17ZR1440200)
文摘Bismuth-based material has been broadly studied due to their potential applications in various areas,especially used as promising photocatalysts for the removal of persistent organic pollutants(POPs) and several approaches have been adopted to tailor their features.Herein,the bismuth-based photocatalysts(BiOCl,BiPO4,BiOPO4/BiOCl) were synthesized by hydrothermal method and advanced characterization techniques(XRD,SEM,EDS elemental mapping,Raman and UV-vis DRS) were employed to analyze their morphology,crystal structure,and purity of the prepared photocatalysts.These synthesized photocatalysts offered a praiseworthy activity as compared to commercial TiO2(P25) for the degradation of model pollutant perfluorooctanoic acid(PFOA) under 254 nm UV light.It was interesting to observe that all synthesized photocatalysts show significant degradation of PFOA and their photocatalytic activity follows the order:bismuth-based catalysts> TiO2(P25)> without catalyst.Bismuth-based catalysts degraded the PFOA by almost 99.99% within 45 min while this degradation efficiency was 66.05% with TiO2 under the same reaction condition.Our work shows that the bismuth-based photocatalysts are promising in PFOA treatment.
基金funding from Evoqua Companythe National Natural Science Foundation of China (Nos. 51878090 and 51808066)the Chinese Scholarship Council for financial support。
文摘When wood-based activated carbon was tailored with quaternary ammonium/epoxide(QAE) forming compounds(QAE-AC), this tailoring dramatically improved the carbon's effectiveness for removing perfluorooctanoic acid(PFOA) from groundwater. With favorable tailoring, QAE-AC removed PFOA from groundwater for 118,000 bed volumes before halfbreakthrough in rapid small scale column tests, while the influent PFOA concentration was 200 ng/L. The tailoring involved pre-dosing QAE at an array of proportions onto this carbon, and then monitoring bed life for PFOA removal. When pre-dosing with 1 mL QAE, this PFOA bed life reached an interim peak, whereas bed life was less following 3 mL QAE pre-dosing, then PFOA bed life exhibited a steady rise for yet subsequently higher QAE pre-dosing levels. Large-scale atomistic modelling was used herein to provide new insight into the mechanism of PFOA removal by QAE-AC. Based on experimental results and modelling, the authors perceived that the QAE's epoxide functionalities cross-linked with phenolics that were present along the activated carbon's graphene edge sites, in a manner that created mesopores within macroporous regions or created micropores within mesopores regions. Also, the QAE could react with hydroxyls outside of these pore, including the hydroxyls of both graphene edge sites and other QAE molecules. This latter reaction formed new pore-like structures that were external to the activated carbon grains. Adsorption of PFOA could occur via either charge balance between negatively charged PFOA with positively charged QAE, or by van der Waals forces between PFOA's fluoro-carbon tail and the graphene or QAE carbon surfaces.
基金funding provided by University at Albany,State University of New York。
文摘Nanophotocatalysts have shown great potential for degrading poly-and perfluorinated substances(PFAS).In light of the fact that most of these catalysts were studied in pure water,this study was designed to elucidate effects from common environmental factors on decomposing and defluorinating perfluorooctanoic acid(PFOA)by In2O3 nanoparticles.Results from this work demonstrated that among the seven parameters,pH,sulfate,chloride,H2O2,In2O3 dose,NOM and O2,the first four had statistically significant negative effects on PFOA degradation.Since PFOA is a strong acid,the best condition leading to the highest PFOA removal was identified for two pH ranges.When pH was between 4 and 8,the optimal condition was:pH=4.2;sulfate=5.00 mg/L;chloride=20.43 mg/L;H2O2=0 mmol/L.Under this condition,PFOA decomposition and defluorination were 55.22 and 23.56%,respectively.When pH was between 2 and 6,the optimal condition was:pH=2;sulfate=5.00 mg/L;chloride=27.31 mg/L;H2O2=0 mmol/L.With this condition,the modeled PFOA decomposition was 97.59%with a defluorination of approximately 100%.These predicted results were all confirmed by experimental data.Thus,In2O3 nanoparticles can be used for degrading PFOA in aqueous solutions.This approach works best when the target contaminated water contains low concentrations of NOM,sulfate and chloride and at a low pH.
基金the German Federal Environmental Foundation for sponsoring the project.
文摘The distribution of polyfluoroalkyl compounds(PFCs)in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied.The PFCs quantified included C_(4)-C_(8) perfluorinated sulfonates(PFSAs),6∶2 fluorotelomer sulfonate(6∶2 FTS),C_(6) and C_(8) perfluorinated sulfinates(PFSiAs),C_(4)-C_(12) perfluorinated carboxylic acids(PFCAs),perfluoro-3,7-dimethyl-octanoic acid(3,7m_(2)-PFOA),perfluorooctane sulfonamide(FOSA),and n-ethyl perfluroctane sulfonamidoethanol(EtFOSE).PFCs were mostly distributed in the dissolved phase,where perfluorooctanoic acid(PFOA)dominated with 2.9–12.5 ng/L.In the suspended particulate matter FOSA and perfluorooctane sulfonate(PFOS)showed the highest concentrations(4.0 ng/L and 2.3 ng/L,respectively).The total flux ofΣPFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate phase.This indicates that the river Elbe acts as a source of PFCs into the North Sea.However,the concentrations of perfluorobutane sulfonate(PFBS)and perfluorobutanoic acid(PFBA)in the North Sea were higher than that in the river Elbe,thus an alternative source must exist for these compounds.
基金supported by the National Natural Science Foundation of China (No.21625702)。
文摘Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and polyfluoroalkyl substances(PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time.The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10^(6) ng/g, and <MDL(method detection limit) to 5.3 × 10^(3) ng/g,respectively.Generally, the levels of PFOA in raw materials were higher than in products,implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps.By tracking a company’s polytetrafluoroethylene(PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10^(6) to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued.High concentrations of HFPO-TrA(2.7 × 10^(5) to 8.2 × 10^(5) ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.
基金supported by the National Basic Research Program(973)of China(No.2010CB933600)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA09030203)+4 种基金the National Natural Science Foundation of China(Nos.2127716141103076)the special fund from the State Key Laboratory of Environmental Aquatic Chemistry(No.10Y10ESPCR)the Youth Innovation Promotion AssociationChinese Academy of Sciences(29QNCX2012005)
文摘Perfluorooctanoic acid(PFOA)is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85℃ under UV light(201–600 nm).The limited degree of decomposition at 25℃ was due to low quantum yield,which was increased by a factor of 12 at 85℃.Under the imposed conditions,the defluorination ratio increased from 8% at 25℃ to 50% at85℃ in 60 min.Production of perfluorinated carboxylic acids(PFCAs,C7–C5),PFCAs(C4–C3)and TFA(trifluoroacetic acid,C2)accelerated and attained a maximum within 30 to 90 min at 85℃.However,these reactions did not occur at 25℃ despite extended irradiation to180 min.PFOA was decomposed in a step-wise process by surrendering one CF2unit.In each cyclical process,increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals.The energy consumption for removing eachμmol of PFOA was reduced from 82.5 k J at 25℃ to 10.9 k J at 85℃ using photolysis.Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.
基金We thank the Arctic Monitoring and Assessment Programme(AMAP)and the national programs in the circumpolar countries for their funding and support of this work.We are especially grateful to Simon Wilson,Cynthia de Wit,and the reviewers that read the chapter on PFASs in the original AMAP assessment.We are thankful to the northern communities in circumpolar regions for their cooperation and collection of biological samples that yielded the data reviewed here.DCGM was supported by the King Carl XVI Gustaf Professorship in Environmental Science at the Dept of Environmental Science and Analytical Chemistry,Stockholm University during 2018-19.
文摘Poly-and perfluoroalkyl substances(PFASs)are important environmental contaminants globally and in the early 2000s they were shown to be ubiquitous contaminants in Arctic wildlife.Previous reviews by Butt et al.and Letcher et al.have covered studies on levels and trends of PFASs in the Arctic that were available to 2009.The purpose of this review is to focus on more recent work,generally published between 2009 and 2018,with emphasis on PFASs of emerging concern such as perfluoroalkyl carboxylates(PFCAs)and short-chain perfluoroalkyl sulfonates(PFSAs)and their precursors.Atmospheric measurements over the period 2006e2014 have shown that fluorotelomer alcohols(FTOHs)as well as perfluorobutanoic acid(PFBA)and perfluoroctanoic acid(PFOA)are the most prominent PFASs in the arctic atmosphere,all with increasing concentrations at Alert although PFOA concentrations declined at the Zeppelin Station(Svalbard).Results from ice cores show generally increasing deposition of PFCAs on the Devon Ice cap in the Canadian arctic while declining fluxes were found in a glacier on Svalbard.An extensive dataset exists for long-term trends of long-chain PFCAs that have been reported in Arctic biota with some datasets including archived samples from the 1970s and 1980s.Trends in PFCAs over time vary among the same species across the North American Arctic,East and West Greenland,and Svalbard.Most long term time series show a decline from higher concentrations in the early 2000s.However there have been recent(post 2010)increasing trends of PFCAs in ringed seals in the Canadian Arctic,East Greenland polar bears and in arctic foxes in Svalbard.Annual biological sampling is helping to determine these relatively short term changes.Rising levels of some PFCAs have been explained by continued emissions of long-chain PFCAs and/or their precursors and inflows to the Arctic Ocean,especially from the North Atlantic.While the effectiveness of biological sampling for temporal trends in long-chain PFCAs and PFSAs has been demonstrated,this does not apply to the C4eC8ePFCAs,perfluorobutane sulfonamide(FBSA),or perfluorobutane sulfonate(PFBS)which are generally present at low concentrations in biota.In addition to air sampling,sampling abiotic media such as glacial cores,and annual sampling of lake waters and seawater would appear to be the best approaches for investigating trends in the less bioaccumulative PFASs.
基金financially supported by the National Natural Science Foundation of China(Nos.22006088 and 42077293)the Natural Science Foundation of Guangdong Province(China)(No.2019QN01L797)+1 种基金the Shenzhen Municipal Science and Technology Innovation Committee(China)(Nos.WDZC20200817103015002 and RCYX20210609104448111)the Tsinghua Shenzhen International Graduate School(China)(Nos.HW2020002 and QD2021010N).
文摘Heterogeneous photocatalysis has gained substantial research interest in treating per-and polyfluoroalkyl substances(PFAS)-contaminated water.However,sluggish degradation kinetics and low defluorination efficiency compromise their practical applications.Here,we report a superior photocatalyst,defected Bi_(3)O(OH)(PO_(4))_(2),which could effectively degrade typical PFAS,perfluorooctanoic acid(PFOA),with high defluorination efficiency.The UV light irradiation could in situ generate oxygen vacancies on Bi_(3)O(OH)(PO_(4))_(2) through oxidation of the lattice hydroxyls,which further promotes the formation of Lewis acidic coordinately unsaturated bismuth sites.Then,the Lewis acidic sites couple with the proximal surface hydroxyls to constitute the surface frustrated Lewis pairs(SFLPs).With the in-depth spectroscopic analysis,we revealed that the photo-induced SFLPs act as collection centers to effectively adsorb PFOA and endow accessible pathways to transfer photogenerated holes to PFOA rapidly.Consequently,activation of the terminal carboxyl,a ratelimiting step for PFOA decomposition,could be easily achieved over the defected Bi_(3)O(OH)(PO_(4))_(2) photocatalyst.These results suggest that SFLPs exhibit great potential in developing highly efficient photocatalysts to degrade persistent organic pollutants.