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1.
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°C under UV light(201–600 nm).The limited degree of decomposition at 25°C was due to low quantum yield,which was increased by a factor of 12 at 85°C.Under the imposed conditions,the defluorination ratio increased from 8% at 25°C to 50% at85°C 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°C.However,these reactions did not occur at 25°C 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°C to 10.9 k J at 85°C using photolysis.Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.  相似文献   

2.
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.  相似文献   

3.
Perfluorooctanoic acid (PFOA), a persistent organic pollutant, receives increasing concerns due to its worldwide occurrence and resistance to most conventional treatment processes. The photochemical decomposition by 185 nm vacuum ultraviolet (VUV) is one of the efficient methods for PFOA decomposition. The effects of pH on PFOA decomposition in nitrogen atmosphere or oxygen atmosphere were investigated. At its original pH (4.5) of PFOA aqueous solution, PFOA decomposed efficiently both in nitrogen and in oxygen atmosphere. However, when the pH increased to 12.0, PFOA decomposition was greatly inhibited in oxygen atmosphere, while it was greatly accelerated in nitrogen atmosphere with a very short half-life time (9 rain). Furthermore, fluorine atoms originally contained in PFOA molecules were almost completely transformed into fluoride ions. Two decomposi- tion pathways have been proposed to explain the PFOA decomposition under different conditions. In acidic and neutral solutions, PFOA predominantly decomposes via the direct photolysis in both atmospheres; while in the alkaline solution and in the absence of oxygen, the decomposition of PFOA is mainly induced by hydrated electrons.  相似文献   

4.
Duloxetine (DUL), an antidepressant drug, has been detected in surface water and wastewater effluents, however, there is little information on the formation of its transformation products (TPs). In this work, hydrolysis, photodegradation (UV irradiation) and chlorination experiments were performed on spiked distillated water, under controlled experimental conditions to simulate abiotic processes that can occur in the environment and wastewater treatment plants (WWTPs). Eleven TPs, nine from reaction with UV light and two from chlorine contact, were formed and detected by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry, and nine of them had their chemical structures elucidated upon analyses of their fragmentation patterns in MS/MS spectra. The formation and degradation of the TPs were observed. The parent compound was completely degraded after 30?min in photodegradation and after 24?hr in chlorination. Almost all TPs were completely degraded in the experiments. The ecotoxicity and mutagenicity of the TPs were predicted based on several in silico models and it was found that a few of these products presented more ecotoxicity than DUL itself and six TPs showed positive mutagenicity. Finally, wastewater samples were analyzed and DUL and one TP, possibly formed by chlorination process, were detected in the effluent, which showed that WWTP not only did not remove DUL, but also formed a TP.  相似文献   

5.
Per-and polyfluoroalkyl substances(PFASs) are ubiquitous in sludge and water from waste water treatment plants, as a result of their incorporation in everyday products and industrial processes. In this study, we measured several classes of persistent PFASs,precursors, transformation intermediates, and newly identified PFASs in influent and effluent sewage water and sludge from three municipal waste water treatment plants in Sweden, sampled in 2015. For sludge, samples from 2012 and 2014 were analyzed as well.Levels of precursors in sludge exceeded those of perfluoroalkyl acids and sulfonic acids(PFCAs and PFSAs), in 2015 the sum of polyfluoroalkyl phosphoric acid esters(PAPs) were 15–20 ng/g dry weight, the sum of fluorotelomer sulfonic acids(FTSAs) was 0.8–1.3 ng/g,and the sum of perfluorooctane sulfonamides and ethanols ranged from non-detected to 3.2 ng/g. Persistent PFSAs and PFCAs were detected at 1.9–3.9 ng/g and 2.4–7.3 ng/g dry weight, respectively. The influence of precursor compounds was further demonstrated by an observed substantial increase for a majority of the persistent PFCAs and PFSAs in water after waste water treatment. Perfluorohexanoic acid(PFHxA), perfluorooctanoic acid(PFOA), perfluorohexane sulfonic acid(PFHxS), and perfluorooctane sulfonic acid(PFOS)had a net mass increase in all WWTPs, with mean values of 83%, 28%, 37% and 58%,respectively. The load of precursors and intermediates in influent water and sludge combined with net mass increase support the hypothesis that degradation of precursor compounds is a significant contributor to PFAS contamination in the environment.  相似文献   

6.
In this work, a method was developed and optimized for the analysis of polyfluoroalkyl and/or perfluoroalkyl substances(PFASs) content in surface water and sediment samples with high instrumental response and good separation. Surface water and sediment samples were collected from the Yangtze River Delta(YRD) to analyze the distribution characteristics of perfluoroalkyl carboxylic acids(PFCAs), perfluoroalkane sulfonic acids(PFSAs), perfluoroalkyl phosphonic acids(PFPAs), perfluoroalkyl phosphinic acids(PFPiAs), and polyfluoroalkyl phosphoric acid diesters(di PAPs). The results showed that the total concentrations of PFCAs and PFSAs in YRD varied from 31 to 902 ng/L. PFCAs(≥ 11 carbons) and PFSAs(≥ 10 carbons atoms) were not detected in any surface water samples. The mean concentrations of all PFCAs and PFSAs in surface water from the sampling areas decreased in the following order:Yangtze river(191 ng/L) ≈ Taihu lake(189 ng/L) Huangpu river(122 ng/L) ≈ Qiantang river(120 ng/L) Jiaxing urban river(100 ng/L). Strong significant(p 0.05) correlations between the concentrations of many of the compounds were found in the sampling areas, suggesting a common source for these compounds. Only perfluorooctanoic acid(PFOA) was observed in all sediment samples, at concentrations varying from 0.02 to 1.35 ng/g. Finally, detection rates of two di PAPs were only 8% and 10%, respectively and the concentration of di PAPs was two to three times lower compared to PFCAs and PFSAs.  相似文献   

7.
In this study, ultraviolet(UV) and vacuum ultraviolet(VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%–35.4% total organic carbon(TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand(COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD5/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%–47% TOC within 8 hr irradiation.Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen(NH+4–N), 17%more nitrite nitrogen(NO-2–N), and 18% more total nitrogen(TN) than UV, producing 35%less nitrite nitrogen(NO-3–N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent.  相似文献   

8.
The levels of six perfluoroalkyl substances(PFASs) in surface sediment and their vertical variations in dated sediment cores from the Haihe River were investigated; studied substances included perfluorooctanoic acid(PFOA),perfluorononanoic acid(PFNA),perfluorooctane sulfonate(PFOS),perfluorodecanoic acid(PFDA),perfluoroundecanoic acid(PFUnA),and perfluorododecanoic acid(PFDoA). Results showed that the total PFAS concentration in surface sediment ranged between 0.52 and 16.33 ng/g dry weight(dw) with an average of3.47 ng/g dw,with PFOS and PFOA as the dominant PFASs. In general,the PFAS concentrations in the mainstream increased from the upper to the lower reaches,except that a drop occurred downstream of the Erdao dam. Although the PFASs in the sediment cores did not show a clear decreasing or increasing trend with depth,the three cores had a similar vertical variation.The PFAS levels were relatively low in the surface sediment,and reached the first high point at8–20 cm as a result of the wide use of PFASs from 1990 to 2000. After that the PFAS levels decreased,and then increased to a second high point at about 40–48 cm,which might be caused by the leaching of PFASs in sediment. Because PFASs have hydrophilic groups and relatively high solubility,the PFASs will transfer from the upper to lower layers of sediment when water infiltration occurs,leading to the fluctuation of PFAS levels in sediment cores. This study suggests that both the temporal variation of sources and transfer processes of PFASs in sediments are important factors influencing the vertical variation of PFASs in sediment cores.  相似文献   

9.
Storing reclaimed water in lakes is a widely used method of accommodating changes in the consumption of reclaimed water during wastewater reclamation and reuse. Solar light serves as an important function in degrading pollutants during storage, and its effect on dissolved organic matter(DOM) was investigated in this study. Solar light significantly decreased the UV_(254) absorbance and fluorescence(FLU) intensity of reclaimed water.However, its effect on the dissolved organic carbon(DOC) value of reclaimed water was very limited. The decrease in the UV_(254) absorbance intensity and FLU excitation–emission matrix regional integration volume(FLU volume) of reclaimed water during solar light irradiation was fit with pseudo-first order reaction kinetics. The decrease of UV_(254) absorbance was much slower than that of the FLU volume. Ultraviolet light in solar light had a key role in decreasing the UV_(254) absorbance and FLU intensity during solar light irradiation. The light fluence-based removal kinetic constants of the UV_(254) and FLU intensity were independent of light intensity. The peaks of the UV_(254) absorbance and FLU intensity with an apparent molecular weight(AMW) of 100 Da to 2000 Da decreased after solar irradiation, whereas the DOC value of the major peaks did not significantly change.  相似文献   

10.
The photodegradation of bisphenol S (BPS) in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH value, light source, and environmental substances in water. The results showed that the photolysis of BPS occurred under UV light, and the rate increased with light source intensity. The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics: the rate was γ= 0.0161CBPS under a 40-W UV-lamp, and the degradation half-life was 43.1 min. Due to its absorption of light, direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species. The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS. The photodegradation rate of BPS increased in the presence of chloride and ferric ions, while the rate was inhibited by nitrate and phosphate in aqueous solution.  相似文献   

11.
全氟羧酸在185 nm真空紫外光下的降解研究   总被引:4,自引:2,他引:4  
陈静  张彭义  刘剑 《环境科学》2007,28(4):772-776
以全氟辛酸为代表的全氟羧酸是一类新的持久性有机污染物,广泛地存在于各种环境介质.研究了全氟辛酸、全氟庚酸、全氟己酸、全氟戊酸和全氟丁酸等5种全氟羧酸在185 nm真空紫外光下的光降解行为,以发展1种有效降解全氟羧酸的方法.结果表明,全氟羧酸在185 nm紫外光照下发生显著地降解并生成氟离子,而在254 nm紫外光照下降解不明显. 反应6h后, 全氟丁酸降解率达到60%以上;而其它4种全氟羧酸的降解率达到90%以上,脱氟率在21%~71%之间,表现出随碳链增长而降低的趋势. 氮气、空气、氧气等3种反应气氛对全氟羧酸在185 nm紫外光下的降解与脱氟没有显著影响. LC/MS分析表明,全氟辛酸光降解时逐级生成短链的全氟庚酸、全氟己酸、全氟戊酸和全氟丁酸. 全氟羧酸在185 nm光照下首先发生脱羧反应,脱羧后的自由基与水反应生成少1个碳原子的全氟羧酸和氟离子.  相似文献   

12.
采用真空紫外灯(VUV)和双模型介孔材料(BMMs)负载磷钨酸(HPW)催化剂构建光催化体系,探究该体系对水中全氟辛酸(PFOA)的脱氟效果.研究了PFOA初始浓度、HPW/BMMs投加量、初始p H值对体系脱氟的影响,并采用响应曲面法(Response Surface Method,RSM)分析了最佳边界反应条件.结果表明,体系对PFOA具有明显的脱氟效果:脱氟效率随PFOA初始浓度的增大而减小;催化剂投加量为0.2 g·L~(-1),脱氟效率最高达50.2%;体系p H为3~4时,体系脱氟效果显著.基于Box-Behnken响应曲面法,各影响因子对脱氟效率的显著性排序为:p HPFOA初始浓度HPW/BMMs投加量.p H值与HPW/BMMs投加量及初始PFOA浓度交互作用显著,模型回归性良好,最佳运行条件为:p H=3.82,HPW/BMMs投加量为0.3 g·L~(-1),PFOA初始浓度为20 mg·L~(-1),反应4 h的脱氟率达到52.6%,与预测值相比偏差为1.2%.本研究为高效降解全氟化合物提供了新思路.  相似文献   

13.
为提高185nm真空紫外光下甲醛与副产物臭氧的分解效率,以MnOx-TiO2复合催化剂取代TiO2光催化剂,发现甲醛与臭氧的转化率分别从44.7%和38.7%提高到77.5%和96.8%.研究比较了真空紫外光下和暗态下(加臭氧)甲醛与臭氧在MnOx-TiO2催化剂上的分解性能,及UV254nm下光催化分解甲醛的效率.结果表明,真空紫外光下气相活性氧物种的氧化与MnOx表面的臭氧催化氧化过程是甲醛分解的主要途径,而MnOx-TiO2上光催化氧化甲醛效率很低;副产物臭氧主要于MnOx表面活性位上由热催化分解.用真空紫外光辐照MnOx-TiO2催化剂,可提高MnOx催化分解臭氧的稳定性.  相似文献   

14.
VUV/TiO_2/O_3去除水中微量硝基苯的研究   总被引:1,自引:0,他引:1       下载免费PDF全文
采用负载在钛片上的二氧化钛(TiO2)薄膜光催化剂,以能发射185 nm真空紫外线(VUV)的紫外灯为光源,研究臭氧强化的真空紫外光催化方法(VUV/TiO2/O3)对水中微量硝基苯的去除效果.结果表明,VUV/TiO2/O3是一种有效地去除水中微量硝基苯的方法,VUV/TiO2/O3的表观一级反应速率常数比UV/TiO2/O3和VUV/O3分别高102.8%和30.8%,去离子水中50 μg/L的硝基苯反应60 s后就降低到检测限以下.VUV/TiO2/O3对硝基苯的降解速率随臭氧投加量的增加而显著增大,臭氧投加量1.52 mg/L时的反应速率比不加臭氧时提高了134.4%;虽然表观一级反应速率常数随初始浓度增加而稍有下降,但初始浓度170 μg/L的硝基苯反应2 min后也无法检出.水中常见的重碳酸盐和腐殖酸对硝基苯降解有显著的抑制作用,两者浓度分别为2 mmol/L和3.2 mg/L时,VUV/TiO2/O3对硝基苯的表观反应速率常数分别下降82.9%和71.6%,反应速率常数的倒数与重碳酸氢根浓度线性相关.VUV/TiO2/O3能快速有效地去除地表水(含碳酸盐和天然有机物)中的微量硝基苯,4 min内初始浓度为90 μg/L的硝基苯去除率达到96%,UV254降低了80%.  相似文献   

15.
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+1COOH, 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 ecb- attacking the carboxyl of CnF2n+1COOH, resulting in decarboxylation and the generation of CnF2n+1·. The produced CnF2n+1· reacted with H2O, forming CnF2n+1OH, then CnF2n+1OH underwent HF loss and hydrolysis to form CnF2n+1COOH.  相似文献   

16.
全氟辛酸(PFOA)的可生物降解性对阐明其环境归趋具有重要意义.根据前人的还原降解研究成果,采用PFOA摩尔回收率、氟离子浓度、乙酸根浓度、2H-PFOA[F(CF_2)_6CHFCOOH]浓度和短链(C8)全氟羧酸(PFCAs)浓度的变化等作为指标,研究PFOA的厌氧可生物降解性.结果表明,活菌降解样中PFOA摩尔回收率由培养期初(3d)的101%±5%降至培养期末(250 d)的85.6%±3.9%,而氟离子浓度则由培养期初(3 d)的0.59 mg·L~(-1)±0.02 mg·L~(-1)增至培养期末(250 d)的0.63 mg·L~(-1)±0.02 mg·L~(-1),且检出了一定量的乙酸根、2H-PFOA和短链PFCAs,但是这却和其对照样中相应指标的变化类似,且不存在显著性差异.由此可见,尽管热力学计算结果表明还原脱氟产生的热量足够维持微生物生命活动,但在本研究的实验条件下却并没有发现PFOA可被生物降解的证据.  相似文献   

17.
以过硫酸盐(PS)对全氟辛酸(PFOA)进行脱氟,考察脱氟率与初始pH值(1~12)、PS初始浓度(0~400.0mmol/L)、温度(25.0~60.0℃)和反应时间(0~24h)的关系,结果表明:初始pH值、PS初始浓度和温度对脱氟率有明显的影响,脱氟率最高可达86.52%;初始pH值为1.5~3的条件明显有利于PFOA的脱氟,而初始pH值为1或12的条件不利于PFOA的脱氟;脱氟动力学模型ln(1-φ)=-kobst可以很好地描述脱氟率φ与反应时间t、温度和PS初始浓度的关系.  相似文献   

18.
高碘酸盐光化学降解水中PFOA研究   总被引:3,自引:2,他引:1       下载免费PDF全文
研究了反应气氛和TiO2对全氟辛酸(PFOA)的光化学降解行为的影响.结果表明,在254 nm紫外光照下,PFOA光解十分微弱,加入IO4-显著增强PFOA光解.与氮气气氛相比,氧气气氛对PFOA光化学降解有抑制作用.PFOA在UV/TiO2/IO4-体系中的降解效果低于在UV/IO4-体系,反应120 min时,PF...  相似文献   

19.
三江平原稻田CO2通量及其环境响应特征   总被引:4,自引:0,他引:4       下载免费PDF全文
 基于涡度相关技术,于2004年生长季对三江平原稻田CO2通量进行了观测.结果表明,CO2通量日变化特征明显;月平均的CO2通量日变化幅度很大,6~9月,夜间最大净排放通量分别为0.23,0.23,0.18,0.12mg/(m2·s);白天最大净吸收通量分别为-0.14,-0.68,-0.66,-0.22mg/(m2·s).白天CO2通量的变化与光合有效辐射明显相关,并且逐月变化.利用摩擦速度(U)的阈值进行筛选,夜间通量与温度之间无明显相关,同期观测的静态箱法结果表明,夜间通量与空气和土壤温度相关,整个生长季,生态系统从大气中吸收的C为5.30t/hm2.  相似文献   

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