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1.
全氟羧酸在185 nm真空紫外光下的降解研究   总被引:6,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   

2.
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.  相似文献   

3.
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.  相似文献   

4.
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   

5.
真空紫外-亚硫酸盐法降解PFOS影响因素   总被引:2,自引:1,他引:1  
韩慧丽  王宏杰  董文艺 《环境科学》2017,38(4):1477-1482
通过试验,考察了亚硫酸盐浓度、pH值、全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)初始质量浓度及共存物质对真空紫外-亚硫酸盐法降解PFOS的影响.结果表明,亚硫酸盐浓度的增加有利于提高活性物种水合电子的量,PFOS降解率及脱氟率均随之提高,亚硫酸盐浓度从1 mmol·L~(-1)增加至20 mmol·L~(-1)时,PFOS降解率及脱氟率分别从45%及40%提高至97%及63%;随着原水pH值的升高,水合电子的生成量也随之增加,PFOS的降解率及脱氟率均提高,且脱氟率对pH值的变化更敏感;PFOS初始质量浓度的提高降低了PFOS的降解率及脱氟率,但PFOS的绝对降解量却大幅提高,当PFOS初始质量浓度从1 mg·L~(-1)提高至50 mg·L~(-1)时,PFOS在4 h内的降解量提高了约50倍,这主要是由于高污染物浓度条件下水合电子的利用率较高;Cl~-或HCO_3~-的存在对PFOS降解率影响较小,但对脱氟的影响较为明显,在试验研究的浓度范围内,PFOS脱氟率随Cl~-浓度的增加而提高,随HCO_3~-浓度的增加呈现先升高后降低的规律;腐殖酸的存在屏蔽了部分用于光化学反应的光,而且可以捕获体系的活性物种,从而降低了降解率及脱氟率.  相似文献   

6.
As a novel alternative to traditional perfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), hexafluoroproplyene oxide trimer acid (HFPO-TA) has been detected worldwide in surface water. Moreover, recent researches have demonstrated that HFPO-TA has stronger bioaccumulation potential and higher hepatotoxicity than PFOA. To treat these contaminants e.g. PFOA and PFOS, some photochemical techniques by adding exogenous substances had been reported. However, there is still no report for the behavior of HFPO-TA itself under direct UV irradiation. The current study investigated the photo-transformation of HFPO-TA under UV irradiation in aqueous solution. After 72 hr photoreaction, 75% degradation ratio and 25% defluorination ratio were achieved under ambient condition. Reducing active species, i.e., hydrated electrons and active hydrogen atoms, generated from water splitting played dominant roles in degradation of HFPO-TA, which was confirmed by different effects of reaction atmospheres and quenching experiments. A possible degradation pathway was proposed based on the products identification and theoretical calculations. In general, HFPO-TA would be transformed into shorter-chain PFASs, including hexafluoropropylene oxide dimer acid (HFPO-DA), perfluoropropionic acid (PFA) and trifluoroacetate (TFA). This research provides basic information for HFPO-TA photodegradation process and is essential to develop novel remediation techniques for HFPO-TA and other alternatives with similar structures.  相似文献   

7.
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 C4-C8 perfluorinated sulfonates (PFSAs), 6:2 fluorotelomer sulfonate (6:2 FTS), C6 and C8 perfluorinated sulfinates (PFSiAs), C4-C12 perfluorinated carboxylic acids (PFCAs), perfluoro-3,7-dimethyl-octanoic acid (3,7m2-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 of ΣPFCs 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.  相似文献   

8.
高碘酸盐光化学降解水中PFOA研究   总被引:3,自引:2,他引:1  
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   

9.
杨宁  李飞  杨志敏  曹威  苑宝玲 《中国环境科学》2021,40(11):4770-4778
研究了维生素B12(VB12)催化纳米零价铁(nFe0)仿生还原降解工业级全氟辛磺酸(PFOS).结果表明,VB12催化nFe0不仅能够降解支链PFOS,而且也能够同时降解直链PFOS,这是首次报道直链PFOS的仿生还原降解.PFOS降解过程可用准一级动力学模型模拟,且升高温度有利于PFOS的还原降解去除和脱氟.超高效液相色谱-四级杆飞行时间质谱(UPLC-QTOF)定性分析表明,PFOS仿生降解产物包括4种全氟磺酸类(全氟碳链长度为C4~C7)、9种全氟羧酸类(全氟碳链长度为C2~C7、C10、C11和C13)和5种多氟代酸类(即H-全氟己酸、H-全氟庚酸、H-全氟辛酸、H2-全氟辛酸和H-全氟辛磺酸)化合物.全氟磺酸类和全氟羧酸类化合物首次在VB12仿生催化降解PFOS的产物之中检出,其中全氟十一烷酸(C10)、全氟十二烷酸(C11)和全氟十四烷酸(C13)等长链化合物第一次在降解PFOS过程中被发现.在降解样中检出的H-全氟烷烃(链长为C2~C7、C10、C11和C13)是否是PFOS的仿生降解产物,还有待进一步研究确认.  相似文献   

10.
杨宁  李飞  杨志敏  曹威  苑宝玲 《中国环境科学》2020,40(11):4770-4778
研究了维生素B12(VB12)催化纳米零价铁(nFe0)仿生还原降解工业级全氟辛磺酸(PFOS).结果表明,VB12催化nFe0不仅能够降解支链PFOS,而且也能够同时降解直链PFOS,这是首次报道直链PFOS的仿生还原降解.PFOS降解过程可用准一级动力学模型模拟,且升高温度有利于PFOS的还原降解去除和脱氟.超高效液相色谱-四级杆飞行时间质谱(UPLC-QTOF)定性分析表明,PFOS仿生降解产物包括4种全氟磺酸类(全氟碳链长度为C4~C7)、9种全氟羧酸类(全氟碳链长度为C2~C7、C10、C11和C13)和5种多氟代酸类(即H-全氟己酸、H-全氟庚酸、H-全氟辛酸、H2-全氟辛酸和H-全氟辛磺酸)化合物.全氟磺酸类和全氟羧酸类化合物首次在VB12仿生催化降解PFOS的产物之中检出,其中全氟十一烷酸(C10)、全氟十二烷酸(C11)和全氟十四烷酸(C13)等长链化合物第一次在降解PFOS过程中被发现.在降解样中检出的H-全氟烷烃(链长为C2~C7、C10、C11和C13)是否是PFOS的仿生降解产物,还有待进一步研究确认.  相似文献   

11.
沈阳市降雪中PFOS和PFOA污染现状调查   总被引:4,自引:0,他引:4  
通过调查降雪中PFOS和PFOA的浓度,阐明了沈阳市大气中PFOS和PFOA的污染状况和污染规律.2006-02-06采集沈阳市区和郊区共计36个采样点的降雪样品,2006-02-25在其中5个采样点再次采集降雪样品.固相萃取融雪水中的PFOS和PFOA,利用LC-MS-SIM法测定样品中PFOS和PFOA浓度.全部样品中均检出PFOS和PFOA.2006-02-06降雪中PFOS和PFOA的浓度几何平均值分别为2.0 ng·L-1(范围:0.4~46.2 ng·L-1)和3.6 ng·L-1(范围:1.6~22.4 ng·L-1),95%置信区间分别为1.5~2.8 ng·L-1和3.1~4.2 ng·L-1.PFOS和PFOA的最高浓度同时出现在郊区采样点朱尔屯,市中心区2种物质的浓度呈显著正相关.2006-02-25的5个采样点降雪中PFOS和PFOA的浓度几何平均值均为2.2 ng·L-1.2次降雪中PFOS浓度差异不显著,2006-02-25降雪中PFOA浓度高于2006-02-06.结果表明,沈阳市区和郊区降雪中广泛存在PFOS和PFOA污染,局部区域可能存在共同的PFOS和PFOA污染来源;沈阳地区有较稳定的PFOS来源持续向大气中输送该类物质;PFOS和PFOA的环境行为可能不同.  相似文献   

12.
为优化全氟辛烷磺酸(PFOS)的紫外光降解条件及探明其降解机理,研究了PFOS在暗反应(Dark)、暗反应/碘化钾体系(Dark/KI)、紫外(UV)、紫外/碘化钾体系(UV/KI)、真空紫外(VUV)及真空紫外/碘化钾体系(VUV/KI)6种反应条件下的降解效果;在VUV/KI体系下,以单因素分析法研究了PFOS初始浓度、pH、KI添加量对PFOS降解效果的影响;通过中间产物分析提出PFOS在紫外光下的降解机理与路径. 结果表明:①在Dark、Dark/KI体系下,PFOS均不会降解;在UV、UV/KI、VUV体系下,PFOS降解率均低于30%;在VUV/KI体系下,初始浓度为200 μg/L、KI添加量为2 mmol/L,PFOS的8 h降解率可达70%. ②降低PFOS的初始浓度、提高pH、增加KI添加量均有助于PFOS的降解. ③轨道阱液质联用仪共鉴定出全氟辛酸(PFOA)、全氟丁酸(PFBA)、五氟乙烷磺酸(PFEtS)、五氟丙酸甲酯(MPFA)、三氟乙酸甲酯(MTFA)和三氟乙酸(TFA)等6种中间产物,PFOS的降解过程包括脱磺酸基团以及脱碳碳键反应. 研究显示,水合电子是PFOS紫外光降解过程中的主要活性因子,VUV/KI反应体系可有效去除PFOS,降解路径及降解机理的分析可为其他全氟化合物的紫外光降解提供参考.   相似文献   

13.
电镀是全氟和多氟烷基物质(PFASs)污染的主要来源之一. 目前关于电镀企业周边地表水中的PFASs污染特征报道较为缺乏. 为了解上海市电镀企业周边地表水中PFASs的污染特征与生态风险水平,选取全氟烷基羧酸(PFCAs)、全氟烷基磺酸(PFSAs)、磺酸调聚物以及1-氯-全氟烷基醚磺酸钾(F-53B)等26种典型PFASs为对象,调查其在上海市电镀企业周边地表水中的污染特征,探讨其污染来源并开展初步的生态风险评估. 结果表明:上海市电镀企业周边地表水中∑PFASs浓度范围为93.3~1 334 ng/L,其中大部分地表水中∑PFASs浓度小于300 ng/L,污染最严重的地表水分布于金山区,∑PFASs浓度是背景值的14.8倍. 地表水中全氟辛酸(PFOA)为普遍的主要污染物,其次为短链PFCAs和PFSAs. 1H,1H,2H,2H-全氟辛烷磺酸钠(6∶2 FTS)和F-53B也普遍存在于地表水中,但只在少数地表水中具有较高浓度,尤其是F-53B,其中金山区采样点浓度高达968 ng/L,主要与镀铬业务有关. 这表明短链PFCAs和PFSAs、PFOA、6∶2 FTS及F-53B等均可能已应用于电镀领域. 据污染源特征分析,地表水中PFASs除了受电镀行业的污染外,同时还可能来源于表面处理工业、前体化合物生物降解等. 初步的生态风险评估结果表明,上海市大部分电镀企业周边地表水中生态风险较低,但个别镀铬企业周边地表水中F-53B污染可能产生高生态风险. 研究显示,上海市电镀企业周边地表水中存在一定程度的PFASs污染,污染水平与特征差异较大;其中PFOA是电镀企业周边地表水中普遍存在的主要污染物,但生态风险较低;而F-53B在个别采样点中具有高残留、高生态风险,需加强污染防控.   相似文献   

14.
考察了碳链长度和官能团对高强UV/SO32-体系降解全氟有机酸的影响,选取典型全氟有机酸PFOA和PFOS,探明其降解机制.结果表明,高强UV/SO32-体系可高效降解5种全氟有机酸.全氟有机酸的降解速率随着碳链长度的增加而增加.官能团对全氟有机酸的降解有重要影响,全氟羧酸在体系中的降解速率显著快于全氟磺酸.全氟羧酸是从与羧基相连的α碳上的氟原子开始,通过逐步脱CF2单元的形式生成短链全氟羧酸进行降解.全氟磺酸主要有三条降解路径:脱磺酸基、α位脱氟以及中心C—C键断裂.  相似文献   

15.
上海市市政污水中全氟有机酸污染特征   总被引:3,自引:0,他引:3       下载免费PDF全文
选择上海市9座市政污水处理厂(WWTPs)作为研究对象,检测其进水和出水中全氟有机酸(PFAs)污染水平.结果表明,市政污水中总PFAs浓度为903~4628ng/L,且中短链(C2~C10)全氟羧酸(PFCAs)的检出率一般高于长链(>C10)PFCAs,而对全氟烷基磺酸(PFSAs)而言,全氟辛磺酸(PFOS)的检出率远高于全氟丁磺酸(PFBS)和全氟己磺酸(PFHxS).三氟乙酸(TFA)一般是市政污水中污染水平最高的PFAs,浓度为359~4129ng/L,占总PFAs的20%~93%.尽管全氟辛酸(PFOA)和PFOS的浓度一般低于TFA,甚至在某些情况下还会低于其他PFAs,但在绝大多数情况下它们依然是2种主要的PFAs类污染物,浓度分别为40.6~1571ng/L和21.3~1027ng/L,分别占总PFAs的2%~57%和1%~30%.在污水处理过程中,短链(C2~C5)和长链(>C10)PFCAs浓度的显著下降,而中等链长(C6~C10)PFCAs和PFSAs浓度则显著增加.此外,PFAs浓度和工业废水比例之间并不存在明显的正相关关系.  相似文献   

16.
采用经口摄食染毒,探讨全氟辛烷磺酸(PFOS)对大鼠血清与脑组织中PFOS浓度及海马细胞内钙离子浓度([Ca2+]i)的影响,观察大鼠大脑皮质、海马和小脑组织病理学变化.结果表明,染毒组大鼠血清与脑组织中PFOS浓度、海马细胞内[Ca2+]i均显著高于对照组,且随着染毒剂量的升高,海马细胞内[Ca2+]i升高.大鼠血清与脑组织中PFOS浓度、脑组织中PFOS浓度与海马细胞[Ca2+]i均呈现显著的正相关关系.染毒组大鼠大脑皮质、海马和小脑组织中未见尼氏体染色变浅等病理性改变.  相似文献   

17.
Perfluorooctane sulfonate(PFOS) is a persistent organic pollutant(POP) and emergent contaminant that are widespread in the environment. Understanding the mechanisms controlling the distribution of PFOS and its isomers between hydrargillite and the water phase is important in order to study their redistribution and mobility in the environment. This study investigated the effects of pH, humic acid, fulvic acid and Na2SO4 on sorption of PFOS isomers to hydrargillite. A mixture...  相似文献   

18.
为了阐明厌氧环境下全氟羧酸(PFCAs)等全氟化合物的迁移归趋,研究了8:2氟调聚醇(8:2FTOH)的厌氧降解性能.结果表明,取自市政污水处理厂的污泥在厌氧条件下可还原降解8:2FTOH,并生成氟离子、全氟类和多氟类降解产物,且降解过程可采用双指数衰减模型拟合.在为期120d的培养中,8:2FTOH的摩尔降解率高达(93.2±0.9)%;摩尔回收率则随着培养时间的增加有下降的趋势,由培养初期(1d)的(97.5±5.1)%下降至末期(120d)的(68.9±4.0)%,这说明在培养后期可能产生了未知的降解产物或生成了未知的挥发性产物.8:2不饱和氟调聚酸(8:2FTUA)和全氟辛酸(PFOA)分别是摩尔产率最高的多氟类和全氟类降解产物,分别介于(6.94±0.10)%~(24.2±1.5)%和(2.67±0.22)%~(14.9±1.0)%的范围内.多氟类降解产物的摩尔产率随培养时间的增加先增加后降低,而全氟类降解产物的摩尔产率则随培养时间的增加持续增加,这说明其可能分别为中间降解产物和最终降解产物.  相似文献   

19.
目前,在土壤、大气、水体等各种环境介质中均检测到了全氟辛基磺酸(PFOS)及其前体物(PrePFOS)的存在.自然条件下,PrePFOS的非生物降解量可以忽略不计,其生物降解的途径和降解量是预测未来PFOS环境行为的基础.本文对PrePFOS在环境介质中的分布以及生物降解进行了综述.在所有的PrePFOS中,关于N-乙基全氟辛基磺酰胺乙醇(EtFOSE)的研究较深入,其在土壤、活性污泥、沉积物中的降解途径及PFOS产量均有报道,EtFOSE的降解速度及其PFOS产量与介质的理化性质、微生物群落结构密切相关,N-乙基全氟辛基磺酰胺乙酸(EtFOSAA)脱羧转化为N-乙基全氟辛基磺酰胺(EtFOSA)是EtFOSE转化为PFOS的主要限速步骤.最新关于EtFOSE在土壤中的好氧生物降解的研究首次提出全氟辛基磺酰胺乙酸(FOSAA)脱羧形成全氟辛基磺酰胺(FOSA)是EtFOSE转化成PFOS的另外一个可能的限速步骤.全氟辛基磷酸酯(DiSAmPAP)在沉积物中的半衰期>380d,其可能的降解途径是先降解为EtFOSE,之后降解为PFOS.最后,在已有研究基础上,提出目前PrePFOS研究存在的问题及今后的研究方向.  相似文献   

20.
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.  相似文献   

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