高碘酸盐光化学降解水中PFOA研究

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...     

TiO2光催化降解PFOA的反应动力学及机制研究

全氟辛酸(PFOA)是一种新的持久性有机污染物,其处置技术是研究的热点.以UV254 nm紫外灯为光源,采用商品TiO2(P25)对PFOA进行光催化降解实验,并考察pH、TiO2用量、初始浓度、反应气氛对降解的影响.结果表明,反应符合准一级动力学方程,pH对反应有重要影响,氧气存在下能提高反应效率.在pH为3,TiO2用量为1.5 g·L-1,通入空气条件下反应7 h实现基本降解,速率常数为0.4206 h-1.投加俘获剂实验表明,空穴(h+)是主要的活性物质,其对反应速率贡献率为66.1%;羟基自由基(·OH)也参与PFOA的降解过程;投加NaF实验表明,PFOA在TiO2上吸附是反应发生的首要条件.UPLC-QTOF/MS分析表明,PFOA光催化降解逐级生成短链全氟羧酸(PFCAs).     

强化混凝消除水中全氟化合物

以十六烷基三甲基溴化铵（CTAB）有机改性膨润土作为助凝剂,采用聚合氯化铝（PAC）协同CTAB-膨润土进行强化混凝实验,对消除水中两类典型的全氟化合物全氟辛烷磺酸（PFOS）/全氟辛酸（PFOA）和浊度进行研究.考察了PAC和CTAB-膨润土投加量、pH值、原水浊度对PFOS/PFOA和浊度去除的影响.结果表明,经有机改性,实现了CTAB对膨润土的插层,增大了层间距,比表面积、阳离子交换容量、有机碳含量也得到较大提高.在PAC投加量为20mg/L、CTAB-膨润土投加量为30mg、pH6~7时,强化混凝去除效果分别达到76%、70%,PFOS/PFOA去除率随着CTAB-膨润土投加量的增大而增大.最佳pH值范围是6~7,混凝过程中Zeta电位在pH值为6.0时达到最大,pH值为7.0时接近于零.PFOS/PFOA的去除率随着原水浊度的增大而增大.     

溶液特性及共存物对纳滤膜去除水中全氟辛酸的影响

利用聚酰胺复合纳滤(NF)膜去除水中的持久性有机污染物—全氟辛酸(PFOA),分别研究了PFOA浓度、溶液离子强度、pH值、典型大分子有机物—牛血清蛋白(BSA)以及BSA与Na+共存对PFOA截留率的影响.结果表明,在0.8MPa下过滤24h,随着PFOA浓度增大,PFOA截留率提高;溶液离子强度、pH值越高,PFO...     

全氟羧酸在185 nm真空紫外光下的降解研究

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.     

沈阳市降雪中PFOS和PFOA污染现状调查

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.     

水稻土中胱氨酸分解产生含硫气体的研究

测定在室内培养情况下南京水稻土中挥发性含硫气体的释放．结果表明,该土壤中产生Ｈ２Ｓ、羰基硫（ＣＯＳ）和二甲基硫（ＭＤＳ）气体．当土壤中加入胱氨酸后,检测到甲硫醇（ＣＨ３ＳＨ）、二硫化碳（ＣＳ２）、ＣＯＳ、Ｈ２Ｓ和ＤＭＳ气体．除ＤＭＳ之外,这些气体的释放量随胱氨酸添加量增加而增加．据此推测,水稻土中胱氨酸的分解可能是ＣＨ３ＳＨ、ＣＳ２、ＣＯＳ、Ｈ２Ｓ等４种气体产生释放的来源之一．在厌氧条件（充氮淹水）下检测到的含硫气体低于好氧条件（普通大气淹水）．光照、ｐＨ值、土壤含水量等对含硫气体的释放量均有影响     

VUV/HPW/BMMs体系对全氟辛酸（PFOA）的脱氟研究

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.     

硫氰根的γ射线辐照降解研究

研究了60Co源γ射线辐照降解SCN-.在溶液pH=1、pH=3时,25 mg/L的SCN-在6kCy下基本能够得到降解,降解率分别达到98.11%、95.97%, pH=7时,在9kCy下, SCN-的降解率为99.33%;但在碱性条件下,18 kGy的剂量下,才能得到降解,达99.64%(PH=10)和99.93%(pH=12).在高浓度下, SEN-溶液的降解则需要更大的剂量.通过对辐照后的SCN-溶液TOC 和TN的测定可知:辐照法对SCN-溶液除去TOC和TN效果不明显,不同剂量辐照后溶液中SO2-4和NO-3浓度的变化表明, SCN-在γ射线辐照过程中可能的反应历程为:硫元素首先被除去,转变成SO2-4而氮元素则很少转变成NO-3主要是以其它形式的氮存在.     

Environmental factors affecting degradation of perfluorooctanoic acid (PFOA) by In2O3 nanoparticles

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.     

氧和氮等离子体改性细旦涤纶的清洁工艺比较

该文对氧、氮低温等离子体改性细旦涤纶进行了研究,分别探讨了氧、氮等离子体放电参数对提高细旦涤纶上染率的影响,得出了2种工艺的最佳放电参数。实验结果表明:经氧、氮等离子体改性后,细旦涤纶的上染率分别提高了17%和5%,说明氧等离子体改性可显著减少印染废水中的污染物排放量,有利于环境治理,氮等离子体改性效果次之。      

钯掺TiO2光催化降解全氟辛酸

全氟辛酸(perfluorooctanoic acid,PFOA)以其分布广泛性、生物蓄积性、生物毒性强而成为全球关注的一种新型持久性有机污染物.采用化学还原法制备钯掺二氧化钛(Pd-Ti O2)催化剂,利用XRD、FESEM、UV-vis DRS对催化剂进行表征,并考察其在365 nm紫外光照射下对PFOA的光催化降解效果.结果表明,化学还原的制备方法使Ti O2粒径减小、比表面积增大且对紫外光的吸收性能增大,但并不引起PFOA光催化效果的改变.而Pd掺杂后大大增强了PFOA的降解效果,反应7 h后溶液中氟离子浓度为6.62 mg·L-1,是Ti O2(P25)的7.3倍.投加俘获剂与通入氮气的实验证明,在PFOA的降解过程中·OH起重要作用,氧气的存在可促进PFOA的降解.采用UPLC-QTOF-MS对产物进行鉴定分析,PFOA的可能降解过程是经h+氧化后发生脱羧基反应,产生的全氟烷烃自由基(·CnF2n+1)被·OH氧化,脱氟生成短链全氟羧酸.Pd能作为电子(e-)捕获剂、加速e-向O2等电子受体的转移,从而缓解e-累积,提高对PFOA的降解效果.     

A型分子筛对WPCBs燃烧特性的影响

利用热重分析法研究不同气氛（空气和N₂）、添加不同催化剂（4A和5A）下,废电路板非金属粉末（WPCBs）的燃烧特性,计算各类综合燃烧特性曲线,并建立燃烧动力学方程。结果表明:空气气氛下,WPCBs燃烧曲线存在3个明显失重峰,即挥发分析出与热解、难燃有机物分解以及固定碳热解;而N₂气氛下,WPCBs燃烧曲线存在1个明显失重峰和1个次失重峰,即挥发分析出与热解、难燃有机物分解。加入催化剂（4A和5A）,WPCBs燃烧特性曲线的水分析出失重峰明显加强,挥发分析出与燃烧和难燃有机物分解失重峰强度明显减弱。在N₂气氛下,WPCBs燃烧具有较高的挥发分释放特性指数D、可燃指数C和综合燃烧特性指数S,而燃尽指数C_b较小。利用Coats-Redfern积分法计算得到不同气氛及催化剂条件下WPCBs燃烧的平均表观活化能E_av,其中E_av约为227.29 kJ/mol（空气或N₂）、72.35~115.99 kJ/mol（空气/N₂+4A/5A）。修正后的质量平均表观活化能E_m为76.38 kJ/mol（空气）、115.09 kJ/mol（N₂）、≤47.26 kJ/mol（空气/N₂+4A/5A）。WPCBs热解的挥发分1峰前反应过程拟合方程为f（α）=（1-α）0.5;而其峰后、挥发分2和固定碳燃尽阶段反应过程拟合方程为f（α）=（1-α）2。     

Catalytic decomposition of low level ozone with gold nanoparticles supported on activated carbon

Highly dispersed gold nanoparticles were supported on coal-based activated carbon (AC) by a sol immobilization method and were used to investigate their catalytic activity for low-level ozone decomposition at ambient temperature. Nitrogen adsorption-desorption, scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts before and after ozone decomposition. The results showed that the supported gold nanoparticles prepared with microwave heating were much smaller and more uniformly dispersed on the activated carbon than those prepared with traditional conduction heating, exhibiting higher catalytic activity for ozone decomposition. The pH values of gold precursor solution significantly influenced the catalytic activity of supported gold for ozone decomposition, and the best pH value was 8. In the case of space velocity of 120000 h⁻¹, inlet ozone concentration of 50 mg/m³, and relative humidity of 45%, the Au/AC catalyst maintained the ozone removal ratio at 90.7% after 2500 min. After being used for ozone decomposition, the surface carbon of the catalyst was partly oxidized and the oxygen content increased accordingly, while its specific surface area and pore volume only decreased a little. Ozone was mainly catalytically decomposed by the gold nanoparticles supported on the activated carbon.     

过硫酸盐对全氟辛酸的脱氟效果及其动力学模型

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）=-k_obst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.     

Decomposition of perfluorooctanoic acid by microwaveactivated persulfate: Effects of temperature, pH, and chloride ions

Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S₂O₈²⁻) 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 of pH (pH = 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01–0.15 mol·L⁻¹), and temperature (60°C, 90°C, and 130°C) 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°C and 0.06 mol·L⁻¹ at 60°C, 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.     

Photocatalytic degradation of perfluorooctanoic acid with β-Ga2O3 in anoxic aqueous solution

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 (e_cb^-) coming from the β-Ga₂O₃ conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, C_nF_2n+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, t_1/2 = 0.48 hr). PFCAs (C_nF_2n+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 e_cb^- attacking the carboxyl of C_nF_2n+1COOH, resulting in decarboxylation and the generation of C_nF_2n+1·. The produced C_nF_2n+1· reacted with H2O, forming C_nF_2n+1OH, then C_nF_2n+1OH underwent HF loss and hydrolysis to form C_nF_2n+1COOH.     

钛基改性DSA电极氧化法去除水中全氟化合物

为了提高金属氧化物电极(DSA电极)的稳定性及催化活性,实现全氟化合物(PFCs)的高效降解,分别以溶胶涂覆法和电沉积法制备了改性DSA(Ti/SnO_2-ZnO)电极,并用于全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)的电化学降解过程研究.实验分别考察了电流密度、溶液初始pH、 PFOA与PFOS初始浓度对PFCs降解效果的影响.结果表明:两种方法制备的改性DSA电极表面均匀负载了SnO_2-ZnO复合涂层.在二维电极体系中,极板面积约为65.0 cm~2,电流密度为20.0 mA·cm~(-2),极板间距为15.0 mm,电解质为1.30 g·L~(-1)次氯酸钠溶液以及电解时间为150 min时,溶胶涂覆法和电沉积法所制备的Ti/SnO_2-ZnO电极对初始浓度为100 mg·L~(-1)的PFOA和PFOS分别在pH为3.50和6.50时去除效果最佳,分别达到了90.6%、94.6%和91.0%、93.7%;循环使用电极3次,其降解过程均符合准一级反应动力学,且电沉积法制备的电极效果优于溶胶涂敷法,表现出对PFCs类污染物稳定、高效的去除能力.     

Radiation-induced reduction of chromium(Ⅵ) in aqueous solution by γ-irradiation in a laboratory-scale

Radiation-induced reduction of chromium(Ⅵ)(Cr(Ⅵ) by γ-irradiation was studied with an initial concentration of 42 mg/L in aqueous solutions. Several factors which might affect the reduction of Cr(Ⅵ) to Cr(Ⅲ) were examined. pH of aqueous solution affects the reduction efficiency significantly. Acidic condition of aqueous solution accelerates the process. At pH 2, a reduction of 86.2%was achieved with the absorbed dose of 15 kGy, while, with the same dose, at pH 5 and 7, the reduction of Cr (Ⅵ) were only 36.3%and 22.2%, respectively. Ethanol (0.1% in V:V) and sodium carbonate (1 mmol/L) were added into the solution respectively as relatively non-toxic hydroxyl radical scavengers. Reduction rate increased greatly in the presence of ethanol at each pH. Reduction efficiency of Cr(Ⅵ) was enhanced in neutral condition with the addition of sodium carbonate, however, no enhancement was found in acidic condition. The reduction of Cr(Ⅵ) was restrained when the solution was saturated with oxygen; however, the restraint was not significant.     

电活化过硫酸盐降解全氟辛酸及其中间产物的探究分析

全氟化合物（PFCs）是一种新兴的持久性有机污染物,具有环境持久性、高毒性和难降解性,因此急需研发高效的降解方法.本文采用电化学恒电位电解法活化过硫酸盐,利用得到的具有强氧化性的SO₄^·-有效降解全氟辛酸（PFOA）,考察了恒定电位值、过硫酸钠的初始浓度、溶液初始pH值和共存离子对电活化过硫酸盐降解PFOA的影响.同时,结合超高效液相色谱-三重串联四级杆质谱联用仪（UPLC-MS/MS）和气相色谱与质谱联用仪（GC-MS）,对其降解的液相和气相中间产物进行探究.结果表明,在控制阴极电位为-1.8 V,初始过硫酸钠溶液浓度为200 mmol·L^-1,初始溶液pH=3.29,恒电位电解4 h后,PFOA去除率约达到60%.当体系中有NO₃^-、异丙醇和过硫酸钠共存时,PFOA降解效率明显提高（91%,4 h）,当有ClO₄^-存在时PFOA去除率约达到76.8%,但HCO₃^-和Cl^-的存在会出现抑制效果.通过对降解中间产物（短链PFCAs和加氢产物）和TOC去除率（62.5%,24 h）的监测分析,进而推断其可能的降解机理为SO₄^·-介导的Kolbe脱羧过程和羧酸逐步被加氢还原的过程.