UV/PMS体系硝基氯酚降解动力学及机理研究

采用紫外光(UV)/单过氧硫酸氢盐(PMS)体系可有效地氧化降解4-氯-2-硝基酚(4C2NP).考察了溶液pH值、底物初始浓度、PMS初始浓度和氯离子、硝酸根离子初始浓度对4C2NP降解效果的影响.在pH2~5时,体系中4C2NP的降解速率并未出现显著差异;随着pH值升高至近中性,其降解过程受到一定程度抑制.初始底物浓度和PMS浓度与体系中4C2NP的降解速率分别呈现负、正相关关系.外加氯离子对4C2NP降解呈现出双重作用,而硝酸盐离子对4C2NP降解抑制作用不显著.脱氯和脱硝过程是4C2NP主要的降解途径.被释放的氯离子会通过自由基反应进行再氯化过程,而脱落的硝基会很快被氧化生成稳定的硝酸盐,从而抑制了硝基的循环过程.最后,根据中间产物推断了4C2NP降解过程的反应机理.     

LED-紫外线/氯高级氧化降解苯妥英钠特性

发光二极管(light emitting diode,LED)作为新型紫外线光源,其与活性氯联用的LED-紫外线/氯高级氧化技术可协同高效降解抗惊厥药微量污染物苯妥英钠(phenytoin sodium,PHT)。LED-紫外线剂量为0. 82 J/cm~2时,LED-紫外线/氯高级氧化对水中的PHT去除率到62%,远高于单独氯化和单独LED-紫外线处理的加和。降解动力学研究发现:LED-紫外线/氯高级氧化降解PHT符合准一级反应动力学。280 nm LED作为光源的LED-紫外线/氯相比310 nm LED-紫外线/氯有更好的PHT去除效果。与LED-紫外线/H_2O_2和LED-紫外线/过硫酸盐相比,氧化剂(氯、H_2O_2和过硫酸盐)浓度为0. 282 mmol/L时,LED-紫外线/氯高级氧化降解PHT的准一级反应动力学常数(0. 096 min~(-1))远高于LED-紫外线/H_2O_2和LED-紫外线/过硫酸盐,分别是其3. 7倍和3. 0倍。优化氯投加量发现,LED-紫外线/氯高级氧化在较低氯投加量(10 mg/L)条件下即可高效降解PHT。对PHT毒性变化研究发现,氯化作用降解PHT过程中,可生成具有急性毒性的中间产物,且持续累积。LED-紫外线/氯高级氧化降解PHT在较低紫外线剂量(0. 08 J/cm~2)下生成了具有急性毒性的中间产物,随着紫外线剂量增加至0. 41 J/cm~2,毒性中间产物被有效去除。     

UV/Cl工艺对三氯生的去除与降解机理研究

对UV/Cl高级氧化工艺降解水中广谱抗菌剂三氯生（TCS）进行研究,对比单一UV、单一Cl和UV/Cl工艺对TCS的去除效果.考察UV光强、余氯初始浓度、溶液pH值和氨氮浓度等因素对反应的影响,探究TCS在UV/Cl工艺中的降解机理,评估其生态风险.结果表明,与单一UV、单一Cl相比,TCS在UV/Cl工艺中降解效果较好,反应符合准一级反应动力学,降解速率常数随UV光强、余氯初始浓度增大而增大,随NH₄⁺-N浓度的增加而减小.基于HRMS Q-TOF解析出17种中间产物,提出了降解反应路径.发光细菌毒性分析和ECOSAR预测均表明,TCS在UV/Cl工艺中产生毒性较高的中间产物,随着反应的进行,产生了毒性较低的中间产物,生态环境风险得以减少.     

UV/H_2O_2体系降解六氯苯动力学及其机理研究

对比了3种不同氧化方法对水中六氯苯(HCB)的去除效果,考察了HCB初始浓度、H2O2投加量及pH值对UV/H2O2降解HCB效果的影响。结果表明,3种工艺对HCB的降解效果是H2O2相似文献   

UV/Fenton光催化氧化降解对氯苯酚废水反应动力学

研究了UV Fenton体系降解对氯苯酚废水的过程及动力学 .研究表明 ,反应降解速率主要与双氧水加入量、污染物初始浓度、亚铁离子浓度、pH值及载气种类有关 .在四分之一双氧水理论投加量的情况下 ,通入氧气 ,总酚的降解率可达到 98% ,CODcr去除率 80 %以上 .反应体系通入氧气 ,可显著提高污染物的去除率 .建立了CODcrUV Fenton降解的动力学模型 ,结果表明 ,该速率方程和实验数据拟合较好 .     

UV/O_3工艺降解水杨酸试验

采用O3、UV和UV/O3三种工艺,降解常见PPCPs物质——水杨酸(Salicylic Acid,SA)的合成废水,比较了不同工艺降解水杨酸的处理效果,并考察了O3浓度、溶液初始pH值等因素对UV/O3工艺降解水杨酸降解效果的影响。试验结果表明:在O3、UV和UV/O3工艺中,水杨酸降解效率由高到低排列依次为:UV/O3>O3>UV,其中UV/O3工艺的降解效率最高;当O3投加量为7 mg/L,水杨酸初始浓度为40 mg/L,溶液初始pH值为4.0,反应15 min时效果最佳,水杨酸可降解97%。此外,在工艺研究的基础上,对于UV/O3工艺降解水杨酸的机理进行初步探索,验证了水杨酸主要羟基化产物为2,5-DHBA和2,3-DHBA,且其浓度呈现先升高后降低的趋势,同时UV/O3体系中捕捉到的·OH的浓度也呈先升高后降低的趋势。     

UV/PMS降解水中罗丹明B的动力学及反应机理

采用紫外(UV)活化过硫酸氢钾(PMS)产生强氧化性硫酸根自由基(SO_4~·-)降解人工染料罗丹明B(RhB).考察了溶液初始p H、氧化剂剂量、RhB初始浓度、天然有机物(NOM)、Fe~(2+)浓度、自由基淬灭剂(甲醇和叔丁醇)及水体中常见阴离子对降解效果的影响,并探测反应体系中生成的无机阳离子及小分子有机酸的种类和浓度.结果表明,降解反应遵循准一级反应动力学,其降解速率受到溶液初始pH的显著影响,当溶液酸性越强或碱性越强时,RhB的降解效果越好,且酸性条件下降解效果优于碱性条件.同时,加大氧化剂剂量及降低底物浓度也会对RhB的降解起促进作用.体系中投加过渡金属Fe~(2+)可显著促进RhB的降解效果,当Fe~(2+)与PMS的浓度比为1∶1时,降解效果最佳.水体中的NO_3~-对RhB的降解有着显著的促进作用,而H_2PO_4~-、C_2O_4~(2-)、Cl~-和NOM则对RhB的降解有抑制作用.采用离子色谱分析了UV/PMS体系降解RhB所产生的NH_4~+,以及甲酸、乳酸、乙酸和草酸,推测RhB在UV/PMS体系中的降解主要是通过共轭结构的破坏、N-位脱乙基并伴有苯环结构的破坏进行的.综合分析表明,UV/PMS工艺可有效运用于罗丹明B污染水体的修复处理过程.     

超声波/零价铁体系降解五氯酚的机理

在超声波/零价铁体系中,以五氯酚为目标污染物,分别对各种形态铁离子浓度和羟基自由基表观生成率进行了定量测定,探讨了超声波与零价铁的协同作用机理.结果表明,在超声波/零价铁体系降解五氯酚过程中,同时存在超声波的羟基自由基氧化作用和零价铁的还原作用,其中超声波的羟基自由基氧化作用占主导,零价铁大大地促进了该体系羟基自由基的生成.同时,采用气相色谱.质谱联用仪测定中间产物,并结合相关研究推测,超声波/零价铁降解五氯酚主要是通过羟基自由基的氧化脱氯、五氯酚氧自由基的自身耦合,以及零价铁的还原脱氯3种降解途径完成的.     

UV/H2O2光化降解水中邻二氯苯的反应机理

通过UV/H2O2光化高级氧化法,对水中邻二氯苯的降解途径及机理,降解反应的影响参数进行了系统的研究.结果表明,光化降解邻二氯苯的反应迅速,弱酸性或中性环境较有利于降解反应的进行,H2O2的投入量在特定的条件下具有一个最佳值.采用离子色谱(IC)、GC/MS等方法鉴定出邻二氯苯降解的中间产物主要为2,3-二氯苯酚、3,4-二氯苯酚、2-氯苯酚、甲酸、乙酸、乙二酸等.依此推导出了邻二氯苯的UV/H2O2光化降解的途径和机理.     

UV/Oxone降解水中扑热息痛的效能及影响模型

采用UV、oxone和UV/Oxone3种工艺降解ACE,同时对体系中氧化活性物质种类和贡献率进行鉴别和计算.采用响应面曲线法研究HCO₃^-、Cl^-、NO₃^-、pH值和温度5因素、3水平条件下UV/Oxone对ACE的去除效果的综合影响,并选用3种实际水体作为原水水质背景来评价UV/Oxone降解ACE的实际降解值和模型预测值的差距,最后比较了3种工艺的效能.结果表明UV、oxone、UV/Oxone3种工艺对ACE的去除率分别为2.1%、53.7%和98.3%.活性物质的鉴别实验发现UV激活oxone会产生^·OH、SO₄^·-和活性氯3种活性物质,且对ACE降解的贡献率分别为37.05%、19.22%和43.73%.通过响应面曲线法得到影响降解ACE效果的回归方程式,该回归方程对应的p值小于0.0001,拟合缺失项不显著,校正决定系数R²>0.8,说明该模型可信度高.选用实际水体进行实际降解和模型预测比较时发现实际降解值基本符合模型预测值.最后对两种不同工艺进行效能比较发现在同等时间和降解率的情况,UV/Oxone耗能最低,是一种高效、快速、可行的降解工艺.     

应用紫外/氯组合工艺去除微污染原水中氨氮的特性研究

针对饮用水中氨氮超标对环境造成的污染问题,采用紫外/氯组合工艺对饮用水中氨氮进行降解研究.结果表明,紫外/氯高级氧化工艺可以有效去除水中氨氮.一方面,自由氯和氨氮之间发生取代反应将氨氮转化为氯胺,254 nm紫外光可有效裂解N—Cl键,一氯胺在254 nm处的摩尔吸光系数为354 L·mol~(-1)·cm~(-1),量子产率为0.68 mol·E~(-1);另一方面,自由氯光解产生的自由基可直接氧化氨氮.随着紫外辐照剂量的增加,氨氮和总溶解性氮(TN)的浓度逐渐减少,当紫外辐照剂量达到1000 mJ·cm~(-2)时,氨氮(起始浓度2 mg·L~(-1))和TN的去除率分别为53%和35%,相比单独氯化条件下分别提高了20%和15%.随着Cl_2/N的增加,氨氮和TN的浓度逐渐减小,当Cl_2/N≥1.6时,紫外/氯组合工艺对氨氮的去除率接近100%,当Cl_2/N1.6时,紫外/氯工艺对TN的去除率相比单独氯化工艺提高了30%左右.此外,氨氮去除率随pH升高而增加,而TN去除率随pH升高而降低.本研究结果可为紫外/氯组合工艺在水厂中的实际应用提供有效的理论和技术支持.     

DBP formation from degradation of DEET and ibuprofen by UV/chlorine process and subsequent post-chlorination

The formation of disinfection by-products(DBPs) from the degradation of N,N-diethyl-3-methyl benzoyl amide(DEET) and ibuprofen(IBP) by the ultraviolet irradiation(UV)/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H_2O_2 process.The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H_2O_2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species U(RCS) and hydroxyl radicals(HO) in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50%after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine(TOCl), respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H_2O_2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%–63% higher,Ulikely due to the generation of more DBP precursors from the attack of RCS, in addition to HO.     

基于不同自由基的高级氧化技术对水中诺氟沙星的去除效果

抗生素在水中的赋存浓度较低,难以被常规的城市污水处理系统有效去除。考察了紫外光联合氯(UV/氯)、双氧水(UV/H2O2)、过硫酸盐(UV/PS) 3种高级氧化体系对诺氟沙星(NFX)的去除效果。结果表明:UV/氯体系降解NFX相比于其他2种具有显著的高效性,当溶液初始pH为7、氯浓度为30 μmol/L时,NFX在2 min内的去除率可达98.67%,相同氧化剂浓度下,UV/H2O2和UV/PS体系10 min内对NFX的去除率仅为41.41%和65.73%;对于UV/氯体系,NFX的去除率随氯浓度的升高而上升,同时考虑成本,最优氯浓度为30 μmol/L;pH影响3种体系对NFX的去除速率,但效果不同,对于UV/氯体系,强碱性条件有利于NFX的去除,对于UV/H2O2和UV/PS体系,中性及弱碱性更有利于NFX的去除;水体基质Cl-对UV/氯体系去除NFX有抑制作用,但对UV/H2O2和UV/PS体系影响不大; HCO 3 - 对3种体系去除NFX均有抑制作用。     

紫外光和基于紫外光的高级氧化工艺降解农药的研究进展

由于农药的环境持久性及毒性,饮用水源中的农药微污染日益受到水处理行业的关注.在众多水处理工艺中,紫外光及基于紫外光的高级氧化工艺因其灭菌效率高、产生消毒副产物少等特点受到广泛关注.本文综述了紫外光及其相关高级氧化工艺对多类广泛使用的农药(包括有机氯、有机磷、氨基甲酸酯、氯乙酰胺和三嗪等)的降解效果,详细讨论了农药的降解...     

O3/UV降解水中的乙酸和硝基苯

利用O3 /UV和O3/H2O2降解了水中的乙酸,结果表明,在相同条件下处理60min后,O3/UV对乙酸的去除率仅比单独臭氧化处理提高了3%,而O3/H2O2在此条件下完全降解乙酸.O3/UV在处理硝基苯过程中却显示较好的氧化降解能力,通过分析表明,硝基苯降解过程中所产生的副产物H2O2对有机物的去除具有很重要的作用.因此,O3/UV氧化降解能力的提高可能有2方面的原因,紫外光对有机物的活化作用;中间产物H2O2催化臭氧分解产生了高活性的羟基自由基. 单独紫外光催化臭氧分解产生羟基自由基的效率极低.     

Mechanism of Cu(Ⅱ) adsorption inhibition on biochar by its aging process

Biochar exposed in the environment may experience a series of surface changes, which is called biochar aging. In order to study the effects of biochar aging on Cu（Ⅱ） adsorption, we analyzed the surface properties before and after biochar aging with scanning electron microscopy（SEM） coupled to an energy-dispersive X-ray spectrometer（EDX） and diffuse reflectance infrared Fourier transform spectroscopy（DRIFTS）, and then explored the influence of the aging process on Cu（Ⅱ） adsorption by batch experiments. After the aging process, the oxygen concentration, phenolic hydroxyl groups, aromatic ethers and other oxygen-containing functional groups on the biochar surface increased, while carboxyl groups slightly decreased. Thus, over a range of pH, the cation exchange capacity（CEC） and adsorption capacity of Cu（Ⅱ） on the aged biochar were smaller than those of new biochar,indicating that when biochar is incubated at constant temperature and water holding capacity in the dark, the aging process may inhibit Cu（Ⅱ） adsorption. Meanwhile, the dissociation characteristics of oxygen-containing functional groups changed through the aging process, which may be the mechanism by which the biochar aging process inhibits the Cu（Ⅱ） adsorption. Carboxyl groups became more easily dissociated at low pH（3.3–5.0）,and the variation of maximum adsorption capability（qm） of Cu（Ⅱ） on the old biochar was enlarged. Phenolic hydroxyl groups increased after the aging, making them and carboxyl groups more difficult to dissociate at high pH（5.0–6.8）, and the variation of qmof Cu（Ⅱ） on the aged biochar was reduced.     

Fe(II)活化O2高级氧化降解罗丹明B染料

基于传统Fenton体系中H₂O₂利用率低,修复费用高,对环境副作用大的缺点,通过向溶液中投加三聚磷酸钠（STPP）,形成Fe（Ⅱ）-STPP配合物,氧气替代H₂O₂作为氧化剂,构建Fe（Ⅱ）/O₂/STPP的新型高级氧化体系,研究了该反应体系对模拟罗丹明B染料废水的降解性能.结果表明该体系对于罗丹明B具有良好的降解效果,并且在较广泛pH值（5-9）条件下罗丹明B降解率均在70%以上,废水中常见金属阳离子对降解效果基本没有影响.通过自由基掩蔽实验证明体系中对罗丹明B起降解作用的主要是·OH.该新型高级氧化体系更加绿色、可持续,在难降解染料等废水的处理中具有广泛的应用前景.     

Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism

Antimony (Sb) is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide (Sb₂O₃) and coexists with manganese (Mn) in weakly alkaline conditions. Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb₂O₃, but few researches concerned the co-transformations of Sb₂O₃ and Mn(II) in environment. This study investigated the mutual effect of abiotic oxidation of Mn(II) and the coupled oxidative dissolution of Sb₂O₃. The influencing factors, such as Mn(II) concentrations, pH and oxygen were also discussed. Furthermore, their co-transformed mechanism was also explored based on the analysis of Mn(II) oxidation products with or without Sb₂O₃ using XRD, SEM and XPS. The results showed that the oxidative dissolution of Sb₂O₃ was enhanced under higher pH and higher Mn(II) loadings. With a lower Mn(II) concentration such as 0.01 mmol/L Mn(II) at pH 9.0, the improved dissolution of Sb₂O₃ was attributed to the generation of dissolved intermediate Mn(III) species with strong oxidation capacity. However, under higher Mn(II) concentrations, both amorphous Mn(III) oxides and intermediate Mn(III) species were responsible for promoting the oxidative dissolution of Sb₂O₃. Most released Sb (∼72%) was immobilized by Mn oxides and Sb(V) was dominant in the adsorbed and dissolved total Sb. Meanwhile, the presence of Sb₂O₃ not only inhibited the removal of Mn(II) by reducing Mn(III) to Mn(II) but also affected the final products of Mn oxides. For example, amorphous Mn oxides were formed instead of crystalline Mn(III) oxides, such as MnOOH. Furthermore, rhodochrosite (MnCO₃) was formed with the high Mn(II)/Sb₂O₃ ratio_, but without being observed in the low Mn(II)/Sb₂O₃ ratio. The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.