Degradation of carbendazim by UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> investigated by kinetic modelling

The transformation of the fungicide carbendazim (methyl-2 benzimidazole carbamate) induced by hydroxyl radical generated by the UV photolysis of H₂O₂ has been studied in dilute aqueous solution. The efficient reaction of hydroxyl radicals with carbendazim led to the rapid degradation of carbendazim. The study of reaction kinetics yielded a second order rate constant of 2.2±0.3 10⁹ M⁻¹ s⁻¹ for HO^· radicals with carbendazim. This value is in agreement with a high reactivity of HO^· radicals with carbendazim. Most degradation products were identified by high performance liquid chromatography mass spectrometry (HPLC-MS). In the presence of hydrogenocarbonate and carbonate ions, hydroxyl radicals were quenched and in turn carbonate radicals CO₃ ^·− were formed. Carbonate radicals are indeed known to react efficiently with compounds containing electron-rich sites such as nitrogen or sulfur atoms. The use of a kinetic modelling software gave evidence for the occurrence of such reactions with carbendazim. The second order rate constant of carbonate radical with carbendazim was equal to 6±2 10⁶ M⁻¹ s⁻¹. Electronic Publication     

优化SO4-·高级氧化技术修复PAHs复合污染土壤

采用硫酸根自由基高级氧化技术（SR-AOPs）修复南京某炼钢厂附近PAHs复合土壤,通过调整过硫酸钠（Na2S2O8）和亚铁离子（Fe²⁺）比例,结合添加不同种类和浓度的螯合剂和表面活性剂,获得修复的最佳条件,并比较分析不同类型PAHs的降解特征.结果表明：Na₂S₂O₈和Fe²⁺的配比显著影响土壤PAHs的降解效果,当Na₂S₂O₈用量为5mmol/g,Fe²⁺用量为0.5mmol/g,二者比例为10：1时,培养24h,PAHs总去除率最高,为29.32%;在此基础上添加螯合剂柠檬酸0.5mmol/g时,PAHs总去除率可提高至49.9%;继续添加0.27mg/g表面活性剂IGEPAL CA-720,PAHs总去除率最大,为80.8%.分析不同条件下SR-AOPs对PAHs的降解效果,得到总体上SR-AOPs对四环PAHs去除效果最好.添加柠檬酸和IGEPAL CA-720可以进一步强化对土壤中3环、6环PAHs的去除.柠檬酸和IGEPAL CA-720的添加可以更有效去除污染土壤中PAHs,尤其是针对高环PAHs.     

Fe (II)活化过硫酸盐处理喹啉工艺参数优化及生物毒性

以喹啉为处理目标物,采用Fe²⁺活化K₂S₂O₈（PS）的高级氧化体系在不同环境因素下降解喹啉.结果表明：与单一PS体系和Fe²⁺体系相比,Fe²⁺/PS体系可以有效降解喹啉.在初始喹啉浓度为250mg/L,喹啉/PS物质的量比为1：10,PS/Fe²⁺物质的量比为3,初始pH3,反应温度为45℃,反应时间为80min的条件下,喹啉降解率可达100%.提高PS和Fe²⁺浓度均能有效提高喹啉降解率,但超过一定限值后对喹啉去除效果不明显.Fe²⁺/PS去除喹啉的过程符合一级反应动力学.溶液初始pH值越高,喹啉去除率越低;反应温度越高,喹啉去除率越高.自由基淬灭实验证实,Fe²⁺活化PS体系中有SO₄^-·和OH·的存在,其中由SO₄^-·产生的OH·对喹啉的降解占主导地位.通过GC/MS检测到2种中间产物8-羟基喹啉和2（1H）-喹啉酮,据此推测基于硫酸根自由基强化喹啉降解的可能路径.大肠杆菌急性毒性实验结果证实,虽然Fe²⁺/PS体系去除喹啉过程中产生了毒性更强的中间产物,但酸性条件和较高的反应温度有利于体系脱毒.     

烟梗生物炭持久性自由基反应活性的比较

本研究选用不同热解温度（300,500和700℃）制备的烟梗生物炭,与有机污染物对硝基苯酚（PNP）进行吸附降解反应,探究反应前后烟梗生物炭上持久性自由基（EPFRs）信号强度与其降解有机污染物活性的关系.结果显示：生物炭中EPFRs信号强度随热解温度的升高而从6.155×10⁴升高至1.343×10⁵后降低至5.458×10⁴,而PNP的液相降解率则表现为随热解温度的升高先保持为31%左右不变后下降至14.64%,表明生物炭的EPFRs信号强度与活性并不成正比.300℃热解制备的生物炭中以氧为中心的自由基可以将电子转移给水中的氧分子生成活性氧并促进PNP的降解.而500与700℃热解制备的生物炭中碳为中心的自由基与污染物进行降解反应后生成了新的自由基并被稳定于生物炭表面,导致其自由基信号增强降解活性却大幅下降.     

SO32-活化S2O82-降解偶氮染料废水的机制研究

为深度处理偶氮染料废水,以甲基橙（MO）为目标污染物,研究了亚硫酸盐活化过硫酸盐产活性物种的新型高级氧化处理方法,并对活化机制、氧化机理及动力学理论进行分析.通过对SO₃^2-/S₂O₈^2-,S₂O₈^2-,SO₃^2-3种体系进行降解对比和ESR等技术表征对比,发现亚硫酸盐能显著活化过硫酸根产生硫酸根自由基,其能氧化破坏MO偶氮双键形成的共轭体系,有较好的脱色降解效果.考察了亚硫酸盐和过硫酸盐摩尔比、过硫酸盐投加量、初始pH值对降解效果的影响,结果表明当初始pH值为3.0,摩尔比1：1,投加量为20.0mmol/L、反应时间在300min下对MO降解率能达到96.1%,进一步发现该体系对初始pH值的适应范围较广（3.0~11.0）.基于Box-behnken设计的响应面模拟和方差分析得到了可达显著水平的二次响应曲面模型,影响因子对MO降解的贡献排序为：过硫酸盐投加量 > 初始pH值 > 摩尔比.初始MO浓度动力学分析发现不同初始浓度下对MO的降解过程遵循准二级反应动力学规律,反应动力学常数从1.8212×10^-4~2.4649×10^-4min^-1.另一方面发现升高反应温度可以促进体系对MO的降解,根据不同温度下活化过程的反应速率常数的阿累尼乌斯准二级反应的活化能计算结果（E_a=44.9kJ/mol）,发现其相比常规金属活化方式较低,因此该体系对有毒有害的工业有机废水处理有潜在的商业应用价值.     

高藻饮用水系统中羟基自由基降解诺氟沙星

在厦门翔安水厂12000t/d常规饮用水处理工艺的基础上建立了"混凝沉淀-砂滤-·OH/NaClO氧化降解抗生素及消毒-清水池"的处理系统,在九龙江流域高藻爆发期完成了工程化试验.结果表明,当砂滤出水总藻密度为2.04x10³cells/mL时,注入相同氧化剂剂量0.5mg/L处理20s后,·OH将56ng/L的诺氟沙星降解至未检出,而NaClO仅降解至54ng/L.·OH在氧化降解抗生素的同时能杀灭全部藻细胞.根据HPLC-MS/MS检测到的降解中间产物分析,·OH氧化降解诺氟沙星通过进攻哌嗪环、萘啶环和氟原子破坏药效团,直至矿化为CO₂和H₂O.·OH消毒后不产生消毒副产物,检测的106项指标均达到国家《生活饮用水卫生标准》（GB 5749-2006）,为我国高藻饮用水中抗生素的安全处理提供技术支撑.     

A hydroxyl radical detection system using gas expansion and fast gating laser-induced fluorescence techniques

An OH radical measurement instrument based on Fluorescence Assay by Gas Expansion(FAGE)has been developed in our laboratory.Ambient air is introduced into a low-pressure fluorescence cell through a pinhole aperture and irradiated by a dye laser at a high repetition rate of 8.5 k Hz.The OH radical is both excited and detected at 308 nm using A-X(0,0)band.To satisfy the high efficiency needs of fluorescence collection and detection,a 4-lens optical system and a self-designed gated photomultiplier(PMT)is used,and gating is actualized by switching the voltage applied on the PMT dynodes.A micro channel photomultiplier(MCP)is also prepared for fluorescence detection.Then the weak signal is accumulated by a photon counter in a specific timing.The OH radical excitation spectrum range in the wavelength of 307.82–308.2 nm is detected and the excited line for OH detection is determined to be Q_1(2)line.The calibration of the FAGE system is researched by using simultaneous photolysis of H_2O and O_2.The minimum detection limit of the instrument using gated PMT is determined to be 9.4×10~5molecules/cm~3,and the sensitivity is 9.5×10~(-7)cps/(OH·cm~(-3)),with a signal-to-noise ratio of 2 and an integration time of 60 sec,while OH detection limit and the detection sensitivity using MCP is calculated to be 1.6×10~5molecules/cm~3and 2.3×10~(-6)cps/(OH·cm~(-3)).The laboratory OH radical measurement is carried out and results show that the proposed system can be used for atmospheric OH radical measurement.     

纳米Fe3O4/H2O2降解诺氟沙星

采用纳米Fe3O4催化H2O2氧化降解水环境中的诺氟沙星.考察了溶液酸度、温度、催化剂和H2O2浓度对诺氟沙星降解的影响,对比不同底物在Fe3O4/H2O2体系中的降解情况,并进一步探讨了其反应机制.结果表明,溶液酸度显著影响诺氟沙星的降解率,在酸性条件下（pH=3.5）诺氟沙星的降解效率最高.诺氟沙星的降解率随纳米F...     

加热与零价铁活化S2O8^2-氧化降解偶氮染料AO7的研究

以偶氮染料酸性橙AO7为目标污染物,研究了单独的热活化及零价铁（ZVI）活化S2O28-（PS）降解AO7过程温度、PS浓度及ZVI投加量对AO7降解率的影响,并将2种活化方式进行了对比,最终将其联合以期获得最好的降解效果.结果表明,热活化体系对AO7的降解符合一级动力学,其反应速率随温度（室温～90℃）升高而增加,随...     

Observation of the nighttime nitrate radical in Hefei, China

Observation of nighttime nitrate radical (NO3) was performed by using long path differential optical absorption spectroscopy (LP-DOAS), on the outskirts of Hefei, China. The time series of NO3 and supporting parameters were simultaneously measured for a week (31 May-7 June 2006). The results indicated that the average concentration of NO3 was 15.6 pptv with an average lifetimes of 96 s, whereas, NO3 production rates varied from 8×105/(cm3·s)to 2.98×107/（cm3·s）. Furthermore, the calculated N2O5 concentration averaged at 380 pptv. Analysis of data indicated that direct sinks were probably dominating the NO3 loss process during this campaign. Finally, the results were compared with other campaigns in the boundary layer.