哒嗪硫磷在液相中的光化学降解

以高压汞灯为光源,研究了哒嗪硫磷在液相中的光化学降解及影响因素.结果表明,哒嗪硫磷浓度为5mg·L-1时,在纯水中光解半衰期为9.82h,哒嗪硫磷在不同有机溶剂中的光解速率大小依次为正己烷>乙酸乙酯>甲醇>乙腈,在碱性溶液中比中性和酸性溶液中光解快.在2～20mg·L-1浓度范围内,哒嗪硫磷在水与甲醇中光解速率均随初始浓度的增加而降低.硝酸盐对哒嗪硫磷水中光解有一定的光敏化作用,而表面活性剂(SDS)则表现出显著的光猝灭作用,且猝灭作用与剂量比正相关.Fe3+和Fe2+对哒嗪硫磷水中光解有极强的光敏作用,并且光敏效应随着离子浓度的提高表现出先增加后减小的现象.光解产物的HPLC-MS检测表明,哒嗪硫磷在水中光解主要的途径是发生光氧化和光异构化作用.     

氟啶虫胺腈在不同有机溶剂中的光化学降解

利用液质联用和气相色谱（HPLC-Mass和GC）,研究了氟啶虫胺腈在两种不同光源下于4种不同溶剂（正己烷、甲醇、乙腈、丙酮）中的光化学降解.结果表明,以氙灯为光源,1.0、5.0、20.0mg·L-1的氟啶虫胺腈在4种溶剂中的降解半衰期分别为11.62、8.33、10.80h（正己烷）,5.30、5.81、7.05h（甲醇）,1.72、1.99、2.79h（乙腈）,83.49、37.46、64.77h（丙酮）.以紫外灯为光源,1.0、5.0、20.0mg·L-1的氟啶虫胺腈在4种溶剂中的降解半衰期分别为5.29、4.25、5.49min（正己烷）,2.19、2.97、5.88min（甲醇）,0.86、1.99、1.13min（乙腈）,330、365、198min（丙酮）.氟啶虫胺腈的降解反应主要为还原、水解反应,影响其降解速率的主要因素是光源和溶剂的种类,氟啶虫胺腈的浓度对其降解速度也有一定影响.     

Efficient visible light photo-Fenton-like degradation of organic pollutants using in situ surface-modified BiFeO3 as a catalyst

The visible light photo-Fenton-like catalytic performance of BiFeO₃ nanoparticles was investigated using Methyl Violet (MV), Rhodamine B (RhB) and phenol as probes. Under optimum conditions, the pseudo first-order rate constant (k) was determined to be 2.21×10^-2, 5.56×10^-2 and 2.01×10^-2 min^-1 for the degradation of MV (30 μmol/L), RhB (10 μmol/L) and phenol (3 mmol/L), respectively, in the BiFeO₃-H₂O₂-visible light (Vis) system. The introduction of visible light irradiation increased the k values of MV, RhB and phenol degradation 3.47, 1.95 and 2.07 times in comparison with those in dark. Generally, the k values in the BiFeO₃-H₂O₂-Vis system were accelerated by increasing BiFeO₃ load and H₂O₂ concentration, but decreased with increasing initial pollutant concentration. To further enhance the degradation of pollutants at high concentrations, BiFeO₃ was modified with the addition of surface modifiers. The addition of ethylenediamineteraacetic acid (EDTA, 0.4 mmol/L) increased the k value of MV degradation (60 μmol/L) from 1.01×10^-2 min^-1 in the BiFeO₃-H₂O₂-Vis system to 1.30 min^-1 in the EDTA-BiFeO₃-H₂O₂-Vis system by a factor of 128. This suggests that in situ surface modification can enable BiFeO₃ nano-particles to be a promising visible light photo-Fenton-like catalyst for the degradation of organic pollutants.     

Environmental chamber study of the photochemical reaction of ethyl methyl sulfide and Nox

A series of experiments were conducted in a self-made smog chamber at 300 ± 1 K and 1.01×105 Pa to simulate the photochemical reaction of ethyl methyl sulfide (EMS) and NOx. The results show that the higher the initial concentration of EMS, the more ozone is generated in the simulative reactions. It is found that the light intensity plays a very important role in the evaluation of ozone formation potential for EMS. The parameters of d(O3-NO) and IR (incremental reactivity) were used to quantify the potential of EMS on ozone formation. The obtained maximum IR values in this paper for the five simulative reactions were 1.55×10-2, 0.99×10-2, 1.36×10-2, 2.47×10-2, and 1.65×10-2, respectively. Comparison between the results we obtained here and the results we obtained before for di-tert-butyl peroxide and acetylene was made and it showed that the potential reactivity of EMS on ozone formation is at a relatively low level.     

2,4,4'-三溴联苯醚的光降解研究

以固相微萃取(SPME)结合气相色谱(GC)、气相色谱-质谱联用(GC/MS)技术作为分析检测手段,研究光源、有机溶剂、无机盐与腐殖酸对BDE-28光降解的影响,实验结果表明,光源是影响其降解的主要因素,其次,丙酮、铜离子和腐殖酸对其降解的影响较显著.光源对BDE-28光降解速率的影响为300 W汞灯500 W金卤灯100 W汞灯500 W氙灯;有机溶剂对BDE-28降解速率的影响为甲醇/水(1∶1)甲醇己烷甲苯乙腈丙酮;无机离子的影响各有差别:K+、Na+、SO2-4、NO-3、Cl-对BDE-28降解影响不明显,而Fe3+、NH+4促进BDE-28的降解,Fe2+、Cu2+、Br-抑制BDE-28的降解;腐殖酸抑制BDE-28的降解.     

Occurrence and infection risk of waterborne pathogens in Wanzhou watershed of the Three Gorges Reservoir, China

The Three Gorges Reservoir (TGR), formed by China’s Yangtze Three Gorges Project, is the largest lake in the world, but there is too little information available about fecal contamination and waterborne pathogen impacts on this aquatic ecosystem. During two successive 1-year study periods (July 2009 to July 2011), the water quality in Wanzhou watershed of the TGR was tested with regard to the presence of fecal indicators and pathogens. According to Chinese and World Health Organization water quality standards, water quality in the mainstream was good but poor in backwater areas. Salmonella, Enterohemorrhagic Escherichia coli (EHEC), Giardia and Cryptosporidium were detected in the watershed. Prevalence and concentrations of the pathogens in the mainstream were lower than those in backwater areas. The estimated risk of infection with Salmonella, EHEC, Cryptosporidium, and Giardia per exposure event ranged from 2.9 × 10 -7 to 1.68 × 10-5 , 7.04 × 10-10 to 2.36 × 10-7 , 5.39 × 10-6 to 1.25 × 10-4 and 0 to 1.2 × 10-3 , respectively, for occupational divers and recreational swimmers exposed to the waters. The estimated risk of infection at exposure to the 95% upper confidence limit concentrations of Salmonella, Cryptosporidium and Giardia may be up to 2.62 × 10-5 , 2.55 × 10-4 and 2.86 × 10-3 , respectively. This study provides useful information for the residents, health care workers and managers to improve the safety of surface water and reduce the risk of fecal contamination in the TGR.     

Determination of photochemically-generated reactive oxygen species in natural water

Reactive oxygen species(ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment.ROS may participate in the indirect photolysis of trace organic pollutants,therefore resulting in changes in their environmental fates and ecological risks in natural water systems.Bisphenol A(BPA),an endocrine-disrupting chemical,exits widely in natural waters.The photodegradation of BPA promoted by ROS(.OH,1O2,HO2./O2·-),which were produced on the excitation of ubiquito...     

An improved GC-ECD method for measuring atmospheric N2O

Gas chromatography equipped with an electron capture detector (GC-ECD) has been widely used for measuring atmospheric N2O,but nonlinear response and the influence of atmospheric CO2 have been recognized as defects for quantification.An original GCECD method using N 2 as carrier gas was improved by introducing a small flow rate of CO2 makeup gas into the ECD,which could well remedy the above defects.The N2O signal of the improved method was 4-fold higher than that of the original method and the relative standard deviation was reduced from > 1% to 0.31%.N2O concentrations with different CO2 concentrations (172.2×10-6-1722×10-6mol/mol) measured by the improved GC-ECD method were in line with the actual N2O concentrations.However,the N2O concentrations detected by the original method were largely biased with a variation range of-4.5%～7%.The N2O fluxes between an agricultural field and the atmosphere measured by the original method were greatly overestimated in comparison with those measured by the improved method.Good linear correlation (R2=0.9996) between the response of the improved ECD and N2O concentrations (93×10-9-1966×10-9mol/mol) indicated that atmospheric N2O could be accurately quantified via a single standard gas.Atmospheric N2O concentrations comparatively measured by the improved method and a high precision GC-ECD method were in good agreement.     

Kinetics and mechanisms of p-nitrophenol biodegradation by Pseudomonas aeruginosa HS-D38

The kinetics and mecswithhanisms of p-nitrophenol (PNP) biodegradation by Pseudomonas aeruginosa HS-D38 were investigated. PNP could be used by HS-D38 strain as the sole carbon, nitrogen and energy sources, and PNP was mineralized at the maximum concentration of 500 mg/L within 24 h in an mineral salt medium (MSM). The analytical results indicated that the biodegradation of PNP fit the first order kinetics model. The rate constant k_PNP is 2.039 × 10⁻²/h in MSM medium, K_PNP+N is 3.603 × 10⁻²/h with the addition of ammonium chloride and K_PNP+C is 9.74 × 10⁻³/h with additional glucose. The addition of ammonium chloride increased the degradation of PNP. On the contrary, the addition of glucose inhibited and delayed the biodegradation of PNP. Chemical analysis results by thin-layer chromatography (TLC), UV-Vis spectroscopy and gas chromatography (GC) techniques suggested that PNP was converted to hydroquinone (HQ) and further degraded via 1,2,4-benzenetriol (1,2,4-BT) pathway.     

Photocatalytic degradation of Rhodamine B bymicrowave-assisted hydrothermal synthesized N-doped titanate nanotubes

Microwave-induced nitrogen-doped titanate nanotubes（NTNTs） were characterized by transmission electron microscopy（TEM）, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, Fourier transform infrared spectroscopy（FT-IR）, Zeta potential analysis,specific surface area（SBET）, and UV-Visible spectroscopy. TEM results indicate that NTNTs retain a tubular structure with a crystalline multiwall and have a length of several hundred nanometers after nitrogen doping. XRD findings demonstrate that the crystalline structure of NTNTs was dominated by anatase, which is favored for photocatalytic application. The Ti-O-N linkage observed in the XPS N 1s spectrum is mainly responsible for narrowing the band gap and eventually enhancing the visible light photoactivity. FT-IR results demonstrated the existence of H3O＋, which could be excited by photo-generated holes to form hydroxyl radicals and degrade environmental pollutants. After sintering at 350°C, the UV-Vis absorbance edges of NTNTs significantly shift to the visible-light region, which indicates N atom doping into the nanotubes. Photocatalytic degradation of Rhodamine B（RhB） via NTNTs show good efficiency, with pseudo first-order kinetic model rate constants of 3.7 × 10-3, 2.4 × 10-3and 8.0 × 10-4sec-1at pH 3, 7, and 11, respectively.     

印刷电路板(PCB)厂挥发性有机物(VOCs)排放指示物筛选

采用VOCs快速测定仪和SUMMA罐采样、GC/MS分析方法,采样分析了上海某工业区3个印刷电路板厂生产车间和废气排放口的VOCs含量水平、组成特征和源成分谱.结果表明,在9月和12月2次采样期间,A、B、H厂生产车间总挥发性有机物(TVOCs)(9月/12月)最高浓度分别为(2.94/2.01)×10-9、(3.18/1.11)×10-6、(0.70/0.18)×10-9;废气排放口TVOCs最高浓度则分别为(0.86/0.90)×10-9、(31.2/12.0)×10-6、(1.24/0.30)×10-9.GC/MS分析结果表明,主要检出了烷烃、烯烃、苯系物、酮类、氯代烷烃、氯代苯类、酯类等7大类共67种VOCs化合物;A、B、H厂生产车间/废气排放口最高检出物和检出浓度分别为:2-丁酮6.73 mg.m-3/2-甲基己烷5.93 mg.m-3、乙酸乙酯8.90 mg.m-3/丙烷9.64 mg.m-3、丙烷2.04 mg.m-3/丙烷1.69 mg.m-3.苯、甲苯、二甲苯检出率均为100%,三厂各点位最高检出浓度/平均浓度分别为0.077 mg.m-3/0.035 mg.m-3、0.56 mg.m-3/0.31 mg.m-3、0.21 mg.m-3/0.12 mg.m-3(间+对-二甲苯)和0.081 mg.m-3/0.050 mg.m-3(邻-二甲苯).源成分谱和PCA分析结果表明,A、B厂的VOCs特征轮廓图谱较相似,特征化合物为苯、甲苯、二甲苯以及丙酮和2-丁酮;H厂主要特征污染物除三苯外,还有氯苯和氯代烷烃类化合物.结合原辅材料及生产工艺分析,溶剂、涂料使用和工艺过程的逸散是生产车间面源VOCs排放的主要来源,废气排放口是VOCs重点排放点源.     

Sensitivity of green and blue-green algae to methyl tert-butyl ether

The toxicity of methyl tert-butyl ether (MTBE) to Chlorella ellipsoidea and Aphanizomenon flos-aquae was tested and assessed for a 15-d incubation with concentrations of MTBE from high (2.00×104 mg/L) to low (2 mg/L). The results showed that the toxicity was low when the concentration of MTBE was in the range 1.00×104-2.00×104 mg/L (the greatest inhibition of growth-rate was 70%-71%, occurred during the day 1-5). Low concentrations (2-500 mg/L) stimulated algal growth up to the greatest effect of 85%-200% w...     

水体系中氧氟沙星的光化学降解研究

研究了高压汞灯和氙灯照射下氧氟沙星(OFLX)在蒸馏水、人工海水和天然海水中的光降解过程,探讨了光源、起始浓度、丙酮、表面活性剂等因素对OFLX光化学降解速率的影响.结果表明,OFLX在高压汞灯下的光反应速率比在氙灯下快得多,均符合一级反应动力学过程;在相同光源下,OFLX在海水中降解最快,其次是人工海水;当OFLX初始浓度为2、4、6mg.L-1时,其光解速率常数分别为0.163、0.140和0.132 min-1,随着OFLX初始浓度增大,其光解率降低;不同浓度的丙酮均能促进OFLX光降解的反应,其反应速率常数为0.084 2～0.102 min-1,且光敏效率与丙酮浓度呈正相关关系;然而当十六烷基三甲基溴化铵(CTAB)、十二烷基苯磺酸钠(SDBS)、吐温-20(TW-20)等表面活性剂的浓度为5 mg.L-1,它们均抑制了水体中OFLX光降解反应的进程.另外,利用金藻8701单种培养进行了OFLX光化学降解前后的毒性试验,表明OFLX光解过程产生风险较高的中间产物,随着光解进行,产物毒性降低.     

Synergistic photocatalytic degradation of pyridine using precious metal supported TiO2 with KBrO3

A series of precious metals catalysts （M/TiO/, M = Ru, Rh, Pd, Ag, Ir, Pt or Au） were prepared by a light deposition method and the synergistic photocatalytic degradations of pyridine （20 mg/L） under UV irradiation （365 nm） using M/TiO2 with electron capture agent KBrO3 have been investigated. The results show that KBrO3 has a greatly synergistic role on M/TiO2 and the photocatalytic activity of M/TiO2 is closely related to its work function. Ag could greatly enhance the activity of TiO2 due to the binding characteristics of pyridine on Ag. Under the conditions of 0.5 wt.% Ag loading, Ag/TiO2 concentration of 0.1 g/L, KlrO3 concentration of 10 mmol/L and reaction liquid pH value at 9, the pyridine can be degraded by 64% within 3 hr, doubled than TiO2 photocatalytic system. The degradation kinetics of pyridine follows first-order kinetics and k = 5.53 × 10-3 min^-1.     

Determination of paraquat in water samples using a sensitive fluorescent probe titration method

Paraquat (PQ), a nonselective herbicide, is non-fluorescent in aqueous solutions. Thus, its determination through direct fluorescent methods is not feasible. The supramolecular inclusion interaction of PQ with cucurbit[7]uril was studied by a fluorescent probe titration method. Significant quenching of the fluorescence intensity of the cucurbit[7]uril-coptisine fluorescent probe was observed with the addition of PQ. A new fluorescent probe titration method with high selectivity and sensitivity at the ng/mL level was developed to determine PQ in aqueous solutions with good precision and accuracy based on the significant quenching of the supramolecular complex fluorescence intensity. The proposed method was successfully used in the determination of PQ in lake water, tap water, well water, and ditch water in an agricultural area, with recoveries of 96.73% to 105.77%. The fluorescence quenching values (ΔF) showed a good linear relationship with PQ concentrations from 1.0×10^-8 to 1.2× 10^-5 mol/L with a detection limit of 3.35×10^-9 mol/L. In addition, the interaction models of the supramolecular complexes formed between the host and the guest were established using theoretical calculations. The interaction mechanism between the cucurbit[7]uril and PQ was confirmed by ¹H NMR spectroscopy.     

Absorption and recovery of n-hexane in aqueous solutions of fluorocarbon surfactants

n-Hexane is widely used in industrial production as an organic solvent. As an industrial exhaust gas, the contribution of n-hexane to air pollution and damage to human health are attracting increasing attention. In the present study, aqueous solutions of two fluorocarbon surfactants(FSN100 and FSO100) were investigated for their properties of solubilization and dynamic absorption of n-hexane, as well as their capacity for regeneration and n-hexane recovery by thermal distillation. The results show that the two fluorocarbon surfactants enhance dissolution and absorption of n-hexane, and their effectiveness is closely related to their concentrations in solution. For low concentration solutions(0.01%–0.30%), the partition coefficient decreases dramatically and the saturation capacity increases significantly with increasing concentration, but the changes for both are more modest when the concentration is over 0.30%. The FSO100 solution presents a smaller partition coefficient and a greater saturation capacity than the FSN100 solution at the same concentration,indicating a stronger solubilization for n-hexane. Thermal distillation is a feasible method to recover n-hexane from these absorption solutions, and to regenerate them. With 90 sec heating at 80–85°C, the recovery of n-hexane ranges between 81% and 85%, and the regenerated absorption solution maintains its original performance during reuse. This study provides basic information on two fluorocarbon surfactants for application in the treatment of industrial n-hexane waste gases.     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

深圳大学城园区典型OVOCs污染特征与来源解析

采用质子转移反应质谱仪（PTR-MS）对深圳大学城园区2017年不同季节（分干湿两季）的6种典型OVOCs和其他非甲烷烃类（NMHCs）进行连续在线监测,分析其干湿季的浓度特征与日变化规律,并应用光化学龄的参数化方法开展OVOCs的来源解析.结果表明,在观测的6种OVOCs中,甲醇的平均浓度最高,达10×10^-9~12×10^-9,其次是乙酸、丙酮和乙醛,约2~5×10^-9,甲酸和丁酮的含量最低,仅1×10^-9~2×10^-9.通过日变化观察到的OVOCs湿季峰值浓度时间明显早于干季,乙醛表现出与臭氧（O₃）相似的日变化特征,揭示了其可能存在二次来源;甲醇和丁酮的峰值浓度时间均早于O₃,可能存在重要的一次排放源.采用光化学龄模型解析出日间污染物来源比例：在污染较重的干季,甲醇、乙醛、丙酮和丁酮的人为一次源占主导,甲酸和乙酸的二次源是主要贡献者;在较清洁的湿季,天然源成为乙醛、丙酮、丁酮、甲酸和乙酸的主要来源.     

Physiological cellular responses and adaptations of Rhodococcus erythropolis IBBPo1 to toxic organic solvents

A new Gram-positive bacterium, Rhodococcus erythropolis IBBPo1（KF059972.1） was isolated from a crude oil-contaminated soil sample by enrichment culture method. R. erythropolis IBBPo1 was able to tolerate a wide range of toxic compounds, such as antibiotics（800–1000 μg/mL）,synthetic surfactants（50–200 μg/mL）, and organic solvents（40%–100%）. R. erythropolis IBBPo1 showed good tolerance to both alkanes（cyclohexane, n-hexane, n-decane） and aromatics（toluene, styrene, ethylbenzene） with logPOW（logarithm of the partition coefficient of the solvent in octanol–water mixture） values between 2.64 and 5.98. However, alkanes were less toxic for R. erythropolis IBBPo1 cells, compared with aromatics. The high organic solvent tolerance of R. erythropolis IBBPo1 could be due to the presence in their large genome of some catabolic（alkB, alkB1, todC1, todM, xylM）, transporter（HAE1） and trehalose-6-phosphate synthase（otsA1, KF059973.1） genes. Numerous and complex physiological cellular responses and adaptations involved in organic solvent tolerance were revealed in R. erythropolis IBBPo1 cells exposed 1 and 24 hr to 1% organic solvents. R. erythropolis IBBPo1 cells adapt to 1% organic solvents by changing surface hydrophobicity, morphology and their metabolic fingerprinting.Considerable modifications in otsA1 gene sequence were also observed in cells exposed to organic solvents（except ethylbenzene）.     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.