单光子/光电子在线质谱实时分析聚氯乙烯热分解/燃烧产物

实验室研制了低能光电子磁场增强电离(MEPEI)和单光子电离(SPI)复合电离源,该电离源具有电离化合物范围宽、碎片离子少、质谱图简单等优点,结合飞行时间质谱(TOF-MS)实现了聚氯乙烯(PVC)热分解/燃烧产物的在线分析.针对不同的目标化合物,MEPEI/SPI复合电离源通过调节电离区电场强度,可以快速在SPI和SPI-MEPEI之间切换.PVC热分解/燃烧产物中电离能大于光子能量(10.60 eV)的HCl和CO2(12.74 eV、13.77 eV)利用MEPEI模式电离;而烯烃、二氯乙烯、苯系物、氯苯、苯乙烯、茚满及萘系物等可通过SPI-MEPEI复合模式电离.通过实时监测PVC主要燃烧产物的信号强度随温度的变化趋势可推断出,PVC燃烧产物主要是通过两种机制生成:①250～370℃时,PVC发生脱氯及分子内环化反应,产生大量的HCl、苯和萘;②380～510℃时,PVC发生分子间交联反应,生成烷基芳烃,如甲苯和二甲苯/乙苯等.实验结果表明,SPI/SPI-MEPEI复合离子源TOF-MS分析速度快,应用范围广,在在线分析中具有广泛的应用前景.     

UV和H2 O2联合消毒灭活饮用水中大肠杆菌研究

以大肠杆菌为研究对象,对单独紫外线(UV)、H2O2及两者不同组合方式的灭活效果进行了分析.结果表明,单独H2O2对大肠杆菌基本无灭活效果,加入浓度为20 mg·L-1的H2O2接触时间为30 min时,灭活率仅为0.02个对数级;单独UV工艺可在一定程度上灭活大肠杆菌,紫外线剂量为10 mJ·cm-2时,灭活率可达到4.51个对数级.紫外线和H2O2联合消毒在一定程度上提高了消毒效果,且不同的组合方式对灭活效果有很大的影响.先UV后H2O2消毒效果优于先H2O2后UV,当紫外线剂量为5 mJ·cm-2时,加入H2O2分别反应2.5、5、10、20 min后,两者的灭活率分别较单独UV消毒增加0.09、0.35、0.38、0.68和0.01、0.07、0.14、0.53个对数级.而UV与H2O2同时消毒效果优于UV与H2O2顺序消毒,当紫外线剂量为5 mJ·cm-2时,加入H2O2反应20 min后,灭活率较UV-H2O2和H2O2-UV工艺分别增加了0.43和0.58个对数级.随着紫外线强度的增加,大肠杆菌的灭活效果不断提高.     

Electrochemical treatment of olive mill wastewater: Treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV- Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13 C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13 C NMR are among the techniques that are introduced for the first time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.     

Biodegradation of 2-methylquinoline by Enterobacter aerogenes TJ-D isolated from activated sludge

Bacterial strain Enterobacter aerogenes TJ-D capable of utilizing 2-methylquinoline as the sole carbon and energy source was isolated from acclimated activated sludge under denitrifying conditions. The ability to degrade 2-methylquinoline by E. aerogenes TJ-D was investigated under denitrifying conditions. Under optimal conditions of temperature (35℃) and initial pH 7, 2-methylquinoline of 100 mg/L was degraded within 176 hr. The degradation of 2-methylquinoline by E. aerogenes TJ-D could be well described by the Haldane model (R² > 0.91). During the degradation period of 2-methylquinoline (initial concentration 100 mg/L), nitrate was almost completely consumed (the removal efficiency was 98.5%), while nitrite remained at low concentration (< 0.62 mg/L) during the whole denitrification period. 1,2,3,4-Tetrahydro-2-methylquinoline, 4-ethyl-benzenamine, N-butyl-benzenamine, N-ethyl-benzenamine and 2,6-diethyl-benzenamine were metabolites produced during the degradation. The degradation pathway of 2-methylquinoline by E. aerogenes TJ-D was proposed. 2-Methylquinoline is initially hydroxylated at C-4 to form 2-methyl-4-hydroxy-quinoline, and then forms 2-methyl-4-quinolinol as a result of tautomerism. Hydrogenation of the heterocyclic ring at positions 2 and 3 produces 2,3-dihydro-2-methyl-4-quinolinol. The carbon-carbon bond at position 2 and 3 in the heterocyclic ring may cleave and form 2-ethyl-N-ethyl-benzenamine. Tautomerism may result in the formation of 2,6-diethyl-benzenamine and N-butyl-benzenamine. 4-Ethyl-benzenamine and N-ethyl-benzenamine were produced as a result of losing one ethyl group from the above molecules.     

Effect of transition metal doping under reducing calcination atmosphere on photocatalytic property of TiO2 immobilized on SiO2 beads

TiO₂ immobilized on SiO₂ (TiO₂/SiO₂) have been prepared by sol-gel method and various ions of transition metals (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) were doped on the photocatalyst using wet impregnation method under reducing calcination atmosphere. The photocatalytic activity of metal doped TiO₂/SiO₂ towards phenol degradation under black light irradiation were investigated and compared with undoped TiO₂/SiO₂. The results showed that the photoresponse of Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂ were larger than undoped TiO₂/SiO₂, indicating that the photogenerated carriers were separated more efficiently in Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂. The reactivity was in the order of Cu²⁺ > Zn²⁺ > Ni²⁺ > Cr³⁺ > Co²⁺. The different photoreactivity was ascribed to combine effect of the different ionic radii and photocorrison tendency of the dopants. The sample was also characterized by surface analytical methods such as X-ray diffraction, scanning electron micrograph/electron dispersive X-ray analyzer and UV-Vis absorption spectrum.     

Adsorption of 2-mercaptobenzothiazole from aqueous solution by organo-bentonite

The adsorption behavior of 2-mercaptobenzothiazole onto organo-bentonite was investigated.Natural bentonite from Gaozhou in Guangdong Province,China was collected.Organo-bentonite was prepared by intercalation of cetyltrimethyl ammonium bromide into the natural bentonite.The physicochemical properties of the prepared organo-bentonite were characterized by X-ray diffraction,N2 adsorption-desorption isotherm and Fourier transform infrared spectroscopy.The results showed that montmorillonite is the main component of the natural bentonite.The basal spacing of the natural bentonite is 1.47 nm,which increased to 1.98 nm on intercalation with cetyltrimethyl ammonium bromide.Moreover,both the surface area and pore volume increased with intercalation.Clear CH2 stretching(3000-2800 cm-1) and scissoring(1480-1450 cm-1) modes of the intercalated surfactants were observed for organobentonite.Compared with the pseudo first-order kinetic model,the pseudo second-order kinetic model is more suitable to describe the adsorption kinetics of 2-mercaptobenzothiazole onto organo-bentonite.The adsorption capacity of 2-mercaptobenzothiazole onto organo-bentonite increased with increasing initial concentration of 2-mercaptobenzothiazole,but decreased with increasing adsorbent dosage.The adsorption isotherm of 2-mercaptobenzothiazole onto organo-bentonite fits well with the Langmuir model.The maximum adsorption capacity of organo-bentonite for 2-mercaptobenzothiazole was 33.61 mg/g,indicating that organo-bentonite is a promising adsorbent for 2-mercaptobenzothiazole.     

Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

我国水泥工业碳排放特征及动态变化分析

水泥工业是温室气体二氧化碳(CO2)的主要排放源,利用碳排放数学模型计算2001-2010年我国水泥工业碳的排放量,分析碳排放量的变化特点和发展趋势。结果表明:水泥工业碳排放总量逐年增长,与水泥产量和排放强度呈线性关系。"十一五"期间单位产品碳排放强度由0.69 t/t下降到0.65 t/t。万元GDP碳排放量2008年达到最低值为0.295 1 t,平均每年万元GDP碳排放量下降2.85%。水泥工业十年间实施节能降耗、资源循环利用、提高经济效益等措施,对于减少碳排放具有明显效果。     

新颖性染料脱色菌株的筛选及脱色效果研究

文章首次尝试以新颖筛选方法对台湾及大陆两岸当地微生物自然生态中,以非偶氮染料脱色作为优势筛选条件,以筛选出可有效电子传递于非偶氮染料RB198脱色的混菌,再进行优势纯化分离,以得到可对非偶氮染料具有强电子传递脱色能力的菌株。再藉此特性来研究其对偶氮染料电子传递生物脱色的特性。结果表明,通过脱色测试及蛋白质电泳初步筛选出4种对非偶氮染料RB198具有较优异脱色能力的菌株,并进行16S rRNA分析,此4株纯菌分别为Microvirgula aerodenitrificans,Acinetobacter guillouiae,Pseudomonas sp.,Rahnella aquatilis。其中Rahnella aquatilis DX2b,Microvirgula aerodenitrificans SH7b为脱色新菌株,文章首度发表其具有脱色性能,对非偶氮染料RB198及偶氮染料RB160,OrangeⅠ有优异脱色能力。     

化学铁盐辅助除磷对生物除磷的影响研究

化学辅助除磷有助于污水厂实现磷达标,但其对生物系统存在潜在的影响。针对除磷药剂对生物除磷过程的影响展开研究,选用硫酸亚铁进行化学辅助除磷。药剂形成的化学污泥干扰生物除磷过程且成分复杂,故以磷酸铁、氢氧化铁模拟化学污泥,由钾离子、K/P摩尔比计算出同步除磷中的生物除磷,来探讨化学污泥对聚磷菌释磷/吸磷过程的影响。结果表明,连续投加硫酸亚铁使聚磷菌的释磷量、吸磷量降低;系统中磷酸铁含量0.075 mmol/L时聚磷菌的释磷和吸磷能力提高了约25%,磷酸铁含量0.15 mmol/L时对聚磷菌吸磷有抑制作用;氢氧化铁对聚磷菌释磷、好氧初期吸磷均有抑制作用。生物污泥与化学污泥存在交互作用。