Simultaneous determination of brominated phenols in soils

Brominated phenols （BPs）, a widely used group of emerging flame retardants, are important environmental contaminants and exhibit endocrine disrupting potential. Method for simultaneous determination of tetrabromobisphenol A （TBBPA）, tribromophenol （TBP）, dibromophenols （DBPs） and monobromophenols （MBPs） in soils using gas chromatography-mass spectrometry analysis （GC/MS） was successfully developed. Cleanup methods for soil extracts including several solid-phase extraction cartridges and different elution solvents were compared and optimized. Florisil cartridge with dichloromethane as the elution reagent was selected for sample cleanup owing to its high and reproducible recoveries of the target analytes in soils. Derivatization conditions were tested and the optimal conditions were obtained with 20 μL silylation reagent at room temperature. The chromatographic separation was optimized with different columns and DB-XLB column was selected for its excellent separation of the analytes. The limits of detection for the target compounds were from 0.04 to 0.19 ng/g. Mean recoveries of the compounds from spiked soils exceeded 84% with a good reproducibility, excepting that the recovery of 2-bromophenol was relatively poor （lower than 55%） due to its instability. The developed method was applied to the determination of the BPs in the soils collected from e-waste sites. The contents of BPs in the soils were at ng/g levels with TBBPA and TBP the most frequently detected. To our knowledge, this is the first report for the simultaneous determination of TBBPA, TBP, DBPs and MBPs in soils.     

A new derivatization method for a determination of MX and related hydroxyfuranones in water

An extremely potent mutagen, 3‐chloro‐4(dichloromethyl)‐5‐hydroxy‐2(5/f)‐furanone (MX) is commonly present in chlorinated drinking water. Due to its high mutagenic activity and according to WHO guidelines its concentration should be controlled in drinking waters. Determination of MX is difficult due to ppt levels at which the compound usually exists in drinking waters. Derivatization with 2‐propanol is presented as a method which significantly lowers GC/MS detection level of MX. Suitability of 2‐propylation for derivatization of other hydroxyfuranones is also shown.     

北京女性尿液中双酚A及氯代双酚A的浓度和风险评价

建立了有机相丹酰化衍生-UPLC-MS-MS人体尿液样品中双酚A(BPA)及4种氯代双酚A(氯代BPA)的检测方法,对北京地区40个女性尿液样品进行了检测.结果表明:BPA和一氯、二氯、三氯、四氯BPA的检出率分别为90%、96%、90%、52%和45%;浓度分别为(1.30±1.24),(0.40±0.37),(0.41±0.51),(0.18±1.49),(0.46±0.35) ng/mL,4种氯代BPA的总浓度为1.45ng/mL,和BPA浓度相仿.4种氯代BPA的BPA等当量浓度为4.84ng/mL,是BPA浓度的2.2倍. 40个尿液样本BPA等当量浓度符合对数正态分布,超过BPA的糖尿病发生阈值(0.05%发病风险)5.7ng/mL的概率为19.2%.人体暴露氯代BPA的健康风险应该引起重视.     

A new photon kinetic-measure based on the kinetics of electron-hole pairs in photodegradation of textile wastewater using the UV-H2O2FS-TiO2 process

Actual textile wastewater and synthesized wastewater containing various textile dyes were photocatalytic degraded by the UVH2O2Fs-TiO2 process in an aimular-flow photocatalytic reactor. In this process, a photon kinetic-measure was adopted to obtain constant rates of dyes decomposition. It was theorized that, by illumination at different UV frequencies, the electrons within the semiconductor were excited from the valence band to the conduction band, yielding the formation of electron-hole pairs which are the pre-requisites for photocatalysis. CPT （critical photonic time） exposure required to cause 90% of vibrations between the double and single bonds along the molecular chain of the dyes to be oxidized, was taken to measure the photocatalytic activities. The CPTs varied with the frequencies of the UV spectral areas. The derivatization of CPT from the first-order kinetic law was presented.     

释放的14C-绿黄隆结合残留物的衍生化及鉴定

利用湿热法可以将 ¹⁴C-绿黄隆结合残留物从土壤中释放出来 .但该残留物的极性较强 ,在 GC- MS分析前 ,需进行衍生化处理 .本研究建立了该残留物的 DMSO(二甲基亚砜 ) - NaH-CH₃I衍生化法 .正交试验的结果表明 ,在反应温度为 35℃ ,反应时间 5min,衍生化试剂加入量 0.15ml时 ,衍生化产率最高 ,其中温度对衍生化产率存在显著影响 .GC- MS分析表明 ,该方法是可行的 .     

Determination of chemical warfare agents

Ethylarsine dichloride was used during WW I as a chemical warfare agent. Residues of this chemical warfare agent and its metabolites are still present today and continue to contaminate soil and water. A gas Chromatographic method for the detection and determination of ethylarsine dichloride is shown. Six dithiols were tested as possible derivatization reagents for ethylarsine dichloride. With selection of the dithiol, matrix interferences can be eliminated because of the different retention times of the derivatives.     

水中微量甲基膦酸类化合物的树脂富集与GC／MS分析

本文使用三种阴离子交换树脂（即大孔弱碱型Ｄ－３０１－Ｒ,强碱型Ｄ－２９６,２０１Ｘ７）柱对水中微量甲基膦酸类化合物的富集方法进行了研究。含磷毒剂降解产物的水样用气相色谱／质谱法进行定性定量分析。结果表明,Ｄ－３０１－Ｒ阴离子交换树脂柱对甲基膦酸的富集回收率高于６０％。     

Formation of multiple trimethylsilyl derivatives in the derivatization of 17α-ethinylestradiol with BSTFA or MSTFA followed by gas chromatography-mass spectrometry determination

N,O-bis(trimethylsily)trifluoroacetamide (BSTFA) and N-methyl-N(trimethylsily) trifluoroacetamide (MSTFA) are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone (E1) and 17(-ethinylestradiol (EE2). In this study, three trimethylsilyl (TMS) steroid derivatives, mono-and di-trimethylsilyl EE2 and mono-trimethylsilyl E1, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz (TMSI) in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.     

醛类化合物检测方法中腙类物质的衍生条件

通过对醛类化合物的DNPH衍生化酸度、摩尔比、时间条件的研究和衍生化结果的验证获得了过量DNPH条件下制备15种醛的腙标准溶液制备方法。实验结果表明,其共同衍生化条件为1.0~2.0 mol/L盐酸溶液中DNPH/醛类摩尔比不小于2∶1条件下,醛类物质与DNPH可充分衍生化。     

衍生化毛细管气相色谱法测定空气中醋酸

空气中的醋酸采集于Na2 CO3吸收液中 ,在浓硫酸存在时 ,醋酸 (钠盐 )和甲醇衍生化反应生成醋酸甲酯 ,经大口径毛细管柱AT -WAX ( 30m 0 53μm 1 2 μm)分离 ,气相色谱测定。