Gas chromatography/ion trap mass spectrometry applied for the analysis of triazine herbicides in environmental waters by an isotope dilution technique

A gas chromatography/ion trap mass spectrometry method was developed for the analysis of simazine, atrazine, cyanazine, as well as the degradation products of atrazine, such as deethylatrazine and deisopropylatrazine in environmental water samples. Isotope dilution technique was applied for the quantitative analysis of atrazine in water at low ng/l levels. One liter of water sample spiked with stable isotope internal standard atrazine-d₅ was extracted with a C₁₈ solid-phase extraction cartridge. The analysis was performed on an ion trap mass spectrometer operated in MS/MS method. The extraction recoveries were in the range of 83-94% for the triazine herbicides in water at the concentrations of 24, 200, and 1000 ng/l, while poor recoveries were obtained for the degradation products of atrazine. The relative standard deviation (R.S.D.) were within the range of 3.2-16.1%. The detection limits of the method were between 0.75 and 12 ng/l when 1 l of water was analyzed. The method was successfully applied to analyze environmental water samples collected from a reservoir and a river in Hong Kong for atrazine detected at concentrations between 3.4 and 26 ng/l.     

超速匀质超声波辅助萃取—气相色谱/质谱法测定沉积物中16种多环芳烃

建立了用于检测沉积物中多环芳烃PAHs的超速匀质超声波辅助萃取—气相色谱/质谱法。以乙腈为提取剂对水体沉积物中16种PAHs进行提取,铜粉净化,所得净化液浓缩丙酮定容用Agilent HP-5MS毛细管柱进行分离,质谱全扫描检测。采用质谱检测器根据NIST 05谱图库比对进行定性分析;外标法进行定量分析。结果表明：16种PAHs的检出限在0.004~0.028 μg?kg-1之间。用标准加入法测得回收率在71.3%~117.2%,相对标准偏差（n＝7）在1.2%~9.8%之间。通过实际样品中PAHs的分析表明,该法快速、溶剂用量小,满足痕量分析的要求。     

超高效液相色谱-串联质谱法同时测定水体中莠去津和呋喃丹的含量

水样中莠去津和呋喃丹通过C18固相萃取柱使之分离并富集。用氮气将固相萃取柱吹干后,用二氯甲烷淋洗使被测组分洗脱,所得洗脱液用氮气吹至尽干,用混合溶剂[甲醇与甲酸-水(0.1+99.9)溶液按40比60的比例混合]1 mL溶解残渣,所得溶液供超高效液相色谱-串联质谱法(UPLC-MS/MS)分析用。用Waters BEH C18色谱柱作分离柱,用不同比例的甲醇和甲酸-水(0.1+99.9)溶液的混合液作流动相进行梯度淋洗,使上述两种农药分离后进行串联质谱测定,所用质谱条件为电喷雾离子源,正离子扫描和多反应监测模式。两种农药质量浓度均在0.10~10.00μg.L-1范围内与相应的峰面积值呈线性关系,检出限(3S/N)均为0.15 ng.L-1。在3个浓度水平上(0.10,0.50,5.00μg.L-1)加入两种农药的标准溶液进行回收试验,测得其平均回收率在77.0%~102.2%之间,相对标准偏差(n=5)在2.9%~7.6%之间。     

The isomer-specific analysis of di- iso -propylnaphthalenes

Di-iso-propylnaphthalenes (DIPN), frequently observed low-level contaminants of the aquatic environment, were analysed as the sum of isomers by GC/MS in Rhine and Lippe river sediments. For future isomer-specific trace analysis, linear retention indices of the components of a technical DIPN formulation were determined on six different GC-columns. Gas-phase infrared spectra aquired by GC/FT–IR analysis on GC capillaries coated with apolar and polar stationary phases showed characteristic patterns of C–H_ar out of plane deformation vibrations which allowed all DIPN isomers to be distinguished. Theoretical IR spectra of all DIPN were calculated with the B3LYP functional using 6-311G(d,p) and 6-311G+(d,p) standard triple zeta basis sets. The resulting frequencies were scaled by a factor derived emprically. Theoretical and experimental IR spectra allowed the structures of seven major DIPN isomers and two minor components to be assigned to the corresponding GC-peaks. All DIPN isomers of a technical formulation were resolved on polar GC capillaries, and the composition of the technical DIPN mixture was determined.     

生物样品中苯丙胺类毒品的小体积液相萃取及GC/MS分析

小体积液相萃取;苯丙胺毒品;唾液;毛发;GC/MS     

GC/MS方法分析豇豆中水胺硫磷等37种农药残留

建立了GC/MS法同时测定豇豆中水胺硫磷等37种农药残留的方法.农药经过乙腈提取,NH2/CARBON复合固相萃取小柱净化,HP-5MS(30 m×0.25 mm×0.25 μm)弹性石英毛细管柱分离后,用GC/MS选择离子模式进行测定.农药在0.020～0.500 mg/L时与峰面积有良好的线性关系(r2>0.990...     

硒芳香杂环化合物的GC/MS分析

本文对合成的7种含硒芳香杂环化合物进行了GC／MS分析研究。结果表明：BS、MB、BBS和DBBS等4个化合物在色谱柱内的保留时间与它们的相对分子质量呈线性关系。所有化合物均可获得特征质谱,表现出含单个硒原子的分子离子或碎片离子特征峰簇,硒的两种主要同位素在峰簇中表现为主要峰M与（M-2）的相对丰度比约为2：1,可为鉴定含硒分子离子或碎片离子提供重要信息。新化合物1,2,5-硒二唑并[3,4-d]嘧啶-5,7-（4H,6H）二酮（SPDO）在色谱柱内出现11．83min和7．96min两个具有相同的质谱的色谱峰,被认为是互变异构体的峰。     

微波辅助萃取-GC/MS联用分析竹子中氨基酸

建立了微波辅助萃取-GC/MS联用测定竹子中谷氨酸、天冬氨酸和苯丙氨酸等10种氨基酸的分析方法, 优化了微波辅助萃取条件, 方法的线性范围在0.100～100 μg/mL之间, 检出限在0.0098～0.36 μg/mL之间, RSD为4.1%～9.7%, 回收率在84.3%～118%之间. 分析了4种不同产地、竹龄竹子的竹叶、竹枝和竹沥中氨基酸含量. 结果表明, 不同竹种、产地及竹龄的竹子中氨基酸总量有较大差异;相同竹种其竹沥中氨基酸含量显著高于竹叶及竹枝中氨基酸含量.     

血液中吗啡类毒品硅烷化气相色谱-质谱分析

建立和确证了血液中吗啡类毒品(吗啡、 6-单乙酰吗啡、可待因)的液相萃取-硅烷化-GC/MS-SIM检测的方法.以乙基吗啡为内标,以V(CHCl3)∶V(异丙醇)∶V(正庚烷)＝50∶17∶33混合溶剂为萃取溶剂,以MSTFA 为硅烷化试剂,采用GC/MS-SIM检测方式,吗啡、6-单乙酰吗啡、可待因的线性相关系数均大于0.99,最低血液检测浓度可达到5 ng/mL;定量范围10～1000 ng/mL;日内重复性小于15%.该方法可用于海洛因吸食者血液中的毒品及其代谢物的检验.     

直接萃取-GC/MS法测定卷烟主流烟气中四种芳香胺

采用气相色谱/质谱法直接测定了卷烟主流烟气中的1-氨基萘、 2-氨基萘、 3-氨基联苯和4-氨基联苯等4种芳香胺.该方法直接用CH2Cl2溶剂超声振荡萃取滤片中的芳香胺,超声萃取的同时加入衍生试剂,使萃取和衍生化同步进行,萃取液过硅酸镁柱进行进一步纯化,然后旋转浓缩后进行GC/MS分析.方法的RSD在1.0%～3.7%之间,加标回收率在92.9%～101.1%之间.     

固相微萃取-气相色谱/质谱联用分析室内空气中的苯系物

自制了一种固相微萃取采样装置,建立了固相微萃取-气相色谱/质谱(SPME-GC/MS)联用测定室内空气中苯系物的分析方法。方法的线性范围为1~300μg/m3,检出限为0.1~0.3μg/m3,RSD(n=6)3.2%~15%。采用该方法研究了广州市内20户新装修民居中苯、甲苯、乙苯、对二甲苯和1,3,5-三甲苯的含量及分布,并探讨了苯系物的来源。     

GC-MS联用分析火龙果花提取液的化学成分

采用GC/MS分析火龙果花无水乙醇、CH2Cl2提取液的化学成分.从无水乙醇和CH2C12提取液中分别分离出60和54个峰,经NIST数据库检索、与标准谱图比较共鉴定出49个化学组分.结果表明,火龙果花中含有维生素E,脂肪酸,烃类和β-谷甾醇、豆甾醇、菜油甾醇等甾醇类化合物.     

对2008年一道高考化学题的实验研究——是对甲基苯酚还是邻甲基苯酚

2008年一道高考化学题曾引起过不小的争论。争论的焦点是,一种甲基苯酚,与溴水反应生成的一溴代物只有2种,它应该是对甲基苯酚还是邻甲基苯酚?为了解决上述问题,用GC/MS法进行了实验研究。结果表明：对甲基苯酚与溴水反应生成的一溴代物只能观察到1种,而邻甲基苯酚与溴水反应生成的一溴代物则能观察到2种,二者均未观察到生成羟基间位溴代产物。由此可得出结论,该化合物应该是邻甲基苯酚。     

喷气燃料的化学组成与理化性质的定量关系研究

利用GC/MS分析了80个喷气燃料样品的烃族化学组成,将其分为直链烃、异构烃、环烷烃、芳烃、十氢萘五大类,并测定了燃料的密度、苯胺点、热值、冰点、闪点及沸程等主要理化性质.构建了喷气燃料组成和性质关系的数据库,考察了喷气燃料的烃族组成及沸程对各种性质的影响.结合Cookson等的理论,建立了八个模型方程,通过多元线性回归预测烃族化学组成与理化性质关系, 与已报道的其他方程比较,新模型的相关系数明显提高.     

固相膜萃取与GC/MS联用测定地下水中痕量半挥发性有机物的野外采样方法研究

C18固相萃取膜适宜处理大体积地下水样现场采样而且易于运输、贮存。利用C18固相膜萃取以及GC／MS联用的方法对地下水中痕量半挥发性有机污染物进行了萃取以及定性、定量分析。优化了固相膜萃取的地下水采样量和浓缩体积。有机氯农药和多环芳烃的平均回收率分别为85％～110．1％、90．3％～115．1％；方法检出限达到10^-9g／L；相对标准偏差均小于15％。本方法用于北京地区地下水中的有机污染物分析，并给出地下水样C18固相膜萃取的GC／MS测定结果。     

Determination of polybrominated diphenyl ethers in freshwater fishes from a river polluted by e-wastes

Analytical method using mass spectrometric techniques was applied for the determination of polybrominated diphenyl ethers (PBDEs) in freshwater fishes. Fish samples collected from Nanyang River contaminated by the recycling electron-wastes (e-wastes) materials were prepared by using Soxhlet extraction and multiple-step column chromatographic clean-up. PBDEs were determined by gas chromatography (GC) coupled with ion trap mass spectrometry (for mono- to hepta-BDEs) and quadrupole mass spectrometry (for BDE-209). The method performance was evaluated with the recovery of ¹³C-labeled internal standards and with the analysis of certified reference biota. The obtained recoveries ranged from 75 to 125% with a relative standard deviation of lower than 10% for 16 PBDE congeners. The total PBDE (ΣPBDE) concentrations in fishes showed the following trend: grass carp < mud carp < crucian carp < silver carp < carp. ΣPBDE concentrations in the abdomen, back and tail muscles of carp ranged from 766, 458 and 530 ng/g w.w., and 53, 52, 45 ng/g w.w. in grass carp, respectively. The ΣPBDE concentrations in abdomen muscles were no significantly higher than in back and tail muscles in carp, crucian carp, grass carp and mud carp. PBDE congener concentrations in muscles correlated well with their lipid content. BDE-47 and BDE-28 were the most abundant congeners followed by BDE-17, BDE-15, BDE-66, BDE-154 and BDE-153 in fishes collected from Guiyu.     

Novel approaches to the analysis of steroid estrogens in river sediments

A wide range of estrogenic contaminants has been detected in the aquatic environment. Among these, natural and synthetic steroid estrogens, typically present in municipal sewage-treatment plant (STP) effluents, are the most potent. In this study a new GC–MS method has been developed for direct analysis of five major steroid estrogens (estrone, 17β-estradiol, 17α-ethinylestradiol, dienestrol, and diethylstilbestrol) in river sediments. Four GC–MS systems used for analysis of underivatized analytes in purified extracts were compared. Relatively low detection limits (1.5–5 ng g⁻¹ dried sediment) and good repeatability of GC splitless injection (RSD 1–2%) were achieved by use of a system combining low-pressure gas chromatography with a single-quadrupole mass analyzer (LP-GC–MS). Use of orthogonal gas chromatography (GC×GC) hyphenated with high-speed time-of-flight mass spectrometry (HSTOF-MS) enabled not only significantly better resolution of target analytes, and their unequivocal identification, but also further improvement (decrease) of their detection limits. In addition to these outcomes, use of this unique GC×GC–TOF-MS system enabled identification of several other non-target chemicals, including pharmaceutical steroids, present in purified sediment extracts.     

GC/MS测定锅巴中丙烯酰胺含量

建立了一种测定市售锅巴中的丙烯酰胺含量的方法.该法样品前处理不必经过溴化衍生,样品脱脂后用水提取丙烯酰胺,提取液过活性炭柱,再用乙酸乙酯将活性炭柱中吸附的丙烯酰胺洗脱.洗脱液浓缩后经气相色谱-质谱(GC-MS)定量分析,检测限为0.06 mg/kg,适合测定市售锅巴中的丙烯酰胺的含量.还考察了丙烯酰胺在水的固液两相中的分配比.     

圆盘固相萃取-GC/MS/SIM法在水体有机氮磷农药测定中的应用研究

通过有机氮磷农药测定的样品前处理技术圆盘固相萃取、GC/MS的测定技术选择离子跳变扫描SIM的应用研究,建立了水体中有机氮磷的分析测定方法.其方法检出限达到了ng/L级的水平.