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.     

气相-质谱联用法测定主流烟气中几种芳香胺

采用固相萃取(SPE)-气相(GC)-质谱(MS)选择离子监测(SIM)法测定主流烟气中4种芳香胺(1-萘胺、2-萘胺、3-氨基联苯、4-氨基联苯)。探讨了萃取方式、萃取液浓度、萃取时间、pH等因素对分离检测的影响。对影响提取主流烟气中芳香胺的参数进行优化,在优化的条件下,用5%HCl在室温下超声萃取40 min,烟气中的芳香胺生成胺盐,用50%NaOH调胺盐pH至12以上,将胺游离出来。用五氟丙酸酐酰化,florisil SPE柱纯化后,上GC/MS检测。在优化的条件下,15 min内可实现4种芳香胺的分离检测。1-萘胺、2-萘胺、3-氨基联苯、4-氨基联苯的检测限分别为0.12、0.09、0.13、0.10 ng/mL,相对标准偏差在3.2%~4.7%之间;标准回收率在93.72%~104.22%之间,方法用于卷烟主流烟气中几种芳香胺的测定。     

气相色谱-质谱法测定卷烟烟气总粒相物中14种芳香胺

以五氟丙酸酐为衍生化试剂,氘代2-氨基萘和氘代邻甲苯胺为双内标,采用DB-35MS石英毛细管柱(30 m×0.25 mm i.d×0.25 μm d.f)和选择离子模式,建立了卷烟烟气总粒相物中芳香胺的气相色谱-质谱分析方法.该方法检出限在0.03～2.13 ng/cig.之间,加标平均回收率在92.6%～110.4%之间,相对标准偏差在0.18%～6.4%之间.已用该方法测定了某品牌卷烟烟气总粒相物中14种芳香胺.     

在线固相萃取和高效液相色谱法测定卷烟主流烟气中几种芳胺

研究了用在线固相萃取富集和高效液相色谱法测定卷烟主流烟气中的几种芳胺(苯胺、对甲基苯胺、2,4-二甲基苯胺、1-萘胺、2-萘胺和4-氨基联苯)的方法,样品中的芳胺用邻甲氧基酚衍生生成偶氮染料,偶氮染料用WatersXterraTMRP18色谱柱在线固相萃取富集,然后以WatersXterraTMRP18色谱柱为固定相,75%的甲醇(内含0.01mol/LpH=8的四氢吡咯-醋酸缓冲液)为流动相分离,二极管矩阵检测器检测;苯胺、对甲基苯胺、2,4-二甲基苯胺、4-氨基联苯、1-萘胺、2-萘胺的检出限分别为005、0.08、0.08、0.06、0.03和0.03μg/L。几种芳胺的相对标准偏差在2.2%~3.4%之间;标准回收率在89%~106%之间,方法用于卷烟主流烟气中几种芳胺的测定,结果令人满意。     

应用固相萃取技术分析主流烟气中的芳香胺

建立了一种定量检测卷烟主流烟气中的芳香胺的新方法:应用第一柱为阳离子交换保留机理而第二柱为吸附保留机理的固相萃取(SEE)净化程序来处理样品,从第一柱上洗脱的芳香胺用五氟丙酸酐进行衍生化后,进入第二柱吸附色素和其它杂质,利用GC/MS进行分析测定.该方法具有灵敏度高、准确度高和易于自动化等优点,检出限为0.09ng/cig.～1.26ng/cig.,回收率为76.4%～103.1%.用该方法测定了某品牌卷烟烟气总粒相物中的14种芳香胺.     

固相萃取毛细管气相色谱法测定卷烟滤嘴中7种挥发性羰基化合物

建立了SPE-GC测定卷烟滤嘴中7种挥发性羰基化合物,采用2,4-二硝基苯肼酸性溶液捕集滤嘴中挥发性羰基化合物,捕集液经Waters C18固相萃取小柱纯化和富集,用GC检测.7种羰基化合物检出限分别为0.02、 0.07、 0.04、 0.03、 0.03、 0.02、 0.03 μg/mL;回收率范围在92.0%～99.5%之间;相对标准偏差均小于5%.方法应用于国内5种烤烟型卷烟滤嘴的分析,得到理想结果.     

分散固相萃取/气相色谱-三重四极杆串联质谱法检测纸张中的20种芳香胺

建立了纸张中的20种芳香胺的分散固相萃取/气相色谱-三重四极杆串联质谱分析方法。纸张中的偶氮染料于(70±2)℃经预处理后还原为芳香胺,向反应后的悬浮液中先加入4 mL 10 mol/L氢氧化钠溶液,将pH值由弱酸性调至碱性,再加入0.5 mL的3内标(氘代萘、2,4,5-三氯苯胺和氘代蒽)工作溶液、10 mL的叔丁基甲醚,最后加入15 g无水硫酸钠除水,振摇40 min萃取芳香胺。萃取液经分散固相萃取试剂盒(d-SPE)进一步净化、离心后,取上层清液以气相色谱-三重四极杆串联质谱法(GC-MS/MS),在多反应离子监测(MRM)模式下检测,内标法定量。目标物在各自浓度范围内线性关系良好(r~20.99),在10、20、50 ng/mL 3个加标水平下的回收率为80.7%～128%,相对标准偏差(RSDs)为0.79%～6.5%,检出限(LOD)为0.05～2.1 ng/mL,定量下限(LOQ)为0.18～5.5 ng/mL。该方法简便快捷,灵敏度高,可用于纸张中芳香胺的快速检测。     

液液萃取-分散液液微萃取-气相色谱-质谱联用测定纺织废水中痕量禁用偶氮染料

建立了液液萃取-分散液液微萃取-气相色谱-质谱联用技术测定纺织废水中痕量偶氮染料的方法。废水中的偶氮染料在碱性条件下经连二亚硫酸钠还原成芳香胺后,先用叔丁基甲醚液液萃取、盐酸反萃进行预浓缩及净化;再以乙腈-氯苯体系进行分散液液微萃取,气相色谱-质谱测定。对前处理条件进行了优化,考察了酸碱度及盐效应对芳香胺萃取效率的影响,结果表明:液液萃取过程中加入30 g NaCl,分散液液微萃取过程中加入1 mL 5 mol/L的NaOH调节体系至碱性才能达到较好的萃取效率。在优化的实验条件下,21种目标物均呈现良好的线性关系,其中13种芳香胺的线性范围为0.05～10μg/L, 7种芳香胺的线性范围为0.05～5μg/L, 2,4-二氨基苯甲醚的线性范围为20～100μg/L,相关系数为0.996～0.999。20种芳香胺的检出限可达0.05μg/L, 2,4-二氨基苯甲醚检出限为20μg/L。印染、机织、印花等实际废水加标试验表明,方法的回收率为75.6%～115.1%。该方法富集倍数高,检出限低,适用于纺织废水中痕量禁用偶氮染料的检测。     

中心切割二维液相色谱-串联质谱法测定卷烟主流烟气中4种芳香胺类化合物的含量

提出了中心切割二维液相色谱-串联质谱法(2DLC-MS/MS)测定卷烟主流烟气中1-氨基萘(1-NA)、2-氨基萘(2-NA)、3-氨基联苯(3-ABP)和4-氨基联苯(4-ABP)等4种芳香胺类化合物含量的方法。用剑桥滤片捕集20支卷烟烟气粒相物,加入200μL 1 mg·L^-1混合内标溶液和20 mL 5%(质量分数)盐酸溶液,超声萃取30 min。分取10 mL,加入1 mL 50%(质量分数)氢氧化钠溶液调节溶液酸度至pH 7,再加入2 mL二氯甲烷,涡旋振荡15 min,有机相经0.2μm聚四氟乙烯滤膜过滤。第一维液相色谱法采用强阳离子交换(SCX)色谱柱对目标物进行分离除杂,通过补偿泵在线稀释、中和有机相,目标物被保留于捕集柱,随后目标物被洗脱至第二维反相(RP)色谱系统,分离后在质谱检测器的多反应监测(MRM)模式下,采用内标法定量分析。结果表明：1-NA和2-NA标准曲线的线性范围为0.50～50.0μg·L^-1,3-ABP和4-ABP标准曲线的线性范围为0.25～50.0μg·L^-1,检出限(3S/N)...     

超高效液相色谱-串联质谱法测定化妆品还原液内的4-氨基联苯

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)检测化妆品还原液中4-氨基联苯的方法.化妆品试样经过连二亚硫酸钠化学还原后,离心、PCX固相萃取小柱提取富集、净化,并经氨化甲醇洗脱、氮吹至近干,定容后通过UPLC-MS/MS仪检测,分离柱为Waters Acquity BEH C18柱;流动相为0.3％乙腈-甲酸水溶液;流速0.5mL/min.5种不同基质中4-氨基联苯在5～250 ng/mL浓度范围内呈良好的线性关系,线性回归系数r2均大于0.999,检测限均为1 ng/mL.5种不同基质中4-氨基联苯的回收率为80.9％～92.6％,相对标准偏差(RSD)为0.51％～3.76％(n=3).     

Analysis of aromatic amines in cigarette smoke

A method for the analysis of o-toluidine, o-anisidine, 2-naphthylamine, and 4-aminobiphenyl in cigarette mainstream smoke has been developed, which combines the sensitivity of their pentafluoropropionyl (PFP) derivatives in negative ion chemical ionization (NICI) mode with the selectivity of the gas chromatography/tandem mass spectrometry (GC/MS/MS) technique. The use of four deuterated analogues as internal standards along with the application of the standard addition method results in accurate and precise results; the interday precision for the aromatic amines was 3-10% and the accuracy ranged from 97-100%. This method was applied to two American-blend University of Kentucky reference cigarettes, eight American-blend market cigarettes, a bright (flue-cured) tobacco cigarette, and an electrically heated cigarette smoking system (EHCSS). For the American-blend cigarettes there was a linear correlation between aromatic amine yields and mainstream smoke 'tar' ('tar' = total particulate matter - (nicotine + water)), whereas the bright tobacco cigarette and the EHCSS demonstrated significantly lower aromatic amine yields on an equal 'tar' basis. The results support the hypothesis that the nitrogen content of the tobacco, and above all the cigarette combustion temperature, are determining factors for the yields of aromatic amines in smoke.     

Effect of ionic liquid on the determination of aromatic amines as contaminants in hair dyes by liquid chromatography coupled to electrochemical detection

The room temperature ionic liquid (IL) 1-butyl-3-methylimidazolium bis-(trifluorometanesulfonyl)imide BMIm[NTf?] was used as a novel medium for improvement of separation and quantization of 16 aromatic amines typically present as contaminants in consumer products and detected by HPLC coupled to an electrochemical detector. The aromatic amines, namely 4,4'-diaminodiphenylmethane, 4-chloroaniline, 2-methoxy-5-methyl-aniline, 3,3'-dimethylbenzidine, 2,4-diaminotoluidine, 2-chloro-4-nitroaniline, 4,4'-oxydianiline, aniline, 3,3'-ichlorobenzidine, benzidine, 4-aminobiphenyl, o-dianisidine, o-anisidine, o-toluidine, 4,4'-methylene-bis-2-chloroaniline and 2-naphthylamine are oxidized in methanol/BMIm[NTf?] at a potential around +0.68V to +0.93V vs. Ag/AgCl at a glassy carbon electrode, which is the base for their determination by HPLC/ED. Using the optimized conditions of methanol/BMIm[NTf?] 70:30 (v/v) as mobile phase, flow-rate of 0.8 mL·min?1, column CLC-ODS, Eap = +1.0 V and T = 40 °C analytical curves were constructed for each of the tested amines. Good linearity was obtained in the concentration range of 1.09 mg·L?1 to 217 mg·L?1, with excellent correlation coefficients. The limits of detection reached 0.021 mg·L?1 to 0.246 mg·L?1 and good relative standard deviations (RSD, n = 3) were obtained from the measurements. Satisfactory recovery for each aromatic amine was achieved, ranging from 95 to 103%. The developed method was successfully applied to determine six aromatic amines present as contaminants in commercial hair dye samples.     

Optimization of parameters for the analysis of aromatic amines in finger-paints

A study for the optimisation of the supercritical fluid extraction (SFE) of some aromatic amines (4-chloro-o-toluidine, 2-naphthylamine, 4-aminobiphenyl and benzidine) in finger-paints was conducted. The influence of different variables related to the technique on recoveries was investigated. The analytes were subsequently analysed by gas chromatography after SFE. The study allowed the estimation of four main factors (temperature, pressure, static time and volume of modifier) on recoveries by the use of a two-level factor design, where most significant parameters as well as second- and third-order interactions were identified. Other factors, such as type and volume of modifier and time of contact between the spiker solution and the sample prior to extraction, were also studied. The influence of matrix on extraction recovery was also evaluated by applying the method to different finger-paints, and recoveries were similar or even higher in some cases. The drying process of samples was also studied, while classical drying in an oven and microwaves were compared, with similar efficiencies in both methods. The method was validated by extracting the aromatic amines from some commercial finger-paints.     

Determination of aromatic amines in environmental water sample by hollow fiber-liquid phase microextraction and microemulsion electrokinetic chromatography

A novel method of microemulsion electrokinetic chromatography (MEEKC) coupled with hollow fiber-liquid phase microextraction (HF-LPME) was developed for determination of six aromatic amines including 4-methylaniline, 3-nitroaniline, 2,4-dimethylaniline, 4-chloroaniline, 3,4-dichloraniline and 4-aminobiphenyl. Baseline separation of six aromatic amines was achieved within 8 min by using the microemulsion buffer containing a 10 mM borate buffer at pH 9.0, 0.8% (v/v) ethyl acetate as oil droplets, 60 mM sodium cholate as surfactant, 5.0% (v/v) 1-butanol as co-surfactant. The influence factors relevant to the HF-LPME process were systemically investigated. The obtained enrichment factors were ranged between 70 and 157 in a 30 min extraction time, and the limits of detection ranged between 0.0021 and 0.0048 μg/mL. This purposed method was successfully applied for the analysis of aromatic amines in water sample and the recoveries were ranged from 87.2% to 99.8%.     

气相色谱-串联质谱法同时测定卷烟滤嘴中15种多环芳烃

建立了气相色谱-串联质谱同时检测卷烟滤嘴中15种多环芳烃的方法。卷烟滤嘴用二氯甲烷振荡萃取后,经0.22μm有机相滤膜过滤,采用DB-5MS色谱柱(30 m×0.25 mm,0.25μm)进行分离,电子轰击源、正离子模式下以多反应监测模式进行检测,内标法进行定量。15种多环芳烃(苊烯、苊、芴、菲、蒽、荧蒽、芘、苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、二苯并[a,h]蒽、苯并[g,h,i]苝和茚并[1,2,3-c,d]芘)的线性关系良好,相关系数(R~2)为0.991 4~0.999 9。15种多环芳烃在低、中、高3个添加水平下的平均回收率为81.6%~111.2%;除了芴在低添加水平时相对标准偏差为19.2%外,其他相对标准偏差均小于16%。15种多环芳烃的检出限为0.02~0.24 ng/滤嘴,定量限为0.04~0.80 ng/滤嘴。方法前处理简便,具有快速、准确、灵敏度高及重复性好的优点,适用于卷烟滤嘴中多环芳烃的分析。     

Rapid and sensitive method for simultaneous determination of six carcinogenic aromatic amines in mainstream cigarette smoke by liquid chromatography/electrospray ionization tandem mass spectrometry

Aromatic amines are one of the sources of carcinogenicity in cigarette and tobacco smoke. Accurate quantification of these chemicals is needed to assess public health risk. A new validated rapid, sensitive and analyte specific liquid chromatography/electrospray ionization tandem mass spectrometric (LC/MS/MS) method has been developed for the simultaneous determination of six aromatic amines in mainstream cigarette smoke using research reference cigarette 2R4F. Three popular Indian brand cigarettes were also analyzed using the same procedure. The limit of detection of this method ranged from 0.04 to 0.59 ng/cig using an injection volume of 7 μl. The identification of each amine was established by chromatographic retention times, analyte specific fragmentation pattern and relative peak area ratios of two product/precursor ion pairs. The method showed excellent reproducibility and was also rapid, selective and robust for aromatic amine determination from cigarette smoke.     

Determination of tocopherols,tocopherolquinones and tocopherolhydroquinones by gas chromatography-mass spectrometry and preseparation with lipophilic gel chromatography

A method has been developed for the simultaneous determination of a range of aromatic amines using cation-exchange chromatography performed on a standard ion chromatography column using d.c. amperometric detection. The analytes separated were 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA), aniline, o-toluidine, benzidine, p-chloroaniline, 4,4'-diaminodiphenyl (4,4'-DDP), m-nitroaniline and 1-naphthylamine. A Dionex CS12 column was used with gradient elution from an initial eluent of 5% CH3CN+35 mM H2SO4 to 27% CH3CN+35 mM H2SO4 (at 35 min). Detection limits in the range 2.6-22.6 microg/l were observed for all analytes except m-nitroaniline, for which the detection limit was 201 microg/l. Linear calibrations and good precision were observed and the method was applied to the determination of benzidine, p-chloroaniline and 1-naphthylamine in wastewater samples. Further, the separation was also used (after some modification of the eluent conditions) for the determination of 2,4- and 2,6-toluene diisocyanate (2,4- and 2,6-TDI) and 4,4'-methylenediphenyl diisocyanate (4,4'-MDI) after their hydrolysis to 2,4-TDA, 2,6-TDA and 4,4'-DDP. Detection limits for 2,6- and 2,4-TDI and 4,4'-MDI were 3.8, 8.2, and 11.2 microg/l, respectively. The method was applied to the determination of diisocyanates in air.     

Continued investigation of the diazotization and coupling spectrophotometric technique for the determination of aromatic amines with 8-amino-1-hydroxynaphthalene-3,6-disulphonic acid and N-(1-naphthyl)ethylenediamine as coupling agents

Twenty more aromatic amines are determined by the diazotization and coupling spectrophotometric technique, with 8-amino-1-hydroxynaphthalene-3,6-disulphonic acid (H-acid) and N-(1-naphthy)ethylenediamine (N-na) as coupling agents. The following are determined by both methods: 2,4-diaminotoluene, 2-aminobenzotrifluoride, 4-benzoxyaniline, 2,4-dimethyl-6-nitroaniline, 4,5-dimethyl-2-nitroaniline, 2-amino-9-fluorenone, naphthionic acid (sodium salt), 3-aminonaphthalene-2, 7-disulphonic acid (monosodium salt), 2-aminonaphthalene-1-sulphonic acid, 4-aminonaphthalene-1-sulphonic acid and 2,4-dibromoaniline. The following are determined only by the N-na method: 5-aminosalicylic acid, 2-amino-4-nitrophenol, 4-amino-2,6-dichlorophenol hydrochloride, 2,5-dimethoxy-aniline, 4-aminothiophenol, 4,4'-diaminodiphenylmethane, 1-naphthylamine, 4,4'-diaminobiphenyl-2,2'-disulphonic acid and 4,4'-diaminostilbine-2,2'-disulphonic acid. The optimum acidities for the different aromatic amines for the N-na method vary considerably. A number of aromatic amines cannot be determined by either method.     

高效液相色谱-质谱法测定电子电气产品塑料部件中偶氮染料释放的致癌芳香胺

采用高效液相色谱-质谱(HPLC-MS)法对电子电气产品塑料部件中偶氮染料还原裂解产生的21种芳香族伯胺进行同时测定。塑料用有机溶剂溶解或溶胀,释放其中存在的偶氮染料,在连二亚硫酸钠的强还原性环境中,偶氮染料被还原为芳香胺。用甲基叔丁基醚提取芳香胺,提取液浓缩后用甲醇-水(1：1,v/v)定容,HPLC-MS检测。采用ZORBAX Eclipse XDB C₁₈色谱柱分离,乙腈和0.1%(v/v)甲酸溶液为流动相,流速0.6 mL/min,选择离子监测(SIM)采集数据,色谱峰保留时间和特征离子定性。21种芳香胺的线性关系良好,r >0.998,方法检出限为0.5 mg/kg。除个别物质外,在空白塑料基质中的加标回收率为60.1%~129.5%,相对标准偏差小于14.0%。本研究表明电子电气塑料部件中的禁用偶氮染料还原产生的芳香胺能够被定性定量测定,本方法的准确度高,精密度好。