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烷烃和多环芳烃(polycyclic aromatic hydrocarbons,PAHs)是大气环境中重要的污染物,与大气细粒子(fine particle,PM2.5)和臭氧(O3)的形成和演化密切相关[1-2],其中以苯并(a)芘为代表的PAHs具有强致癌性[3],严重影响人体健康;根据饱和蒸气压浓度,可将其划分为挥发性有机污染物(volatile organic compounds,VOCs)和半/中等挥发性有机物(semi-/intermediate-volatile organic compounds,S/IVOCs)[4]. VOCs是二次有机气溶胶(secondary organic aerosol,SOA)的重要前体物,但并不能很好地解释城市站点中观测到有机气溶胶的总量[5-6]. 烟雾箱研究表明,S/IVOCs对SOA的生成有重要贡献,但其形成机制尚不明确且严重被低估[7-9],近年来越来越受到重视[10-12]. 机动车尾气是我国城市大气中烷烃和PAHs的重要来源[13],现阶段机动车尾气中烷烃和PAHs的研究多为颗粒态 [14-17],而气态烷烃和PAHs的相关报道较少,且以VOCs为主[18]. 因此完善机动车尾气中气态烷烃和PAHs、尤其S/IVOCs的成分谱和排放因子,对SOA来源解析的研究具有重要意义.
目前我国针对废气中PAHs的检测制定的标准方法较少,主要包括气质联用法(HJ646—2013)[19]和高效液相色谱法(HJ647—2013)[20],但分析的PAHs组分及苯环数均较少;此外采样复杂、易污染、目标物易发生反应等问题有待解决[21];而对于废气中烷烃的检测,目前还没制定相应的标准方法. 吸附管采样-热脱附/气相色谱质谱法有采样过程简单、目标物被填料富集后不易反应、吸附管可重复使用等优势;且样品分析无需复杂前处理,可检测沸点高、碳数多的化合物[22].
为了探索机动车尾气中烷烃和PAHs的检测方法,同时尽可能准确分析更多的S/IVOCs物种,本研究借鉴环境气溶胶中烷烃和PAHs检测方法的最新研究成果[23],以吸附管采样,采用热脱附-气相色谱-质谱联用系统(thermal desorption-gas chromatography-mass spectrometry,TD-GC-MS),建立了适用于机动车废气样品中30种正构烷烃(C7—C36)、2种支链烷烃(植烷、姥鲛烷)和19种PAHs(2—6环)的检测方法;其中C12—C36烷烃及PAHs属S/IVOCs[4];该法具有检出限低、稳定性好、精密度高、定量准确等特点,可满足机动车尾气中烷烃和PAHs的检测需求.
热脱附-气相色谱-质谱法测定机动车尾气中气相烷烃和多环芳烃含量
Determination of gas phase alkanes and polycyclic aromatic hydrocarbons in vehicle exhaust by thermal desorption-gas chromatography-mass spectrometry
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摘要: 采用热脱附结合气相色谱质谱联用仪(TD-GC-MS),建立了机动车尾气中30种正构烷烃(C7—C36)、2种支链烷烃(植烷、姥鲛烷)和19种多环芳烃(PAHs)的分析方法. 利用Tenax-TA吸附管采集机动车尾气样品,加入定量的内标物;热解吸后经HP-5色谱柱分离、在选择性离子监测(SIM)模式下用GC-MS检测,内标法定量. 为提高方法的灵敏度、精准度等指标,优化了脱附管解吸温度、解吸时间,冷阱捕集温度、脱附温度、脱附时间和GC-MS分析条件. 结果表明,51种目标物在1—50 ng范围内线性良好,相关系数(R2)均大于0.994,方法检出限为0.05—0.48 μg.m−3,定量下限为0.20—1.90 μg.m−3,在低、中、高的3个加标水平下的回收率为86.7%—119.9%,相对标准偏差(RSD,n=7)为1.0%—5.7%,将其应用于轻型柴油车尾气样品的测定,共检测出44种目标物,包括28种正构烷烃、2种支链烷烃、14种PAHs. 该方法简便快速、稳定灵敏、准确度高,可满足机动车尾气中烷烃和PAHs的测定需求.Abstract: An analytical method was established for the determination of 30 n-alkanes (C7—C36), 2 branched alkanes (phytane, pristane) and 19 polycyclic aromatic hydrocarbons (PAHs) in vehicle emission by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Samples were collected by Tenax-TA adsorption tube, and the internal standard was added. After desorbed by thermal desorption, the analytes were determined by GC-MS in selected ion monitor (SIM) mode after separation by HP-5 column, and quantified by internal standard method. In order to improve the sensitivity and precision of method, various parameters such as desorption temperature and time of adsorption tube / cold trap, capture temperature of cold trap, and the analysis conditions of GC-MS were optimized. Results showed that the calibration curves for 51 compounds exhibited good linearity in the concentration range of 1-50 ng, with all the correlation coefficients (R2) morn than 0.994. The limits of detection and the limits of quantification were in the ranges of 0.05—0.48 μg·m−3 and 0.20—1.90 μg·m−3, espectively. The average recoveries at low, medium and high spiked levels ranged from 86.7% to 119.9% with the relative standard deviations (RSDs, n = 7) of 1.0%—5.7%. The method was applied to the determination of alkane and PAHs in the exhaust of light diesel vehicle. A total of 44 targets were detected, including 28 n-alkanes, 14 PAHs and 2 branched alkanes. The method was simple, rapid, stable, sensitive and accurate, and was suitable for the determination of alkane and PAHs in motor vehicle emissions.
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表 1 51种目标化合物的CAS号、保留时间、定性及定量离子
Table 1. CAS No, retention time, qualitative and quantitative ions of 51 target compounds
序号
No.中文名称
Chinese name英文名称
English nameCAS号
CAS No.保留时间/min
Retention time定量离子(m/z)
Quantitative ion定性离子(m/z)
Qualitative ion目标物 Analytes 1 正庚烷 Heptane 142-82-5 4.338 43 41,71 2 正辛烷 Octane 111-65-9 5.355 43 57,29 3 正壬烷 Nonane 111-84-2 6.387 43 57,85 4 正癸烷 Decane 124-18-5 7.397 57 43,71 5 正十一烷 Undecane 1120-21-4 8.408 57 43,41 6 正十二烷 Dodecane 112-40-3 9.458 57 43,71 7 萘 Naphthalene 91-20-3 9.506 128 127,129 8 正十三烷 Tridecane 629-50-5 10.568 57 43,71 9 正十四烷 Tetradecane 629-59-4 11.7 57 43,71 10 苊烯 Acenaphthylene 208-96-8 12.574 152 153,151 11 正十五烷 Pentadecane 629-62-9 12.839 57 43,71 12 苊 Acenaphthene 83-32-9 12.976 153 154,152 13 正十六烷 Hexadecane 544-76-3 13.963 57 43,71 14 芴 Fluorene 86-73-7 14.092 166 165,167 15 正十七烷 Heptadecane 629-78-7 15.061 57 43,71 16 姥鲛烷 Pristane 1921-70-6 15.131 57 43,71 17 正十八烷 Octadecane 593-45-3 16.119 57 43,71 18 植烷 Phytane 638-36-8 16.218 57 43,71 19 菲 Phenanthrene ‘85-01-8 16.271 178 176,179 20 蒽 Anthracene 120-12-7 16.372 178 176,179 21 正十九烷 Nonadecane 629-92-5 17.132 57 43,71 22 正二十烷 Eicosane 112-95-8 18.108 57 71,43 23 正二十一烷 Heneicosane 629-94-7 19.046 58 71,44 24 荧蒽 Fluoranthene 206-44-0 19.088 202 203,200 25 芘 Pyrene 129-00-0 19.61 202 203,200 26 正二十二烷 Docosane 629-97-0 19.946 57 71,43 27 正二十三烷 Tricosane 638-67-5 20.809 57 71,43 28 1-甲基芘 1-Methylpyrene 2381-21-7 20.984 216 215,217 29 正二十四烷 Tetracosane 646-31-1 21.641 57 71,43 30 正二十五烷 Pentacosane 629-99-2 22.446 57 71,43 31 环戊烯(c,d)芘 Cyclopenta(c,d)pyrene 27208-37-3 22.502 226 227,224 32 苯并(a)蒽 Benzo(a)anthracene 56-55-3 22.509 228 226,229 33 䓛 Chrysene 218-01-9 22.607 228 226,229 34 正二十六烷 Hexacosane 630-01-3 23.22 57 71,43 35 正二十七烷 Heptacosane 593-49-7 23.967 57 71,43 36 正二十八烷 Octacosane 630-02-4 24.681 57 71,43 37 苯并(b)荧蒽 Benzo(b)fluorathene 205-99-2 25.018 252 253,250 38 苯并(k)荧蒽 Benzo(k)fluoranthene 207-08-9 25.038 252 250,253 39 正二十九烷 Nonacosane 630-03-5 25.385 57 71,43 40 苯并(e)芘 Benzo(e)pyrene 192-97-2 25.55 252 253,250 41 苯并(a)芘 Benzo(a)pyrene 50-32-8 25.655 252 253,250 42 正三十烷 Triacontane 638-68-6 26.135 57 71,43 43 正三十一烷 Hentriacontane 630-04-6 26.961 57 43,71 44 正三十二烷 Dotriacontane 544-85-4 27.885 57 71,43 45 茚并(1,2,3-cd)芘 Indeno(1,2,3-c,d)pyrene 193-39-5 28.477 276 277,274 46 二苯并(a,h)蒽 Dibenz(a,h)anthtacene 53-70-3 28.571 278 279,139 47 正三十三烷 Tritriacontane 630-05-7 28.942 57 71,43 48 苯并(g,h,i)苝 Benzo(g,h,i)perylene 191-24-2 29.196 276 277,138 49 正三十四烷 Tetratriacontane 14167-59-0 30.204 57 71,43 50 正三十五烷 Pentatriacontane 630-07-9 31.742 57 71,43 51 正三十六烷 Hexatriacontane 630-06-8 33.634 57 71,43 内标物Internal standards 52 氘代荧蒽 Fluoranthene-d10 93951-69-0 19.045 212 57 53 氘代二十四烷 n-Tetracosane-d50 204244-81-5 21.304 66 82 表 2 51种目标物的线性范围、相关系数、回收率、相对标准偏差(n=7)、检出限及定量下限
Table 2. Linear ranges, correlation coefficient(R2), recoveries,RSDs(n=7), MDLs and LOQs of 51 target compounds
序号
No.化合物
Compound线性方程
Linear equation相关系数R2 检出限/
(μg·m−3)
MDL定量下限/
(μg·m−3)
LOQ回收率/%
Recovery相对标准偏差/%
RSD1 正庚烷 Heptane y=0.26x 0.999 0.07 0.29 102.3, 86.7, 95.8 2.4, 4.5, 2.8 2 正辛烷 Octane y=0.64x+0.03 0.999 0.05 0.21 102.9, 96.2, 94.7 1.3, 4.7, 3.5 3 正壬烷 Nonane y=0.62x+0.03 1.000 0.11 0.45 100.4, 94.8, 95.7 1.3, 3.1, 3.6 4 正癸烷 Decane y=0.70x+0.04 1.000 0.10 0.42 100.6, 93.9, 96.6 1.8, 4.0, 2.8 5 正十一烷 Undecane y=0.73x+0.05 1.000 0.15 0.59 103.8, 94.3, 97.3 2.4, 3.9, 3.0 6 正十二烷 Dodecane y=0.77x+0.03 1.000 0.14 0.55 101.5, 94.3, 95.6 2.8, 3.5, 2.8 7 萘 Naphthalene y=0.92x+0.04 0.999 0.39 1.56 92.6, 99.0, 90.2 2.2, 3.8, 4.8 8 正十三烷 Tridecane y=0.75x+0.02 1.000 0.17 0.68 98.5, 93.5, 97.7 3.6, 3.6, 2.8 9 正十四烷 Tetradecane y=0.76x+0.06 0.999 0.16 0.66 100.8, 93.9, 98.0 3.9, 3.6, 2.4 10 苊烯 Acenaphthylene y=0.92x-0.01 0.999 0.40 1.62 91.6, 98.8, 98.1 3.1, 3.4, 3.7 11 正十五烷 Pentadecane y=0.78x 0.999 0.24 0.95 103.9,93.3, 98.8 3.1, 2.8, 1.9 12 苊 Acenaphthene y=0.55x+0.01 0.999 0.46 1.85 97.0, 101.3, 97.1 2.9, 1.9, 2.1 13 正十六烷 Hexadecane y=0.78x 0.999 0.20 0.81 105.8, 92.7, 98.9 4.1, 2.0, 1.7 14 芴 Fluorene y=0.64x 0.999 0.23 0.93 111.2, 96.8, 92.8 5.1, 3.9, 4.4 15 正十七烷 Heptadecane y=0.74x 0.999 0.33 1.31 107.2, 92.4, 99.0 4.7, 2.8, 2.2 16 姥鲛烷 Pristane y=0.68x+0.01 1.000 0.23 0.93 98.7, 95.2, 93.1 2.3, 2.5, 1.7 17 正十八烷 Octadecane y=0.76x 1.000 0.23 0.94 103.0, 90.8, 100.5 4.7, 4.1, 2.6 18 植烷 Phytane y=0.70x+0.01 1.000 0.16 0.66 99.5, 96.2, 96.2 2.2, 1.6, 1.9 19 菲 Phenanthrene y=0.86x 0.999 0.18 0.71 95.2, 91.3, 99.5 1.4, 2.8, 4.4 20 蒽 Anthracene y=0.87x-0.03 0.999 0.47 1.86 119.7, 93.3, 92.2 2.2, 4.9, 4.9 21 正十九烷 Nonadecane y=0.73x 0.999 0.33 1.31 106.2, 89.7, 99.3 4.0, 4.9, 2.4 22 正二十烷 Eicosane y=0.72x 0.999 0.46 1.84 108.2, 91.4, 99.1 4.7, 2.3, 2.3 23 正二十一烷 Heneicosane y=0.69x-0.01 0.999 0.33 1.34 105.9, 91.4, 98.9 5.2, 2.1, 2,7 24 荧蒽 Fluoranthene y=0.89x+0.01 0.999 0.41 1.62 96.4, 94.9, 90.7 1.5, 3.4, 5.0 25 芘 Pyrene y=0.94x+0.01 0.999 0.37 1.47 91.3, 96.3, 97.7 4.9, 2.6, 2.9 26 正二十二烷 Docosane y=0.75x-0.01 0.999 0.34 1.36 102.6, 90.6, 98.8 4.8, 1.9, 3.1 27 正二十三烷 Tricosane y=0.76x-0.01 0.999 0.27 1.06 105.6, 93.7, 103.1 3.8, 2.4, 3.5 28 1-甲基芘
1-Methylpyreney=0.63x-0.01 0.999 0.48 1.90 118.7, 96.3, 94.9 2.0, 3.1, 4.1 29 正二十四烷 Tetracosane y=0.75x 0.998 0.25 1.00 115.9, 92.0, 97.4 4.5, 3.0, 4.5 30 正二十五烷 Pentacosane y=0.73x-0.01 0.999 0.37 1.48 114.5, 93.9, 98.0 5.1, 3.9, 2.5 31 环戊烯(c,d)芘 Cyclopenta(c,d)pyrene y=0.16x-0.01 0.999 0.17 0.70 107.3, 92.4, 101.8 3.0, 2.5, 4.3 32 苯并(a)蒽 Benzo(a)anthracene y=0.65x-0.01 0.999 0.20 0.78 104.5, 102.1, 96.2 3.6, 4.1, 3.0 33 䓛 Chrysene y=0.67x+0.01 0.999 0.32 1.27 100.7, 94.2, 95.2 2.8, 4.8, 4.2 34 正二十六烷 Hexacosane y=0.67x 0.999 0.39 1.55 104.7, 93.6, 97.9 3.2, 3.8, 3.2 35 正二十七烷 Heptacosane y=0.63x 0.999 0.18 0.72 106.8, 93.2, 98.9 3.2, 3.5, 3.7 36 正二十八烷 Octacosane y=0.61x 0.999 0.42 1.68 117.2, 90.4, 98.5 1.9, 3.2, 4.1 37 苯并(b)荧蒽 Benzo(b)fluorathene y=1.38x+0.02 0.998 0.24 0.96 111.6, 97.1, 97.8 4.5, 3.2, 2.4 38 苯并(k)荧蒽 Benzo(k)fluoranthene y=1.37x+0.04 0.998 0.28 1.12 111.9, 102.1, 105.7 3.1, 3.0, 4.8 39 正二十九烷 Nonacosane y=0.57x-0.01 0.998 0.37 1.48 101.8, 92.1, 99.6 3.9, 2.4, 4.8 40 苯并(e)芘 Benzo(e)pyrene y=0.40x+0.02 0.999 0.44 1.75 103.3, 99.4, 101.9 1.7, 3.1, 3.1 41 苯并(a)芘 Benzo(a)pyrene y=0.33x+0.01 0.998 0.39 1.55 108.6, 101.5, 98.2 3.6, 4.2, 3.9 42 正三十烷 Triacontane y=0.50x-0.02 0.998 0.45 1.82 111.6, 105.2, 103.9 4.4, 5.7, 4.8 43 正三十一烷 Hentriacontane y=0.36x 0.999 0.39 1.55 116.0, 105.2, 103.9 3.2, 2.7, 2.7 44 正三十二烷 Dotriacontane y=0.33x-0.01 0.999 0.43 1.74 115.9, 99.4, 106.0 2.7, 5.3, 4.2 45 茚并(1,2,3-cd)芘 Indeno(1,2,3-c,d)pyrene y=0.07x+ 0.02 0.995 0.32 1.28 119.9, 101,8, 106.4 1.0, 4.3, 4.0 46 二苯并(a,h)蒽 Dibenz(a,h)anthtacene y=0.03x+0.02 0.996 0.16 0.64 105.9, 104.3, 97.8 4.4, 3.1, 2.5 47 正三十三烷 Tritriacontane y=0.24x 0.997 0.36 1.44 109.3, 94.6, 105.5 3.3, 3.4, 2.9 48 苯并(g,h,i)苝 Benzo(g,h,i)perylene y=0.05x+0.06 0.994 0.12 0.47 119.6, 102.2, 100.6 1.0, 3.9, 5.3 49 正三十四烷 Tetratriacontane y=0.15x+0.13 0.998 0.09 0.35 116.8, 100.5, 97.0 1.6, 4.3, 2.5 50 正三十五烷 Pentatriacontane y=0.06x+0.02 0.999 0.07 0.27 113.9, 103.2, 109.3 1.7, 5.5, 4.4 51 正三十六烷 Hexatriacontane y=0.03x+0.04 0.996 0.05 0.20 106.1, 101.2, 104.5 1.3, 4.3, 3.5 表 3 轻型柴油车尾气中烷烃和PAHs含量(μg·m−3)
Table 3. Concentration of alkanes and PAHs in exhaust gas from light diesel vehicle (μg·m−3)
序号
No.化合物
Compound浓度
Concentration序号
No.化合物
Compound浓度
Concentration1 正庚烷 Heptane 681.15 24 荧蒽 Fluoranthene 28.06 2 正辛烷 Octane 244.41 25 芘 Pyrene 27.01 3 正壬烷 Nonane 94.87 26 正二十二烷 Docosane 74.54 4 正癸烷 Decane 145.65 27 正二十三烷 Tricosane 91.89 5 正十一烷 Undecane 102.06 28 1-甲基芘 1-Methylpyrene 33.73 6 正十二烷 Dodecane 219.51 29 正二十四烷 Tetracosane 119.11 7 萘 Naphthalene 74.25 30 正二十五烷 Pentacosane 228.38 8 正十三烷 Tridecane 120.93 31 环戊烯(c,d)芘 Cyclopenta(c,d)pyrene 56.61 9 正十四烷 Tetradecane 346.03 32 苯并(a)蒽 Benzo(a)anthracene 24.01 10 苊烯 Acenaphthylene 10.47 33 䓛 Chrysene 45.17 11 正十五烷 Pentadecane 933.98 34 正二十六烷 Hexacosane 179.61 13 正十六烷 Hexadecane 792.22 35 正二十七烷 Heptacosane 168.57 14 芴 Fluorene 5.34 36 正二十八烷 Octacosane 139.84 15 正十七烷 Heptadecane 642.17 37 苯并(b)荧蒽 Benzo(b)fluorathene 7.82 16 姥鲛烷 Pristane 92.19 38 苯并(k)荧蒽 Benzo(k)fluoranthene 12.23 17 正十八烷 Octadecane 312.47 39 正二十九烷 Nonacosane 151.16 18 植烷 Phytane 118.88 40 苯并(e)芘 Benzo(e)pyrene 9.74 19 菲 Phenanthrene 34.23 42 正三十烷 Triacontane 140.27 20 蒽 Anthracene 49.39 43 正三十一烷 Hentriacontane 98.18 21 正十九烷 Nonadecane 92.15 44 正三十二烷 Dotriacontane 76.14 22 正二十烷 Eicosane 103.48 47 正三十三烷 Tritriacontane 25.42 23 正二十一烷 Heneicosane 77.21 49 正三十四烷 Tetratriacontane 66.21 -
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