Research on Rapid Analysis Methods for Benzene Series, Methane, and Total Hydrocarbons in Ambient Air
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摘要: 无组织排放的苯系物和总烃对生态环境及人类健康具有不可逆转的危害性,实现苯系物和总烃的快速准确分析一直以来是环境空气监测的研究热点。本文基于双FID检测器的多维气相色谱仪,开发出用于总烃、甲烷、苯、甲苯、乙苯、对二甲苯、间二甲苯、邻二甲苯以及苯乙烯的快速分析方法。结果表明,一次进样可在12 min内完成目标组分的准确快速分析,组分在测量浓度范围内呈现良好的线性和重复性。该方法具有优异的方法检出限,准确性在−7.7%~0.2%之间。方法可在不同时空场景下对分析仪器进行在线校准,在环境空气现场走航监测方面具有潜在应用价值。Abstract: Fugitive emission of benzene series and total hydrocarbons has irreversible harm to the ecological environment and human health. The quick and accurate analysis of benzene series and total hydrocarbons has always been a research focus of ambient air monitoring. A quick method for the analysis of total hydrocarbons, methane, benzene, toluene, ethylbenzene, p-xylene, m-xylene, o-xylene and styrene was developed based on the multi-dimensional gas chromatograph with double FID detector. The results show that the target components can be analyzed accurately and quickly in 12 minutes by one injection, and the components show good linearity and repeatability over the measurement range. This method has excellent detection limit and the accuracy ranged from −7.7% to 0.2%. This method can be used for on-line calibration of analytical instruments in different spatiotemporal scenarios, and has potential application value in field navigation monitoring of ambient air.
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Key words:
- metrology /
- gas chromatography /
- benzene derivatives /
- methane /
- total hydrocarbon /
- quick analysis
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表 1 气体标准物质各组分浓度值
Table 1. The concentration value of each component of the gas reference material
瓶号 HM6071 组分 甲烷 丙烷 苯 甲苯 乙苯 苯乙烯 对二甲苯 间二甲苯 邻二甲苯 氮气 浓度(μmol/mol) 19.6 20.0 20.1 20.3 20.2 20.1 19.9 20.3 20.0 余量 表 2 分析条件参数
Table 2. Analyze condition parameters
项目 参数 柱箱温度 100℃保持 检测器温度 FID1: 250℃ FID2: 250℃ 定量环 0.5 mL(THCs:总烃) 1.0 mL(CH4) 0.1 mL(BTX:苯系物) 色谱柱 CH4: P-N(2 m*1.0 mm)+ MS-13X (2 m*1.0 mm) BTX: BTX(2 m*1.0 mm) THCs:熔融石英毛细柱(2m*0.3mm) 燃气流量 FID1:空气200 mL/min FID2:空气200 mL/min 助燃气流量 FID1:氢气32 mL/min FID2:氢气32 mL/min 尾吹气流量 氮气:24 mL/min 载气 氮气 表 3 各待测组分的测定范围及线性方程
Table 3. The measuring range and linear equation of each component to be measured
组分 浓度范围(μmol/mol) 线性方程 相关系数R2 总烃(以碳计) 1.15~22.93 y = 4056x − 1908.4 0.9963 甲烷 0.0392~0.98 y = 3627.0x – 124.10 0.9958 苯 0.0201~0.402 y = 4051.3x + 38.855 0.9995 甲苯 0.0203~0.406 y = 4922.1x + 52.748 0.9999 乙苯 0.0202~0.404 y = 6781.4x + 68.932 0.9999 对二甲苯 0.0199~0.398 y = 6829.2x + 79.239 0.9997 间二甲苯 0.0203~0.406 y = 6996.1x + 86.893 0.9996 邻二甲苯 0.0200~0.400 y = 7754.6x + 50.473 0.9992 苯乙烯 0.0201~0.402 y = 8319.2x + 116.95 0.9988 表 4 各组分的仪器检出限
Table 4. The instrumental detection limit of each component
组分 峰高 N0 IDL
(μmol/mol)1 2 3 4 5 6 7 H 总烃 2820 2619 2481 2411 2381 2329 2351 2484.57 14.96 0.014 甲烷 19 21 18 20 19 23 21 20.14 14.96 0.058 苯 28 32 30 30 31 30 29 30.00 9.16 0.012 甲苯 21 23 23 24 23 22 23 22.70 9.16 0.016 乙苯 19 22 19 21 21 17 20 19.90 9.16 0.019 对二甲苯 20 18 16 20 19 18 22 19.00 9.16 0.019 间二甲苯 21 19 18 20 19 23 18 19.71 9.16 0.019 邻二甲苯 17 20 18 23 21 18 20 19.57 9.16 0.019 苯乙烯 19 17 23 19 20 19 17 19.14 9.16 0.019 表 5 各待测组分的方法检出限
Table 5. Method detection limits for each component to be measured
组分 计算得到的浓度值(μmol/mol) MDL
(μmol/mol)1 2 3 4 5 6 7 S 总烃 1.79 1.73 1.66 1.62 1.61 1.59 1.60 0.077 0.24 甲烷 0.055 0.058 0.054 0.053 0.054 0.058 0.056 0.0019 0.0058 苯 0.019 0.025 0.024 0.023 0.024 0.019 0.020 0.0026 0.0082 甲苯 0.014 0.022 0.019 0.021 0.019 0.018 0.024 0.0033 0.010 乙苯 0.022 0.025 0.019 0.026 0.020 0.015 0.022 0.0038 0.012 对二甲苯 0.025 0.020 0.015 0.028 0.016 0.017 0.027 0.0055 0.017 间二甲苯 0.031 0.030 0.020 0.025 0.021 0.017 0.021 0.0051 0.016 邻二甲苯 0.026 0.018 0.023 0.025 0.030 0.027 0.021 0.0040 0.013 苯乙烯 0.024 0.027 0.020 0.031 0.018 0.024 0.017 0.0051 0.016 表 6 各待测组分的浓度重复性
Table 6. Repeatability of each concentration of components to be measured
组分 浓度(μmol/mol) 峰面积 RSD7 总烃 1.15 4815 6.5% 2.29 8271 1.5% 5.73 19542 0.6% 11.5 41754 0.9% 22.9 92751 0.4% 苯 0.0201 127 8.3% 0.0402 207 3.2% 0.100 447 1.6% 0.201 830 2.1% 0.402 1678 1.7% 甲苯 0.0203 149 11.0% 0.0406 260 2.9% 0.102 551 2.0% 0.203 1048 1.5% 0.406 2053 1.6% 乙苯 0.0202 212 12.2% 0.0404 349 2.7% 0.101 745 1.7% 0.202 1430 1.9% 0.404 2814 0.9% 对二甲苯 0.0199 220 18.5% 0.0398 371 3.5% 0.0995 745 1.9% 0.199 1415 2.8% 0.398 2810 1.7% 间二甲苯 0.0203 250 14.4% 0.0406 378 2.9% 0.102 781 1.7% 0.203 1479 1.2% 0.406 2944 0.5% 邻二甲苯 0.0200 237 13.2% 0.0400 378 2.9% 0.100 776 1.5% 0.200 1586 2.5% 0.400 3169 1.2% 苯乙烯 0.0201 308 13.8% 0.0402 492 3.0% 0.100 910 1.6% 0.201 1735 1.3% 0.402 3494 1.0% 甲烷 0.0392 77 8.8% 0.0980 287 2.9% 0.196 567 3.2% 0.390 1140 2.4% 0.980 3486 1.2% 表 7 方法准确性评估
Table 7. Method accuracy evaluation
组分 理论浓度(μmol/mol) 峰面积 计算浓度(μmol/mol) 偏差(%) 总烃 5.732 19541.70 5.290 -7.7% 甲烷 0.1960 567.14 0.1906 -2.8% 苯 0.1005 446.86 0.1007 0.2% 甲苯 0.1015 550.71 0.1012 -0.3% 乙苯 0.1010 745.00 0.0997 -1.3% 对二甲苯 0.0995 744.57 0.0974 -2.1% 间二甲苯 0.1015 780.71 0.0992 -2.3% 邻二甲苯 0.1000 775.57 0.0935 -6.5% 苯乙烯 0.1005 909.71 0.0953 -5.2% -
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