温室气体CFCs、HFCs、SF_6和CF_4的分析方法与应用研究
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摘要
温室气体(Greenhouse Gas, GHG)指大气中由自然或人为产生的能够吸收和阻挡地球表面、大气和云射出的热红外辐射谱段特定波长辐射的气体成分,从而使大气圈的温度升高,该特性导致温室效应。大气中的氟利昂(CFCs)、氢氟碳化物(HFCs)、全氟化碳(PFCs)、六氟化硫(SF6)等温室气体由人类活动产生,具有较高的增温潜势。
CFCs、HFCs、PFCs和SF6类温室气体的浓度极低,通常在10-9v/v至10-12v/v数量级,在我国环境监测领域缺乏系统的的实验室分析监测方法。因此,开发和研究具有高灵敏度、广泛性和易操作性的温室气体实验室分析监测方法成为摆在我国环境工作者面前的重要任务之一
针对环境中存在且增温潜势较大的CFCs、HFCs、PFCs、SF6类温室气体,选择了具有代表性的12种痕量温室气体进行分析测定,分别是Halon1211(溴氯二氟甲烷)、HFC134a(四氟乙烷)、CFC115(五氟氯乙烷)、HFC125(五氟乙烷)Halon1301(三氟溴甲烷)、HCFC142b(二氟一氯乙烷)、HFC152(二氟乙烷)、HCFC22(一氯二氟甲烷)、HFC32(二氟甲烷)、HFC23(三氟甲烷)、CF4(四氟甲烷),SF6(六氟化硫)。实验选用大气预浓缩仪对气体样品进行冷凝浓缩和去杂质,然后用气相色谱-质谱仪对样品进行分析测定。实验选择Gas Pro毛细管柱,在对前处理方法和升温程序进行优化的基础上,分别用三套方法对12种温室气体完成定性定量分析。CFCs和HFCs类气体的检出限范围从8.47×10-12v/v到28.09×10-12v/v,相对标准偏差范围从9.86%-17.64%,回收率的范围从61.10%到92.10%。SF6气体的检出限为6.00×10-12v/v,相对标准偏差为8.17%,回收率为87.2%。CF4气体的检出限为0.19×10-9v/v,相对标准偏差为15.24%,回收率为119.70%。
采用SUMMA不锈钢罐进行采样,在2010年1月13日至2010年2月23日,采集了昆明市市区,昆明市王家桥云铜,安宁市昆钢,玉溪市市区,曲靖市市区的大气样品。
经过分析,大气样品中检测出HFC134a、HFC125、HCFC142b、HFC152a、HCFC22、HFC23、SF6、CFC11、CFC12、CFC40和HFC227等种类的温室气体。对标准品涵盖的痕量温室气体进行了定量分析,浓度范围为28.45×10-12v/v-320.49×10-12v/v。从获得的数据来看,痕量温室气体的浓度变化具有一定特征。在人口稠密的地区,其浓度较大,证明了痕量温室气体的排放和人类活动息息相关。
Greenhouse gases (Greenhouse Gas, GHG) refers to the gas components, whcih produced by natural or man-made,can absorb and stop the Earth's surface, atmosphere and cloud emitted thermal infrared radiation spectrum specific wavelengths of radiation, result in increases of the atmosphere's temperature.This feature led to the greenhouse effect. Freon (CFCs), Hydrofluorocarbons (HFCs), Perfluorocarbons (PFCs), Sulfur hexafluoride (SF6) and other greenhouse gases come from human activities, which have higher warming potential.
The concentrations of CFCs, HFCs, SF6, CF4 are very low, the magnitude range from 10-9v/v to 10-12v/v.In China, we are short of monitoring laboratory analysis in the field of environmental monitoring. Therefore, it is necessary to develop a laboratory analysis monitoring method with high sensitivity, easy to operate,and we should take the responsibility.
Aimed at higher global warming potential gases, such as CFCs, HFCs, CF4, SF6 12 species were chosen to analyse, including Halon1211 (bromochlorodifluoromethane) HFC 134a (tetrafluoroethane), CFC115 (5 fluoroethyl), HFC 125 (5 fluoroethane), Halon1301 (trifluoromethylbromide), HCFC142b (2 fluoro-1 ethyl), HFC152 (difluoroethane), HCFC22 (monochlorodifluoromethane), HFC32 (difluoromethane), HFC23(trifluoromethane),CF4 (PTFE methane), SF6 (sulfur hexafluoride).
In this paper, used the freeze and preconcentration system and Gas Chromoto-graphy Mass spectrometry(GC-MS), selected Gas Pro capillary column, optimized method confirmed pre-concentration condition and GC-MS temperature program, finally selected three kinds of conditions to complete the analysis of qualitative and quantitative. The detection limit of CFCs and HFCs from 8.47 x 10-12v/v to 28.09 x 10-12v/v), the relative standard deviation from 9.86% to 17.64%), recovery from 61.10% to 92.10%. The detection limit of SF6 is 6.00 x 10-12v/v, the relative standard deviation is 8.17%, recovery is 87.2%. The detection limit of CF4 is 0.19 x 10-9v/v, the relative standard deviation is 15.24%, recovery is 119.70%.
Took Samples by SUMMA Canister, in the January 13,2010 to February 23,2010, collected air samples from Kunming city, Yunnan Copper in Kunming Wangjiaqiao, Kunming Iron and Steel Corp in Annning, Yuxi urban area, Qujing urban area. After analysed, HFC 134a, HFC 125, HCFC142b, HFC 152a, HCFC22, HFC23, SF6, CFC11, CFC12, CFC40, and HFC227 were detected from these air sample. Took quantitative analysis with standard substances and got the concentration range from 28.45×10-12v/v to 320.49×10-12v/v.
From these data, the concentration of trace greenhouse gases has a kind of character. Populous area has a higher concentration. It is evidenced that the release of greenhouse gases has a relationship with human activities.
CFCs、HFCs、PFCs和SF6类温室气体的浓度极低,通常在10-9v/v至10-12v/v数量级,在我国环境监测领域缺乏系统的的实验室分析监测方法。因此,开发和研究具有高灵敏度、广泛性和易操作性的温室气体实验室分析监测方法成为摆在我国环境工作者面前的重要任务之一
针对环境中存在且增温潜势较大的CFCs、HFCs、PFCs、SF6类温室气体,选择了具有代表性的12种痕量温室气体进行分析测定,分别是Halon1211(溴氯二氟甲烷)、HFC134a(四氟乙烷)、CFC115(五氟氯乙烷)、HFC125(五氟乙烷)Halon1301(三氟溴甲烷)、HCFC142b(二氟一氯乙烷)、HFC152(二氟乙烷)、HCFC22(一氯二氟甲烷)、HFC32(二氟甲烷)、HFC23(三氟甲烷)、CF4(四氟甲烷),SF6(六氟化硫)。实验选用大气预浓缩仪对气体样品进行冷凝浓缩和去杂质,然后用气相色谱-质谱仪对样品进行分析测定。实验选择Gas Pro毛细管柱,在对前处理方法和升温程序进行优化的基础上,分别用三套方法对12种温室气体完成定性定量分析。CFCs和HFCs类气体的检出限范围从8.47×10-12v/v到28.09×10-12v/v,相对标准偏差范围从9.86%-17.64%,回收率的范围从61.10%到92.10%。SF6气体的检出限为6.00×10-12v/v,相对标准偏差为8.17%,回收率为87.2%。CF4气体的检出限为0.19×10-9v/v,相对标准偏差为15.24%,回收率为119.70%。
采用SUMMA不锈钢罐进行采样,在2010年1月13日至2010年2月23日,采集了昆明市市区,昆明市王家桥云铜,安宁市昆钢,玉溪市市区,曲靖市市区的大气样品。
经过分析,大气样品中检测出HFC134a、HFC125、HCFC142b、HFC152a、HCFC22、HFC23、SF6、CFC11、CFC12、CFC40和HFC227等种类的温室气体。对标准品涵盖的痕量温室气体进行了定量分析,浓度范围为28.45×10-12v/v-320.49×10-12v/v。从获得的数据来看,痕量温室气体的浓度变化具有一定特征。在人口稠密的地区,其浓度较大,证明了痕量温室气体的排放和人类活动息息相关。
Greenhouse gases (Greenhouse Gas, GHG) refers to the gas components, whcih produced by natural or man-made,can absorb and stop the Earth's surface, atmosphere and cloud emitted thermal infrared radiation spectrum specific wavelengths of radiation, result in increases of the atmosphere's temperature.This feature led to the greenhouse effect. Freon (CFCs), Hydrofluorocarbons (HFCs), Perfluorocarbons (PFCs), Sulfur hexafluoride (SF6) and other greenhouse gases come from human activities, which have higher warming potential.
The concentrations of CFCs, HFCs, SF6, CF4 are very low, the magnitude range from 10-9v/v to 10-12v/v.In China, we are short of monitoring laboratory analysis in the field of environmental monitoring. Therefore, it is necessary to develop a laboratory analysis monitoring method with high sensitivity, easy to operate,and we should take the responsibility.
Aimed at higher global warming potential gases, such as CFCs, HFCs, CF4, SF6 12 species were chosen to analyse, including Halon1211 (bromochlorodifluoromethane) HFC 134a (tetrafluoroethane), CFC115 (5 fluoroethyl), HFC 125 (5 fluoroethane), Halon1301 (trifluoromethylbromide), HCFC142b (2 fluoro-1 ethyl), HFC152 (difluoroethane), HCFC22 (monochlorodifluoromethane), HFC32 (difluoromethane), HFC23(trifluoromethane),CF4 (PTFE methane), SF6 (sulfur hexafluoride).
In this paper, used the freeze and preconcentration system and Gas Chromoto-graphy Mass spectrometry(GC-MS), selected Gas Pro capillary column, optimized method confirmed pre-concentration condition and GC-MS temperature program, finally selected three kinds of conditions to complete the analysis of qualitative and quantitative. The detection limit of CFCs and HFCs from 8.47 x 10-12v/v to 28.09 x 10-12v/v), the relative standard deviation from 9.86% to 17.64%), recovery from 61.10% to 92.10%. The detection limit of SF6 is 6.00 x 10-12v/v, the relative standard deviation is 8.17%, recovery is 87.2%. The detection limit of CF4 is 0.19 x 10-9v/v, the relative standard deviation is 15.24%, recovery is 119.70%.
Took Samples by SUMMA Canister, in the January 13,2010 to February 23,2010, collected air samples from Kunming city, Yunnan Copper in Kunming Wangjiaqiao, Kunming Iron and Steel Corp in Annning, Yuxi urban area, Qujing urban area. After analysed, HFC 134a, HFC 125, HCFC142b, HFC 152a, HCFC22, HFC23, SF6, CFC11, CFC12, CFC40, and HFC227 were detected from these air sample. Took quantitative analysis with standard substances and got the concentration range from 28.45×10-12v/v to 320.49×10-12v/v.
From these data, the concentration of trace greenhouse gases has a kind of character. Populous area has a higher concentration. It is evidenced that the release of greenhouse gases has a relationship with human activities.
引文
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