气相色谱法测试土壤中分段石油烃的标准化定量方法初探
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摘要
目前土壤样品中分段石油烃的分析方法中石油烃包括的碳原子数范围和采用的校准物质不统一,造成不同实验室的量值不具有可比性。为保证不同实验室之间结果的可比性,本文尝试建立一种石油烃相邻碳原子数标准化定量方法。该方法主要包括:(1)规定了石油烃包括的碳原子数范围为气相色谱峰中正己烷和正四十碳烷之间所有的烃(含正己烷);(2)总石油烃(TPH)分为挥发性石油烃(VPH)和半挥发性石油烃(SPH),分别选取碳原子数为6～10的5个正构烷烃作为VPH校准物质,选取碳原子数为10～40的31个正构烷烃作为SPH校准物质。采用平均响应因子法或一次线性回归法,建立校准物质的峰面积-浓度的校准关系;(3)采用相邻峰标准化校准方法,逐一定量所有的目标色谱峰;(4)计算正构烷烃含量、总石油烃含量和任意分段的石油烃含量。该方法为环境样品中石油烃分析方法的标准化建设提供了数据基础。
BACKGROUND: Inter-laboratory measurement results of total petroleum hydrocarbons(TPH) in soils determined by current Gas Chromatography-Flame Ionization Detector,are not comparable due to specified TPH ranges of alkanes and/or different calibration standards between laboratories.OBJECTIVES: To establish a standardized calibration and quantitation method of TPH and to develop the adjacent-peak calibration and quantitation method(APCQM).METHODS: The APCQM mainly includes:(1) defining TPH range as all compounds eluting between n-hexane and n-tetracontane;(2) division of TPHs into volatile petroleum hydrocarbons(VPH) and semivolatile petroleum hydrocarbons(SPH). Specify and calibrate procedure of TPH. Reference materials(RM) for VPH are 5 n-alkanes,from n-hexane to n-decane,whereas SPH RMs are 31 n-alkanes,from n-decane to n-tetracontane.Calibration equations of peak area and concentration of n-alkanes can be constructed by average response factor or linear regression methods;(3) quantitative concentrations of all target chromatographic peaks acquired by adjacent standard peak calibration;(4) calculation of the contents of n-alkanes,TPH and optional TPH fractions.RESULTS: Using the normal calibration and quantitation method,TPH recoveries of laboratory fortified blanks and laboratory fortified sample matrices could be underestimated or overestimated by 10%. By using the APCQM the paradox in quality control processes was resolved,and thus reliable measurement results of TPH were obtained in laboratories.CONCLUSIONS: The APCQM is applicable to standardization analysis of TPH fractions in environmental samples.
BACKGROUND: Inter-laboratory measurement results of total petroleum hydrocarbons(TPH) in soils determined by current Gas Chromatography-Flame Ionization Detector,are not comparable due to specified TPH ranges of alkanes and/or different calibration standards between laboratories.OBJECTIVES: To establish a standardized calibration and quantitation method of TPH and to develop the adjacent-peak calibration and quantitation method(APCQM).METHODS: The APCQM mainly includes:(1) defining TPH range as all compounds eluting between n-hexane and n-tetracontane;(2) division of TPHs into volatile petroleum hydrocarbons(VPH) and semivolatile petroleum hydrocarbons(SPH). Specify and calibrate procedure of TPH. Reference materials(RM) for VPH are 5 n-alkanes,from n-hexane to n-decane,whereas SPH RMs are 31 n-alkanes,from n-decane to n-tetracontane.Calibration equations of peak area and concentration of n-alkanes can be constructed by average response factor or linear regression methods;(3) quantitative concentrations of all target chromatographic peaks acquired by adjacent standard peak calibration;(4) calculation of the contents of n-alkanes,TPH and optional TPH fractions.RESULTS: Using the normal calibration and quantitation method,TPH recoveries of laboratory fortified blanks and laboratory fortified sample matrices could be underestimated or overestimated by 10%. By using the APCQM the paradox in quality control processes was resolved,and thus reliable measurement results of TPH were obtained in laboratories.CONCLUSIONS: The APCQM is applicable to standardization analysis of TPH fractions in environmental samples.
引文
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[7] Coulon F,Wu G. Determination of Petroleum Hydrocarbon Compounds from Soils and Sediments Using Ultrasonic Extraction[M]//McGenity T,Timmis K,Nogales B(eds). Hydrocarbon and Lipid Microbiology Protocols. Heidelberg:Springer,2014:31-46.
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[10] Faustorilla M V,Chen Z L,Dharmarajan R,et al. Determination of total petroleum hydrocarbons in Australian groundwater through the improvised gas chromatographyflame ionization detection technique[J]. Journal of Chromatographic Science,2017,55(8):775-783.
[11]李胜勇,李先国,邓伟,等.超声萃取气相色谱法检测海洋沉积物中的总石油烃[J].海洋湖沼通报,2013,35(2):93-98.Li S Y,Li X G,Deng W,et al. Determination of total petroleum hydrocarbons in marine sediments using gas chromatography with FID detector after ultrasonic extraction[J]. Transactions of Oceanology and Limnology,2013,35(2):93-98.
[12]周艳红,李凌波.废水中萃取性石油烃的测定[J].石油炼制与化工,2012,43(5):88-92.Zhou Y H,Li L B. Determination of extractable petroleum hydrocarbons in wastewater[J]. Petroleum Processing and Petrochemicals,2012,43(5):88-92.
[13]张劲强,顾骏.利用Agilent Intuvo 9000进行水和土壤样品中柴油类总石油烃含量的快速分段检测方法[J].环境化学,2017,36(8):1877-1879.Zhang J Q,Gu J. Fast analysis of total petroleum hydrocarbon fractions as diesel range organics in water and soil samples using Agilent Intuvo 9000 gas chromatography[J]. Environmental Chemistry,2017,36(8):1877-1879.
[14]钟灿红,孙丹,张慧,等.水中萃取性石油烃的气相色谱分析方法[J].浙江化工,2017,48(6):51-54.Zhong C H,Sun D,Zhang H,et al. EPH determination in water matrix by GC[J]. Zhejiang Chemical Industry,2017,48(6):51-54.
[15] Sui H,Hua Z T,Li X G,et al. Influence of soil and hydrocarbon properties on the solvent extraction of highconcentration weathered petroleum from contaminated soils[J]. Environmental Science Pollution Research,2014,21:5774-5784.
[16]陈帅,赵洋甬,高飞.土壤中总石油烃预处理方法研究[J].环境科学与管理,2017,42(7):85-90.Chen S,Zhao Y Y,Gao F. Research on testing method of total petroleum hydrocarbons in soil[J]. Environmental Science and Management,2017,42(7):85-90.
[2] Guarino C,Spada V,Sciarrillo R. Assessment of three approaches of bioremediation(natural attenuation,landfarming and bioagumentation-assistited landfarming)for a petroleum hydrocarbons contaminated soil[J].Chemosphere,2017,170:10-16.
[3]杨慧娟,刘五星,骆永明,等.气相色谱-质谱法分段测定土壤中的可提取总石油烃[J].土壤,2014,46(1):134-138.Yang H J,Liu W X,Luo Y M,et al. The sectional determination of extractable total petroleum hydrocarbons in soil by gas chromatography-mass spectrometry[J].Soils,2014,46(1):134-138.
[4]曹云者,李发生.基于风险的石油烃污染土壤环境管理与标准值确立方法[J].农业环境科学学报,2010,29(7):1225-1231.Cao Y Z,Li F S. Risk-based environmental management of petroleum hydrocarbons contaminated soil and development of standards:A review[J]. Journal of AgroEnvironment Science,2010,29(7):1225-1231.
[5]李桂香,高岩,张青.环境样品中石油烃的分类/分段检测技术[J].实验室研究与探索,2016,35(4):30-33.Li G X,Gao Y,Zhang Q. Testing technology of total petroleum hydrocarbon speciation/fractions in the environmental samples[J]. Research and Exploration in Laboratory,2016,35(4):30-33.
[6]张欢燕,王臻,周守毅.环境中总石油烃的气相色谱分析测定[J].环境监控与预警,2013,5(2):24-27.Zhang H Y,Wang Z,Zhou S Y. TPH Determination in environmental matrix by GC-FID[J]. Environmental Monitoring and Forewarning,2013,5(2):24-27.
[7] Coulon F,Wu G. Determination of Petroleum Hydrocarbon Compounds from Soils and Sediments Using Ultrasonic Extraction[M]//McGenity T,Timmis K,Nogales B(eds). Hydrocarbon and Lipid Microbiology Protocols. Heidelberg:Springer,2014:31-46.
[8] Brown D M,Okoro S,van Gils J,et al. Comparison of landfarming amendments to improve bioremediation of petroleum hydrocarbons in Niger Delta soils[J]. Science of the Total Environment,2017,596-597:284-292.
[9] Kwon M J,Hwang Y. Assessing the potential of organic solvents on total petroleum hydrocarbon extraction from diesel-contaminated soils[J]. Water Air and Soil Pollution,2017,228:189.
[10] Faustorilla M V,Chen Z L,Dharmarajan R,et al. Determination of total petroleum hydrocarbons in Australian groundwater through the improvised gas chromatographyflame ionization detection technique[J]. Journal of Chromatographic Science,2017,55(8):775-783.
[11]李胜勇,李先国,邓伟,等.超声萃取气相色谱法检测海洋沉积物中的总石油烃[J].海洋湖沼通报,2013,35(2):93-98.Li S Y,Li X G,Deng W,et al. Determination of total petroleum hydrocarbons in marine sediments using gas chromatography with FID detector after ultrasonic extraction[J]. Transactions of Oceanology and Limnology,2013,35(2):93-98.
[12]周艳红,李凌波.废水中萃取性石油烃的测定[J].石油炼制与化工,2012,43(5):88-92.Zhou Y H,Li L B. Determination of extractable petroleum hydrocarbons in wastewater[J]. Petroleum Processing and Petrochemicals,2012,43(5):88-92.
[13]张劲强,顾骏.利用Agilent Intuvo 9000进行水和土壤样品中柴油类总石油烃含量的快速分段检测方法[J].环境化学,2017,36(8):1877-1879.Zhang J Q,Gu J. Fast analysis of total petroleum hydrocarbon fractions as diesel range organics in water and soil samples using Agilent Intuvo 9000 gas chromatography[J]. Environmental Chemistry,2017,36(8):1877-1879.
[14]钟灿红,孙丹,张慧,等.水中萃取性石油烃的气相色谱分析方法[J].浙江化工,2017,48(6):51-54.Zhong C H,Sun D,Zhang H,et al. EPH determination in water matrix by GC[J]. Zhejiang Chemical Industry,2017,48(6):51-54.
[15] Sui H,Hua Z T,Li X G,et al. Influence of soil and hydrocarbon properties on the solvent extraction of highconcentration weathered petroleum from contaminated soils[J]. Environmental Science Pollution Research,2014,21:5774-5784.
[16]陈帅,赵洋甬,高飞.土壤中总石油烃预处理方法研究[J].环境科学与管理,2017,42(7):85-90.Chen S,Zhao Y Y,Gao F. Research on testing method of total petroleum hydrocarbons in soil[J]. Environmental Science and Management,2017,42(7):85-90.
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