An Infrared Standard Curve Method for Calculating the Total Amount of Petroleum in Environmental Samples
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摘要:
石油类是环境监测必测指标之一，主要以烃类形式存在，所以红外分光光度法是公认测定石油类总量最可靠的检测方法。红外分光光度法测定石油类总量目前有三波数的校正系数法和非色散的单波数标准曲线法。校正系数法计算步骤多、工作量大；单波数标准曲线法虽然简单，但是文献中有的未明确使用哪个波数进行计算，有的由于计算结果偏差较大而被限制适用范围或被直接舍弃。本文针对标准曲线法计算石油类总量的方法开展研究，通过三个波数处吸光度建立了5种标准曲线法，并对原油、高温润滑油、机油、0#柴油和92#汽油五种配制油品进行计算结果比对，确定了三波数吸光度之和标准曲线法是5种标准曲线法中的最佳方法。用芳香烃占比试验考察了油品适用范围，并进行了样品加标实验和实际样品实验验证其实用性，结果表明在芳香烃占比小于50%时。该方法精密度为5.9%~8.0%，加标回收率为76.4%~98.2%，满足环境标准要求。该方法拓展了标准曲线法的适用范围、简单易懂、操作性强，是现行校正系数法的有益补充。
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关键词:
- 环境样品 /
- 石油类总量 /
- 红外分光光度法 /
- 三波数之和标准曲线法
Abstract:BACKGROUND Petroleum oil is one of the necessary indicators for environmental monitoring, which mainly exists in the form of hydrocarbons. Therefore, infrared spectrophotometry is one of the most reliable methods to determine the total amount of petroleum oil. At present, there are two methods for the determination of petroleum by infrared spectrophotometry, which are the three-wave number correction coefficient method and the non-dispersive single wave number standard curve method. The correction coefficient method has many calculation steps and a heavy workload; the single wave number standard curve method does not specify which wave number to use for calculation or is abandoned due to the limited scope of application.
OBJECTIVES To establish a simple standard curve method for calculating the total amount of petroleum.
METHODS Five kinds of oils were scanned by Fourier transform infrared (FTIR) spectroscopy. The absorbance of the three scanning wavenumbers was arranged and combined to obtain five standard curve methods. After comparing the calculated concentration with the prepared concentration, the standard curve method of the sum of three-wave number absorbance was established.
RESULTS When the proportion of aromatic hydrocarbons was less than 50%, the calculation results of this method were consistent with those of the correction coefficient method. The precision of this method was 5.9%-8.0%, and the recovery rate of standard addition was 76.4%-98.2%, which meets the requirements of China's petroleum pollution determination and environmental standards.
CONCLUSIONS This method expands the application scope of the standard curve method. It is simple and easy to understand and has strong operability. It is a useful supplement to the correction coefficient method.
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表 1 标准曲线方程与相关系数
Table 1. Standard curve equations and correlation coefficients
标准曲线名称 回归方程 相关系数(R) 2930cm-1标准曲线 y=0.0135x+0.015 0.9996 2960cm-1标准曲线 y=0.0078x-0.0041 0.9998 3030cm-1标准曲线 y=0.0011x-0.0013 0.9996 两波数吸光度之和标准曲线 y=0.0214x-0.008 0.9998 三波数吸光度之和标准曲线 y=0.0225x-0.0065 0.9999 
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表 2 芳香烃占比试验结果
Table 2. Results of the proportion test for aromatic hydrocarbons
三种烃比例(正十六烷∶异辛烷∶苯) 芳香烃占比(%) 配制浓度(mg/L) 三波数之和标准曲线法 计算值(mg/L) 回收率(%) 7 ∶ 3 ∶ 0 0 50.00 59.98 119.96 6 ∶ 3 ∶ 1 10 50.00 55.42 110.83 6 ∶ 2 ∶ 2 20 50.00 52.93 105.86 5 ∶ 2 ∶ 3 30 50.00 46.70 93.39 5 ∶ 1 ∶ 4 40 50.00 43.66 87.32 3 ∶ 2 ∶ 5 50 50.00 36.55 73.10 3 ∶ 1 ∶ 6 60 50.00 33.47 66.94 2 ∶ 1 ∶ 7 70 50.00 28.24 56.48 1 ∶ 1 ∶ 8 80 50.00 22.43 44.86 1 ∶ 0 ∶ 9 90 50.00 18.65 37.29 0 ∶ 0 ∶ 10 100 50.00 13.85 27.69
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表 3 空白加标样品精密度结果
Table 3. Precision results of blank spiked samples
测定次数 土壤空白加标样品石油类物质含量(mg/kg) 水质空白加标样品石油类物质含量(mg/kg) 10mg/kg 50mg/kg 100mg/kg 0.10mg/L 0.50mg/L 2.50mg/L 1 9.11 47.6 93.4 0.0823 0.458 2.36 2 7.93 48.3 92.5 0.0764 0.403 2.13 3 9.29 47.4 91.6 0.0951 0.471 2.08 4 8.26 49.1 94.1 0.0876 0.427 2.41 5 8.74 45.7 95.7 0.0811 0.452 2.24 6 7.73 48.2 90.6 0.0798 0.485 2.33 平均值 8.51 47.7 93 0.0837 0.45 2.26 回收率(%) 77.3~92.9 91.4~98.2 91.6~95.7 76.4~95.1 80.6~97.0 83.2~96.4 RSD(%) 7.5 6.7 5.9 8.0 6.7 5.9
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表 4 实际样品的计算结果对比
Table 4. Comparison of calculation results for actual samples
土壤样品编号 土壤样品中石油类物质含量(mg/kg) 水样品编号 水样品中石油类物质含量(mg/L) 校正系数法
(标准方法)三波数之和标准曲线法
(本文方法)相对偏差
(%)校正系数法
(标准方法)三波数之和标准曲线法
(本文方法)相对偏差
(%)T-1 17.4 18.5 -3.1 S-1 0.08 0.07 6.7 T-2 9.73 9.82 -0.5 S-2 0.11 0.12 -4.3 T-3 87.9 90.9 -1.7 S-3 0.09 0.1 -5.3 T-4 104 94.8 4.6 S-4 0.67 0.65 1.5 T-5 374 393 -2.5 S-5 0.88 0.92 -2.2 T-6 646 689 -3.2 S-6 0.79 0.84 -3.1 T-7 1235 1304 -2.7 S-7 1.25 1.18 2.9 T-8 1647 1723 -2.3 S-8 1.34 1.26 3.1 T-9 5386 5839 -4.0 S-9 1.87 1.67 5.6 T-10 20880 22342 -3.4 S-10 2.07 2.14 -1.7 注：相对偏差=(推荐方法测定值-两次测定值的平均值)/两次测定值平均值×100%。
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