Determination of Petroleum Oil in Soil by Fluorescence Spectrophotometry with Oscillatory Extraction
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摘要:
石油类物质是中国建设用地土壤污染风险管控的污染物之一，开展土壤中石油类物质的检测对土壤污染防治工作具有重要意义。本文采用正己烷为萃取溶剂，土壤经振荡提取后，以荧光光度法为检测手段，建立了一种绿色环保、灵敏高效的土壤石油类物质检测方法。通过对实验过程进行优化，该方法的线性相关系数r≥0.999，检出限为3mg/kg。使用10种不同类型土壤进行方法精密度和准确度验证，精密度为2.5%~9.2%，基体加标回收率为80.0%～110%。为验证方法可比性，分别使用本方法和《土壤 石油类的测定 红外分光光度法》(HJ 1051—2019)对5种不同类型土壤进行检测比对，测定结果相对偏差在5.0%~15%之间，具有较好的一致性。
Abstract:BACKGROUND As an important index of soil environmental quality, the determination of petroleum oil has become one of the must-test items in environmental monitoring. The gravimetric method is not suitable for the purpose of environmental monitoring because it can only be used for the determination of non-volatile substances and has low sensitivity. Gas chromatography is mainly used for the determination of C10-C40 saturated alkanes in samples. The infrared spectrometry used characteristic absorption at different wavenumber to characterize the content of petroleum substances in the samples, but the response of infrared spectrometry to aromatic hydrocarbons is not sensitive.
OBJECTIVES To establish a simple pre-treatment efficiency, low detection limit and good reproducible method for determination of petroleum oil in soil.
METHODS Using n-hexane as the solvent, adsorption column as the extraction method and oscillatory as the pretreatment method, petroleum oil was extracted from soil and determined by fluorescence spectrophotometry.
RESULTS Under the optimal conditions that with 275nm as the excitation wavelength and 315nm as the emission wavelength, the extraction solvent was n-hexane and the extraction method was adsorption column, the calibration curves of petroleum oil were linear with correlation coefficients 0.999, and the detection limit was 3mg/kg. The relative standard derivations (RSDs) were from 2.5% to 9.2% and the average spiked recoveries were between 80.0% and 110%. Compared with the currently valid infrared spectrometry method (HJ 1051—2019), the results of the two methods were consistent.
CONCLUSIONS The solvent of n-hexane has higher toxicity and stability than tetrachloroethene, and better environmental friendliness. The oscillatory extraction method is simple and easy to operate. The detection limit of this method is lower than that of infrared spectrometry (4mg/kg), and the precision and accuracy of the method is good. This method can be used as a supplement to the existing methods for the detection of petroleum in soil.
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Key words:
- soil /
- petroleum oil /
- oscillatory extraction /
- fluorescence spectrophotometry /
- hexane
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表 1 实际样品石油类物质的测定精密度
Table 1. The precision results of petroleum oil in different actual soil samples
测定次数 实际样品石油类物质的测定结果(mg/kg) 样品1-1 样品1-2 样品1-3 样品1-4 样品1-5 样品1-6 样品2-1 样品2-2 样品2-3 样品2-4 1 32 48 3 12 12 24 <3 <3 <3 <3 2 30 43 4 13 13 23 <3 <3 <3 <3 3 35 50 3 15 11 23 <3 <3 <3 <3 4 32 47 4 12 14 22 <3 <3 <3 <3 5 35 48 4 14 12 23 <3 <3 <3 <3 6 31 44 4 14 12 22 <3 <3 <3 <3 平均值(mg/kg) 32 47 4 13 12 23 / / / / SD(mg/kg) 2.1 2.7 0.1 1.2 1.0 0.8 / / / / RSD(%) 6.6 5.7 2.5 9.2 8.3 3.5 / / / / 
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表 2 化工厂厂界周边土壤样品中石油类物质的准确度测定结果
Table 2. The accuracy results of petroleum oil in perimeter soil samples from the chemical plant
测定
次数样品1-1 样品1-2 样品1-3 样品1-4 样品1-5 样品1-6 样品(mg/kg) 加标样品(mg/kg) 样品(mg/kg) 加标样品(mg/kg) 样品(mg/kg) 加标样品(mg/kg) 样品(mg/kg) 加标样品(mg/kg) 样品(mg/kg) 加标样品(mg/kg) 样品(mg/kg) 加标样品(mg/kg) 1 32 79 48 149 3 13 12 25 12 30 24 76 2 30 73 43 145 4 13 13 22 13 28 23 64 3 35 90 50 140 3 13 15 25 11 30 23 70 4 32 74 47 155 4 12 12 21 14 29 22 71 5 35 85 48 150 4 12 14 25 12 27 23 76 6 31 70 44 138 4 11 14 25 12 28 22 68 平均值 32 78 47 146 4 12 13 24 12 29 23 71 加标量 50 100 10 10 20 50 回收率
(%)92.0 99.0 80.0 110.0 85.0 96.0
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表 3 农用地土壤样品中石油类物质的准确度测定结果
Table 3. The accuracy results of petroleum oil in soil samples from agricultural land
测定次数 2-1 2-2 2-3 2-4 样品
(mg/kg)加标样品
(mg/kg)样品
(mg/kg)加标样品
(mg/kg)样品
(mg/kg)加标样品
(mg/kg)样品
(mg/kg)加标样品
(mg/kg)1 <3 9 <3 10 <3 10 <3 9 2 <3 9 <3 9 <3 9 <3 8 3 <3 9 <3 10 <3 9 <3 8 4 <3 8 <3 9 <3 8 <3 8 5 <3 9 <3 8 <3 10 <3 9 6 <3 8 <3 8 <3 9 <3 9 平均值 9 9 9 8 加标量 10 10 10 10 回收率(%) 90.0 90.0 90.0 80.0
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表 4 采用不同硅酸镁净化方式石油类物质的测定结果
Table 4. The results of petroleum oil determined with different purification modes of magnesium silicate
测定
次数振荡吸附法
(玻璃漏斗+玻纤滤膜)吸附柱吸附法 振荡吸附法
(玻璃漏斗+玻纤滤膜)吸附柱吸附法 净化后测定值
(mg/kg)杂质
去除率(%)净化后测定值
(mg/kg)杂质
去除率(%)测定值
(mg/kg)空白加标回收率
(%)测定值
(mg/kg)空白加标回收率
(%)1 5 90.0 <3 100.0 18 90.0 20 100.0 2 6 88.0 <3 100.0 18 90.0 19 95.0 3 6 88.0 <3 100.0 18 90.0 21 105.0 4 5 90.0 <3 100.0 18 90.0 19 95.0 5 4 92.0 <3 100.0 19 95.0 19 95.0 6 5 90.0 <3 100.0 19 95.0 20 100.0 平均值 5 90.0 <3 100.0 18 90.0 20 100.0
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表 5 不同硅酸镁填充高度对植物油的吸附效率
Table 5. The absorption efficiency of vegetable oil with different height of magnesium silicate extraction column
参数 100mL浓度为500mg/L的植物油溶液 硅酸镁高度(mm) 40 60 80 100 120 植物油测定浓度(mg/L) 9.83 3.32 0.00 0.00 0.00 吸附效率(%) 99.0 99.6 100.0 100.0 100.0
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表 6 本文的荧光分光光度法与红外分光光度法(现行标准方法)比对结果
Table 6. Comparison of analytical results of petroleum oil determined with fluorescence spectrophotometry (this method) and infrared spectrophotometry (standard methods)
实际样品
编号红外分光光度法(mg/kg) 荧光分光光度法(mg/kg) 红外分光光度法和
荧光分光光度法
相对偏差(%)样品3-1 <4 <3 / 样品3-2 <4 <3 / 样品3-3 16 12 15 样品3-4 53 48 5.0 样品3-5 39 32 9.9
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