加速溶剂萃取-QuEChERS-气相色谱质谱联用法测定土壤中增塑剂

唐会智; 宋冬梅

doi:10.16495/j.1006-3757.2023.01.016

加速溶剂萃取-QuEChERS-气相色谱质谱联用法测定土壤中增塑剂

doi: 10.16495/j.1006-3757.2023.01.016

湖南溯源实验室管理咨询有限公司，湖南长沙　410000

详细信息

作者简介:
唐会智（1984−），男，工程师，从事环境检测研究工作，E-mail：1577061892@qq.com

中图分类号: O657.63
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- 文章访问数: 170
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- 被引次数: 0
出版历程
- 收稿日期: 2022-10-17
- 录用日期: 2022-12-14
- 修回日期: 2022-12-14
- 网络出版日期: 2023-04-08
- 刊出日期: 2023-03-31

Detection of Plasticizers in Soil by Accelerated Solvent Extraction-QuEChERS-Gas Chromatography/Mass Spectrometry

Hunan Traceability Laboratory Management Consulting Co. Ltd., Changsha 410000, China

摘要

摘要: 建立加速溶剂萃取-QuEChERS-气相色谱质谱联用法对土壤样品中17种增塑剂进行检测. 土壤样品以正己烷饱和乙腈萃取，经25 mg 乙二胺-N-丙基硅烷和25 mg硅胶净化，气相色谱质谱联用法选择离子监测（SIM）模式下检测，以外标法进行定量分析. 17种增塑剂在0.01~2 mg/L质量浓度内线性关系良好，各化合物相关系数均在0.999以上. 方法的检出限在0.01~0.05 mg/kg之间，定量限在0.03~0.15 mg/kg之间，17种增塑剂在0.5、1.0、5.0 mg/kg添加水平下，加标回收率和精密度分别为72.8%~116.2%和1.73%~6.15%. 方法简易便捷、灵敏度和准确度高，适合于检测土壤中17种增塑剂.
- 加速溶剂萃取 /
- QuEChERS /
- 气相色谱质谱联用 /
- 土壤 /
- 增塑剂
Abstract: A method for the detection of 17 plasticizers in soil samples by the accelerated solvent extraction（ASE）-QuEChERS-gas chromatography/mass spectrometry（GC/MS） has been established. The soil samples were extracted with hexane saturated acetonitrile, and purified by 25 mg PSA (primary secondary amine) and 25 mg Silica. GC/MS was used for the detection in the selected ion monitoring (SIM) mode, and the matrix-matched external standard calibration curves were used for the quantitative analysis. The standard solution of 17 plasticizers showed a good linearity in the concentration range of 0.01 to 2 mg/L, and the correlation coefficient (r) were above 0.999. The limit of detection was between 0.01 and 0.05 mg/kg, and the limit of quantitation was between 0.03 and 0.15 mg/kg. The spiked recoveries and precisions of 17 plasticizers were ranged from 72.8% to 116.2% and 1.73% to 6.15% at the three spiked concentration levels (0.5, 1.0, 5.0 mg/kg), respectively. The method is simple, convenient, sensitive and accurate, and is suitable for the detection of 17 plasticizers in soil.
- ASE /
- QuEChERS /
- GC/MS /
- soil /
- plasticizers

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图 1 17种PAEs总离子流色谱图

Figure 1. Total ion chromatogram of 17 PAEs

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表 1 17种PAEs保留时间和特征离子

Table 1. Retention times and characteristic ions of 17 PAEs

待测物	保留时间/min	定量离子/（m/z）	定性离子/（m/z）
DMP	7.834	163	77, 133, 194
DEP	8.699	149	105, 177, 222
DAP	9.620	149	41, 132, 189
DIBP	10.456	149	104, 167, 223
DBP	11.200	149	104, 205, 223
DMEP	11.530	149	59, 104, 176
BMPP	12.282	149	85, 167, 251
DEEP	12.594	149	72, 104, 193
DPP	12.972	149	104, 219, 237
DHXP	15.096	149	104, 233, 251
BBP	15.258	149	91, 104, 206
DBEP	16.712	149	85, 101, 193
DCHP	17.447	149	104, 167, 249
DEHP	17.646	149	113, 167, 279
DPhP	17.763	225	77, 104, 153
DNOP	19.304	149	104, 261, 279
DNP	20.987	149	167, 275, 293

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表 2 PSA不同质量对17种PAEs回收率的影响

Table 2. Effect of different dosages of PSA on recoveries of 17 PAEs /（%, n=3）

序号	化合物	加标回收率
序号	化合物	5 mg	10 mg	25 mg	50 mg	100 mg
1	DMP	68.1	72.3	81.2	87.6	84.5
2	DEP	130.2	123.4	109.3	103.4	103.7
3	DAP	56.2	67.7	74.2	75.4	78.9
4	DIBP	78.3	82.6	89.4	93.7	91.2
5	DBP	71.8	80.5	87.7	92.9	91.6
6	DMEP	123.2	116.5	109.2	105.7	105.1
7	BMPP	108.1	103.1	101.2	102.3	99.5
8	DEEP	82.5	84.8	88.2	89.7	91.1
9	DPP	82.3	85.2	89.4	93.6	94.8
10	DHXP	73.4	79.8	83.1	88.4	87.2
11	BBP	117.5	107.3	101.4	103.2	100.9
12	DBEP	105.9	107.3	106.7	108.4	103.2
13	DCHP	87.1	90.4	92.1	91.5	91.8
14	DEHP	70.3	71.4	80.5	83.7	82.9
15	DPhP	122.6	118.3	108.5	106.3	105.3
16	DNOP	81.2	83.3	88.4	89.2	86.6
17	DNP	76.1	75.3	81.4	87.2	91.6

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表 3 Silica不同质量对17种PAEs回收率的影响

Table 3. Effect of different dosages of Silica on recoveries of 17 PAEs /（%, n=3）

序号	化合物	加标回收率
序号	化合物	5 mg	10 mg	25 mg	50 mg	100 mg
1	DMP	61.2	75.8	81.4	85.5	89.3
2	DEP	125.3	115.6	109.5	108.3	106.7
3	DAP	62.4	71.4	74.7	76.3	79.5
4	DIBP	80.6	85.1	90.1	92.5	93.4
5	DBP	70.9	74.8	86.6	88.7	90.6
6	DMEP	128.7	121.6	109.7	105.3	107.8
7	BMPP	123.3	112.1	103.6	104.4	100.5
8	DEEP	80.1	85.1	88.9	91.2	92.7
9	DPP	74.7	79.8	87.6	89.2	90.6
10	DHXP	60.9	71.1	84.2	89.1	90.1
11	BBP	119.8	109.7	102.1	102.4	100.7
12	DBEP	78.6	82.3	107.7	104.3	99.5
13	DCHP	74.5	82.8	91.6	93.4	93.9
14	DEHP	61.8	72.3	80.4	84.6	84.2
15	DPhP	131.3	121.5	109.8	104.7	107.2
16	DNOP	68.4	77.4	88.5	93.6	91.0
17	DNP	75.3	79.1	82.3	87.3	88.5

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表 4 17种PAEs的回归方程、相关系数、检出限和定量限

Table 4. Linear equations, correlation coefficients, LOD and LOQ of 17 PAEs

序号	待测物	回归方程	相关系数	LOD/(mg/kg)	LOQ/(mg/kg)
1	DMP	Y=251 476X−103 39	0.999 1	0.02	0.05
2	DEP	Y=310 549X−109 54	0.999 0	0.01	0.03
3	DAP	Y=321 850X−123 03	0.999 2	0.01	0.03
4	DIBP	Y=247 749X−103 53	0.999 4	0.03	0.10
5	DBP	Y=412 578X−201 74	0.999 3	0.02	0.05
6	DMEP	Y=169 756X−649 90	0.999 0	0.01	0.03
7	BMPP	Y=315 074X−210 32	0.999 2	0.05	0.15
8	DEEP	Y=265 019X−837 60	0.999 1	0.02	0.05
9	DPP	Y=413 583X−198 58	0.999 0	0.03	0.10
10	DHXP	Y=310 125X−281 08	0.999 1	0.01	0.03
11	BBP	Y=329 471X−242 38	0.999 2	0.02	0.05
12	DBEP	Y=839 48X−510 10	0.999 3	0.03	0.10
13	DCHP	Y=193 371X−102 37	0.999 1	0.03	0.10
14	DEHP	Y=185 487X−139 05	0.999 2	0.02	0.05
15	DPhP	Y=405 328X−258 49	0.999 3	0.01	0.03
16	DNOP	Y=231 375X−207 48	0.999 0	0.05	0.15
17	DNP	Y=183 749X−694 70	0.999 1	0.02	0.05

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表 5 17种PAEs的精密度和加标回收率

Table 5. Spiked recoveries and precisions of 17 PAEs /（%, n=6）

序号	待测物	加标水平（0.5 mg/kg）		加标水平（1.0 mg/kg）		加标水平（5.0 mg/kg）
序号	待测物	平均回收率	RSD	平均回收率	RSD	平均回收率	RSD
1	DMP	75.2	3.50	81.4	2.52	84.5	5.06
2	DEP	108.4	4.65	109.2	3.21	102.7	4.86
3	DAP	72.8	5.01	74.1	3.89	80.5	4.24
4	DIBP	83.6	3.81	90.0	4.07	94.7	3.45
5	DBP	80.2	5.12	87.6	3.50	91.1	3.59
6	DMEP	113.7	5.64	108.5	4.96	104.4	3.07
7	BMPP	108.5	4.52	101.3	2.64	100.7	3.58
8	DEEP	82.5	6.15	89.9	4.67	92.5	5.31
9	DPP	83.4	4.35	90.2	3.08	94.6	1.73
10	DHXP	76.6	3.98	82.6	4.47	86.9	2.93
11	BBP	81.0	5.82	101.6	3.17	103.6	3.31
12	DBEP	109.9	4.09	106.5	3.72	102.9	3.45
13	DCHP	87.3	5.51	92.1	4.76	95.1	3.57
14	DEHP	75.6	3.09	80.9	3.56	83.5	4.17
15	DPhP	116.2	5.01	108.2	4.37	105.7	3.93
16	DNOP	80.3	4.23	89.0	3.32	92.6	2.67
17	DNP	76.8	5.76	81.7	4.81	83.5	4.69

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