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摘要:
邻苯二甲酸酯类化合物(Phthalates，PAEs)作为一类持续释放并存在于环境中的有机污染物，被列入优先控制污染物名单。土壤是PAEs在环境中的最后归宿之一，中国对土壤中PAEs的污染调查和防控已全面展开。分析测试是环境监测和科学研究的基础，土壤基体标准物质是保证实验数据的准确性和可靠性的重要手段，然而，目前现有的相关标准物质无法满足实际需要。本文针对中国土壤中PAEs污染特征及实际样品分析质量控制需求，采用多家实验室联合定值的方式，研制了4种适用于土壤中不同污染水平PAEs分析的标准物质。候选物样品主要采自农田土壤、地膜覆盖土壤、塑料垃圾回收站周围土壤和塑料制品加工厂周围土壤，经过均匀性、长期稳定性和短期稳定性检验，结果表明均匀性和稳定性均满足要求；在定值过程中，针对PAEs分析空白不易控制的难点，对空白的污染源进行识别和确认，制定严格的质量控制措施，保证了全流程空白值稳定在一定范围内；9家实验室采用气相色谱-质谱法(GC-MS)对候选物中4种PAEs进行协作定值，并评估其不确定度，特性量值范围在36～2870µg/kg，同时邀请权威实验室采用同位素稀释质谱法对定值结果进行验证，确保定值结果的准确性。该系列标准物质已被批准为国家一级标准物质（编号GBW07595～GBW07598），可以满足PAEs分析质量保证与质量控制的要求，为生态地质调查评价提供技术支撑。
Abstract:Phthalates (PAEs) are a class of organic pollutants that are continuously released and present in the environment and are listed as priority-controlled pollutants. Soil is one of the main final fates of PAEs in the environment, and China has fully launched investigations and controls on soil pollution of PAEs. Analysis is the foundation of environmental monitoring and scientific research, and the certified reference materials in soil are important means to ensure the accuracy and reliability of determination for soil. However, the existing relevant reference materials do not meet the actual needs of pollution monitoring in China. In this study, according to the characteristics of PAEs pollution and quality control requirements of actual samples, four certified reference materials for PAEs analysis in soils have been developed through the nine laboratories’ collaborative analysis. The candidates were mainly collected from agricultural soils, plastic film mulched soil, industrial soil, and plastic recycling station soil. After homogeneity and stability testing, the results show that both homogeneity and stability meet the requirements. During the certification process, in response to the difficulty of controlling the PAEs analysis blank, the pollution source of the blank was identified and confirmed, and strict quality control measures were formulated to ensure that the blank concentration throughout the entire process remained stable within a certain range. Nine laboratories used gas chromatography-mass spectrometry (GC-MS) to collaboratively determine the values of 4 PAEs and evaluated their uncertainty in soils. The certified values of 4 PAEs in soils ranging from 36g/kg to 2.87mg/kg. The authoritative domestic laboratory used isotope dilution mass spectrometry to verify the accuracy of the certification results. This series of reference materials have been approved as a national first-class reference material, numbered from GBW07595 to GBW07598, which meets the requirements of PAEs analysis quality assurance and quality control, and provides technical support for ecological geological survey and evaluation.
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表 1 候选物GSSO-12均匀性检验结果
Table 1. Homogeneity test for candidate GSSO-12
参数 DMP DiBP DBP DEHP 目标物平均值 (µg/kg) 37.5 409 754 653 RSD (%) 10.4 7.59 7.39 10.7 $ {M}_{\mathrm{b}\mathrm{e}\mathrm{t}\mathrm{w}\mathrm{e}\mathrm{e}\mathrm{n}} $ (µg 2/kg2)15.84 1029 2924 5255 $ {M}_{\mathrm{w}\mathrm{i}\mathrm{t}\mathrm{h}\mathrm{i}\mathrm{n}} $ (µg 2/kg2)12.62 816 2263 4156 F实测值 1.292 1.261 1.291 1.265 $ {S}_{\mathrm{b}\mathrm{b}} $ (µg/kg)1.05 8.43 14.9 19.2 注：F0.05(24，50) = 1.737。 
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表 2 候选物GSSO-12长期稳定性检验(4℃)数据和短期稳定性检验(50℃)数据
Table 2. Long stability test (4℃) and short stability test (50℃) data for candidate GSSO-12
PAEs
化合物长期稳定性检验(4℃) 短期稳定性检验(50℃) 含量平均值
(µg/kg)RSD
(%)b1 $t_{0.05} \times S(b_1) $ us1
(µg/kg)含量平均值
(µg/kg)RSD
(%)b1 $t_{0.05} \times S(b_1) $ uss
(µg/kg)DMP 36.5 5.84 −0.062 0.981 3.71 36.2 4.29 0.0095 0.829 2.61 DiBP 406 5.05 −0.242 9.57 36.2 401 2.93 −0.279 6.43 20.3 DBP 769 5.56 4.86 16.7 63.2 750 3.17 −2.917 11.1 34.9 DEHP 642 5.62 0.016 16.8 63.4 654 2.56 1.244 8.56 27.0
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表 3 候选物GSSO-12定值校准用溶液标准物质引入的不确定度
Table 3. The uncertainty introduced by certified reference materials in calibration solutions for candidate GSSO-12
PAEs
化合物定值用溶液标准物质 候选物GSSO-12校准溶液引入的不确定度 标准物质编号 标准值
(µg/mL)相对扩展不确定度(%)
(k=2)相对不确定度
(%)量值
(µg/kg)uB1
(µg/kg)DMP GBW(E)100221 237 2 1 35.9 0.36 DiBP GBW(E)100284 1000 2 1 397 3.97 DBP GBW10134 500 3 1.5 757 11.4 DEHP GBW10165 500 3 1.5 669 10.1
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表 4 候选物GSSO-12溶液配制引入的不确定度
Table 4. The uncertainty introduced by calibration solution preparation for candidate GSSO-12
PAEs
化合物候选物GSSO-12 量值
(µg/kg)相对不确定度
(%)uB2
(µg/kg)DMP 35.9 0.287 0.11 DiBP 397 0.457 1.83 DBP 757 0.287 2.18 DEHP 669 0.287 1.93
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表 5 候选物GSSO-12标准曲线拟合引入的不确定度
Table 5. The uncertainty introduced by calibration curve fitting for candidate GSSO-12
PAEs
化合物候选物GSSO-12 量值
(µg/kg)uB3
(µg/kg)相对不确定度
(%)DMP 35.9 1.02 2.85 DiBP 397 2.45 0.61 DBP 757 3.23 0.43 DEHP 669 4.80 0.72
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表 6 候选物GSSO-12样品称量引入的不确定度uB4和添加内标溶液引入的不确定度uB5
Table 6. The uncertainty introduced by sampling weigh and adding internal standard solution for candidate GSSO-12
PAEs化合物 候选物GSSO-12 量值
(µg/kg)样品称量引入的不确定度 添加内标量引入的不确定度 相对不确定度
(%)uB4
(µg/kg)相对不确定度
(%)uB5
(µg/kg)DMP 35.9 0.0892 0.032 0.326 0.12 DiBP 397 0.0892 0.36 0.326 1.31 DBP 757 0.0892 0.68 0.326 2.47 DEHP 669 0.0892 0.60 0.326 2.19
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表 7 候选物GSSO-12的不确定度
Table 7. The uncertainty of candidate GSSO-12
PAEs化合物 量值
(µg/kg)ubb
(µg/kg)usl
(µg/kg)uss
(µg/kg)uA
(µg/kg)uB1
(µg/kg)uB2
(µg/kg)uB3
(µg/kg)uB4
(µg/kg)uB5
(µg/kg)uCRM
(µg/kg)UCRM
(µg/kg)DMP 35.9 1.05 3.71 2.61 1.38 0.36 0.11 1.02 0.032 0.12 4.98 10 DiBP 397 8.43 36.2 20.3 10.7 3.97 1.83 2.45 0.36 1.31 44.0 88 DBP 757 14.9 63.2 34.9 19.5 11.4 2.18 3.23 0.68 2.47 77.2 160 DEHP 669 19.2 63.4 27.0 13.7 10.1 1.93 4.80 0.60 2.19 73.9 150
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表 8 四个PAEs成分分析标准物质的标准值及扩展不确定度
Table 8. Certified values and expanded uncertainties for four PAE certified reference materials
特性量 标准物质的特性量值及扩展不确定度(µg/kg) GBW07595
(GSSO-12)GBW07596
(GSSO-13)GBW07597
(GSSO-14)GBW07598
(GSSO-15)DMP 36±10 74±18 — — DiBP 397±88 1.13×103±0.25×103 88±24 314±73 DBP 0.76×103±0.16×103 1.21×103±0.26×103 413±96 302±69 DEHP 0.67×103±0.15×103 2.87×103±0.53×103 412±98 2.46×103±0.48×103 注：“—”表示该化合物未定值。
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| 引用本文: |
田芹, 佟玲, 潘萌, 安子怡, 许春雪, 张苗苗, 汪丽萍. 土壤中邻苯二甲酸酯成分分析标准物质研制[J]. 岩矿测试, 2024, 43(4): 603-613. doi: 10.15898/j.ykcs.202403050031
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| Citation: |
TIAN Qin, TONG Ling, PAN Meng, AN Ziyi, XU Chunxue, ZHANG Miaomiao, WANG Liping. Development of Certified Reference Materials of Phthalates in Soils[J]. Rock and Mineral Analysis, 2024, 43(4): 603-613. doi: 10.15898/j.ykcs.202403050031
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