【引用本文】 田芹, 佟玲, 安子怡, 等. 沉积物中多环芳烃、有机氯农药和多氯联苯成分分析标准物质研制[J]. 岩矿测试, 2022, 41(3): 511-520. doi: 10.15898/j.cnki.11-2131/td.202110130149
TIAN Qin, TONG Ling, AN Ziyi, et al. Development of Certified Reference Materials of Polycyclic Aromatic Hydrocarbons, Organochlorine Pesticides and Polychlorinated Biphenyls in Sediments[J]. Rock and Mineral Analysis, 2022, 41(3): 511-520. doi: 10.15898/j.cnki.11-2131/td.202110130149

沉积物中多环芳烃、有机氯农药和多氯联苯成分分析标准物质研制

1. 

国家地质实验测试中心,北京 100037

2. 

自然资源部生态地球化学重点实验室,北京 100037

3. 

中国农业大学,北京 100193

收稿日期: 2021-10-13  修回日期: 2021-12-08  接受日期: 2022-01-28

基金项目: 中国地质调查局地质调查项目(DD20221838,DD20190475);中国地质科学院基本科研业务费项目(CSJ-2021-01);中国地质调查局地质调查项目(12120115054901)

作者简介: 田芹,博士,正高级工程师,主要从事有机污染物分析技术及标准化研究。E-mail:tqname81@163.com

通信作者: 佟玲,硕士,高级工程师,主要从事有机污染物分析技术研究。E-mail:winter_tl@sina.com

Development of Certified Reference Materials of Polycyclic Aromatic Hydrocarbons, Organochlorine Pesticides and Polychlorinated Biphenyls in Sediments

1. 

National Research Center for Geoanalysis, Beijing 100037, China

2. 

Key Laboratory of Eco-geochemistry, Ministry of Natural Resources, Beijing 100037, China

3. 

China Agricultural University, Beijing 100193, China

Corresponding author: TONG Ling, winter_tl@sina.com

Received Date: 2021-10-13
Revised Date: 2021-12-08
Accepted Date: 2022-01-28

摘要:多环芳烃(PAHs)、有机氯农药(OCPs)和多氯联苯(PCBs)具有致畸、致癌、致突变效应,是优先控制的污染物。污染调查和治理对策的制定依赖于精准的分析测试数据,而标准物质是数据质量控制的重要保证,然而目前现有的相关标准物质无法满足实际需要。本文针对中国主要湖泊和河流分布特点,以及污染特征及沉积物调查现状,严格按照《国家一级标准物质技术规范》(JJF 1006—1994)和《地质分析标准物质的研制规范》(JJF 1646—2017),研制了适合中国环境监测和科学研究需求的多环芳烃、有机氯农药和多氯联苯分析沉积物标准物质4个。研制过程中,为解决有机化合物标准物质的稳定性技术难点,考察了60Co灭菌和温度对有机化合物稳定性的影响,评估了长期稳定性和短期稳定性,结果表明样品稳定性良好。针对沉积物样品基体复杂的特点,采用不同的提取和净化技术,建立合理的量值溯源链,利用传统的液相色谱法、气相色谱电子捕获器法、气相色谱-质谱法和气相色谱-同位素稀释质谱法等多种分析方法,完成了9家实验室的协作定值。定值指标包括16种多环芳烃、3种有机氯农药和3种多氯联苯,含量范围为8.0ng/g~5.7μg/g,可以满足多环芳烃、有机氯农药和多氯联苯同时分析的质量保证与质量控制的要求。该系列标准物质已被批准为国家一级标准物质(编号GBW07352~GBW07355),可用于分析方法验证、实验室质量控制、实验室分析能力考核等方面的需要。

关键词: 沉积物, 标准物质, 多环芳烃, 有机氯农药, 多氯联苯, 认定值, 气相色谱-质谱法, 气相色谱-同位素稀释质谱法

要点

(1) 研制了中国河流和湖泊不同水系沉积物标准物质,定值化合物种类多:16种多环芳烃、3种有机氯农药和3种多氯联苯;特性量值覆盖范围广(ng/g到μg/g水平),可以满足不同分析测试需求。

(2) 9家实验室采用涵盖高精准的同位素稀释质谱法等3种不同原理的分析方法进行协作定值,确保了定值准确。

(3) 定值方法、不确定评定、定值准确度等达到同类标准物质水平。

Development of Certified Reference Materials of Polycyclic Aromatic Hydrocarbons, Organochlorine Pesticides and Polychlorinated Biphenyls in Sediments

ABSTRACT

BACKGROUND:

Polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) have teratogenic, carcinogenic and mutagenic effects, which are priority pollutants. The formulation of pollution investigation and treatment measures depends on accurate analysis and test data, and certified reference materials (CRMs) are an important guarantee for data quality control. However, the existing relevant reference materials cannot meet the actual needs of pollution monitoring in China.

OBJECTIVES:

To prepare four CRMs of sediments for analysis of PAHs, OCPs and PCBs, and to meet the needs of environmental monitoring and scientific research for the monitoring of priority pollutants in China.

METHODS:

In this study, according to the specifications of certified reference materials (JJF 1006—1994, JJF1343—2012 and JJF 1646—2017), 4 CRMs of PAHs, OCPs and PCBs in different sediments (GBW07352-GBW07355) have been developed for Chinese environmental monitoring and scientific research. In the development process, in order to solve the technical difficulties of the stability of organic compound reference materials, the effects of 60Co sterilization and temperature on the stability of organic compounds were investigated. In view of the complex characteristics of the sediment sample matrix, different extraction and purification technologies were adopted to reduce or eliminate the influence of the complex matrix on the extraction solution and reduce the matrix effect of instrument measurement. Nine laboratories' collaborative analysis was carried out by using traditional methods including high performance liquid chromatography (HPLC), gas chromatography-electron capture detector (GC-ECD), gas chromatography-mass spectrometry (GC-MS) and new techniques of gas chromatography-isotope dilution mass spectrometry (GC-IDMS).

RESULTS:

The sediment candidates have good homogeneity and stability. The certified values and expanded uncertainty for 16 PAHs, 3 OCPs and 3 PCBs are given, and the concentrations range from 9.0ng/g to 5.7μg/g, which meets the requirements of quality assurance and quality control for analysis of PAHs, OCPs and PCBs.

CONCLUSIONS:

This series of reference materials has been approved as a national first-class reference material, numbered from GBW07352 to GBW07355. This series of CRMs can be used in analytical method validation, laboratory quality control, laboratory analysis ability assessment.

KEY WORDS: sediments, certified reference materials, polycyclic aromatic hydrocarbons, organochlorine pesticides, polychlorinated biphenyls, certified values, gas chromatography-mass spectrometry, gas chromatography-isotope dilution mass spectrometry

HIGHLIGHTS

(1) The certified reference materials of sediments from different stream systems of rivers and lakes in China have been developed. This series of reference materials not only have three kinds of certified values: 16 PAHs, 3 OCPs and 3 PCBs, but also have a wide content range from ng/g to μg/g levels, which meet the needs of different analyses.

(2) Nine laboratories used three analytical methods for collaborative analysis, including high-precision isotope dilution mass spectrometry, which ensured the accuracy of the certified values.

(3) The method of certified values, accuracy and uncertainty have achieved the level of research and development of similar reference materials in the world.

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沉积物中多环芳烃、有机氯农药和多氯联苯成分分析标准物质研制

田芹, 佟玲, 安子怡, 许春雪, 孙慧中, 刁金玲