Development of Certified Reference Materials of Polycyclic Aromatic Hydrocarbons, Organochlorine Pesticides and Polychlorinated Biphenyls in Sediments
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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。
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.
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表 1 国内外研制的有关土壤/沉积物中PAHs、OCPs和PCBs分析标准物质
Table 1. CRMs of PAHs, OCPs and PCBs standard materials in soils/sediments
标准物质来源 标准物质个数 标准物质编号 定值组分 中国 12 GBW(E)081518、GBW(E)081519、GBW07474 土壤中7种PCBs GBW08307 土壤中14种PCBs GBW(E)081937 土壤中15种OCPs GBW07473 土壤中8种OCPs GBW07469、GBW07470 土壤中8种OCPs和2种PCBs GBW07471、GBW07472 土壤中8种OCPs和7种PCBs GBW(E)081938 底泥中16种PAHs GBW(E)082042 底泥中11种OCPs 美国国家标准与技术研究院(NIST) 2 SRM 1941b
SRM1944海洋沉积物中7种OCPs、29种PCBs、24种PAHs
港口积物中3种OCPs、29种PCBs、22种PAHs欧盟联合研究中心标准物质与测量研究所(IRMM) 5 ERM-CC007a
BCR-481
BAM-U019
BCR-535
BCR-536土壤中6种OCPs
土壤中13种PCBs
土壤中7种PCBs
淡水沉积物中7种PAHs
淡水沉积物中13种PCBs英国政府化学家实验室(LGC) 2 LGC6114
LGC6188港口沉积物中7种PCBs
河流沉积物中16种PAHs国际原子能机构(IAEA) 3 IAEA-408
IAEA-417
IAEA-383河口沉积物中5种OCPs、13种PAHs和14种PCBs
湖泊沉积物中4种OCPs、17种PAHs和24种PCBs
沉积物中1种OCPs、19种PAHs和18种PCBs日本国家计量研究院(NMIJ) 3 NMIJ CRM 7304-a、NMIJ CRM 7305-a
NMIJ CRM 7307-a沉积物中4种OCPs和14种PCBs
沉积物中16种PAHs
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表 2 候选物GSSO-7均匀性检验结果
Table 2. Homogeneity test for candidate material GSSO-7
参数 萘 苊烯 苊 芴 菲 蒽 荧蒽 芘 苯并[a]蒽 䓛 平均值(ng/g) 1258 228 268 308 5785 350 3725 3224 1012 1258 样品数量(件) 25 25 25 25 25 25 25 25 25 25 最小值(ng/g) 1068 189 224 256 4886 284 3239 2819 875 1038 最大值(ng/g) 1485 253 300 349 6748 414 4225 3691 1178 1595 RSD(%) 6.77 5.68 5.87 8.49 9.39 8.90 6.63 7.82 9.43 9.67 F实测值 1.594 1.545 1.703 1.542 1.367 1.444 1.425 1.256 1.587 1.670 Sbb(ng/g) 34.7 5.10 6.88 10.2 180 11.2 87.1 70.7 38.7 52.1 参数 苯并[b] 荧蒽 苯并[k] 荧蒽 苯并[a]芘 二苯并[a, h]蒽 苯并[g, h, i]苝 茚并[1, 2, 3-cd]芘 平均值(ng/g) 826 452 769 111 908 782 样品数量(件) 25 25 25 25 25 25 最小值(ng/g) 703 390 681 97.4 802 658 最大值(ng/g) 954 518 897 131 1039 874 RSD(%) 8.72 8.01 6.63 6.56 7.54 6.67 F实测值 1.593 1.682 1.688 1.373 1.506 1.665 Sbb(ng/g) 29.3 15.7 22.1 2.43 26.1 22.3
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表 3 候选物GSSO-7长期稳定性检验结果
Table 3. Long stability tests for candidate material GSSO-7(-18℃)
化合物 含量平均值
(ng/g)RSD
(%)b1 t0.05×S(b1) usl 萘 1288 4.91 -1.289 7.800 113 苊烯 209 4.59 -0.172 1.199 17.4 苊 240 4.53 0.065 1.407 20.2 芴 279 3.81 -0.319 1.224 17.6 菲 5652 4.59 -3.614 35.59 513 蒽 315 4.21 -0.543 1.347 19.4 荧蒽 4053 3.65 4.697 16.83 243 芘 3280 3.79 0.246 13.13 233 苯并[a]蒽 1007 4.73 -1.475 5.454 78.5 䓛 1396 3.85 -1.679 6.135 88.2 苯并[b]荧蒽 870 3.63 -0.427 4.007 57.7 苯并[k]荧蒽 474 3.04 -0.115 1.854 26.6 苯并[a]芘 812 4.61 -0.480 4.757 68.4 二苯并[a, h]蒽 110 4.71 -0.145 0.612 8.82 苯并[g, h, i]苝 939 5.07 -0.796 5.969 86.0 茚并[1, 2, 3-cd]芘 771 5.44 -0.738 5.238 75.3
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表 4 候选物GSSO-7短期稳定性检验结果
Table 4. Short stability tests for candidate material GSSO-7(25℃)
化合物 含量平均值
(ng/g)RSD
(%)b1 t0.05×S(b1) uss 萘 1232 3.48 -4.261 17.74 55.9 苊烯 196 3.05 -0.625 2.438 7.67 苊 243 3.35 -1.185 2.965 9.33 芴 266 2.89 -0.237 3.45 10.9 菲 5393 3.82 -31.802 72.57 229 蒽 290 2.91 -1.115 3.221 10.2 荧蒽 4189 3.26 -17.31 52.90 167 芘 3128 5.06 -27.27 50.83 160 苯并[a]蒽 955 2.42 0.1402 10.46 32.9 䓛 1353 2.07 -1.224 12.20 38.4 苯并[b]荧蒽 856 3.24 -1.917 12.04 37.9 苯并[k]荧蒽 466 3.66 0.281 7.697 24.2 苯并[a]芘 812 3.30 -0.781 12.03 37.9 二苯并[a, h]蒽 103 3.76 0.0566 1.744 5.49 苯并[g, h, i]苝 906 3.03 0.441 12.39 39.0 茚并[1, 2, 3-cd]芘 745 2.92 0.128 9.839 31.0
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表 5 九家协作定值实验室所用分析方法
Table 5. Analytical methods used in nine collaborative laboratories
协作实验室 样品前处理方法 目标物含量测定方法 本文项目组 ASE提取，SPE净化 GC-ECD，GC-MS，GC-IDMS，HPLC 浙江省地质矿产研究所 ASE提取，SPE净化 GC-ECD，HPLC，GC-MS 安徽省地质实验研究所 索氏提取，SPE净化 GC-ECD，HPLC，GC-MS 南京地质矿产研究所 ASE提取，SPE净化 GC-MS 青岛海洋地质研究所 ASE提取，SPE净化 GC-MS 中国农业科学院农业质量标准与检测技术研究所 ASE提取，GPC净化 GC-MS 浙江省农业科学院农产品质量标准研究所 ASE提取，SPE净化 GC-MS 江苏地质调查研究院 ASE提取，SPE净化 GC-ECD，HPLC，GC-MS 中国计量科学研究院 ASE提取，SPE净化 GC-IDMS
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表 6 沉积物标准物质认定值及扩展不确定度
Table 6. Certified values and expanded uncertainties for sediments reference materials
特性量 特性量值及扩展不确定度 GBW07352
(μg/g)GBW07353
(ng/g)GBW07354
(ng/g)GBW07355
(ng/g)萘 1.31±0.29 (53) (23) (61) 苊烯 0.20±0.05 - - - 苊 0.25±0.06 - - - 芴 0.29±0.06 (12) (9) (13) 菲 5.7±1.3 (92) (66) (172) 蒽 0.30±0.06 (9) (8) (12) 荧蒽 4.10±0.66 80±13 71±13 159±27 芘 3.24±0.61 46±10 46±9 111±22 苯并[a]蒽 1.03±0.20 30±8 24±7 101±20 䓛 1.46±0.24 54±13 34±10 104±21 苯并[b]荧蒽 0.90±0.17 51±11 31±9 119±20 苯并[k]荧蒽 0.50±0.09 (18) 15±5 35±9 苯并[a]芘 0.84±0.18 25±6 18±6 40±9 二苯并[a, h]蒽 0.11±0.03 (12) (10) (15) 苯并[g, h, i]苝 0.95±0.21 43±11 24±7 83±18 茚并[1, 2, 3-cd]芘 0.77±0.18 34±8 20±6 56±12 p, p’-DDE - - 61±14 - 甲体六六六 - - 26±7 12±4 乙体六六六 - - 43±10 29±7 PCB 28 - - 39±9 - PCB 52 - - 46±11 - PCB 101 - - 43±11 - 注：括号内数据表示参考值；“-”表示该化合物未定值。
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[1] Yang J, Qadeer A, Liu M, et al. Occurrence, source and partition of PAHs, PCBs and OCPs in the multiphase system of an urban lake, Shanghai[J]. Applied Geochemistry, 2019, 106: 17-25. doi: 10.1016/j.apgeochem.2019.04.023
[2] 张文博, 刘宾绪, 江涛, 等. 环渤海渔港沉积物多环芳烃的污染特征和生态风险评价[J]. 环境化学, 2022, 41(2): 1-11. https://www.cnki.com.cn/Article/CJFDTOTAL-HJHX202202015.htm
Zhang W B, Liu B X, Jiang T. et al. Pollution characteristics and ecological risk assessment of polycyclic aromatic hydrocarbons in sediments from fishing ports along the coast of Bohai Sea[J]. Environmental Chemistry, 2022, 41(2): 1-11. https://www.cnki.com.cn/Article/CJFDTOTAL-HJHX202202015.htm
[3] 李玉芳, 潘萌, 顾涛, 等. 北京哺乳期女性及婴幼儿多环芳烃暴露风险变化特征[J]. 岩矿测试, 2020, 39(4): 578-586. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201912040167
Li Y F, Pan M, Gu T, et al. Exposure of mother and infants to polycyclic aromatic hydrocarbons during lactation, Beijing[J]. Rock and Mineral Analysis, 2020, 39(4): 578-586. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201912040167
[4] Hou J, Yin W J, Li P, et al. Joint effect of polycyclic aromatic hydrocarbons and phthalates exposure on telomere length and lung function[J]. Journal of Hazardous Materials, 2020, 386: 121663. doi: 10.1016/j.jhazmat.2019.121663
[5] Ye X Q, Pan W Y, Li C M, et al. Exposure to polycyclic aromatic hydrocarbons and risk for premature ovarian failure and reproductive hormones imbalance[J]. Journal of Environmental Sciences, 2020, 91: 1-9. doi: 10.1016/j.jes.2019.12.015
[6] Donat-Vargas C, Åkesson A, Berglund M, et al. Dietary exposure to polychlorinated biphenyls and risk of breast, endometrial and ovarian cancer in a prospective cohort[J]. British Journal of Cancer, 2016, 115: 1113-1121. doi: 10.1038/bjc.2016.282
[7] Abbassy M A, Khalifa M A, Nassar A M K, et al. Analysis of organochlorine pesticides residues in fish from Edko Lake (North of Egypt) using eco-friendly method and their health implications for humans[J]. Toxicology Research, 2021, 37: 495-503. doi: 10.1007/s43188-020-00085-8
[8] Yin S J, Sun Y, Yu J H, et al. Prenatal exposure to organochlorine pesticides is associated with increased risk for neural tube defects[J]. Science of the Total Environment, 2021, 770: 145284. doi: 10.1016/j.scitotenv.2021.145284
[9] 赵亚静, 邹立, 牛增元, 等. 液相色谱-高分辨质谱技术在沉积物和颗粒物中有机污染物分析的研究进展[J]. 分析测试学报, 2021, 40(9): 1396-1408. https://www.cnki.com.cn/Article/CJFDTOTAL-TEST202109020.htm
Zhao Y J, Zou L, Niu Z Y, et al. Advances in the analysis of organic contaminants in sediments and particulate matters by liquid chromatography-high resolution mass spectrometry[J]. Journal of Instrumental Analysis, 2021, 40(9): 1396-1408. https://www.cnki.com.cn/Article/CJFDTOTAL-TEST202109020.htm
[10] 刘烨, 王玉洁, 汪福顺, 等. 多环芳烃在新安江河流-水库体系表层沉积物中的分布、来源及生态风险评估[J]. 上海大学学报(自然科学版), 2020, 26(1): 113-122. https://www.cnki.com.cn/Article/CJFDTOTAL-SDXZ202001011.htm
Liu Y, Wang Y J, Wang F S, et al. Occurrence, sources and ecological risk assessment of polycyclic aromatic hydrocarbons in surface sediments from Xin'anjiang river-reservoir system[J]. Journal of Shanghai University (Natural Science Edition), 2020, 26(1): 113-122. https://www.cnki.com.cn/Article/CJFDTOTAL-SDXZ202001011.htm
[11] 许妍, 陈佳枫, 徐磊, 等. 白洋淀表层沉积物中有机氯农药和全多氯联苯的分布特征及风险评估[J]. 湖泊科学, 2020, 32(3): 654-664. https://www.cnki.com.cn/Article/CJFDTOTAL-FLKX202003006.htm
Xu Y, Chen J F, Xu L, et al. Distribution and risk assessment of organochlorine pesticides and polychlori-nated biphenyls in surficial sediments from Lake Baiyangdian[J]. Lake Science, 2020, 32(3): 654-664. https://www.cnki.com.cn/Article/CJFDTOTAL-FLKX202003006.htm
[12] 范晨子, 刘永兵, 赵文博, 等. 云南安宁水系沉积污染物分布特征与风险评价[J]. 岩矿测试, 2021, 40(4): 570-582. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.202103080035
Fan C Z, Liu Y B, Zhao W B, et al. Pollution distribution characteristics and ecological risk assessment of heavy metals and polycyclic aromatic hydrocarbons in the river sediments in Anning, Yunnan Province[J]. Rock and Mineral Analysis, 2021, 40(4): 570-582. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.202103080035
[13] Li H X, Jiang W W, Pan Y L, et al. Occurrence and partition of organochlorine pesticides (OCPs) in water, sediment, and organisms from the eastern sea area of Shandong Peninsula, Yellow Sea, China[J]. Marine Pollution Bulletin, 2021, 162: 111906. doi: 10.1016/j.marpolbul.2020.111906
[14] Wang P, Shang H T, Li H H, et al. PBDEs, PCBs and PCDD/Fs in the sediments from seven major river basins in China: Occurrence, congener profile and spatial tendency[J]. Chemosphere, 2016, 144: 13-20. doi: 10.1016/j.chemosphere.2015.08.045
[15] 雷沛, 潘科, 张洪, 等. 水体沉积物中16种优控PAHs的快速萃取[J]. 环境化学, 2019, 38(3): 494-502. https://www.cnki.com.cn/Article/CJFDTOTAL-HJHX201903006.htm
Lei P, Pan K, Zhang H, et al. A device for the rapid extraction of 16 priority PAHs in aquatic sediments[J]. Environmental Chemistry, 2019, 38(3): 494-502. https://www.cnki.com.cn/Article/CJFDTOTAL-HJHX201903006.htm
[16] Itoh N, Aoyagi Y, Takatsu A, et al. Certified reference material for quantification of polycyclic aromatic hydrocarbons in sediment from the National Metrology Institute of Japan[J]. Analytical and Bioanalytical Chemistry, 2009, 393: 2039-2049. doi: 10.1007/s00216-009-2675-2
[17] SRM (1941b) organics in marine sediment[R]. Gaithersburg: National Institute of Standards and Technology (NIST), 2015.
[18] SRM (1944) certificate of analysis. New York/New Jersey waterway sediment[R]. Gaithersburg: National Institute of Standards and Technology (NIST), 2017.
[19] Wise S A, Poster D L, Schantz M M, et al. Two new marine sediment standard reference materials (SRMs) for the determination of organic-contaminants[J]. Analytical and Bioanalytical Chemistry, 2004, 378: 1251-1264. doi: 10.1007/s00216-003-2431-y
[20] Wegener J W M, Cofino W P, Maier E A, et al. The preparation, testing andvertification of two freshwater sediment reference materials for polycyclic aromatic hydrocarbons and polychlorinated biphenyls: BCR CRM535 and CRM536[J]. Trends in Analytical Chemistry, 1999, 18(1): 14-25. doi: 10.1016/S0165-9936(98)00087-9
[21] Wegener J W M, Maier E A, Kramer G N, et al. The certification of the contents (mass fractions) of polycyclic aromatic hydrocarbons: Pyrene, benz[a]anthracene, benzo[a] pyrene, benzo[e]pyrene, benzo[b]fluoranthene and indeno[1, 2, 3-cd]pyrenein freshwater harbour sediment CRM 535, EUR 17795EN[R]. Commission of the European Communities: Community Bureau of Reference, 1997.
[22] LGC 6188. Statement of measurement. River sediment-PAHs (Latest Amendment)[R]. Laboratory of the Government Chemist (LGC), 2020.
[23] Tolosa1 I, Cassi1 R, Huertas D. A new marine sediment certified reference material (CRM) for the determination of persistent organic contaminants: IAEA-459[J]. Environmental Science and Pollution Research, 2019, 26: 7347-7355. doi: 10.1007/s11356-018-1895-4
[24] 田芹, 吴淑琪, 佟玲, 等. 中国典型类型土壤中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, 2015, 34(2): 238-244. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.02.015
Tian Q, Wu S Q, Tong L, et al. Preparation of certified reference materials of organochlorine pesticides and polychlorinatedbipenyl in Chinese typical soils[J]. Rock and Mineral Analysis, 2015, 34(2): 238-244. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.02.015
[25] 全国标准物质管理委员会. 标准物质目录[M]. 北京: 中国质检出版社, 中国标准出版社, 2017.
National Administrative Committee for Certified Reference Materials. List of standard substances[M]. Beijing: Quality Inspection of China Press, Standards Press of China, 2017.
[26] 房丽萍, 吴忠祥, 王伟, 等. 河流沉积物多环芳烃标准样品的制备与定值[J]. 岩矿测试, 2013, 32(5): 767-774. doi: 10.3969/j.issn.0254-5357.2013.05.015 http://www.ykcs.ac.cn/article/id/5834e3b4-ce28-4a05-b381-894c3f6c50ba
Fang L P, Wu Z X, Wang W, et al. Preparation and certification of river sediment reference material for polycyclic aromatic hydrocarbons[J]. Rock and Mineral Analysis, 2013, 32(5): 767-774. doi: 10.3969/j.issn.0254-5357.2013.05.015 http://www.ykcs.ac.cn/article/id/5834e3b4-ce28-4a05-b381-894c3f6c50ba
[27] 全国标准物质管理委员会. 标准物质的研制管理与应用[M]. 北京: 中国计量出版社, 2010.
National Administrative Committee for Certified Reference Materials. Preparation, management and application of reference materials[M]. Beijing: China Metrology Publishing House, 2010.
[28] 全国标准物质管理委员会. 标准物质定值原则和统计学原理[M]. 北京: 中国质检出版社, 2011.
National Administrative Committee for Certified Reference Materials. Reference material general and statistical principles for certification[M]. Beijing: Quality Inspection of China Press, 2011.
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