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。
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。
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.
Abstract:BACKGROUNDPolycyclic 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.
OBJECTIVESTo 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.
METHODSIn 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).
RESULTSThe 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.
CONCLUSIONSThis 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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致谢: 9家实验室：中国计量科学研究院、浙江省地质矿产研究所、安徽省地质实验研究所、南京地质矿产研究所、青岛海洋地质研究所、江苏地质调查研究院、中国农业科学院农业质量标准与检测技术研究所、浙江省农业科学院农产品质量标准研究所、中国科学院生态环境研究中心参加了该标准物质的协作定值或结果验证；标准物质的制备由中国地质科学院地球物理地球化学勘查研究所协助完成。在此一并表示感谢！
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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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