Preparation and Certification of River Sediment Reference Material for Polycyclic Aromatic Hydrocarbons
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摘要: 多环芳烃环境标准样品是保证多环芳烃环境监测和污染调查数据可靠性以及不同实验室间分析数据可比性必不可少的计量工具。美国NIST、欧盟IRMM、英国LGC等研究机构已有沉积物多环芳烃环境标准样品，但浓度水平大部分集中在mg/kg浓度水平，与我国当前的污染水平存在一定差距，难以满足痕量分析(μg/kg)质量保证与质量控制的要求。而我国受天然基体标准样品制备技术和定值分析技术的制约，尚没有研制沉积物多环芳烃环境标准样品。本文研制了适合我国多环芳烃环境监测和科学研究需要的河流沉积物标准样品。沉积物样品采集自松花江哈尔滨段流域，经过自然阴干、研磨、筛分、混匀和灭菌等加工处理，分层随机抽取15瓶样品对16种多环芳烃进行均匀性研究，结果表明样品均匀性良好。在30℃避光保存条件下，采用线性模型进行稳定性研究，标准样品在16个月稳定性检验期间未发现不稳定变化趋势。11家实验室对该河流沉积物标准样品采用气相色谱-质谱法和液相色谱法进行联合定值，经统计分析处理评定出14种多环芳烃的标准值和不确定度，并给出2种多环芳烃的参考值，特性量值在6.9~158 μg/kg之间，不确定度在1.5~25 μg/kg之间，可以满足多环芳烃痕量分析质量保证与质量控制的要求。该标准样品被批准为国家标准样品，填补了国内此类标准样品和标准物质空白，已成功应用于土壤和沉积物样品中多环芳烃的监测，可为进一步开展有机污染物环境基体标准样品研制提供参考和借鉴。Abstract: Matrix-type certified reference materials (CRMs) prepared from real environmental samples are used to ensure the reliability of environmental analyses and the comparability of results from different laboratories. Internationally, the National Institute of Standards and Technology (NIST) in the USA, the Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre (JRC) in the European Union, and the UK Laboratory of the Government Chemist (LGC) have developed sediment CRMs for Polycyclic Aromatic Hydrocarbons (PAHs). Although some matrix-type CRMs are available for the quantification of PAHs in sediment and soils, their PAH contamination is mostly at the mg/kg level. Thus, they are not suitable for the QA of analyses of PAHs at the μg/kg level. In China, by restricting preparative techniques and value-assignment techniques of natural matrix CRMs, no CRMs of PAHs in sediment have been developed. Therefore, based on the foreign research experience, CRMs of PAHs in river sediment have been developed for Chinese environmental monitoring and scientific research. A method for developing CRMs of PAHs in sediment is described in this paper. Sediment sample was collected from Songhua River, and air-dried, ground, homogenized and sterilized. A good homogeneity was obtained by the testing for 16 kinds of PAHs from 15 units selected by a random stratified scheme covering the whole batch, and 3 sub-samples were analyzed in each unit. At 30℃ without direct sunlight, the concentrations of 16 PAHs were not changed during monitoring period of 16 months. Based on the results from difference analytical techniques including Gas Chromatography/Mass Spectrometry and Reversed-phase Liquid Chromatography by 11 collaborating laboratories, reference values for 14 PAHs are given, and reference values for 2 PAHs are in the range of 6.9-158 μg/kg. Expanded uncertainty of each PAH is 1.5-25 μg/kg. Since the values of PAHs in the CRM are much lower than those in other CRMs and are comparable to the actual PAHs content in sediment or soil, the CRMs are suitable for PAH monitoring in sediment and soil samples and method validation.
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表 1 国外沉积物多环芳烃标准样品研制情况
Table 1. CRMs for PAHs in sediment
机构 名称 基质 计量单位 定值组分(标准值±不确定度) NIST(美国) SRM-1941b 港口沉积物 μg/kg 萘(848±95)，芴(85±15)，菲(406±44)，蒽(184±18)，3-甲基菲(105±13)，2-甲基菲(128±14)，1-甲基菲(73.2±5.9)，荧蒽(651±50)，芘(581±39)，苯并[a]蒽(335±25)，䓛 (291±31)，苯并菲(108±5)，苯并[b]荧蒽(453±21)，苯并[k]荧蒽(225±18)，苯并[e]芘(325±25)，苯并[a]芘(358±17)，苝(397±45)，苯并[g,h,i]苝(307±45)，茚并[1,2,3-cd]芘(341±57)，二苯并[a,j]蒽(48.9±4.6)，二苯并[a,c]蒽(36.7±5.2)，二苯并[a,h]蒽(53±10)，苯并[b]䓛(53±12)，苯并[a]䓛(46.6±4.7) SRM-1944 海洋沉积物 mg/kg 萘(1.65±0.31)，菲(5.27±0.22)，蒽(1.77±0.33)，荧蒽(8.92±0.32)，芘(9.70±0.42)，苯并[c]菲(0.76±0.10)，苯并[a]蒽(4.72±0.11)，䓛(4.86±0.10)，苯并菲(1.04±0.27)，苯并[b]荧蒽(3.87±0.42)，苯并[j]荧蒽(2.09±0.44)，苯并[k]荧蒽(2.30±0.20)，苯并[a]荧蒽(0.78±0.12)，苯并[e]芘(3.28±0.11)，苯并[a]芘(4.30±0.13)，苝(1.17±0.24)，苯并[g,h,i]苝(2.84±0.10)，茚并[1,2,3-cd]芘(2.78±0.10)，二苯并[a,j]蒽(0.500±0.044)，二苯并[a,c]蒽(0.335±0.013)，二苯并[a,h]蒽(0.424±0.069)，二苯并[b,h]菲(0.288±0.026)，苯并[b]䓛(0.63±0.10)，苯并[a]䓛(0.518±0.093) IRMM(欧盟) BCR-535 淡水港口沉积物 mg/kg 芘(2.52±0.18)，苯并[a]蒽(1.54±0.10)，苯并[a]芘(1.16±0.10)，苯并[e]芘(1.86±0.13)，苯并[b]荧蒽(2.29±0.15)，苯并[k]荧蒽(1.09±0.15)，茚并[1,2,3-cd]芘(1.56±0.14) LGC(英国) LGC6188 河流沉积物 mg/kg 萘(0.22±0.11)，苊(0.1)，二氢苊(0.07±0.02)，芴(0.12±0.04)，菲(1.04±0.30)，蒽(0.36±0.11)，荧蒽(1.79±0.35)，芘(1.48±0.50)，䓛(0.83±0.16)，苯并[a]蒽(0.83±0.18)，苯并[b]荧蒽(0.82±0.19)，苯并[k]荧蒽(0.50±0.08)，苯并[a]芘(0.65±0.14)，二苯并[a,h]蒽(0.13±0.05)，茚并[1,2,3-cd]芘(0.37±0.14)，苯并[g,h,i]苝(0.36±0.13) NMIJ(日本) CRM 7307-a 湖泊沉积物 μg/kg 芴(5.98±1.08)，菲(24.46±3.96)，蒽(3.59±1.14)，荧蒽(25.11±2.52)，芘(22.24±3.54)，苯并[c]菲(3.21±0.19)，苯并[a]蒽(7.15±0.92)，䓛(8.39±0.74)，苯并[b]荧蒽(24.87±7.72)，苯并[k]荧蒽(5.28±1.46)，苯并[j]荧蒽(7.00±2.76)，苯并[a]荧蒽(1.56±0.70)，苯并[e]芘(9.73±2.70)，苯并[a]芘(4.57±0.53)，苝(2.08×103±0.58×103)，茚并[1,2,3-cd]芘(5.61±2.13)，苯并[g,h,i]苝(6.76±1.89)，二苯并[a,h]蒽(0.92±0.44) 
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表 2 标准样品均匀性检验结果
Table 2. Homogeneity tests of the reference material
特性名称 总均值
w/(μg·kg-1)总RSD/% 相对偏差
sr/%相对不确定度
ubb/%相对不确定度
ubb′/%检验结果 萘 68.5 6.0 7.2 4.3 2.1 均匀 苊 10.1 4.1 3.1 3.7 0.9 均匀 二氢苊 10.7 2.3 2.9 1.6 0.9 均匀 芴 26.5 2.6 4.6 - 1.4 均匀 菲 163.6 2.6 3.2 1.8 1.0 均匀 蒽 22.7 3.2 4.0 2.2 1.2 均匀 荧蒽 139.2 2.9 4.9 0.3 1.4 均匀 芘 112.8 3.9 4.5 2.9 1.3 均匀 苯并[a]蒽 35.0 2.7 3.9 1.5 1.2 均匀 䓛 50.6 3.1 3.1 2.5 0.9 均匀 苯并[b]荧蒽 45.8 3.8 5.7 1.9 1.7 均匀 苯并[k]荧蒽 21.7 4.2 6.9 1.3 2.0 均匀 苯并[a]芘 30.9 4.5 4.2 3.8 1.2 均匀 茚并[1,2,3-cd]芘 34.1 6.3 7.6 4.8 2.2 均匀 二苯并[a,h]蒽 9.9 4.0 6.4 1.5 1.9 均匀 苯并[g,h,i]苝 37.8 5.1 6.6 3.5 1.9 均匀
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表 3 标准样品稳定性检验结果
Table 3. Stability tests of the reference material
多环芳烃 总均值
w/(μg·kg-1)RSD/% b0 b1 sb1 tcal 相对不确定度ults/% 萘 58.6 13.3 64.0 -0.682 0.594 1.15 16.2 苊 9.3 18.7 7.3 0.254 0.06 4.23 10.3 二氢苊 8.7 18.6 7.3 0.171 0.11 1.56 20.2 芴 25.8 6.9 24.8 0.120 0.15 0.82 9.1 菲 164.9 4.4 164.2 0.089 0.658 0.14 6.4 蒽 23.2 5.9 22.0 0.156 0.088 1.77 6.1 荧蒽 134.0 4.5 137.1 -0.389 0.505 0.77 6.0 芘 106.3 6.2 109.6 -0.406 0.554 0.73 8.3 苯并[a]蒽 38.9 9.6 35.9 0.375 0.263 1.43 10.8 䓛 49.7 10.9 51.1 -0.178 0.482 0.37 15.5 苯并[b]荧蒽 47.7 5.7 48.3 -0.080 0.242 0.33 8.1 苯并[k]荧蒽 23.2 11.0 22.4 0.095 0.225 0.42 15.6 苯并[a]芘 30.5 7.7 29.5 0.119 0.204 0.59 10.7 茚并[1.2.3 -cd]芘 34.0 6.3 35.1 -0.144 0.176 0.82 8.3 二苯并[a,h]蒽 8.2 24.0 7.2 0.130 0.164 0.79 31.8 苯并[g,h,i]苝 33.7 12.7 32.5 0.153 0.382 0.40 18.1 Σ16PAHs 796.7 2.7 798.6 -0.228 1.98 0.12 4.0 注： 置信概率95%、自由度3的t检验临界值为t0.95,3=3.18；置信概率99%、自由度3的t检验临界值为t0.99,3=5.84。
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表 4 沉积物标准样品量值评定结果
Table 4. Certified and reference values for 16 PAHs in sediment environmental reference materials
特性量值 计量单位 标准值 总不确定度
(k=3)萘 μg/kg 58 17 苊 μg/kg 8.9 3.6 二氢苊 μg/kg 8.4 1.6 芴 μg/kg 21.8 4.5 菲 μg/kg 158 25 蒽 μg/kg 19.4 3.9 荧蒽 μg/kg 119 19 芘 μg/kg 101 20 苯并[a]蒽 μg/kg 39.3 7.1 䓛 μg/kg 47.8 8.7 苯并[b]荧蒽 μg/kg 51.3 8.0 苯并[k]荧蒽 μg/kg 20.1 3.4 苯并[a]芘 μg/kg 30.5 5.6 茚并[1,2,3-cd]芘 μg/kg 32.9 6.7 二苯并[a,h]蒽 μg/kg 6.9 1.5 苯并[g,h,i]苝 μg/kg 39 13
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