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摘要:
水体富营养化与沉积物中磷元素的形态有密切关系。为了准确测定沉积物中不同形态的磷的含量, 欧盟在2000年研制了第一个湖泊沉积物中磷形态标准物质(BCR 684), 但基本用尽已不能满足需求, 而且该标准物质采集于欧洲某湖泊, 沉积物类型及污染情况与我国湖泊不相匹配。本文结合我国沉积物的类型和湖泊污染状况, 研制了我国首批2个湖泊沉积物中磷形态标准物质(编号为GBW 07462和GBW 07463)。候选物样品采集地点为江苏太湖和湖南洞庭湖, 样品经过自然干燥、研磨、灭菌、陈化等加工处理, 随机抽取15个子样采用单因素方差分析(F检验法)进行均匀性检验, 检验的F实测值均小于临界值, 表明样品均匀性良好。根据ISO导则35推荐方法对候选物样品在一年内进行四次稳定性检查, 分析结果无方向性变化, 再通过2次验证实验, 样品稳定性良好。此批磷形态标准物质采用8家实验室联合定值, 定值参数包括五种磷形态:总磷、无机磷、有机磷、磷灰石态磷、非磷灰石态磷; 磷形态提取方法采用欧盟SMT法, 测定方法采用钼锑钪光度法和电感耦合等离子体发射光谱法(实验过程中用欧盟BCR 684作为质量监控); 按照《一级标准物质研制规范》(JJG 1006—1994) 和ISO导则35的要求给出了五种磷形态的标准值和不确定度。此批磷形态标准物质样品代表了我国典型富营养化湖泊的沉积物类型, 采样点的区域代表性强, 定值项目选择合理、量值准确, 可应用于环境、地质、农业、地球化学等研究领域沉积物的磷形态样品质量监控。
Abstract:Eutrophication in water bodies has a close relationship with the phosphorus speciation in sediments. The European Union developed the first reference material for phosphorus speciation of sediments BCR 684 in 2000 in order to determine accurately the contents of phosphorus speciation in sediments. However, supplies of BCR 684 are now exhausted. Moreover, the reference material of BCR 684 was collected from a lake in Europe which does not match the type and conditions of pollution in sediments in China. To this end, two phosphorus speciation reference materials of lake sediments (serial numbers: GBW 07462 and GBW 07463) on the fundamental of BCR 684, which were collected from Tai Lake, Jiangsu province and Dongting Lake, Hunan province in China, have been developed. The reference material was prepared by being dried, ground, sterilized and aged. Homogeneity and stability tests were conducted according to the JJG 1006—1994 and ISO Guide 35. For the homogeneity test, the variance test F value of 15 subsamples was less than the threshold value. During one year, four analysis results showed that there were no significant statistical changes in stability. The stability of the samples was checked twice in 2012 and 2013. The results show that the stability of the two reference materials is perfectly matched. Collaboration with eight laboratories was adopted in order to obtain certified value and uncertainty calculations. Parameter for certified values includes total phosphorus, inorganic phosphorus, organic phosphorus, apatite phosphorus and non-apatite phosphorus. SMT was used as the extraction method and the determined methods are molybdenum antimony anti Spectrophotometry and ICP-AES. BCR 684 was used as the quality control. The certified values and uncertainty were obtained under the JJG 1006—1994 and ISO Guide 35. These reference materials represent sediments in lakes with high eutrophication in China. The advantages of good representation of the sampling area, reasonable proxy selection and accurate certification values deem the reference materials suitable for quality monitoring of phosphorus speciation in sediments in the fields of environment, geology, agriculture and geochemistry.
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表 1 样品采集概况
Table 1. Brief description of candidates
参数 太湖样品 洞庭湖样品 水深 0.9 m 0.8 m GPS坐标 N30°31′25.1″
E120°13′11.5″N28°48′50.2″
E112°48′31.2″水温 13.6℃ 13.1℃ pH 7.57 7.68 
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表 2 候选物样品均匀性检验结果
Table 2. The results of homogeneity test for candidate samples
样品 参数 全量磷 总磷 无机磷 有机磷 磷灰
石态磷非磷灰
石态磷太湖
候选物x(mg/kg) >541 528 220 147 118 108 s(%) 8.44 11.17 7.01 5.20 4.70 1.98 RSD(%) 1.65 2.12 3.19 3.56 4.00 1.84 F 2.38 0.92 0.47 1.03 1.96 0.60 洞庭湖
候选物x(mg/kg) 806 768 324 228 101 260 s(%) 11.23 12.42 4.48 5.30 2.07 9.80 RSD(%) 1.39 1.62 1.38 2.32 2.04 3.76 F 2.14 0.59 0.76 1.52 0.47 2.07 注：x为含量平均值，s为标准偏差，RSD为相对标准偏差，F为实测值，F列表临界值F0.05(14, 15)=2.42。
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表 3 候选物样品稳定性检验结果
Table 3. The results of stability test for candidate samples
样品 检验日期 总磷 无机磷 有机磷 磷灰
石态磷非磷灰
石态磷太湖
候选物2010年12月测定值(mg/kg) 438 247 141 104 115 2011年2月测定值(mg/kg) 443 233 135 106 123 2011年6月测定值(mg/kg) 433 225 142 108 123 2011年12月测定值(mg/kg) 407 231 145 109 112 平均值(mg/kg) 430 234 141 107 118 标准偏差s(%) 16.204 9.141 4.388 2.297 5.220 RSD (%) 3.767 3.910 3.122 2.146 4.420 b1 -2.85774 -1.09833 0.599683 0.16119 0.293571 t0.05·s(b1) 3.345 4.054 1.741 0.816 6.840 洞庭湖
候选物2010年12月测定值(mg/kg) 692 334 219 93 304 2011年2月测定值(mg/kg) 696 328 220 97 308 2011年6月测定值(mg/kg) 684 318 216 92 298 2011年12月测定值(mg/kg) 685 325 230 98 280 平均值(mg/kg) 689 326 221 95 297 标准偏差s(%) 5.876 6.904 6.076 2.932 12.420 RSD (%) 0.853 2.116 2.746 3.082 4.176 b1 -0.81179 -0.77909 0.873413 0.244286 -2.2331 t0.05·s(b1) 2.304 3.202 2.267 1.512 2.20
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表 4 稳定性验证结果
Table 4. The verification results of stability
样品验证日期 各磷形态含量(mg/kg) 总磷 无机磷 有机磷 磷灰
石态磷非磷灰
石态磷太湖
候选物2012年10月 429 219 145 111 144 2013年10月 422 232 148 119 137 洞庭湖
候选物2012年10月 649 312 227 105 237 2013年10月 667 329 239 102 246 BCR 684 2012年10月 1338 1092 217 525 531 2013年10月 1343 1133 221 531 542
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表 5 湖泊沉积物中磷形态标准物质认定值和总不确定度数据
Table 5. The certified values and total uncertainty of candidate samples
样品 项目 总磷 无机磷 有机磷 磷灰
石态磷非磷灰
石态磷太湖
样品认定值(mg/kg) 417 239 138 112 126 总不确定度
(U总，mg/kg)18 20 6 7 31 有效测量组数(N) 8 8 8 8 8 洞庭湖
样品认定值(mg/kg) 677 330 235 99 257 总不确定度
(U总，mg/kg)35 17 13 7 40 有效测量组数(N) 8 8 8 8 8 BCR 684 认定值(mg/kg) 1373 1113 209 536 550 总不确定度
(U总，mg/kg)35 24 9 28 21 有效测量组数(N) 12 13 13 14 15
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| 引用本文: |
袁建, 王亚平, 许春雪. 湖泊沉积物中磷形态标准物质研制[J]. 岩矿测试, 2014, 33(6): 857-862.
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| Citation: |
YUAN Jian, WANG Ya-ping, XU Chun-xue. Preparation of Phosphorus Speciation Reference Materials from Lake Sediments[J]. Rock and Mineral Analysis, 2014, 33(6): 857-862.
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