ISO ISO Guide GBT 15000 1 1994 ISO

国标系列导则与ISO指南的对应关系 国�系列�� ISO Guide GB/T 15000. 1 -1994 参照采用ISO Guide 6: 1978 GB/T 15000. 2 -1994 参照采用ISO Guide 30: 1991 GB/T 15000. 3 -2008 等同采用ISO Guide 35: 2006 GB/T 15000. 4 -2003 等同采用ISO Guide 31: 2000 GB/T 15000. 7 -2001 等同采用ISOGuide 34: 2000 GB/T 15000. 8 -2003 等同采用ISO Guide 33: 2000

有关标准样品的ISO指南文件 � ISO Guide 30: 1992 Terms and definitions used in connection with reference materials � ISO Guide 31: 2000 Reference materials-Contents of certificates and labels � ISO Guide 32: 1997 Calibration in analytical chemistry and use of certified reference materials � ISO Guide 33: 2000 Uses of certified reference materials � ISO Guide 34: 2000 General requirements for the competence of reference material producers � ISO Guide 35: 2006 Reference materials-General and statistical principles for certification

ISO Guide 35简介 � 1981年ISO Committee on Reference Materials (REMCO)会议决定制定该指南文件； � 1985年发布第 1版； � 1989年发布第 2版； � 2006年发布第 3版。

ISO Guide 35 � 1989版 1 Scope 2 Definitions 3 The role of reference materials in measurement science 4 Measurement uncertainty 5 Homogeneity of materials 6 General principles of certification 7 Certification by a definitive method 8 Certification by interlaboratory testing 9 Certification based on a metrological approach � 2006版 1 Scope 2 Normative references 3 Terms, definitions and symbols 4 Symbols 5 Design of a certification project 6 Evaluating measurement uncertainty 7 Homogeneity study 8 Stability study 9 Determination of the property values 10 Data and uncertainty evaluation 11 Certification Annex A (informative) Statistical approaches Annex B (informative) Examples

ISO Guide 30: 1992中的31个术语 p Terms related to materials (8) ü Reference material (RM) ü Certified reference material (CRM) Primary standard Secondary standard ü Characterization ü Homogeneity ü Stability Sample p Terms related to measurement and testing (10) Certified value Uncertified value Consensus value (of a given quantity) Uncertainty of a certified value Precision Accuracy Accepted reference value Traceability Interlaboratory test Reference method p Terms related to certification and issuance of reference materials (5) Certification of a reference material Reference material certificate Certification report Certifying body Certified reference material producer p Additional terms (8) (production) batch Value (of a quantity) True value (of a quantity) Systematic error Random error Level of confidence Repeatability (of results of measurements) Reproducibility (of results of measurements)

GB/T 15000. 3 -2008中的术语和定义 1、标准样品（RM） reference material 2、有证标准样品（CRM）certified reference material 3、（标准样品的）特性值 property value (of a reference material) 4、（标准样品的）测定 characterization ( of a reference material) 5、瓶间均匀性 between-bottle homogeneity 6、瓶内均匀性 within-bottle homogeneity 7、混合 blending 8、基体材料 matrix material 9、加料 spiking 10、短期稳定性 short-term stability 11、长期稳定性 long-term stability 12、（标准样品的）使用寿命 life time (of a reference material) 13、（RM/CRM的）有效期 shelf life (of an RM/CRM)

有证标准样品以往的一些定义 u ISO Guide 30： 1992 certified reference material (CRM): Reference Material, accompanied by a certificate, one or more of whose property values are certified by a procedure which establishes its tracebility to accurate realization of the unit in which the property values are expressed, and for which each certified value is accompanied by an uncertainty at a stated level of confidence. u GB/T 15000. 2 -1994《标准样品常用术语及定义》 有证标准样品是具有一种或多种性能特征，经过技术鉴定附有 说明上述性能特征的证书，并经国家标准化管理机构批准的标准 样品。 u JJF 1005 -2005《标准物质常用术语和定义》 附有认定证书的标准物质，其一种或多种特性量值用建立了溯源 性的程序确定，使之可溯源到准确复现的表示该特性值的测量单 位，每一种认定的特性量值都附有给定置信水平的不确定度。

（标准样品的）特性值 property value (of a reference material) �赋予（有证）标准样品的物理、化学或生物特性量 的值。 � value attributed to a quantity representing a physical, chemical or biological property of a (certified) reference material.

（标准样品的）测定 characterization (of a reference material) �确定标准样品特性值的过程，是定值过程的一部分。 注 1；测定过程提供被定量特性的值。 注 2：批定值时，测定的是批的特性值。 l process of determining the property values of a reference material, as part of the certification process. NOTE 1 The characterization process provides the values for the properties to be quantified. NOTE 2 In batch certifications, the characterization refers to the property values of the batch.

关于“Characterization”的翻译问题 � GB/T 15000. 2 -1994 测定（characterization）：对于标准样品而言，是指 和其最终用途有关的一种或多种化学的、物理的、生物 学的、 程技术的或感官的特性的确定。 � JJF 1005 -2005 定值（characterization）：对与标准物质预期用途有 关的一个或多个物理、化学、生物或 程技术等方面的 特性量值的测定。 � ISO Guide 30: 1992 Characterization: For a reference material, determination of one or more physical, chemical, biological, or technological property values that are relevant to its intended end use.

均匀性Homogeneity � 均匀性 Homogeneity 具有一种或多种特性的材料以相同的结构或组成存在的一种状态。通 过测量取自不同包装单元（如瓶、包等）或取自同一包装单元、特定大小 的样品，测量结果落在规定不确定度范围内，则可认为标准样品对指定的 特性是均匀的。 Condition of being of uniform structure or composition with respect to one or more specified properties. A reference material is said to be homogeneous with respect to a specified property if the property value, as determined by tests on samples of specified size, is found to lie within the specified uncertainty limits, the samples being taken either from different supply units (bottles, packages, etc. ) or from a single supply unit. � 瓶间均匀性 between-bottle homogeneity 标准样品的特性在瓶与瓶之间的差异。 bottle-to-bottle variation of a property of a reference material. � 瓶内均匀性 within-bottle homogeneity 标准样品的特性在一瓶中的差异。 variation within one bottle of a property of a reference material. 注：“瓶”可以是其它类型的包装、其它物理形状及试片。

稳定性 stability � 稳定性stability 在规定的贮存条件和时间间隔内，标准样品的特性值保持 在规定范围内的能力。 Ability of a reference material, when stored under specified conditions, to maintain a stated property value within specified limits for a specified period of time. � 短期稳定性 short-term stability 在规定运输条件下标准样品特性在运输过程中的稳定性。 stability of a property of a reference material during transport under specified transport conditions � 长期稳定性 long-term stability 在CRM生产者规定贮存条件下标准样品特性的稳定性。 stability of a property of a reference material under specified storage conditions at the CRM-producer

不确定度评估的一些指南性文件 �BIPM, IEC, IFCC, ISO, IUPAC, IUPAP and OIML， Guide to the expression of uncertainty in measurement (GUM), 1993. Corrected and reprinted 1995. �JJF 1059 -1999 《测量不确定度评定与表示》 �Eurachem/Citac Guide－Quantifying uncertainty in analytical measurement, 2 nd edition, 2001. ü CNAS-GL 06《化学分析中不确定度的评估指南》 (可以从www. cnas. org. cn下载）

瓶间均匀性研究实验设计方案 (1) Within groups Bottle No. 1 Bottle No. 2 Bottle No. a n subsamples n transformation s n transformations n measurements Between groups

瓶间均匀性研究实验设计方案 (2) Within groups Bottle No. 1 Bottle No. 2 Bottle No. a transformation n measurements n measurements Between groups

土壤中钡的均匀性研究（1） mg/kg Bottle Data-1 Data-2 Data-3 1 323 301 310 2 340 334 316 3 320 321 309 4 315 338 321 5 326 338 325 6 325 302 304 7 324 331 317 8 310 331 9 336 321 328 10 328 312 11 314 302 12 329 300 299 13 320 329 311 14 322 311 15 332 317 299 16 313 294 293 17 324 314 335 18 321 342 316

土壤中钡的均匀性研究（2） ANOVA Table for Barium in soil 差异源 SS df MS F P-value �� 3488. 981 17 205. 2342 1. 689685 0. 091567 1. 915321 �内 4372. 667 36 121. 463 �� 7861. 648 53 =318 mg/kg =11 mg/kg (~3. 5%) = 5. 2 mg/kg (~1. 6%) F crit

其它计算ubb的方法 Federer计算方法： from “Federer WT (1968) J. Royal Stat Soc C 17: 171 -174”.

酸雨标准样品中钠离子的均匀性检验 重复�定数据（ mg/L) �品�号 1 0. 218 0. 230 0. 226 2 0. 215 0. 218 0. 214 3 0. 211 0. 230 0. 210 4 0. 221 0. 223 0. 208 5 0. 216 0. 219 0. 218 6 0. 234 0. 218 0. 230 7 0. 231 0. 215 0. 228 8 0. 226 0. 212 0. 218 9 0. 223 0. 225 0. 215 10 0. 224 0. 230 0. 218 11 0. 231 0. 211 0. 227 12 0. 229 0. 207 0. 221 13 0. 223 0. 207 0. 228 14 0. 230 0. 215 0. 231 15 0. 234 0. 216 0. 224

酸雨标准样品中钠离子的均匀性检验结果 方差分析�果 差异源 SS df MS F P-value �� 0. 000577 14 4. 12 E-05 0. 611444 0. 834296 �内 0. 002021 30 6. 74 E-05 �� 0. 002597 44 sr 0. 008207043 sbb 2 -8. 72381 E-06 ubb' ubb (Federer) 0. 002407705 0. 001859673 F crit 2. 03742

瓶内均匀性研究实验设计 Bottle Subsample No. 1 Subsample No. 2 Subsample No. a Transformatio n Transformation n measurements n measurement s Within n Groups measurements Among groups

同步稳定性研究的实验方法 Storage time (months) 0 1 2 3 4 5 6 7 8 9 10 11 12 T 1(e. g. +18℃) T 2(e. g. +4℃) T 3(e. g. -20℃) Tref(e. g. - 50℃) X Analysis Storage at temperature T Storage at reference temperature

稳定性趋势分析示例（t检验） 测定序号 1 2 3 4 求和 n Lxy Lxx Lyy r 2 斜率b 1 截距b 0 Sy sb 1 t计算值 时间（X） 特性值（Y） 0 97. 76 12 101. 23 24 102. 14 36 97. 72 XX 0 144 576 1296 YY 9557 10248 10433 9549. 2 XY 0 1214. 76 2451. 36 3517. 92 72 4 4. 74 720 15. 977875 0. 001953013 0. 006583333 99. 594 2. 82370944 0. 105233438 0. 06255933 2016 39786 7184. 04 r 0. 0442 t临界值 4. 30 398. 85

稳定性趋势分析示例（F检验） 回 � � � Multiple R 0. 044192908 R Square 0. 001953013 Adjusted R -0. 49707048 Square �准�差 2. 82370944 ��� 4 方 差 分 析 回�分析 残差 �� df SS MS F F 0. 95 1 2 3 0. 031205 15. 94667 15. 977875 0. 0312 7. 9733 0. 0039 0. 95581

双因素重复测量方差分析表 来源 平方和 自由度 均方 F�算 因素A SSA νA=a-1 MSA=SSA/νA FA=MSA/MSe 因素B SSB νB=b-1 MSB=SSB/νB FB=MSB/MSe AB交互 SSAx. B νAx. B=(a-1)(b-1) MSAx. B=SSAx. B/νA FAx. B=MSAx. B/MSe x. B 残差e SSe νe=ab(n-1) �和 SS ν=abn-1 MSe=SSe/νe

同步稳定性实验示例（原始数据） Results of stability tests for total glucosinolate in rapeseed. (BCR 190 R) Bottle 1 Bottle 2 t=0 months t=6 months t=9 months t=12 months 21. 84 23. 26 23. 25 22. 25 21. 74 21. 62 22. 39 22. 22 22. 45 22. 51 22. 22 22. 32 23. 42 22. 54 23. 89 21. 89 23. 16 22. 61 22. 78 21. 37 22. 75 23. 73 22. 84

同步稳定性实验示例（双因素方差分析） 来源 SS df MS F P-value F 0. 95 F 0. 99 瓶 1. 04167 1 1. 0417 3. 758 0. 07040 4. 494 8. 53 �� 3. 25177 3 1. 0839 3. 910 0. 02856 3. 239 5. 29 交互 1. 00797 3 0. 3360 1. 212 0. 33734 3. 239 5. 29 残差 4. 4347 16 0. 2772 �� 9. 7361 23

同步稳定性实验示例（t检验） �定序号 1 ��（ X） 特性�（ Y） 0 21. 935 XX 0 YY 481. 1442 XY 0 2 6 22. 793 36 519. 5208 136. 758 3 4 求和 n Lxy Lxx Lyy r 2 斜率b 1 截距b 0 Sy sb 1 t�算� 9 12 27 4 5. 4045 78. 75 0. 541629 0. 684792 0. 068629 22. 10326 0. 292169 0. 032924 2. 08447 22. 838 22. 7 90. 266 81 144 261 521. 5742 515. 29 2037. 529 205. 542 272. 4 614. 7 r 0. 827521 T表�： 4. 30

同步稳定性实验示例（F检验） df SS MS F F 0. 95 回� 1 0. 370903 4. 345 0. 1725 残差 2 0. 170726 0. 085363 �� 3 0. 541629

标准样品特性值溯源（2） Sample Subsample Digestion Extraction Derivatization Separation Measurement Calculation of result (+uncertainty) Matrix CRM/ QC material Blank material Spiked sample/ extract Blank extract Calibration by reference material Correction Blank values Reporting of result (+uncertainty) chain Part of a measurement

协作研究测定的一般程序 Preparation of the material Stability and homogeneity testing � � No Homogeneity confirmed? � No Yes Measurement campaign Yes Continuation of measurement campaign Calculation of property value Yes � � Objectives met? No Improvement possible? Yes Material can be certified No Material cannot be certified

气体标准样品的测定 � 气体标准样品一般采取与基准气体比对的方法进行测定 （GC或其他气体分析），而基准气体则采用称量法制 备。 � ISO已发布了有关技术标准，我国也已对其进行了转化。 ISO 6142: 2001 Gas analysis-Preparation of calibration gas mixtures-Gravimetric method ISO 6143: 2001 Gas analysis-Comparison methods for determining and checking the composition of calibration gas mixtures GB/T 5274－? ? 《气体分析 校准用混合气体的制 备 称量法》 GB/T 10628－2008 《气体分析 校准混合气组成的测 定和校验》

数据处理的一般程序 Measurement campaign Yes Technically invalid results Discard or replace data No Statistically invalid results Yes No No Sufficient homogeneity/ stability Discard or replace data Material cannot be certified Yes Calculation of property value and its uncertainty No Criteria for certification Yes Report Material cannot be certified