EN71-3方法确认

1、EN71-3方法确认 Bureau Veritas Consumer Products （G.Z.） Co.Ltd广州立德技术检测有限公司 Linearity （ 线性）（For ICP-OES） （AN-0160） 1 Scope（目的 ） The purpose of this validation is to estimate the linearity of Soluble elements for EN71-3（ISO8124/ASTM F963-2003） with ICP-OES. 本实验目的是来确认用 ICP 测定可迁移元素 的线性。 2 Procedure（ 过程 ） 2.1

2、 Prepare a series of standard solutions as below: 0.1mg/L,0.2 mg/L,0.4 mg/L,1.0 mg/L,2.0 mg/L for As,Hg,Sb,Se 0.5mg/L,1.0 mg/L,2.0 mg/L,5.0 mg/L,10.0mg/L for Ba,Pb,Cd,Cr 配制一系列的标准溶液如下： 砷，汞，锑， 硒为 0.1mg/L,0.2 mg/L,0.4 mg/L,1.0 mg/L,2.0 mg/L 钡，铅，铬， 镉为 0.5mg/L,1.0 mg/L,2.0 mg/L,5.0 mg/L,10.0mg/L 2.2 Anal

3、yze the solutions as samples with ICP-OES. 用 ICP 来分析上述溶液。 2.3 Calculate the correlation coefficient （R） with minimum requirement of R0.995. 检验其标准曲线的相关系数（ R ）达到最低要 求： R0.995。 3 Results（结果 ） The linearity of As,Hg,Sb,Se ,Ba,Pb,Cd,Cr in 0.07NHCL As,Hg,Sb,Se ,Ba,Pb,Cd,Cr 在 0.07N HCL 中的线性范围 广州立德技术检测有限公司

4、Bureau Veritas Consumer Products (G.Z.) Co.Ltd Concentration of As standard working solutions (ppm) Intensity(c/s) Concentration of Ba standard working solutions (ppm) Intensity(c/s) 0.1 163.832 0.5 62173 0.2 304.492 1 120378 0.4 611.61 2 243331 1 1470.58 5 583033 2 2960.14 10 1155306 Concentration

5、of Cd standard working solutions (ppm) Intensity(c/s) Concentration of Cr standard working solutions (ppm) Intensity(c/s) 0.5 38905.7 0.5 35531.2 1 75553.9 1 70354.2 2 152807 2 141176 5 374995 5 347859 10 723010 10 650584 Concentration of Pb standard working solutions (ppm) Intensity(c/s) Concentrat

6、ion of Hg standard working solutions (ppm) Intensity(c/s) 0.5 2264.64 0.1 454.521 1 4415.19 0.2 887.705 2 8858.63 0.4 1738.74 5 21858.9 1 4421.65 10 43296.3 2 8757.17 Concentration of Sb standard working solutions (ppm) Intensity(c/s) Concentration of Se standard working solutions (ppm) Intensity(c/

7、s) 0.1 255.79 0.1 154.019 0.2 462.193 0.2 281.501 0.4 879.191 0.4 564.169 1 2138.65 1 1407.66 2 4254.23 2 2868.31 Bureau Veritas Consumer Products (G.Z.) Co.Ltd 广州立德技术检测有限公司 The graph of As concentration(0.1ppm to 2ppm) against Intensity 4000.0 3000.0 2000.0 1000.0 2 2.5 0.0 0 0.5 1 1.5 Concentratio

8、n(ppm) )s/c(ytisnetn The graph of Ba concentration(0.5ppm to10ppm) against Intensity 1200000.0 900000.0 600000.0 300000.0 0.0 0 2 4 6 8 10 12 Concentration(ppm) The graph of Cd concentration(0.5ppm to 10ppm) against Intensity 800000.0 400000.0 600000.0 200000.0 0.0 02 4 6 8 10 Concentration(ppm) 12

9、)s/c(ytisnet The graph of Cr concentration(0.5ppm to 10ppm) against Intensity 800000.0 600000.0 400000.0 200000.0 0.0 10 12 02468 Concentration(ppm) Bureau Veritas Consumer Products (G.Z.) Co.Ltd 广州立德技术检测有限公司 The graph of Pb concentration(0.5ppm to10.0ppm) against Intensity 36000.0 )s/c(ytisnetn 240

10、00.0 12000.0 0.0 0 2 46 Concentration(ppm) 8 10 12 )s/c(ytisnetn 2 2.5 3600.0 2400.0 1200.0 0.0 0 2 0.5 1 1.5 Concentration(ppm) 2.5 The graph of Hg concentration(0.1ppm to2.0ppm) against Intensity 10000.0 7500.0 5000.0 2500.0 0.0 0 0.5 1 1.5 Concentration(ppm) The graph of Sb concentration(0.1ppm t

11、o2.0ppm) against Intensity The graph of Se concentration(0.1ppm to2.0ppm) against Intensity 3200.0 1600.0 2400.0 800.0 0.0 Concentration(ppm) 4 Conclusion( 结论 ). The calibration curve is linear with R0.995 for 广州立德技术检测有限公司 Bureau Veritas Consumer Products （G.Z.） Co.Ltd Ba,Pb,Cd,Cr from 0.5ppm to 5pp

12、m; As,Hg,Sb,Se from 0.1ppm to 2.0ppm. 最终确认在 0.07N 盐酸中的砷，汞，锑，硒其 线性范围 0.1ppm 到 5ppm ，钡，铅，铬，镉其线 性范围 0.05ppm 到 10ppm 均达到 R0.995。 注：根据 CPSD-AN-00003-MTHD 要求，现行 使用砷，汞，锑，硒 0.2ppm,0.4ppm,1.0ppm 和钡，铅，铬，镉 1.0ppm,2.0ppm,5.0ppm 作为校准工作曲线。 Instrument detection limit（ 仪器检出限 ） 1 Scope（目的 ） 广州立德技术检测有限公司 Bureau Verit

13、as Consumer Products (G.Z.) Co.Ltd The purpose of this validation is to determine the instrument detection limit (IDL)of soluble elements for EN71-3(ISO8124/ASTM F963-2003) with ICP-OES. 做仪器检出限的目的是来确认仪器对可迁移元 素元素的检出限 . 2 Procedure( 过程 ) 2.1 Place the reagent blank to the ICP 将试剂空白打入 ICP 中。 2.2 Take a

14、 series of seven replicate measurements for soluble elements 重复读 7 次试剂空白，记录可迁移元素的 强度。 2.3 Analyze the seven replicates and calculate the IDL as 1.645 standard deviation. 分析这七次重复测量值并计算理论仪器检出 限(等于 1.645标准偏差)。 2.4 Verify the calculated IDL until the signal to noise ratio reaches 3:1. 校验仪器检出限直到信背比为 3：1。

15、 3 Results(结果 ) The IDL of Soluble elements in 0.07N HCl 可溶出元素在 0.07N 盐酸中的仪器检出限 Trial Measured As(mg/L) Measured Ba(mg/L) Measured Cd(mg/L) Measured Cr(mg/L) Measured Hg(mg/L) Measured Pb(mg/L) Measured Sb(mg/L) Measured Se(mg/L) 1 -0.0019 0.0000 -0.0001 -0.0004 -0.0013 0.0000 0.0060 0.0052 2 0.0013

16、 0.0000 -0.0002 -0.0003 -0.0013 -0.0019 0.0003 0.0039 3 -0.0022 -0.0001 -0.0001 -0.0002 -0.0002 -0.0007 0.0020 -0.0019 4 -0.0024 -0.0001 -0.0002 -0.0003 -0.0011 -0.0015 0.0044 0.0055 5 -0.0020 0.0000 -0.0002 -0.0002 -0.0008 -0.0008 0.0017 0.0007 6 -0.0021 -0.0002 -0.0001 -0.0002 -0.0005 -0.0010 -0.0

17、001 -0.0078 7 -0.0093 0.0000 -0.0001 -0.0003 -0.0009 -0.0014 0.0035 -0.0058 Standard Derivation 0.0032 0.0001 0.0001 0.0001 0.000414 0.0006 0.0022 0.005358 Instrumental 0.0053 0.0001 0.0001 0.0001 0.0007 0.0011 0.0036 0.008813 广州立德技术检测有限公司 Bureau Veritas Consumer Products (G.Z.) Co.Ltd Detection Lim

18、it(1.645 SD) Verified IDL 0.0300 0.0008 0.0008 0.0008 0.0100 0.0200 0.0500 0.0400 Verified IDL of As,Hg,Sb,Se ,Ba,Pb,Cd,Cr in 0.07N HCL As,Hg,Sb,Se ,Ba,Pb,Cd,C 在 0.07N HCL 中的校验仪器检出限 Trail Count Blank Pb 0.0200mg/L Signal to Noise Ratio 1 30.7716 127.262 4.14 2 22.1958 127.262 5.73 3 27.7183 127.262

19、4.59 4 24.0611 127.262 5.29 5 24.0826 127.262 5.28 6 26.1864 127.262 4.86 7 24.7588 127.262 5.14 Verified IDL of Pb 0.0200 mg/L Trail Count Blank As 0.0300mg/L Signal to Noise Ratio 1 13.7240 64.0326 4.67 2 18.2396 64.0326 3.51 3 13.2481 64.0326 4.83 4 12.9732 64.0326 4.94 5 13.5238 64.0326 4.73 6 1

20、3.4412 64.0326 4.76 7 15.0662 64.0326 4.25 Verified IDL of As 0.0300 mg/L Trail Count Blank Ba 0.0008mg/L Signal to Noise Ratio 1 47.6875 152.871 3.21 2 39.5933 152.871 3.86 3 30.4613 152.871 5.02 4 34.1127 152.871 4.48 5 44.3013 152.871 3.45 6 22.7092 152.871 6.73 7 43.0437 152.871 3.55 Verified ID

21、L of Ba 0.0008 mg/L Trail Count Blank Cd 0.0008mg/L Signal to Noise 广州立德技术检测有限公司 Bureau Veritas Consumer Products (G.Z.) Co.Ltd Ratio 1 29.3847 91.4211 3.11 2 18.0108 91.4211 5.08 3 22.8931 91.4211 3.99 4 21.7983 91.4211 4.19 5 22.3136 91.4211 4.10 6 29.5695 91.4211 3.09 7 28.7477 91.4211 3.18 Verif

22、ied IDL of Cd 0.0008 mg/L Trail Count Blank Cr 0.0008mg/L Signal to Noise Ratio 1 18.2995 95.7543 5.23 2 21.5417 95.7543 4.45 3 27.6204 95.7543 3.47 4 25.2868 95.7543 3.79 5 28.1169 95.7543 3.41 6 26.5177 95.7543 3.61 7 23.0814 95.7543 4.15 Verified IDL of Cr 0.0008 mg/L Trail Count Blank Hg 0.01mg/

23、L Signal to Noise Ratio 1 12.7314 60.2842 4.74 2 12.7385 60.2842 4.73 3 17.6735 60.2842 3.41 4 13.6835 60.2842 4.41 5 14.9606 60.2842 4.03 6 16.2640 60.2842 3.71 7 14.6059 60.2842 4.13 Verified IDL of 0.01 mg/L Hg Trail Count Blank Sb 0.05mg/L Signal to Noise Ratio 1 25.3820 77.2350 3.04 2 13.5101 7

24、7.2350 5.72 3 16.9009 77.2350 4.57 4 21.9270 77.2350 3.52 5 16.3218 77.2350 4.73 6 12.5923 77.2350 6.13 7 20.1290 77.2350 3.84 Verified IDL of Sb 0.05 mg/L Bureau Veritas Consumer Products (G.Z.) Co.Ltd 广州立德技术检测有限公司 Trail Count Blank Se 0.04mg/L Signal to Noise Ratio 1 19.2417 68.8310 3.58 2 17.4998

25、 68.8310 3.93 3 9.46298 68.8310 7.27 4 19.6852 68.8310 3.50 5 13.0459 68.8310 5.28 6 1.40121 68.8310 49.12 7 4.11653 68.8310 16.72 Verified IDL of Se 0.04 mg/L (Criteria: signal to noise ratio 3:1) 4 Conclusion( 结论 ) The claimed IDL of soluble elements for EN71-3(ISO8124/ASTM F963-2003) is as below,

26、As 0.03mg/L,Ba 0.0008 mg/L, Cd 0.0008 mg/L, Cr 0.0008 mg/L, Hg 0.01 mg/L, Pb 0.02 mg/L, Sb 0.05 mg/L, Se 0.04 mg/L. EN71-3(ISO8124/ASTM F963-2003)方法最终 确认的仪器检出限为 : As 0.03mg/L,Ba 0.0008 mg/L, Cd 0.0008 mg/L, Cr 0.0008 mg/L, Hg 0.01 mg/L, Pb 0.02 mg/L, Sb 0.05 mg/L, Se 0.04 mg/L. Method detection limi

27、t( 方法检出限 ) 1 Scope(目的 ) The purpose of this validation is to determine the method detection limit (MDL) of Pb, As, Cr, 广州立德技术检测有限公司 Bureau Veritas Consumer Products (G.Z.) Co.Ltd Cd, Ba,Sb,Se,Hg for materials using ICP-OES(AN-0160). 确认 ICP-OES 对铅，砷，铬，镉，钡，锑，硒， 汞的方法检出限。 2 Procedure( 过程 ) 2.1 For extra

28、ctable/ soluble test, MDL is estimated from verified IDL x 5. The est. MDL is spike into extraction solution without go through sample preparation. (According to CPSD-AN-TSOP Method Validation Procedure-Ver3) 根据CPSD-AN-TSOP Method Validation Procedure-Ver3 ，萃取测试的方法检出限相当于 仪器检出限的 5倍。通过在已经过处理的空白样 品溶液中加

29、标准溶液制备。 2.2 Verify the MDL until the signal to noise is greater than three. Recoveries shall be between 50% and 150%, RSD shall be 20% ) 校验仪器检出限直到信背比为 3：1；回收率 在 50%间；相对标准偏差不大于 20% 3 Results(结果 ) Calculated MDL of Pb, As, Cr, Cd, Ba,Sb,Se,Hg in 0.07N HCL Pb, As, Cr, Cd, Ba,Sb,Se,Hg 在 0.07N 盐酸中的理论方法检出

30、限 Trial Measured Pb Measured As Measured Cd Measured Ba (mg/L) Recover y (%) (mg/L) Recovery (%) (mg/L) Recovery (%) (mg/L) Recovery (%) Spike Concentratio n 0.1000 - 0.1500 - 0.0040 - 0.0040 1 0.107 107 0.151 101 0.0036 90.2 0.0033 82.5 2 0.100 99.6 0.150 99.9 0.0036 90.7 0.0036 90.0 3 0.101 101 0.

31、149 99.4 0.0036 91.2 0.0033 82.5 4 0.101 101 0.150 100 0.0036 90.5 0.0033 82.5 5 0.100 99.8 0.151 101 0.0035 88.4 0.0034 85.0 广州立德技术检测有限公司 Bureau Veritas Consumer Products (G.Z.) Co.Ltd 6 0.103 103 0.149 99.6 0.0036 91.1 0.0035 87.5 7 0.102 102 0.151 101 0.0036 90.2 0.0036 90.0 Mean 0.102 102 0.150

32、100 0.0036 90.3 0.0034 85.7 Standard Derivation (SD) 0.0027 - 0.0007 - 0.00004 - 0.0001 - % RSD 2.65 0.47 1.11 2.94 Verified MDL 0.1000 mg/L 0.1500 mg/L 0.0040 mg/L 0.0040 mg/L (Criteria: Recovery =100 50%, RSD 20%) Trial Measured Cr Measured Hg Measured Sb Measured Se (mg/L) Recover y (%) (mg/L) Re

33、covery (%) (mg/L) Recovery (%) (mg/L) Recovery (%) Spike Concentratio n 0.0040 - 0.0500 - 0.2500 - 0.2000 - 1 0.0039 97.1 0.0463 92.6 0.2523 101 0.1980 99 2 0.0040 99.7 0.0483 96.6 0.2573 103 0.2067 103 3 0.0039 98.3 0.0461 92.2 0.2537 101 0.2060 103 4 0.0038 94.1 0.0472 94.4 0.2544 102 0.1990 100 5

34、 0.0036 90.6 0.0472 94.4 0.2561 102 0.2038 102 6 0.0037 93.0 0.0471 94.2 0.2532 101 0.2077 104 7 0.0038 95.9 0.0500 100 0.2572 103 0.2048 102 Mean 0.0038 95.5 0.0475 94.9 0.2549 102 0.2037 102 Standard Derivation (SD) 0.0001 - 0.0013 - 0.0020 - 0.0038 - % RSD 2.63 2.74 0.78 1.87 Verified MDL 0.0040

35、mg/L 0.0500 mg/L 0.2500 mg/L 0.2000 mg/L (Criteria: Recovery =100 50%, RSD 20%) Verified MDL of Pb, As, Cr, Cd, Ba,Sb,Se,Hg in 0.07N HCL Pb, As, Cr, Cd, Ba,Sb,Se,Hg 在 0.07N 盐酸中的校验方法检出限 Trail Count Blank Pb 0.100mg/L Signal to Noise Ratio 1 37.22 572 15.37 2 37.22 533 14.32 广州立德技术检测有限公司 Bureau Verita

36、s Consumer Products (G.Z.) Co.Ltd 3 37.22 539 14.48 Verified MDL of Pb 0.100ppm Trail Count Blank As 0.0150mg/L Signal to Noise Ratio 1 23.80 258 10.84 2 23.80 270 11.34 3 23.80 262 11.01 Verified MDL of As 0.0150ppm Count Blank Cr 0.0040mg/L Signal to Noise Ratio 1 63.11 381 6.04 2 63.11 390 6.18 3

37、 63.11 385 6.10 Verified MDL of Cr 0.0040ppm Trail Count Blank Cd 0.0040mg/L Signal to Noise Ratio 1 33.49 391 11.68 2 33.49 393 11.73 3 33.49 386 11.53 Verified MDL of Cd 0.0040ppm Trail Count Blank Sb 0.250mg/L Signal to Noise Ratio 1 14.86 630 42.40 2 14.86 642 43.20 3 14.86 633 42.60 Verified MD

38、L of Sb 0.250ppm Trail Count Blank Se 0.200mg/L Signal to Noise Ratio 1 25.92 342 13.19 2 25.92 356 13.73 3 25.92 355 13.70 Verified MDL of Se 0.200ppm Trail Count Blank Hg 0.050mg/L Signal to Noise Ratio 1 18.9 259 13.70 2 18.9 269 14.23 3 18.9 258 13.65 Verified MDL of Hg 0.050ppm Trail Count Blan

39、k Ba 0.004mg/L Signal to Noise Ratio 1 47.6 631 13.26 2 47.6 626 13.15 3 47.6 629 13.21 Verified MDL of Ba 0.004ppm (Criteria: signal to noise ratio 3:1) 广州立德技术检测有限公司 Bureau Veritas Consumer Products (G.Z.) Co.Ltd 4 Conclusion( 结论 ) The verified MDL of Pb, As, Cr, Cd, Ba,Sb,Se,Hg in 0.07N HCL are as

40、 below: Pb 0.10mg/L, As 0.15mg/L, Cd 0.004mg/L, Cr 0.04 mg/L, Sb 0.25mg/L,Se 0.20mg/L,Ba 0.004mg/L,Hg 0.05mg/L. 最终确认在 0.07N 盐酸中的方法检出限为 : Pb 0.10mg/L, As 0.15mg/L, Cd 0.04mg/L, Cr 0.04 mg/L, Sb 0.25mg/L Ba 0.004mg/L, Hg 0.05mg/L,Se 0.20mg/L. Precision( 精密度 )(For ICP-OES) 1 Scope(目的 ) The purpose of this validation is to determine the precision of soluble elements for EN71