EN71-3方法确认.doc

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 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 Analyze 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 0.07NHCLAs,Hg,Sb,Se ,Ba,Pb,Cd,Cr在0.07N HCL中的线性范围Concentration of As standard working solutions (ppm)Intensity(c/s)Concentration of Ba standard working solutions (ppm)Intensity(c/s)0.1163.8320.5621730.2304.49211203780.4611.61224333111470.58558303322960.14101155306Concentration of Cd standard working solutions (ppm)Intensity(c/s)Concentration of Cr standard working solutions (ppm)Intensity(c/s)0.538905.70.535531.2175553.9170354.221528072141176537499553478591072301010650584Concentration of Pb standard working solutions (ppm)Intensity(c/s)Concentration of Hg standard working solutions (ppm)Intensity(c/s)0.52264.640.1454.52114415.190.2887.70528858.630.41738.74521858.914421.651043296.328757.17Concentration of Sb standard working solutions (ppm)Intensity(c/s)Concentration of Se standard working solutions (ppm)Intensity(c/s)0.1255.790.1154.0190.2462.1930.2281.5010.4879.1910.4564.16912138.6511407.6624254.2322868.314 Conclusion(结论).The calibration curve is linear with R0.995 for Ba,Pb,Cd,Cr from 0.5ppm to 5ppm; 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)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 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。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TrialMeasuredAs(mg/L) MeasuredBa(mg/L)MeasuredCd(mg/L)MeasuredCr(mg/L)MeasuredHg(mg/L)MeasuredPb(mg/L)MeasuredSb(mg/L)MeasuredSe(mg/L)1-0.00190.0000-0.0001-0.0004-0.00130.00000.00600.005220.00130.0000-0.0002-0.0003-0.0013-0.00190.00030.00393-0.0022-0.0001-0.0001-0.0002-0.0002-0.00070.0020-0.00194-0.0024-0.0001-0.0002-0.0003-0.0011-0.00150.00440.00555-0.00200.0000-0.0002-0.0002-0.0008-0.00080.00170.00076-0.0021-0.0002-0.0001-0.0002-0.0005-0.0010-0.0001-0.00787-0.00930.0000-0.0001-0.0003-0.0009-0.00140.0035-0.0058Standard Derivation0.00320.00010.00010.00010.0004140.00060.00220.005358Instrumental Detection Limit(1.645SD)0.00530.00010.00010.00010.00070.00110.00360.008813Verified IDL0.03000.00080.00080.00080.01000.02000.05000.0400Verified IDL of As,Hg,Sb,Se ,Ba,Pb,Cd,Cr in 0.07N HCLAs,Hg,Sb,Se ,Ba,Pb,Cd,C在0.07N HCL中的校验仪器检出限TrailCountBlankPb 0.0200mg/LSignal to Noise Ratio130.7716 127.2624.14222.1958127.2625.73327.7183127.2624.59424.0611127.2625.29524.0826127.2625.28626.1864127.2624.86724.7588127.2625.14Verified IDL of Pb0.0200 mg/LTrailCountBlankAs 0.0300mg/LSignal to Noise Ratio113.724064.03264.67218.239664.03263.51313.248164.03264.83412.973264.03264.94513.523864.03264.73613.441264.03264.76715.066264.03264.25Verified IDL of As0.0300 mg/LTrailCountBlankBa 0.0008mg/LSignal to Noise Ratio147.6875152.8713.21239.5933152.8713.86330.4613152.8715.02434.1127152.8714.48544.3013152.8713.45622.7092152.8716.73743.0437152.8713.55Verified IDL of Ba0.0008 mg/L TrailCountBlankCd 0.0008mg/LSignal to Noise Ratio129.384791.42113.11218.010891.42115.08322.893191.42113.99421.798391.42114.19522.313691.42114.10629.569591.42113.09728.747791.42113.18Verified IDL of Cd0.0008 mg/LTrailCountBlankCr 0.0008mg/LSignal to Noise Ratio118.299595.75435.23221.541795.75434.45327.620495.75433.47425.286895.75433.79528.116995.75433.41626.517795.75433.61723.081495.75434.15Verified IDL of Cr0.0008 mg/LTrailCountBlankHg 0.01mg/LSignal to Noise Ratio112.731460.28424.74212.738560.28424.73317.673560.28423.41413.683560.28424.41514.960660.28424.03616.264060.28423.71714.605960.28424.13Verified IDL of Hg0.01 mg/LTrailCountBlankSb 0.05mg/LSignal to Noise Ratio125.382077.23503.04213.510177.23505.72316.900977.23504.57421.927077.23503.52516.321877.23504.73612.592377.23506.13720.129077.23503.84Verified IDL of Sb0.05 mg/LTrailCountBlankSe 0.04mg/LSignal to Noise Ratio119.241768.83103.58217.499868.83103.9339.4629868.83107.27419.685268.83103.50513.045968.83105.2861.4012168.831049.1274.1165368.831016.72Verified IDL of Se0.04 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,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 limit(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, 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 extractable/ 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 HCLPb, As, Cr, Cd, Ba,Sb,Se,Hg在0.07N 盐酸中的理论方法检出限TrialMeasuredPbMeasuredAsMeasuredCdMeasuredBa(mg/L)Recovery (%)(mg/L)Recovery (%)(mg/L)Recovery (%)(mg/L)Recovery (%)Spike Concentration0.1000-0.1500-0.0040-0.0040-10.1071070.1511010.003690.20.003382.5 20.10099.60.15099.90.003690.70.003690.0 30.1011010.14999.40.003691.20.003382.5 40.1011010.1501000.003690.50.003382.5 50.10099.80.1511010.003588.40.003485.0 60.1031030.14999.60.003691.10.003587.5 70.1021020.1511010.003690.20.003690.0 Mean0.1021020.1501000.003690.30.003485.7 Standard Derivation (SD)0.0027-0.0007-0.00004-0.0001-% RSD2.650.471.112.94Verified MDL0.1000 mg/L0.1500 mg/L0.0040 mg/L0.0040 mg/L (Criteria: Recovery =10050%, RSD20%)TrialMeasuredCrMeasuredHgMeasuredSbMeasuredSe(mg/L)Recovery (%)(mg/L)Recovery (%)(mg/L)Recovery (%)(mg/L)Recovery (%)Spike Concentration0.0040-0.0500-0.2500-0.2000-10.003997.10.046392.60.25231010.19809920.004099.70.048396.60.25731030.206710330.003998.30.046192.20.25371010.206010340.003894.10.047294.40.25441020.199010050.003690.60.047294.40.25611020.203810260.003793.00.047194.20.25321010.207710470.003895.90.05001000.25721030.2048102Mean0.003895.50.047594.90.25491020.2037102Standard Derivation (SD)0.0001-0.0013-0.0020-0.0038-% RSD2.632.740.781.87Verified MDL0.0040 mg/L0.0500 mg/L0.2500 mg/L0.2000 mg/L(Criteria: Recovery =10050%, RSD20%)Verified MDL of Pb, As, Cr, Cd, Ba,Sb,Se,Hg in 0.07N HCLPb, As, Cr, Cd, Ba,Sb,Se,Hg 在 0.07N 盐酸中的校验方法检出限TrailCountBlankPb 0.100mg/LSignal to Noise Ratio137.2257215.37237.2253314.32337.2253914.48Verified MDL of Pb0.100ppmTrailCountBlankAs 0.0150mg/LSignal to Noise Ratio123.8025810.84 223.8027011.34 323.8026211.01 Verified MDL of As0.0150ppmCountBlankCr 0.0040mg/LSignal to Noise Ratio163.113816.04 263.113906.18 363.113856.10 Verified MDL of Cr0.0040ppmTrailCountBlankCd 0.0040mg/LSignal to Noise Ratio133.4939111.68 233.4939311.73 333.4938611.53 Verified MDL of Cd0.0040ppmTrailCountBlankSb 0.250mg/LSignal to Noise Ratio114.8663042.40 214.8664243.20 314.8663342.60 Verified MDL of Sb0.250ppm TrailCountBlankSe 0.200mg/LSignal to Noise Ratio125.9234213.19 225.9235613.73 325.9235513.70 Verified MDL of Se0.200ppmTrailCountBlankHg 0.050mg/LSignal to Noise Ratio118.925913.70 218.926914.23 318.925813.65 Verified MDL of Hg0.050ppmTrailCountBlankBa 0.004mg/LSignal to Noise Ratio147.663113.26 247.662613.15 347.662913.21 Verified MDL of Ba0.004ppm (Criteria: signal to noise ratio 3:1)4 Conclusion(结论) The verified MDL of Pb, As, Cr, Cd, Ba,Sb,Se,Hg in 0.07N HCL are as 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 EN71-3(ISO8124/ASTM F963-2003) with ICP-OES. 本实验的目的是来确认EN71-3(ISO8124/ASTM F963-2003)方法的精密度。2 Procedure(过程) 2.1 Place standard solution into ICP-OES. 将校正标准溶液打入ICP中 2.2 Take a series of seven replicate measurements for soluble elements. 重复7次读取溶液中各元素的浓度. 2.3 Calculate the RSD of the replicate measurements. RSD shall be less than 20%. 计算此重复测量值的RSD。RSD不能超过百分之二十。3 Results(结果)The precision of soluble elements in 0.07N HCl.各元素在0.07N盐酸中的精密度.TrialMeasuredAs(mg/L) MeasuredBa(mg/L)MeasuredCd(mg/L)MeasuredCr(mg/L)MeasuredHg(mg/L)MeasuredPb(mg/L)MeasuredSb(mg/L)MeasuredSe(mg/L)Spike concentration0.21.01.01.00.21.00.20.210.21281.05311.03621.02810.19591.03060.20860.180120.21301.06601.04971.03930.20721.04520.21580.202930.21241.05661.04171.03100.20761.02730.21960.206140.21161.05901.04671.03570.21011.03370.22010.201550.21001.05871.04391.03040.21131.03550.21840.208760.20981.06381.04821.03750.21571.04220.21880.210070.21191.05101.03901.02550.21411.02430.21960.2135RSD(%)0.59400.50890.47440.49483.12220.73151.87190.5939(Criteria: RSD20%)4 Conclusion(结论)The calculated RSD is less than 20%计算出7次测量结果的RSD小于20%