EN71-3 重金属测试方法确认.docx

洋紫荆油墨（中山）有限公司检测实验室EN71-3 重金属测试方法验证报告1目的确定实验室具有实施该标准的检验能力，验证该标准在实验室运行的稳定性、准确性。2. 测试方法： EN71-3：20113. 方法描述: 样品加入一定量的0.07mol/L的盐酸溶液，模拟材料在吞咽后与胃酸持续接触一段时间的条件下，从玩具材料中提取出的溶出物用ICP-OES测定可溶性元素的含量。4. 试剂：-盐酸溶液I:c( HCl)=(0.07士0.005) mol/L;-盐酸溶液2:c(HCD=(0.14士0.010)mol/L;-盐酸溶液3:c(HCI)约等于1 mol/L;-盐酸溶液4:c(HC1)约等于2 mol/L;-盐酸溶液5:c(HCI)约等于6 mol/L;-正庚烷;-水（三级或以上）5. 仪器： 电子天平、离心机、孔径为0.5mm的金属筛、ICP-OES6. 测试过程： 称取过筛后的样品0.2g于50mL锥形瓶中，加入10mL 37的0.07mol/L的盐酸溶液，摇动1min，调PH值为1-1.5，避光、在37恒温条件下震动1h再静置1h，接着立即过滤，滤液用ICP-OES测试。7. 工作曲线:根据标准要求，同时结合实验室样品的需求选择工作曲线的线性工作范围，在此范围内具有良好的线性，相关结果见下表：表1测试项目线性范围（mg/L）拟合公式相关系数（R）铝（Al）0-5y=261400x+4082.80.99998锑（Sb）0-5y=12710x-1143.70.99996砷（As）0-5y=10560x+159.10.99996钡（Ba）0-5y=449300x+7078.50.99996硼（B）0-5y=186800x+1184.40.99999镉（Cd）0-1y=332500x+543.60.99998铬（Cr）0-5y=413600x+3868.30.99997钴（Co）0-5y=273500x+4385.40.99997铜（Cu）0-5y=542000x+3006.50.99998铅（Pb）0-5y=61880x+72.30.99999锰（Mn）0-5y=2732000x-23617.80.99999汞（Hg）0-1y=26770x+67.60.99998镍（Ni）0-5y=232000x+3434.00.99997硒（Se）0-5y=11920x+331.50.99989锶（Sr）0-0.2y=35230000x-3114.11.00000锡（Sn）0-5y=30280x-868.10.99995锌（Zn）0-5y=352400x+7742.40.999938. 方法检出限 分析低浓度标液10次，计算标准偏差（SD），检出限即为3SD。相关检测数据及计算结果如下：表2 低浓度标液10次检测数据测试项目12345678910铝（Al）0.0430.0450.0450.0470.0450.0450.0470.0480.0460.046锑（Sb）0.0440.0450.0450.0460.0460.0450.0460.0460.0440.044砷（As）0.0450.0460.0450.0460.0460.0450.0460.0460.0440.044钡（Ba）0.0460.0480.0490.0500.0490.0490.0500.0490.0490.049硼（B）0.0560.0560.0510.0490.0460.0510.0510.0500.0490.048镉（Cd）0.00080.00090.00090.00080.00090.00090.00100.00100.00100.0010铬（Cr）0.0460.0440.0450.0450.0450.0460.0460.0470.0470.045钴（Co）0.01030.01000.00910.01040.01080.01040.01030.01040.01020.0104铜（Cu）0.0490.0510.0510.0550.0520.0520.0530.0530.0530.051铅（Pb）0.01020.00950.00960.01070.01010.00970.01100.01070.00970.0089锰（Mn）0.0010.0010.0010.0010.0010.0010.0010.0010.0010.001汞（Hg）0.0120.0110.0100.0100.0090.0090.0090.0090.0080.009镍（Ni）0.0500.0510.0520.0520.0520.0520.0520.0520.0520.051硒（Se）0.0460.0490.0490.0470.0480.0510.0490.0480.0480.048锶（Sr）0.0100.0100.0110.0100.0110.0110.0100.0110.0110.011锡（Sn）0.0520.0530.0540.0540.0540.0550.0550.0550.0560.055锌（Zn）0.0480.0500.0510.0520.0510.0510.0510.0520.0510.050根据标准偏差计算公式=i=1n(xi-x)2n-1 计算各化合物的标准偏及方法检出限表3测试项目标准偏差(mg/L)方法检出限（样液）(mg/L)方法检出限（试样）(mg/kg)铝（Al）0.0010.0030.15锑（Sb）0.0010.0030.15砷（As）0.0010.0030.15钡（Ba）0.0010.0030.15硼（B）0.0030.0090.45镉（Cd）0.0000.0000铬（Cr）0.0010.0030.15钴（Co）0.0010.0030.15铜（Cu）0.0020.0050.25铅（Pb）0.0010.0030.15锰（Mn）0.0000.0000汞（Hg）0.0010.0030.15镍（Ni）0.0010.0030.15硒（Se）0.0010.0030.15锶（Sr）0.0010.0030.15锡（Sn）0.0010.0030.15锌（Zn）0.0010.0030.15由于以上检出限由统计而来，所以需要对其进行验证，重复测试10次期望的检出限浓度，计算平均值与标称值的偏差，以下为验证结果：表4测试项目12345678910铝（Al）0.0430.0450.0450.0470.0450.0450.0470.0480.0460.046锑（Sb）0.0440.0450.0450.0460.0460.0450.0460.0460.0440.044砷（As）0.0450.0460.0450.0460.0460.0450.0460.0460.0440.044钡（Ba）0.0460.0480.0490.0500.0490.0490.0500.0490.0490.049硼（B）0.0560.0560.0510.0490.0460.0510.0510.0500.0490.048镉（Cd）0.00080.00090.00090.00080.00090.00090.00100.00100.00100.0010铬（Cr）0.0460.0440.0450.0450.0450.0460.0460.0470.0470.045钴（Co）0.01030.010.00910.01040.01080.01040.01030.01040.01020.0104铜（Cu）0.0490.0510.0510.0550.0520.0520.0530.0530.0530.051铅（Pb）0.01020.00950.00960.01070.01010.00970.01100.01070.00970.0089锰（Mn）0.0010.0010.0010.0010.0010.0010.0010.0010.0010.001汞（Hg）0.0120.0110.0100.0100.0090.0090.0090.0090.0080.009镍（Ni）0.0500.0510.0520.0520.0520.0520.0520.0520.0520.051硒（Se）0.0460.0490.0490.0470.0480.0510.0490.0480.0480.048锶（Sr）0.0100.0100.0110.0100.0110.0110.0100.0110.0110.011锡（Sn）0.0520.0530.0540.0540.0540.0550.0550.0550.0560.055锌（Zn）0.0480.0500.0510.0520.0510.0510.0510.0520.0510.050经验证的方法检出限及报告限如下表：表5 测试项目10次测试平均值标称值偏差偏差要求方法检出限（样液）(mg/L)方法检出限（试样）(mg/kg)报告限(mg/kg)铝（Al）0.04570.050-8.6100.0502.55锑（Sb）0.04510.050-9.8100.0502.55砷（As）0.04530.050-9.4100.0502.52.5钡（Ba）0.04880.050-2.4100.0502.55硼（B）0.05070.0501.4100.0502.55镉（Cd）0.000920.001-8.0100.0010.050.1铬（Cr）0.04560.050-8.8100.0502.55钴（Co）0.01020.0102.0100.0100.52铜（Cu）0.0520.0504.0100.0502.55铅（Pb）0.01000.0100100.0100.52锰（Mn）0.00100.0010100.0010.055汞（Hg）0.00960.010-4.0100.0100.51镍（Ni）0.05160.0503.2100.0502.55硒（Se）0.04830.050-3.4100.0502.55锶（Sr）0.01060.0106.0100.0100.51锡（Sn）0.05430.0508.6100.0502.55锌（Zn）0.05070.0501.4100.0502.559. 方法的准确性和重复性方法的准确性通过回收率试验进行测试，加标回收率的计算公式为：回收率=加标样品浓度-样品浓度加标浓度100% ，相关结果见下表表6测试项目样品浓度(mg/kg)加标样品浓度(mg/kg)加标浓度(mg/kg)回收率(%)铝（Al）52525100锑（Sb）5202580砷（As）2202580钡（Ba）5232592硼（B）52825112镉（Cd）1202580铬（Cr）30522588钴（Co）2212584铜（Cu）5222588铅（Pb）5212584锰（Mn）5212584汞（Hg）12.62.5104镍（Ni）5222588硒（Se）5202580锶（Sr）12.22.588锡（Sn）5232592锌（Zn）5222588方法的重复性通过重复对样品进行确定，对样品进行8次重复测量，相关如下：表7测试项目测试结果 （mg/kg）RSD(%)12345678铝（Al）999888886.2锑（Sb）55555555砷（As）2.52.52.52.52.52.52.52.5钡（Ba）91929290919289911.2硼（B）55555555镉（Cd）0.10.10.10.10.10.10.10.1铬（Cr）55555555钴（Co）22222