汞砷原子荧光方法验证

1、*检测有限公司方法证实报告方法名称：水质 汞、碎、硒、胡、狒的测定原子荧光法方法来源：HJ694-2014分析项目：汞、碑、硒、韧、狒证实日期：2018.11.19-2018.11.24目录 TOC o 1-5 h z HYPERLINK l bookmark4 o Current Document 一、概述3. HYPERLINK l bookmark6 o Current Document 二、方法原理3. HYPERLINK l bookmark8 o Current Document 三、 人员3. HYPERLINK l bookmark10 o Current Document 四

2、、主要仪器设备3. HYPERLINK l bookmark12 o Current Document 五、方法所需标准（物质）溶液及试剂要求 3 HYPERLINK l bookmark14 o Current Document 六、 分析步骤4. HYPERLINK l bookmark16 o Current Document 七、环境条件4. HYPERLINK l bookmark18 o Current Document 八、样品采集4. HYPERLINK l bookmark20 o Current Document 九、标准曲线及样品测定数据表 4 HYPERLINK l b

3、ookmark22 o Current Document 十、检出限7.十一、精密度9. HYPERLINK l bookmark26 o Current Document 十二、准确度 1.1 HYPERLINK l bookmark28 o Current Document 十三、加标回收率 1.4 HYPERLINK l bookmark30 o Current Document 十五、方法证实结论 1.6表26方法证实汇总16、概述本文验证水质中汞、神、硒、钿、睇的测定，采用原子荧光法。方法标准 号HJ694-2014本次方法证实由我公司检测人员多次试验完成。本标准适用于地表水、地下水

4、、生活污水和工业废水中汞、神、硒、钿、 睇的溶解态和总量的测定。本方法测定汞检出限为 0.04ug/L,测定下限为 0.16ug/L;种的检出限为 0.3ug/L,测定下限为1.2ug/L;硒检出限为0. 4ug/L,测定下限为1.6ug/L;钿、 睇检出限为0.2ug/L,测定下限为0.8ug/L。二、方法原理样品经预处理后进入原子荧光仪，在酸性条件下的硼氢化钾溶液还原作用 下，生成神化氢、钿化氢、睇化氢、硒化氢气体和汞原子，氢化物在氧氢火焰中 形成基态原子，具基态原子和汞原子在相应元素灯发射光的激发下产生原子荧 光，原子荧光强度与试液中元素含量在一定范围内呈正比。三、 人员.采样人员为，检

5、测人员均为大专以上学历，均已经通过公司内部培训考核并 领取上岗证。上岗证见附件2,培训记录见附件3,技术人员能力确认表见附件 4四、主要仪器设备1、吉天AFS-8220原子荧光光度计，仪器编号为,仪器经检定合格，经确认符合要求，检定证书见附件 5,维护保养记录见附件6。五、方法所需标准（物质）溶液及试剂要求同HJ694-2014 “6试剂和材料”，其中汞、神、硒、钿、睇的标准储备 液均购买的市售有证标准物质，相关证书见附件。六、分析步骤依据HJ694-2014 ”9分析步骤”进行操作。七、环境条件本方法对测试环境无特殊要求，符合实验室日常环境控制条件即可。 即满足 仪器室温湿度要求即可，即温度

6、要求：10 C35C；湿度要求： 80%o本次方法验证检测日期为2018年11月1111日，实验室环境记录见附件7。 仪器室环境配备了空调和温湿度计，根据不同时间对仪器室环境温湿度测试，温 度满足10c35c要求，湿度满足0 80%要求，符合环境条件满足设备及检测工 作环境要求。八、样品采集样品采集参照HJ/T91和HJ/T164的相关规定采集，样品保存参照HJ493的规定进行。表1青松河采样日期采样时间采样点位样品编号检测项目2018.9.2408:30汞、神、硒、钿、睇13:30汞、神、硒、钿、睇14:30汞、神、硒、钿、睇九、标准曲线及样品测定数据表.调整仪器的条件，以盐酸为载流，硼氨化

7、钾溶液为还原剂，浓度由低到高依次测定各个元素的荧光强度，以质量浓度为横坐标，绘制标准曲线。数据如下表1不同人员汞标准曲线数据表九素/人贝项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?7 7汞/jack浓度ug/L0.000.100.200.400.600.801.00荧光值0.00191.40456.78817.761254.511641.392031.39曲线方程：I=2034.9*C+12.1项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?7 7汞/TOM浓度ug/L0.000.100.200.400.600.801.00荧光值0.00151.52388.78688.31

8、1025.831325.501649.70曲线方程：I=1645.9*C+18.2表2不同人员种标准曲线数据表九素/人贝项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?7 7神 /jack浓度ug/L0.001.002.004.006.008.0010.00荧光值0.00206.69358.68696.451041.141378.561740.44曲线方程：I=171.8*C+14.0项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?7 7神/TOM浓度ug/L0.001.002.004.006.008.0010.00荧光值0.00222.65394.86764.061139.1

9、11486.801912.68曲线方程：I=187.6*C+14.8表3不同人员硒标准曲线数据表九素/人贝项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?7 75硒 /jack浓度ug/L0.001.002.004.006.008.0010.00荧光值0.00129.01262.96532.18785.781044.401326.41曲线方程：I=131.9*C-1.37项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?夜7硒/TOM浓度ug/L0.001.002.004.006.008.0010.00荧光值0.00123.68269.22550.48814.291128.581

10、418.69曲线方程：I=142.2*C-14.6表4不同人员钿标准曲线数据表九素/人贝项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?夜7州/jack浓度ug/L0.001.002.004.006.008.0010.00荧光值0.00191.44300.68636.72986.741295.771667.29曲线方程：I164.9*C-4.94项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?夜7州/TOM浓度ug/L0.001.002.004.006.008.0010.00荧光值0.00371.70634.061195.311815.532446.073138.49曲线方程：

11、I=307.6*C+9.49表5不同人员睇标准曲线数据表九素/人贝项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?夜7睇/jack浓度ug/L0.001.002.004.006.008.0010.00荧光值0.0092.27188.03408.85645.50884.931129.22曲线方程：I=113.7*C-25.1TOft项目标?夜1标1夜2标1夜3标?夜4标1夜5标1夜6标?夜7睇/TOM浓度ug/L0.001.002.004.006.008.0010.00荧光值0.00187.35351.52728.391100.261515.201880.75曲线方程：I=188.9*C

12、-13.0.样品的测定根据HJ694-2014中9.3处理样品，并同步测定空白样品，结果如下检测点位检测人员jackTOMjackTOM样品编号1112汞NDNDNDND神NDNDNDND硒NDNDNDND秘NDNDNDND睇NDNDNDND十、检出限根据多次对实验 室空白进行重复性测定来计算方法检出限和测定下限，测定结果见下表，其中检出限计算公式如下MDL t S本次空白测定平行测定次数为 8次，t值为2.998。表6汞方法检出限、测定下限数据表测定结果12345678荧光值49.4240.8258.0558.5713.6536.0130.7834.45空白测定结果(ug/L)0.0420.

13、0340.050.0510.0250.030.0250.029平均值x (ug/L)0.03575标准偏差S0.011t值2.998检出PM ( ug/L)0.032测定卜限(ug/L)0.128表7种方法检出限、测定下限数据表测定结果12345678荧光值8.3910.7611.419.428.527.938.158.87空白测定结果（ug/L）0.2880.3010.3050.2940.2890.2860.2870.291平均值又（ug/L）0.293标准偏差S0.0069t值2.998检出PM ( ug/L)0.021测定卜限（ug/L）0.084表8硒方法检出限、测定下限数据表测定结果

14、12345678荧光值1.10.527.317.098.2611.248.236.15空白测定结果（ug/L）0.0320.0290.0640.0630.0690.0840.0690.058平均值x (ug/L)0.058标准偏差S0.020t值2.998检出PM ( ug/L)0.061测定卜限（ug/L）0.244表9钿方法检出限、测定下限数据表测定结果12345678荧光值2.694.3713.836.778.18.349.026.63空白测定结果（ug/L）0.0020.0070.0370.0150.0190.020.0220.014平均值x (ug/L)0.017标准偏差S0.010

15、t值2.998检出PM ( ug/L)0.030测定卜限（ug/L）0.12表10睇方法检出限、测定下限数据表测定结果12345678荧光值5.148.439.794.318.0511.445.398.38空白测定结果（ug/L）0.1450.1100.0960.1450.1140.0790.1420.111平均值x (ug/L)0.118标准偏差S0.0244t值2.998检出PM ( ug/L)0.07380.292测定下限(ug/L)0.292两名检测人员按分析步骤对3个不同浓度的汞种硒钿睇样品进行 6次测量,考察其精密度，结果如下表相对标准偏差RSD,%=5 100 x表11汞样品精密

16、度情况一览表/jackTOM测定结果(ug/L)10.2030.3950.8150.2120.4560.81020.2020.3780.8120.2090.4340.81330.1740.3870.7940.2100.4610.83840.1980.4100.8390.2030.4300.82950.1930.4170.8130.2040.4430.81460.2330.4140.8150.2030.4580.864平均值x ( ug/L)0.2010.4000.8150.2070.4470.828标准偏差S0.0190.0160.0140.0040.0130.021相对标准偏差()9.543

17、.971.761.922.952.50表12种样品精密度情况一览表/jackTOM测定结果(ug/L)12.283.877.882.154.347.8122.233.737.862.113.977.7932.163.707.842.124.177.82942.163.747.972.144.277.7652.103.597.882.114.447.9562.093.667.982.124.327.78平均值又(ug/L)2.173.727.902.134.257.82标准偏差 S (ug/L)0.0740.0950.0590.0160.1640.068相对标准偏差()3.402.550.740

18、.773.850.87表13硒样品精密度情况一览表jackTOM测定结果(ug/L)12.263.858.331.993.827.8322.253.868.051.973.997.8132.223.778.101.943.847.8942.113.867.802.013.917.6352.043.797.572.033.897.7962.053.867.642.033.887.59平均值x ( ug/L)2.153.837.911.993.897.76标准偏差 S (ug/L)0.100.040.290.030.060.12相对标准偏差()4.631.053.721.741.531.55表14

19、钿样品精密度情况一览表/jackTOM2ug/L4ug/L8ug/L2ug/L4ug/L8ug/L测定结果(ug/L)11.983.937.792.074.208.1421.933.947.782.024.217.8132.003.937.912.044.188.2242.003.987.821.944.057.921051.983.897.822.024.037.8161.973.927.861.984.017.82平均值又(ug/L)1.983.937.832.014.117.95标准偏差 S (ug/L)0.030.030.050.050.090.18相对标准偏差()1.270.800.

20、622.282.252.29表15睇样品精密度情况一览表/jackTOM测定结果(ug/L)11.903.978.551.933.908.1221.874.078.691.833.727.9731.924.038.481.943.937.9241.853.948.451.883.787.9751.903.958.571.863.817.9561.903.948.491.883.838.01平均值X (ug/L)1.893.988.541.893.837.99标准偏差 S (ug/L)0.020.050.090.040.080.07相对标准偏差()1.251.361.042.172.010.88

21、十二、准确度两名检测人员对有证标准物测量，考察方法的准确度，结果见下表计算公式：相对误差(，)=L 100L表16汞准确度情况一览表11测定结果(ug/L)14.3415.84.7416.624.1415.84.4416.834.315.24.7217.444.2216.64.0615.5平均值x (ug/L)4.2515.94.4916.6有证标准物质浓度4.57 力.5716.0 :0.94.57 =0.5716.0 划9相对误差()-7.00-0.31-1.753.59表17种准确度情况一览表、,.、丁人员及标物编号jackTOM测定结果(ug/L )131.271.332.170.52

22、32.172.033.372.3331.672.633.371.3431.372.532.671.9平均值x (ug/L)31.572.132.871.5有证标准物质浓度32.5 1.970.2 B532.5 1.970.2 B5相对误差()-2.952.710.971.85表18硒准确度情况一览表jackTOMB1908073B1908081B1908073B1908081测定结果(ug/L )7.7917.428.0616.4016.407.4317.667.3717.9117.917.5317.938.1017.8917.897.2717.637.8518.3718.37平均值x (ug

23、/L)7.5017.667.8517.64有证标准物质浓度7.87 M.6617.5 1.17.87 d0.6617.5 1.112相对误差()-4.640.92-0.320.81表19钿准确度情况一览表员及标物编号jackTOM测定结果(ug/L)151.404.7246.404.72250.204.7650.004.86347.604.8047.104.69452.704.6646.404.70平均值x (ug/L)50.484.7447.484.74有证标准物质浓度51.0 =4.84.88 :0.2351.0 =4.84.88 垃23相对误差()-1.03-2.97-6.91-2.82

24、表20睇准确度情况一览表及标物编号jackTOMB1906025B1905152B1906025B1905152测定结果(ug/L )116.460.32117.400.345217.010.33217.200.341317.080.32517.340.339418.400.33717.000.337平均值x (ug/L)17.240.32917.2360.341有证标准物质浓度(ug/L)17.7 1.30.339 0.0217.7 1.30.339 也02相对误差()-2.63-3.00-2.620.4613由上表可知，质控样的值的波动在误差允许范围内，实验取得了较好的准确度。十三、加标回

25、收率对两个浓度的样品进行加标，进行加标回收测试，结果如下:表21汞加标测试数据jackTOM样品1样品2样品1样品2样品1 浓度加标样 品浓度样品2加标样 品浓度样品1 浓度加标样 品浓度样品2加标样 品浓度测定 结果(ug/L)10.2030.4450.3950.8050.2120.5560.4560.9320.2020.4080.3780.8540.2090.530.4340.93830.1740.4030.3870.8340.210.5410.4610.95540.1980.4300.410.8300.2030.5160.430.98450.1930.4140.4170.8390.204

26、0.5390.4430.97060.2330.4220.4140.8350.2030.5080.4580.983平均值x (ug/L)0.2010.4200.4000.8330.2070.5320.4470.960加林里(ug/L)0.200.400.300.50加标回收率()109.9108.2108.3102.6表22种加标测试数据jackTOM样品1样品2样品1样品2样品1 浓度加标样 品浓度样品2加标样 品浓度样品1 浓度加标样 品浓度样品2加标样 品浓度测定12.33.43.97.52.23.74.37.9结果22.23.53.77.32.13.84.08.1(ug/32.23.43

27、.77.42.13.84.27.914L)42.23.53.77.22.13.74.37.952.13.53.67.32.13.84.48.262.13.63.77.12.13.64.38.1平均值x (ug/L)2.23.53.77.32.13.74.38.0加林里(ug/L)1.504.001.504.00加标回收率()87.8989.48107.3393.79表23硒加标测试数据jackTOM样品1样品2样品1样品2样品1 浓度加标样 品浓度样品2加标样 品浓度样品1 浓度加标样 品浓度样品2加标样 品浓度测定结果(ug/L)12.263.673.857.741.994.003.827.

28、8222.253.713.867.821.973.843.997.8232.223.853.777.681.943.953.848.0542.114.563.867.622.014.033.917.8352.044.603.797.722.033.933.898.1762.054.483.867.712.034.003.887.87平均值X (ug/L)2.154.153.837.721.993.963.897.93加林里(ug/L)2.004.002.004.00加标回收率()99.6097.1398.15100.97表24钿加标测试数据jackTOM样品1样品2样品1样品2样品1 浓度加标样 品浓度样品2加标样 品浓度样品1 浓度加标样 品浓度样品2加标样 品浓度测定 结果(ug/L)11.984.033.937.772.074.014.207.8521.933.993.947.822.023.904.217.6732.003.973.937.962.043.844.187.8842.004.033.987.861.943.904.057.5851.983.953.897.842.0