汞砷原子熒光方法驗證

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方法證實報告方法名稱：水質(zhì)汞、砷、硒、鉍、銻的測定原子熒光法方法來源：HJ694-2014分析項目：汞、珅、硒、鉍、銻證實日期：2018.11.19-2018?11?24目錄TOC\o"1-5"\h\z\o"CurrentDocument"一、概述 3\o"CurrentDocument"二、方法原理 3\o"CurrentDocument"三、人員 3\o"CurrentDocument"四、主要儀器設(shè)備 3\o"CurrentDocument"五、方法所需標(biāo)準(zhǔn)（物質(zhì)）溶液及試劑要求 3\o"CurrentDocument"六、分析步驟 4\o"CurrentDocument"七、環(huán)境條件 4\o"CurrentDocument"八、樣品采集 4\o"CurrentDocument"九、標(biāo)準(zhǔn)曲線及樣品測定數(shù)據(jù)表 4\o"CurrentDocument"十、檢出限 7\o"CurrentDocument"十^一、精密度 9\o"CurrentDocument"十二、準(zhǔn)確度 11\o"CurrentDocument"十三、加標(biāo)回收率 14\o"CurrentDocument"十五、方法證實結(jié)論 16表26方法證實匯總 16一、概述本文驗證水質(zhì)中汞、砷、硒、秘、銻的測定，采用原子熒光法。方法標(biāo)準(zhǔn)號HJ694-2014。本次方法證實由我公司檢測人員多次試驗完成。本標(biāo)準(zhǔn)適用于地表水、地下水、生活污水和工業(yè)廢水中汞、砷、硒、秘、銻的溶解態(tài)和總量的測定。本方法測定汞檢出限為0.04ug/L，測定下限為0.16ug/L；砷的檢出限為0.3ug/L，測定下限為1.2ug/L;硒檢出限為0.4ug/L，測定下限為1.6ug/L;秘、銻檢出限為0.2ug/L，測定下限為0.8ug/L。二、方法原理樣品經(jīng)預(yù)處理后進入原子熒光儀，在酸性條件下的硼氫化鉀溶液還原作用下，生成砷化氫、秘化氫、銻化氫、硒化氫氣體和汞原子，氫化物在氬氫火焰中形成基態(tài)原子，其基態(tài)原子和汞原子在相應(yīng)元素?zé)舭l(fā)射光的激發(fā)下產(chǎn)生原子熒光，原子熒光強度與試液中元素含量在一定范圍內(nèi)呈正比。三、人員.采樣人員為，檢測人員均為大專以上學(xué)歷，均已經(jīng)通過公司內(nèi)部培訓(xùn)考核并領(lǐng)取上崗證。上崗證見附件2,培訓(xùn)記錄見附件3,技術(shù)人員能力確認(rèn)表見附件4四、主要儀器設(shè)備1、吉天AFS-8220原子熒光光度計，儀器編號為，儀器經(jīng)檢定合格，經(jīng)確認(rèn)符合要求，檢定證書見附件5,維護保養(yǎng)記錄見附件6五、方法所需標(biāo)準(zhǔn)（物質(zhì)）溶液及試劑要求同HJ694-2014“6試劑和材料”，其中汞、砷、硒、秘、銻的標(biāo)準(zhǔn)儲備液均購買的市售有證標(biāo)準(zhǔn)物質(zhì)，相關(guān)證書見附件。六、分析步驟依據(jù)HJ694-2014“9分析步驟”進行操作。七、環(huán)境條件本方法對測試環(huán)境無特殊要求，符合實驗室日常環(huán)境控制條件即可。即滿足儀器室溫濕度要求即可，即溫度要求：10℃?35℃；濕度要求：W80%。本次方法驗證檢測日期為2018年11月11~11日，實驗室環(huán)境記錄見附件7。儀器室環(huán)境配備了空調(diào)和溫濕度計，根據(jù)不同時間對儀器室環(huán)境溫濕度測試，溫度滿足10℃?35℃要求，濕度滿足W80%要求，符合環(huán)境條件滿足設(shè)備及檢測工作環(huán)境要求。八、樣品采集樣品采集參照HJ/T91和HJ/T164的相關(guān)規(guī)定采集，樣品保存參照HJ493的規(guī)定進行。表1青松河采樣日期采樣時間采樣點位樣品編號檢測項目2018.9.2408:30汞、砷、硒、秘、銻13:30汞、砷、硒、秘、銻14:30汞、砷、硒、秘、銻

九、標(biāo)準(zhǔn)曲線及樣品測定數(shù)據(jù)表.調(diào)整儀器的條件，以鹽酸為載流，硼氫化鉀溶液為還原劑，濃度由低到高依次測定各個元素的熒光強度，以質(zhì)量濃度為橫坐標(biāo)，繪制標(biāo)準(zhǔn)曲線。數(shù)據(jù)如下表1不同人員汞標(biāo)準(zhǔn)曲線數(shù)據(jù)表元素/人員項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7水/jack濃度ug/L0.000.100.200.400.600.801.00熒光值0.00191.40456.78817.761254.511641.392031.39曲線方程：I=2034.9*C+12.1元素項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7汞/TOM濃度ug/L0.000.100.200.400.600.801.00熒光值0.00151.52388.78688.311025.831325.501649.70曲線方程：I=1645.9*C+18.2表2不同人員碑標(biāo)準(zhǔn)曲線數(shù)據(jù)表元素/人員項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7砷/jack濃度ug/L0.001.002.004.006.008.0010.00熒光值0.00206.69358.68696.451041.141378.561740.44曲線方程：I=171.8*C+14.0元素項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7砷/TOM濃度ug/L0.001.002.004.006.008.0010.00熒光值0.00222.65394.86764.061139.111486.801912.68曲線方程：I=187.6*C+14.8表3不同人員硒標(biāo)準(zhǔn)曲線數(shù)據(jù)表元素/人員項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液75

硒/jack濃度ug/L0.001.002.004.006.008.0010.00熒光值0.00129.01262.96532.18785.781044.401326.41曲線方程：I=131.9*C-1.37元素項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7硒/TOM濃度ug/L0.001.002.004.006.008.0010.00熒光值0.00123.68269.22550.48814.291128.581418.69曲線方程：I=142.2*C-14.6表4不同人員鉍標(biāo)準(zhǔn)曲線數(shù)據(jù)表兀素/人員項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7鉍/jack濃度ug/L0.001.002.004.006.008.0010.00熒光值0.00191.44300.68636.72986.741295.771667.29曲線方程：I164.9*C-4.94元素項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7鉍/TOM濃度ug/L0.001.002.004.006.008.0010.00熒光值0.00371.70634.061195.311815.532446.073138.49曲線方程：I=307.6*C+9.49表5不同人員銻標(biāo)準(zhǔn)曲線數(shù)據(jù)表兀素/人員項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7銻/jack濃度ug/L0.001.002.004.006.008.0010.00熒光值0.0092.27188.03408.85645.50884.931129.22曲線方程：I=113.7*C-25.1元素項目標(biāo)液1標(biāo)液2標(biāo)液3標(biāo)液4標(biāo)液5標(biāo)液6標(biāo)液7

銻/TOM濃度ug/L0.001.002.004.006.008.0010.00熒光值0.00187.35351.52728.391100.261515.201880.75曲線方程：I=188.9*C-13.0.樣品的測定根據(jù)HJ694-2014中9.3處理樣品，并同步測定空白樣品，結(jié)果如下檢測點位檢測人員jackTOMjackTOM樣品編號1112汞NDNDNDND碑NDNDNDND硒NDNDNDND鉍NDNDNDND銻NDNDNDND十、檢出限根據(jù)多次對實驗室空白進行重復(fù)性測定來計算方法檢出限和測定下限，測定結(jié)果見下表，其中檢出限計算公式如下MDLMDL=t(n-1,0.99)本次空白測定平行測定次數(shù)為8次，t值為2.998。表6汞方法檢出限、測定下限數(shù)據(jù)表測定結(jié)果12345678熒光值49.4240.8258.0558.5713.6536.0130.7834.45空白測定結(jié)果（ug/L）0.0420.0340.050.0510.0250.030.0250.029平均值?。╱g/L）0.03575標(biāo)準(zhǔn)偏差S0.011t值2.998檢出限（ug/L）0.032測定下.限（ug/L）0.128

表7砷方法檢出限、測定下限數(shù)據(jù)表測定結(jié)果12345678熒光值8.3910.7611.419.428.527.938.158.87空白測定結(jié)果（ug/L）0.2880.3010.3050.2940.2890.2860.2870.291平均值元（ug/L）0.293標(biāo)準(zhǔn)偏差S0.0069t值2.998檢出限（ug/L）0.021測定下.限（ug/L）0.084表8硒方法檢出限、測定下限數(shù)據(jù)表測定結(jié)果12345678熒光值1.10.527.317.098.2611.248.236.15空白測定結(jié)果（ug/L）0.0320.0290.0640.0630.0690.0840.0690.058平均值元（ug/L）0.058標(biāo)準(zhǔn)偏差S0.020t值2.998檢出限（ug/L）0.061測定下.限（ug/L）0.244表9秘方法檢出限、測定下限數(shù)據(jù)表測定結(jié)果12345678熒光值2.694.3713.836.778.18.349.026.63空白測定結(jié)果（ug/L）0.0020.0070.0370.0150.0190.020.0220.014平均值元（ug/L）0.017標(biāo)準(zhǔn)偏差S0.010t值2.998檢出限（ug/L）0.030測定下.限（ug/L）0.12表10銻方法檢出限、測定下限數(shù)據(jù)表測定結(jié)果12345678熒光值5.148.439.794.318.0511.445.398.38空白測定結(jié)果（ug/L）0.1450.1100.0960.1450.1140.0790.1420.111平均值元（ug/L）0.118標(biāo)準(zhǔn)偏差S0.0244t值2.998檢出限（ug/L）0.0738測定下.限（ug/L）0.292十一、精密度兩名檢測人員按分析步驟對3個不同濃度的汞碑硒秘銻樣品進行6次測量，考察其精密度，結(jié)果如下表計算公式：標(biāo)準(zhǔn)偏差（s）=■,；］（一K）,n-1ii i=1相對標(biāo)準(zhǔn)偏差Ss。,％”上X100x表11汞樣品精密度情況一覽表/jackTOM測定結(jié)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標(biāo)準(zhǔn)偏差S0.0190.0160.0140.0040.0130.021相對標(biāo)準(zhǔn)偏差（％）9.543.971.761.922.952.50表12砷樣品精密度情況一覽表/jackTOM測定結(jié)果（ug/L）12.283.877.882.154.347.8122.233.737.862.113.977.7932.163.707.842.124.177.829

42.163.747.972.144.277.7652.103.597.882.114.447.9562.093.667.982.124.327.78平均值?。╱g/L）2.173.727.902.134.257.82標(biāo)準(zhǔn)偏差S（ug/L）0.0740.0950.0590.0160.1640.068相對標(biāo)準(zhǔn)偏差（％）3.402.550.740.773.850.87表13硒樣品精密度情況一覽表jackTOM測定結(jié)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標(biāo)準(zhǔn)偏差S（ug/L）0.100.040.290.030.060.12相對標(biāo)準(zhǔn)偏差（％）4.631.053.721.741.531.55表14秘樣品精密度情況一覽表/jackTOM2ug/L4ug/L8ug/L2ug/L4ug/L8ug/L測定結(jié)果（ug/L）11.983.937.792.074.208.1421.933.947.782.024.217.8132.003.937.912.044.188.2242.003.987.821.944.057.9210

51.983.897.822.024.037.8161.973.927.861.984.017.82平均值x(ug/L)1.983.937.832.014.117.95標(biāo)準(zhǔn)偏差S(ug/L)0.030.030.050.050.090.18相對標(biāo)準(zhǔn)偏差(％)1.270.800.622.282.252.29表15銻樣品精密度情況一覽表/jackTOM測定結(jié)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標(biāo)準(zhǔn)偏差S(ug/L)0.020.050.090.040.080.07相對標(biāo)準(zhǔn)偏差(％)1.251.361.042.172.010.88十二、準(zhǔn)確度兩名檢測人員對有證標(biāo)準(zhǔn)物測量，考察方法的準(zhǔn)確度，結(jié)果見下表計算公式：相對誤差(3,%)=匚Lx100L表16汞準(zhǔn)確度情況一覽表11

測定結(jié)果(ug/L)14.3415.84.7416.624.1415.84.4416.834.315.24.7217.444.2216.64.0615.5平均值亍(ug/L)4.2515.94.4916.6有證標(biāo)準(zhǔn)物質(zhì)濃度4.57±0.5716.0±0.94.57±0.5716.0±0.9相對誤差(％)-7.00-0.31-1.753.59表17神準(zhǔn)確度情況一覽表jackTOM測定結(jié)果(ug/L)131.271.332.170.5232.172.033.372.3331.672.633.371.3431.372.532.671.9平均值元(ug/L)31.572.132.871.5有證標(biāo)準(zhǔn)物質(zhì)濃度32.5±1.970.2±3.532.5±1.970.2±3.5相對誤差(％)-2.952.710.971.85表18硒準(zhǔn)確度情況一覽表人員及標(biāo)物編號jackTOMB1908073B1908081B1908073B1908081測定結(jié)果(ug/L)7.7917.428.0616.4016.407.4317.667.3717.9117.917.5317.938.1017.8917.897.2717.637.8518.3718.37平均值元(ug/L)7.5017.667.8517.64有證標(biāo)準(zhǔn)物質(zhì)濃度7.87±0.6617.5±1.17.87±0.6617.5±1.112

相對誤差（％）-4.640.92-0.320.81表19鉍準(zhǔn)確度情況一覽表“、人員及標(biāo)物編號jackTOM測定結(jié)果（ug/L）151.404.7246.404.72250.204.7650.004.86347.604.8047.104.69452.704.6646.404.70平均值元（ug/L）50.484.7447.484.74有證標(biāo)準(zhǔn)物質(zhì)濃度51.0±4.84.88±0.2351.0±4.84.88±0.23相對誤差（％）-1.03-2.97-6.91-2.82表20銻準(zhǔn)確度情況一覽表人員及標(biāo)物編號jackTOMB1906025B1905152B1906025B1905152測定結(jié)果（ug/L）116.460.32117.400.345217.010.33217.200.341317.080.32517.340.339418.400.33717.000.337平均值元（ug/L）17.240.32917.2360.341有證標(biāo)準(zhǔn)物質(zhì)濃度（ug/L）17.7±1.30.339±0.0217.7±1.30.339±0.02相對誤差（％）-2.63-3.00-2.620.4613由上表可知，質(zhì)控樣的值的波動在誤差允許范圍內(nèi)，實驗取得了較好的準(zhǔn)確度。十三、加標(biāo)回收率對兩個濃度的樣品進行加標(biāo)，進行加標(biāo)回收測試，結(jié)果如下:表21汞加標(biāo)測試數(shù)據(jù)jackTOM樣品1樣品2樣品1樣品2樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度測定結(jié)果（ug/L）10.2030.4450.3950.8050.2120.5560.4560.9320.2020.4080.3780.8540.2090.530.4340.93830.1740.4030.3870.8340.210.5410.4610.95540.1980.4300.410.8300.2030.5160.430.98450.1930.4140.4170.8390.2040.5390.4430.97060.2330.4220.4140.8350.2030.5080.4580.983平均值X（ug/L）0.2010.4200.4000.8330.2070.5320.4470.960加林量〃（ug/L）0.200.400.300.50加標(biāo)回收率（％）109.9108.2108.3102.6表22砷加標(biāo)測試數(shù)據(jù)jackTOM樣品1樣品2樣品1樣品2樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度測定12.33.43.97.52.23.74.37.9結(jié)果22.23.53.77.32.13.84.08.1(ug/32.23.43.77.42.13.84.27.914

L)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平均值元(ug/L)2.23.53.77.32.13.74.38.0加林量日(ug/L)1.504.001.504.00加標(biāo)回收率(％)87.8989.48107.3393.79表23硒加標(biāo)測試數(shù)據(jù)jackTOM樣品1樣品2樣品1樣品2樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度測定結(jié)果(ug/L)12.263.673.857.741.994.003.827.8222.253.713.867.821.973.843.997.8232.223.853.777.681.943.953.848.0542.114.563.867.622.014.033.917.8352.044.603.797.722.033.933.898.1762.054.483.867.712.034.003.887.87平均值元(ug/L)2.154.153.837.721.993.963.897.93加標(biāo)量日(ug/L)2.004.002.004.00加標(biāo)回收率(％)99.6097.1398.15100.97表24秘加標(biāo)測試數(shù)據(jù)jackTOM樣品1樣品2樣品1樣品2樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度樣品1濃度加標(biāo)樣品濃度樣品2加標(biāo)樣品濃度測定結(jié)果(ug/L)11.984.033.937.772.074.014.207.8521.933.993.947.822.023.904.217.6732.003.973.937.962.043.844.187.8842.004.033.987.861.943.904.057.5851.983.953.897.842.023.8