螢石化學(xué)分析方法 第12部分：砷含量的測定 編制說明

本項目是依據(jù)國家標準化管理委員會國標委發(fā)[2023]63號文“關(guān)于下達2023年第四批推薦性國家標準計劃及相關(guān)標準外文版計劃的通知”下達的項目砷含量的測定”。本項目是修訂項目，代替GB/T5195.12-2016,GB/T5195.19-2018。經(jīng)工作組及有關(guān)專家研討后，對標準草案初稿進行了認真的修改，于2025年1會秘書處將標準征求意見稿和編制說明發(fā)送到全國鋼標委冶金非金屬礦產(chǎn)品分主要成員:劉曙、朱志秀、閔紅、徐杰、嚴德天、嚴承琳、王曉遠所做的工作:劉曙任工作組組長，主持全面協(xié)調(diào)工作，負責(zé)對各階段標準的一性、協(xié)調(diào)性、適用性、一致性和規(guī)范性的原則來進年美國地質(zhì)調(diào)查局公布的世界螢石儲量數(shù)據(jù)，2021年底世界螢石總儲量為3.2定了原子熒光光譜法檢測螢石中砷含量，GB/T5195.19-2018《螢石砷含量的測定二乙基二硫代氨基甲酸銀光度法》規(guī)定了二乙基二硫代氨基甲酸銀光度法檢相同，分析方法不同，技術(shù)內(nèi)容整合，便于標原子熒光光譜法測定范圍（質(zhì)量分數(shù)0.00001%～0.010%；二乙基二硫代原子熒光光譜法：試料用硝酸、高氯酸溶解，在稀鹽酸介質(zhì)中，加入硫脲-GB/T5195.19—2018《螢石砷含量的測定二乙基二硫代氨液，用水稀釋至刻度，搖勻，靜置0.5h，用氫化物發(fā)生-原子熒光光譜儀進行測化學(xué)家協(xié)會(AOAC)單實驗室驗證導(dǎo)則規(guī)定，檢出限大小等于樣品空白值加上3表1方法檢出限和定量限濃度(ng/mL)0.035、0.031、0.013、11次檢測結(jié)果0.013、0.010、0.037、0.027、0.011、0.046、0.042、0.047平均值0.0283標準偏差0.0145檢測限0.07定量限0.17同時做加標回收實驗，并且計算每個樣品檢測結(jié)果的相對標準偏差（表2結(jié)表2方法精密度和準確度樣品加標量（%）測得總量（%）回收率（%）A0.00001053.60.000050.000058495.7B0.0001664.50.00020.000372103.7C0.0003580.00040.00074496.5D0.001690.00200.00375103.1E0.007645.00.00300.010585.0采用二乙基二硫代氨基甲酸銀光度法、原子熒光光譜法分別測定螢石D、E算值小于F臨界值（表3說明兩種方法測定表3二乙基二硫代氨基甲酸銀光度法與原檢測項目樣品D砷含量（%）0.00163、0.00162、0.00164、0.00170、0.001700.00160、0.00162、0.00165、0.00165、0.00162樣品E砷含量（%）0.00720、0.00763、0.00714、0.00728、0.007410.00673、0.00728、0.00718、0.00695、0.00727表4二乙基二硫代氨基甲酸銀光度法與原子熒光光譜法顯著樣品平均含量（%）FF0.1(4,4)tt0.025顯著性差異判斷樣品D原子熒光光譜法二乙基二硫代氨基甲酸銀光度法原子熒光光譜法0.001660.001630.007456.3882.306否樣品E二乙基二硫代氨基甲酸銀光度法0.007086.3882.002.306否果的可靠性。參與協(xié)同試驗驗證的儀器型號有北京吉天AFS-930、AFS-8220、10個協(xié)同實驗室均采用上述試驗方法一檢測5個水平試樣中砷含量，每一10個協(xié)同實驗室的檢驗原始數(shù)據(jù)見表5，單位為表5原始數(shù)據(jù)：螢石中砷含量實驗室i水平j(luò)1450.00000910.0001470.0003720.001410.0079110.00000800.0001730.0003830.001440.007820.00000880.0001480.0003710.001450.007700.00000900.0001690.0003480.001730.0076020.00002200.0001680.0003980.001630.008010.00001800.0001650.0004100.001760.007500.00001710.0001740.0003120.001560.0070930.00001510.0001700.0003420.001490.006590.00001790.0001750.0003320.000160.006930.00001000.0001900.0004060.001730.0076340.00001400.0001560.0003680.001590.007830.00001300.0001740.0003790.001690.007790.00001000.0001980.0004210.001740.0076350.00001100.0001960.0004300.001750.007860.00001000.0001900.0004120.001680.007740.00001000.0001610.0003500.001680.0070960.00001100.0001650.0003480.001680.007110.00001000.0001640.0003510.001690.007110.00000900.0001750.0003740.001800.0081370.00000900.0001780.0003790.001860.008370.00001000.0001720.0003690.001860.008010.00000990.0001960.0003860.001970.0077680.00000960.0001980.0004010.001990.007720.00001090.0001890.0003880.001970.008270.00001100.0001680.0003560.001680.0076590.00001100.0001630.0003580.001710.007660.00001000.0001640.0003600.001690.007640.00000990.0001730.0003510.001710.007740.00000950.0001700.0003610.001700.008130.00001050.0001880.0003570.001690.00764表6試樣中As含量的單元平均值實驗室i（nij=3）水平j(luò)1234510.00000860.0001560.0003750.001430.0078120.00001630.0001670.0003850.001710.0077030.00001670.0001730.0003290.001550.0068740.00001230.0001730.0003840.001670.0077550.00001030.0001950.0004210.001720.0077560.00001030.0001630.0003500.001680.0071170.00000930.0001750.0003740.001840.0081780.00001010.0001940.0003920.001980.0079190.00001070.0001650.0003580.001690.007650.00001000.0001770.0003560.001700.00784表7試樣中砷含量的標準方差實驗室i水平j(luò)1234510.000000600.000014730.000006660.000020980.0001059320.000006660.000002080.000032880.000069220.0002727030.000001440.000002650.000015280.000062270.0002547240.000002080.000017010.000019550.000072810.0001020550.000000580.000004160.000009000.000040290.0001130460.000000580.000002080.000001530.000004930.0000141570.000000580.000003000.000005000.000036390.0001827680.000000710.000004730.000008140.000009290.0003063990.000000580.000002650.000002000.000011790.000011020.000000500.000009640.000005030.000010000.00025891分別見公式（1）和公式（2計算結(jié)果列表8。分別將一致性h統(tǒng)計量和k統(tǒng)ij為曼德爾統(tǒng)計量h；pj為j水平下的實驗室數(shù)；yj為j水平下的總平均值。ij為曼德爾統(tǒng)計量k；sij為單元標準偏差。表8曼德爾統(tǒng)計量h值和k值檢驗實驗室i水平j(luò)123451-1.00800.2607-1.41601.87590.11280.4774-1.81780.52300.40480.552021.72132.8870-0.50930.26510.50182.35770.05481.72520.12311.421031.85110.6253-0.05600.3369-1.70231.0952-1.00481.5520-2.04421.327340.30470.9026-0.02932.16610.46291.4019-0.17811.81470.24270.53185-0.40360.25031.67730.53021.88900.64530.17131.00410.23150.58906-0.40360.2503-0.82930.2651-0.88550.1095-0.10500.1230-1.43240.07387-0.75780.25030.10400.38200.06090.35850.98650.90691.34500.95238-0.48510.30571.65060.60180.74810.58391.90680.23160.67001.59659-0.28560.2503-0.69600.3369-0.56140.1434-0.03430.2939-0.00940.0574-0.53350.21820.10400.7953-0.62620.36090.02060.24920.46891.3491圖2螢石中砷含量：按實驗室進行分組的曼德爾統(tǒng)計量h圖3螢石中砷含量：按實驗室進行分組的曼德爾統(tǒng)計量kj為一單元的科克倫檢驗統(tǒng)計量；Sij為單元標準偏差；Smax為同一水平中單表9單元方差的科克倫檢驗Smax所在實驗室iCj樣品A樣品B樣品C樣品E242480.8335(10)**0.4692(10)*0.5559(10)** 0.2994(10) 0.2549(10)注：歧離值以單星號*標注，離群值以雙星號**標注，括號內(nèi)表示實驗室數(shù)目。均為正常值。（4）（5）均值最小值的格拉布斯統(tǒng)計量；yij,max為j水平下單元平均值最大值；yij,min為jSS表10單元平均值的格拉布斯檢驗Gj,min所在實驗室i單個低值Gj,minGj,max所屬實驗室iCj樣品A11.0080（10）31.8511（10）樣品B11.4160（10）81.6773（10）樣品C31.5771（10）51.8627（10）樣品D11.8178（10）8樣品E32.0442（10）7注：括號內(nèi)表示實驗室數(shù)目。根據(jù)公式（6）~（11）計算總平均值j、重復(fù)性方差Srj2、實驗室間方差 SRj2=Srj2+SLj2（9）R=2.8SR表11總體平均值、重復(fù)性和再現(xiàn)性（%）水平j(luò)實驗室數(shù)jSrSRrR10.000011470.000002310.000002550.000006460.0