鋅精礦分析方法 編制說明（預(yù)審稿）主編單位2024年10月第頁任務(wù)根據(jù)《關(guān)于征集2023年度全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會年會論證的標(biāo)準(zhǔn)項(xiàng)目計(jì)劃的通知》（有色標(biāo)委[2023]79號）的要求。2023年11月，全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會在昆明市召開了《鋅精礦化學(xué)分析方法第15部分：汞量的測定》國家標(biāo)準(zhǔn)任務(wù)落實(shí)會會議，根據(jù)任務(wù)安排，對GB/T8151—2005鋅精礦化學(xué)分析方法中第15部分新增冷原子吸收光譜法測汞量,整合第23部分固體直接進(jìn)樣法。由葫蘆島鋅業(yè)股份公司負(fù)責(zé)主起草。銅陵有色金屬集團(tuán)控股有限公司、深圳市中金嶺南有色金屬股份有限公司韶關(guān)冶煉廠、江西銅業(yè)鉛鋅金屬有限公司、昆明冶金研究院有限公司、中國有色桂林礦產(chǎn)地質(zhì)研究院有限公司、金隆銅業(yè)有限公司參與一驗(yàn)工作，防城海關(guān)綜合技術(shù)服務(wù)中心、防城港市東途礦產(chǎn)檢測有限公司、陽新弘盛銅業(yè)有限公司、紫金礦業(yè)集團(tuán)股份有限公司、北礦檢測技術(shù)股份有限公司、長沙礦冶院檢測技術(shù)有限責(zé)任公司、株洲冶煉集團(tuán)股份有限公司、山西北方銅業(yè)有限公司、五礦銅業(yè)（湖南）有限公司參與二驗(yàn)工作。葫蘆島鋅業(yè)股份有限公司、防城海關(guān)綜合技術(shù)服務(wù)中心、銅陵有色金屬集團(tuán)控股有限公司，深圳市中金嶺南有色金屬股份有限公司韶關(guān)冶煉廠、中國檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司、蘭州海關(guān)技術(shù)中心、江西銅業(yè)鉛鋅金屬有限公司、廣西壯族自治區(qū)冶金產(chǎn)品質(zhì)量檢驗(yàn)站、昆明冶金研究院有限公司、鲅魚圈海關(guān)綜合技術(shù)服務(wù)中心、中國有色桂林礦產(chǎn)地質(zhì)研究院有限公司、中華人民共和國連云港海關(guān)、金隆銅業(yè)有限公司、山東省地質(zhì)礦產(chǎn)勘查開發(fā)局第六地質(zhì)大隊(duì)、防城港市東途礦產(chǎn)檢測有限公司、廣西壯族自治區(qū)分析測試研究中心、防城海關(guān)綜合技術(shù)服務(wù)中心、陽新弘盛銅業(yè)有限公司、紫金礦業(yè)集團(tuán)股份有限公司、北礦檢測技術(shù)股份有限公司、長沙礦冶院檢測技術(shù)有限責(zé)任公司、株洲冶煉集團(tuán)股份有限公司、山西北方銅業(yè)有限公司、五礦銅業(yè)（湖南）有限公司。銅陵有色金屬集團(tuán)有限公司、江西銅業(yè)鉛鋅金屬有限公司、昆明冶金研究院有限公司、中國有色桂林礦產(chǎn)地質(zhì)研究院陽新弘盛銅業(yè)有限公司、紫金礦業(yè)集團(tuán)股份有限公司、北礦檢測技術(shù)股份有限公司、長沙礦冶院檢測技術(shù)有限責(zé)任公司、株洲冶煉集團(tuán)股份有限公司、山西北方銅業(yè)有限公司、五礦銅業(yè)（湖南）有限公司防城海關(guān)綜合技術(shù)服務(wù)中心，中國檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司、蘭州海關(guān)技術(shù)中心、廣西壯族自治區(qū)冶金產(chǎn)品質(zhì)量檢驗(yàn)站、鲅魚圈海關(guān)綜合技術(shù)服務(wù)中心、中華人民共和國連云港海關(guān)、山東省地質(zhì)礦產(chǎn)勘查開發(fā)局第六地質(zhì)大隊(duì)、廣西壯族自治區(qū)分析測試研究中心，為其他驗(yàn)證單位。本標(biāo)準(zhǔn)主要起草人及工作職責(zé)見表1。表1本標(biāo)準(zhǔn)主要起草人及工作職責(zé)序號單位名稱人員分工1葫蘆島鋅業(yè)股份有限公司方法1、方法2起草單位2深圳市中金嶺南有色金屬股份有限公司韶關(guān)冶煉廠一驗(yàn)單位3銅陵有色金屬集團(tuán)控股有限公司一驗(yàn)單位4江西銅業(yè)鉛鋅金屬有限公司一驗(yàn)單位5昆明冶金研究院有限公司一驗(yàn)單位6中國有色桂林礦產(chǎn)地質(zhì)研究院有限公司一驗(yàn)單位7金隆銅業(yè)有限公司一驗(yàn)單位8防城港市東途礦產(chǎn)檢測有限公司二驗(yàn)單位9防城海關(guān)綜合技術(shù)服務(wù)中心二驗(yàn)單位10陽新弘盛銅業(yè)有限公司二驗(yàn)單位11紫金礦業(yè)集團(tuán)股份有限公司二驗(yàn)單位12北礦檢測技術(shù)股份有限公司二驗(yàn)單位13長沙礦冶院檢測技術(shù)有限責(zé)任公司二驗(yàn)單位14株洲冶煉集團(tuán)股份有限公司二驗(yàn)單位15山西北方銅業(yè)有限公司二驗(yàn)單位16五礦銅業(yè)（湖南）有限公司二驗(yàn)單位17防城海關(guān)綜合技術(shù)服務(wù)中心方法3起草單位18中國檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司驗(yàn)證單位19蘭州海關(guān)技術(shù)中心驗(yàn)證單位20廣西壯族自治區(qū)冶金產(chǎn)品質(zhì)量檢驗(yàn)站驗(yàn)證單位21鲅魚圈海關(guān)綜合技術(shù)服務(wù)中心驗(yàn)證單位22中華人民共和國連云港海關(guān)驗(yàn)證單位23山東省地質(zhì)礦產(chǎn)勘查開發(fā)局第六地質(zhì)大隊(duì)驗(yàn)證單位24廣西壯族自治區(qū)分析測試研究中心驗(yàn)證單位1.3主要工作過程(1)根據(jù)工業(yè)和信息化部標(biāo)準(zhǔn)計(jì)劃項(xiàng)目的安排要求，(2)2023年11月，確定標(biāo)準(zhǔn)制訂方案和研制計(jì)劃進(jìn)度計(jì)劃。(3)2024年1月，，(4)年2月～2024年6月，開展方法試驗(yàn)工作，先后完成了樣品溶解方法試驗(yàn)、條件選擇試驗(yàn)、共存元素干擾試驗(yàn)、加標(biāo)回收試驗(yàn)和精密度試驗(yàn)等研究，(5)年8月，陸續(xù)收到各驗(yàn)證單位的試驗(yàn)報(bào)告及反饋意見，根據(jù)驗(yàn)證單位的反饋準(zhǔn)征求意見稿進(jìn)行意見征詢。進(jìn)行數(shù)理統(tǒng)計(jì)分析確定測定方法及測定范圍。采用操作簡便、精密度高、準(zhǔn)確度好、在行業(yè)內(nèi)應(yīng)用普及的分析方法，能很好的滿足行業(yè)對鋅精礦中汞含量的測定要求，提高了本標(biāo)準(zhǔn)的可操作性和適用性。試料量、試液體積、分取體積、測定體積及補(bǔ)加鹽酸量無需調(diào)整，只在基礎(chǔ)上做了儀器條件、精密度試驗(yàn)。樣品溶解方法參照本方法一原子熒光光譜法的溶樣方式將試料置于150mL燒杯中，加入10mL鹽酸，,80°C?100°C水浴加熱數(shù)分鐘以除去硫化氫，再加入5mL硝酸繼續(xù)溶解完全，取下冷卻后，移入100mL容量瓶中，用水稀釋至刻度，混勻。測定酸度的影響本實(shí)驗(yàn)采取硫酸介質(zhì)測定，試驗(yàn)考察了介質(zhì)硫酸濃度對測定結(jié)果的影響。選取3#樣品和0.005μg/mL汞標(biāo)準(zhǔn)溶液，在不同硫酸體積分?jǐn)?shù)下進(jìn)行測定，結(jié)果見表2。表2硫酸加入量樣品或標(biāo)準(zhǔn)溶液1mL硫酸2mL硫酸5mL硫酸3#（吸光度）0.0430.0480.0450.005(μg/mL)Hg（吸光度）0.0460.0500.048試驗(yàn)表明，加入1mL、2mL、5mL硫酸對汞的測定無明顯影響。為考慮測定體積及成本，故選擇加入1mL硫酸作為測定介質(zhì)。高錳酸鉀溶液加入量的選擇本試驗(yàn)采取加入高錳酸鉀作為強(qiáng)氧化劑進(jìn)行測定，試驗(yàn)考察了高錳酸鉀加入量對測定結(jié)果的影響。選取1#樣品和0.005μg/mL汞標(biāo)準(zhǔn)溶液在不同高錳酸鉀加入量的情況下進(jìn)行測定，結(jié)果見表3。表3高錳酸鉀加入量樣品或標(biāo)準(zhǔn)溶液1mL高錳酸鉀2mL高錳酸鉀5mL高錳酸鉀1#（吸光度）0.0150.0170.0160.005(μg/mL)Hg（吸光度）0.0450.0500.047試驗(yàn)表明，加入1mL、2mL、5mL高錳酸鉀對汞的測定結(jié)果無明顯影響。為考慮測定體積及成本，故選擇加入1mL高錳酸鉀作為氧化劑。3.2.3測試液移取量對測定結(jié)果的影響選取0.001μg/mL汞標(biāo)準(zhǔn)溶液和4#樣品進(jìn)行試驗(yàn)在移取不同溶液量的條件下進(jìn)行測試，結(jié)果見表4。表4測試液移取量樣品或標(biāo)準(zhǔn)溶液1mL2mL5mL10mL0.001μg/mL（吸光度）0.0020.0050.0160.0424#（吸光度）0.0210.0480.0880.201試驗(yàn)表明，測定時，溶液移取量以5.0mL為宜。對低含量的樣品，應(yīng)加大溶液的移取量，高含量的樣品應(yīng)該減小移取量，綜合考慮，溶液移取量為5.0mL時最為合適。3.2.4還原劑二氯化錫加入量對測定結(jié)果的影響選取0.005μg/mL汞標(biāo)準(zhǔn)溶液和0.020μg/mL汞標(biāo)準(zhǔn)溶液在加入不同量還原劑的條件下進(jìn)行測試，結(jié)果見表5。表5二氯化錫加入量標(biāo)準(zhǔn)溶液1mL2mL5mL0.005μg/mL（吸光度）0.0470.0480.0490.020μg/mL（吸光度）0.1860.1880.184試驗(yàn)表明，加入二氯化錫1～5mL均能滿足要求，為保證還原劑用量和還原效果，以5mL為宜。3.2.5測定時間對結(jié)果的影響標(biāo)準(zhǔn)和樣品處理后應(yīng)立即測定，因測定隨著時間的延長吸光度值呈下降趨勢，標(biāo)準(zhǔn)系列下降較樣品更明顯。結(jié)果見表6。表6標(biāo)準(zhǔn)（樣品）測定時間0.001μg/mL(吸光度）0.005μg/mL(吸光度）0.010μg/mL（吸光度）0.015μg/mL（吸光度）0.020μg/mL（吸光度）3#(吸光度)立即測定0.0090.0460.0900.1360.1820.0550.5h0.0040.0380.0780.1220.1730.0471.0h0.0010.0230.0590.0960.1210.043試驗(yàn)表明，隨著時間的延長，吸光度下降，為保證試驗(yàn)準(zhǔn)確性，需要立即測定。按樣品中共存元素的最大含量（Zn50mg、Cu2mg、Pb3mg、Fe20mg、As1mg、SiO25mg、Cd1mg、Co1mg、Sb1mg），分別向汞標(biāo)準(zhǔn)液0.005μg/mL，0.015μg/mL按下表加入共存元素，加入1mL硫酸，1mL高錳酸鉀，用水稀釋至刻度，混勻。結(jié)果見表7。分別對5#～9#等5個樣品獨(dú)立進(jìn)行11次測定，精密度試驗(yàn)結(jié)果見表8（其他參與起草單位的精密度數(shù)據(jù)見“十三、附件-試驗(yàn)數(shù)據(jù)處理及精密度計(jì)算”）。表8精密度試驗(yàn)結(jié)果(%)試樣編號5#6#7#8#9#10.000550.00260.0140.0480.1620.000540.00250.0140.0480.1630.000500.00280.0150.0520.1740.000480.00270.0130.0500.1750.000510.00270.0150.0510.1860.000520.00260.0130.0530.1570.000510.00240.0130.0540.1680.000490.00250.0150.0490.1790.000500.00260.0130.0500.18100.000540.00270.0160.0510.16110.000550.00250.0130.0520.15平均值0.000520.00260.0140.0510.16SD0.0000250.000120.00110.00200.010RSD4.814.627.853.926.25試驗(yàn)結(jié)論：精密度試驗(yàn)的RSD在3.92%～7.85%之間，方法重復(fù)性好，精密度較高。分別對1#～4#等4個樣品獨(dú)立進(jìn)行11次測定，精密度試驗(yàn)結(jié)果見表9（其他參與起草單位的精密度數(shù)據(jù)見“十三、附件-試驗(yàn)數(shù)據(jù)處理及精密度計(jì)算”）。表9精密度試驗(yàn)結(jié)果(%)試樣編號1#2#3#4#10.000120.00110.00280.05220.000120.00100.00300.05330.000100.00120.00270.05040.000100.00100.00300.05050.000100.00100.00260.05460.000110.00110.00270.05070.000120.00120.00270.05480.000100.00100.00260.04890.000100.00100.00250.049100.000100.00100.00270.052110.000110.00120.00290.050平均值0.000110.00110.00270.051SD0.00000900.0000900.000160.0020RSD8.188.185.933.92試驗(yàn)結(jié)論：精密度試驗(yàn)的RSD在3.92%～8.18%之間，方法重復(fù)性好，精密度較高。按樣品中含汞量的0.5倍、1倍加入汞，分別對試樣6#和8#進(jìn)行加標(biāo)回收試驗(yàn)，試驗(yàn)結(jié)果見表10。表10加標(biāo)回收試驗(yàn)結(jié)果試樣編號稱樣量/g試樣含汞量/μg加入汞量/μg測得汞量/μg回收率/%6#0.10002.600513.553295.27%0.10002.582524.6354102.65%8#0.100050.96842577.0252104.23%0.100051.263250101.254899.98%試驗(yàn)結(jié)論：加標(biāo)回收率在95.27%～104.23%之間，測定結(jié)果準(zhǔn)確。按樣品中含汞量的0.5倍、1倍加入汞，分別對試樣6#和8#進(jìn)行加標(biāo)回收試驗(yàn)，試驗(yàn)結(jié)果見表11。樣品編號試樣質(zhì)量/g試樣汞含量(μg）加入汞量（μg）測得汞量（μg）回收率%2#0.10001.05980.51.5764103.320.10001.032612.032599.993#0.10002.608724.6320101.170.10002.663035.7482102.84表11加標(biāo)回收試驗(yàn)結(jié)果 試驗(yàn)結(jié)論：加標(biāo)回收率在99.99%～103.32%之間，測定結(jié)果準(zhǔn)確。根據(jù)《GB/T6379.2-2004確定標(biāo)準(zhǔn)測量方法重復(fù)性和再現(xiàn)性的基本方法》規(guī)定，對16家起草單位提供的精密度試驗(yàn)數(shù)據(jù)進(jìn)行了數(shù)理統(tǒng)計(jì)分析，詳情見本文件“十三、附件-試驗(yàn)數(shù)據(jù)處理及精密度計(jì)算”。重復(fù)性限和再現(xiàn)性限計(jì)算結(jié)果分別見表13～表16。在重復(fù)性條件下獲得的兩次獨(dú)立測試結(jié)果的測試值，在表13-14給出的平均值范圍內(nèi)，這兩個測試結(jié)果的絕對差值不超過重復(fù)性限（r），超過重復(fù)性限（r）的情況不超過5%。重復(fù)性限（r）按表13-14數(shù)據(jù)采用線性內(nèi)插法或外延法求得。表13方法1重復(fù)性限（r）ωHg/%0.000510.00250.0150.0530.16r/%0.000070.00030.0020.0030.02表14方法2重復(fù)性限（r）ωHg/%0.000120.00100.00260.052r/%0.000020.00020.00020.004在再現(xiàn)性條件下獲得的兩次獨(dú)立測試結(jié)果的測試值，在表15-16給出的平均值范圍內(nèi)，兩個測試結(jié)果的絕對差值不超過再現(xiàn)性限（R），超過再現(xiàn)性限（R）的情況不超過5%。再現(xiàn)性限（R）按表15-16數(shù)據(jù)采用線性內(nèi)插法或外延法求得。表15方法1再現(xiàn)性限（R）ωHg/%0.000510.00250.0150.0530.16R/%0.000150.00050.0040.0100.05表16方法2再現(xiàn)性限（R）ωHg/%0.000120.00100.00260.052R/%0.000060.00040.00070.010本標(biāo)準(zhǔn)不涉及專利問題。常用的汞的測定方法有：原子熒光光譜法、冷原子吸收光譜法和固體進(jìn)樣直接法等。冷原子吸收光譜法0.0001%～0.050%冷原子吸收光譜法普遍應(yīng)用于低含量汞的測定，檢測方法公認(rèn)度高，冷原子吸收光譜儀是實(shí)驗(yàn)室普遍使用的檢測設(shè)備。經(jīng)過資料搜索，目前國內(nèi)標(biāo)準(zhǔn)中無冷原子吸收光譜法測定鋅精礦中汞含量的分析標(biāo)準(zhǔn)。本標(biāo)準(zhǔn)是首次制訂，填補(bǔ)了國內(nèi)冷原子吸收光譜法測定鋅精礦中汞含量標(biāo)準(zhǔn)的空白，有一定的前瞻性和創(chuàng)新性。該標(biāo)準(zhǔn)的編寫符合GB/T1.1-2020《標(biāo)準(zhǔn)化工作導(dǎo)則》的編制要求。標(biāo)準(zhǔn)方法成熟，分析數(shù)據(jù)準(zhǔn)確可靠、可行，能夠準(zhǔn)滿足現(xiàn)有的產(chǎn)品標(biāo)準(zhǔn)要求，與其他GB/T8151—202x標(biāo)準(zhǔn)銜接配套，互為補(bǔ)充。該標(biāo)準(zhǔn)技術(shù)先進(jìn)、結(jié)構(gòu)合理、文字簡練、條理清晰、可操作性強(qiáng)，達(dá)到了國內(nèi)先進(jìn)水平。無七、與現(xiàn)行法律、、強(qiáng)制性國家標(biāo)準(zhǔn)及相關(guān)標(biāo)準(zhǔn)協(xié)調(diào)配套情況本標(biāo)準(zhǔn)與有關(guān)的現(xiàn)行法律、法規(guī)和強(qiáng)制性國家標(biāo)準(zhǔn)沒有沖突。本標(biāo)準(zhǔn)與現(xiàn)行標(biāo)準(zhǔn)及制定中的標(biāo)準(zhǔn)無重復(fù)交叉情況。八、重大分歧意見的處理經(jīng)過和依據(jù)本標(biāo)準(zhǔn)規(guī)范了鋅精礦中汞含量的測定，有利于整個行業(yè)分析水平的提升。本標(biāo)準(zhǔn)發(fā)布執(zhí)行后，建議標(biāo)準(zhǔn)主管單位積極向生產(chǎn)廠家及國內(nèi)外用戶進(jìn)行推廣。本標(biāo)準(zhǔn)首次更改了鋅精礦原子熒光光譜法汞含量的測定方法。本標(biāo)準(zhǔn)在制定過程中，調(diào)研了國內(nèi)多家冶煉企業(yè)，標(biāo)準(zhǔn)技術(shù)先進(jìn)，具有充分的可操作性、適用性，完全能夠滿足國內(nèi)外用戶、市場的需求。十一、廢止現(xiàn)行標(biāo)準(zhǔn)的建議建議本標(biāo)準(zhǔn)代替GB/T8151.15--2005《鋅精礦化學(xué)分析方法汞量的測定原子熒光光譜法》。鋅精礦化學(xué)分析方法第15部分：汞含量的測定原子熒光光譜法和冷原子吸收光譜法試驗(yàn)數(shù)據(jù)處理及精密度計(jì)算2024年7月-2024年11月，銅陵有色金屬集團(tuán)有限公司、江西銅業(yè)鉛鋅金屬有限公司、昆明冶金研究院有限公司、中國有色桂林礦產(chǎn)地質(zhì)研究院陽新弘盛銅業(yè)有限公司、紫金礦業(yè)集團(tuán)股份有限公司、北礦檢測技術(shù)股份有限公司、長沙礦冶院檢測技術(shù)有限責(zé)任公司、株洲冶煉集團(tuán)股份有限公司、山西北方銅業(yè)有限公司、五礦銅業(yè)（湖南）有限公司等16家單位共同參與了《鋅精礦化學(xué)分析方法第15部分：汞含量的測定原子熒光光譜法和冷原子吸收光譜法》標(biāo)準(zhǔn)起草試驗(yàn)。各實(shí)驗(yàn)室按照標(biāo)準(zhǔn)草案要求，對編號為1#～9#的9個樣品各進(jìn)行11次獨(dú)立測定。按照《GB/T6379.2-2004確定標(biāo)準(zhǔn)測量方法重復(fù)性和再現(xiàn)性的基本方法》的規(guī)定，對試驗(yàn)數(shù)據(jù)進(jìn)行如下統(tǒng)計(jì)分析。1實(shí)驗(yàn)室編號表SEQ表\*ARABIC1實(shí)驗(yàn)室編號編號實(shí)驗(yàn)室名稱編號實(shí)驗(yàn)室名稱1葫蘆島鋅業(yè)股份有限公司9防城海關(guān)綜合技術(shù)服務(wù)中心2深圳市中金嶺南有色金屬股份有限公司韶關(guān)冶煉廠10陽新弘盛銅業(yè)有限公司3銅陵有色金屬集團(tuán)控股有限公司11紫金礦業(yè)集團(tuán)股份有限公司4江西銅業(yè)鉛鋅金屬有限公司12北礦檢測技術(shù)股份有限公司5昆明冶金研究院有限公司13長沙礦冶院檢測技術(shù)有限責(zé)任公司6中國有色桂林礦產(chǎn)地質(zhì)研究院有限公司14株洲冶煉集團(tuán)股份有限公司7金隆銅業(yè)有限公司15山西北方銅業(yè)有限公司8防城港市東途礦產(chǎn)檢測有限公司16五礦銅業(yè)（湖南）有限公司2試驗(yàn)數(shù)據(jù)及實(shí)驗(yàn)室內(nèi)格拉布斯檢驗(yàn)為防止實(shí)驗(yàn)室內(nèi)變異來自某個異常的測試結(jié)果，對各實(shí)驗(yàn)室內(nèi)每個水平的試驗(yàn)數(shù)據(jù)進(jìn)行Grubbs檢驗(yàn)。各實(shí)驗(yàn)室原始數(shù)據(jù)、單元平均值、單元標(biāo)準(zhǔn)偏差等試驗(yàn)數(shù)據(jù)及格拉布斯檢驗(yàn)結(jié)果按方法1和方法2分別列表，詳見表2-1表2-38，單位為質(zhì)量百分?jǐn)?shù)。經(jīng)Grubbs檢驗(yàn)，實(shí)驗(yàn)室8的6#水平試驗(yàn)結(jié)果0.0029，9#水平試驗(yàn)結(jié)果0.016為歧離值，予以保留；實(shí)驗(yàn)室8的7#水平試驗(yàn)結(jié)果0.016，2#水平試驗(yàn)結(jié)果0.0011、實(shí)驗(yàn)室9的6#水平試驗(yàn)結(jié)果0.0026、實(shí)驗(yàn)室16的2#水平試驗(yàn)結(jié)果0.0013為離群值，作舍棄處理。其余試驗(yàn)結(jié)果無異常。表2-1試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#110.000550.00260.0140.0490.1620.000540.00250.0140.0490.1630.000500.00280.0150.0520.1740.000480.00270.0130.0500.1750.000510.00270.0150.0510.1860.000520.00260.0140.0530.1570.000510.00240.0130.0520.1680.000490.00250.0150.0490.1790.000500.00260.0130.0500.18100.000540.00270.0140.0510.16110.000550.00250.0140.0520.15測定次數(shù)n1111111111平均值0.0005170.002600.01400.05070.165SD2.45E-050.0001180.0007750.001420.0104RSD/%4.744.625.542.806.25Max0.000550.00280.0150.0530.18Min0.000480.00240.0130.0490.15Gmax1.3451.6951.2901.6201.442Gmin1.5081.6951.2901.1971.442G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-2試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#110.000120.00110.00280.05220.000120.00110.00290.05230.000100.00110.00270.05040.000100.00100.00280.05050.000100.00100.00270.05360.000110.00110.00270.05070.000120.00110.00270.05380.000100.00100.00270.05090.000100.00110.00260.050100.000100.00100.00270.052110.000110.00120.00290.050測定次數(shù)n11111111平均值0.0001070.001070.002750.0511SD9.04E-066.47E-059.34E-050.00130RSD/%8.456.053.402.54Max0.000120.00120.00290.053Min0.000100.00100.00260.050Gmax1.4372.0091.6061.535Gmin0.7741.0821.6060.846G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-3試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#210.000420.00210.0130.0440.16220.000430.00210.0130.0450.14030.000530.00230.0140.0440.16740.000490.00230.0130.0450.15850.000500.00210.0140.0420.16060.000500.00240.0140.0400.15370.000440.00230.0150.0470.14480.000480.00230.0140.0500.16690.000510.00220.0130.0430.163100.000520.00210.0150.0440.151110.000450.00230.0140.0450.142測定次數(shù)n1111111111平均值0.0004790.002230.01380.04450.155SD3.81E-050.0001100.0007510.002580.00973RSD/%7.954.935.435.806.26Max0.000530.00240.0150.0500.167Min0.000420.00210.0130.0400.142Gmax1.3401.5451.5982.1321.233Gmin1.5501.1811.0651.7441.336G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-4試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#210.000110.000820.00220.04720.000110.000780.00220.04730.000120.000790.00240.04440.000120.000780.00230.04650.000130.000730.00220.04360.000110.000760.00240.04270.000140.000830.00240.04780.000130.000860.00220.05090.000130.000810.00230.045100.000120.000750.00220.043110.000110.000840.00240.046測定次數(shù)n11111111平均值0.0001210.0007950.002290.0455SD1.04E-054.03E-059.44E-050.00234RSD/%8.605.074.125.41Max0.000140.000860.00240.050Min0.000110.000730.00220.042Gmax1.8191.6111.1651.829Gmin1.0531.6110.9541.423G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-5試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#310.000520.00230.0160.0540.1620.000530.00240.0150.0530.1830.000540.00230.0150.0530.1640.000530.00240.0160.0540.1750.000510.00230.0160.0530.1660.000520.00250.0160.0560.1670.000520.00240.0160.0560.1880.000530.00260.0160.0560.1690.000520.00240.0160.0550.17100.000540.00250.0150.0540.16110.000520.00240.0160.0550.16測定次數(shù)n1111111111平均值0.0005250.002410.01570.05450.165SD9.34E-069.44E-050.0004670.001210.00820RSD/%1.783.922.972.224.96Max0.000540.00260.0160.0560.18Min0.000510.00230.0150.0530.16Gmax1.6062.0130.6421.2401.829Gmin1.6061.1651.4991.2400.610G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-6試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#310.000100.00110.00270.05420.000100.00100.00280.05830.000110.00100.00270.05840.000110.00100.00270.05850.000110.00100.00270.05960.000100.00100.00300.05570.000100.00100.00280.05780.000100.00100.00290.05690.000100.00100.00290.056100.000100.00100.00280.058110.000110.00110.00290.059測定次數(shù)n11111111平均值0.0001040.001020.002810.0571SD5.05E-064.05E-050.0001040.00164RSD/%4.863.973.552.74Max0.000110.00110.00300.059Min0.000100.00100.00270.054Gmax1.1891.9781.8271.159Gmin0.7930.4941.0581.890G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-7試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#410.000530.00200.0130.0470.1220.000500.00200.0130.0450.1330.000520.00200.0120.0450.1240.000520.00210.0120.0460.1350.000520.00210.0120.0460.1260.000530.00200.0130.0450.1270.000530.00210.0130.0460.1280.000510.00200.0130.0470.1290.000510.00210.0130.0450.13100.000520.00200.0130.0460.13110.000520.00200.0120.0460.13測定次數(shù)n1111111111平均值0.0005190.002040.01260.04580.125SD9.44E-065.05E-050.0005050.0007510.00522RSD/%1.822.484.011.644.18Max0.000530.00210.0130.0470.13Min0.000500.00200.0120.0450.12Gmax1.1651.1890.7921.5980.958Gmin2.0130.7931.1881.0650.958G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-8試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#410.000140.00100.00260.05420.000150.00100.00260.05330.000140.00100.00250.05340.000150.00110.00250.05450.000150.00110.00250.05460.000140.00100.00260.05370.000140.00100.00260.05380.000140.00100.00260.05390.000140.00110.00260.053100.000150.00100.00260.054110.000140.00100.00250.054測定次數(shù)n11111111平均值0.0001440.001030.002560.0535SD5.05E-064.67E-055.05E-050.000522RSD/%3.514.531.9730.976Max0.000150.00110.00260.054Min0.000140.00100.00250.053Gmax1.1881.4990.7920.958Gmin0.7920.6421.1880.958G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-9試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#510.000420.00260.0160.0520.1520.000420.00250.0150.0510.1430.000430.00250.0150.0500.1540.000420.00270.0160.0500.1550.000420.00260.0150.0510.1560.000420.00260.0150.0520.1670.000420.00260.0150.0520.1680.000430.00260.0150.0530.1690.000420.00270.0150.0520.14100.000420.00260.0150.0500.14110.000430.00260.0150.0500.14測定次數(shù)n1111111111平均值0.0004230.002600.01520.05120.149SD4.67E-066.32E-050.0004050.001080.00831RSD/%2.032.432.662.115.58Max0.000430.00270.0160.0530.16Min0.000420.00250.0150.0500.14Gmax0.8571.5751.9751.6671.324Gmin1.2851.5750.4941.1111.083G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-SEQ表\*ARABIC10試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#510.000120.00130.00240.05220.000120.00120.00250.05130.000130.00120.00250.05240.000130.00140.00260.05250.000130.00120.00260.05160.000130.00120.00240.05270.000120.00140.00250.05280.000120.00130.00250.05390.000130.00130.00250.052100.000120.00130.00250.053110.000120.00130.00260.053測定次數(shù)n11111111平均值0.0001250.001280.002510.0521SD5.22E-067.51E-057.01E-050.000701RSD/%4.185.872.791.35Max0.000130.00140.00260.053Min0.000120.00120.00240.051Gmax0.9581.5981.2841.284Gmin0.9581.0651.5691.569G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-SEQ表\*ARABIC11試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#610.00130.00240.0140.0500.1420.00120.00250.0150.0510.1530.00120.00250.0160.0520.1440.00120.00260.0150.0520.1650.00140.00270.0140.0530.1560.00130.00240.0160.0520.1570.00130.00260.0150.0510.1680.00140.00250.0140.0520.1590.00130.00260.0150.0530.16100.00120.00240.0160.0520.14110.00130.00250.0150.0510.16測定次數(shù)n1111111111平均值0.001280.002520.01500.05170.151SD7.51E-059.82E-050.0007750.0009050.00831RSD/%5.873.905.171.755.50Max0.00140.00270.0160.0530.16Min0.00120.00240.0140.0500.14Gmax1.5981.8331.2901.4361.083Gmin1.0651.2221.2901.8781.324G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-SEQ表\*ARABIC12試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#610.000120.00110.00230.04920.000140.00100.00240.05130.000120.00120.00220.05040.000130.00110.00230.04950.000140.00120.00240.05160.000130.00110.00230.04970.000120.00120.00230.05080.000130.00130.00240.05190.000140.00120.00220.050100.000140.00110.00230.049110.000130.00120.00240.048測定次數(shù)n11111111平均值0.0001310.001150.002320.0497SD8.31E-068.20E-057.51E-050.00101RSD/%6.347.133.242.03Max0.000140.00130.00240.051Min0.000120.00100.00220.048Gmax1.0831.8291.0651.287Gmin1.3241.8291.5981.683G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-SEQ表\*ARABIC13試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#710.000520.00240.0150.0520.1820.000470.00250.0150.0530.1630.000580.00250.0150.0530.1640.000530.00270.0160.0550.1750.000550.00280.0160.0540.1760.000550.00270.0150.0530.1570.000540.00240.0160.0550.1680.000560.00270.0170.0520.1890.000530.00230.0170.0540.16100.000500.00240.0160.0530.16110.000610.00270.0160.0530.18測定次數(shù)n1111111111平均值0.0005400.002550.01580.05340.166SD3.77E-050.0001690.0007510.001030.0103RSD/%6.986.634.751.936.20Max0.000610.00280.0170.0550.18Min0.000470.00230.0150.0520.15Gmax1.8571.4791.5981.5531.359Gmin1.8571.4791.0651.3591.553G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-SEQ表\*ARABIC14試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#710.00009580.0008780.002520.0509620.00009620.0009100.002540.0528430.00008740.0008900.002580.0479140.00008710.0009430.002520.0501550.00007970.0009080.002630.0527460.00008830.0009190.002580.0545470.00010320.0008830.002600.0554180.00009120.0008830.002590.0485490.00009380.0008600.002580.05312100.00009720.0009080.002580.05071110.00009780.0008720.002580.05480測定次數(shù)n11111111平均值9.25E-050.0008960.002580.0520SD6.55E-062.41E-053.35E-050.00252RSD/%7.082.690.914.85Max0.00010320.0009430.002630.05541Min0.00007970.0008600.002520.04794Gmax1.6341.9501.4931.353Gmin1.9541.4941.7911.611G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-SEQ表\*ARABIC15試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#810.000570.00240.0150.0540.1520.000540.00260.0150.0540.1530.000550.00240.0150.0530.1540.000550.00240.0150.0530.1550.000550.00250.0150.0520.16(*)60.000570.00250.0150.0540.1570.000520.00240.0150.0540.1580.000540.00260.0150.0540.1590.000530.00250.0150.0540.15100.000590.00280.0150.0530.16(*)110.000520.0029(*)0.016(**)0.0530.15測定次數(shù)n1111111111平均值0.0005480.002510.01510.05350.150SD2.18E-050.0001690.0003020.0006880.00405RSD/%3.986.732.011.292.70Max0.000590.00290.0160.0540.16Min0.000520.00240.0150.0520.15Gmax1.9272.3082.9800.7272.469Gmin1.2840.6510.3312.1800.000G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常0.0029為歧離值(保留）0.016為離群值(舍棄)無異常0.16為歧離值(保留)表2-SEQ表\*ARABIC16試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#810.000040.00100.00290.05420.000040.00100.00300.05430.000050.00100.00300.05440.000060.00100.00290.05350.000040.00100.00290.05360.000030.00100.00290.05270.000050.00100.00280.05280.000040.00100.00280.05290.000030.00100.00280.053100.000030.0011(**)0.00280.054110.000060.00100.00280.053測定次數(shù)n11111111平均值4.27E-050.001010.002870.0531SD1.10E-053.02E-057.86E-050.000831RSD/%25.832.992.741.57Max0.000060.00110.00300.054Min0.000030.00100.00280.052Gmax1.5722.9801.6541.083Gmin1.1550.3310.8911.324G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常0.011為離群值(舍棄)無異常無異常表2-SEQ表\*ARABIC17試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#910.000460.00250.01680.05600.1620.000470.00250.01650.05580.1730.000480.0026(**)0.01670.05620.1940.000460.00250.01670.05670.1850.000460.00250.01680.05600.1660.000460.00250.01620.05490.1870.000460.00250.01730.05530.1680.000460.00250.01740.05470.1890.000460.00250.01740.05550.16100.000470.00250.01740.05480.17110.000470.00250.01620.05480.16測定次數(shù)n1111111111平均值0.0004650.002510.01690.05550.170SD6.88E-063.02E-050.0004610.0006740.0110RSD/%1.481.202.731.216.47Max0.000480.00260.01740.05670.19Min0.000460.00250.01620.05470.16Gmax2.1802.9801.0851.7801.818Gmin0.7270.3311.5181.1870.909G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常0.0026為離群值(舍棄)無異常無異常無異常表2-18試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#1010.000550.00270.0200.0570.1820.000580.00270.0190.0580.1730.000570.00250.0190.0570.1940.000610.00240.0210.0570.1650.000600.00230.0180.0540.1760.00067(*)0.00250.0200.0560.1770.000570.00260.0190.0560.1880.000570.00240.0180.0580.1890.000600.00230.0190.0600.17100.000560.00280.0170.0620.17110.000580.00270.0200.0600.19測定次數(shù)n1111111111平均值0.0005870.002540.01910.05770.175SD3.29E-050.0001750.001140.002240.00934RSD/%5.606.895.973.885.34Max0.000670.00280.0210.0620.19Min0.000550.00230.0170.0540.16Gmax2.5231.4861.6671.9201.606Gmin1.1251.3711.8421.6521.606G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果0.00067為歧離值(保留)無異常無異常無異常無異常表2-19試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#1110.0004930.002550.01430.04910.12520.0004750.002570.01510.05160.13730.0004530.002510.01530.05070.12040.0004430.002480.01420.05210.12050.0004460.002520.01530.05160.12760.0004320.002540.01510.05000.13370.0004530.002480.01450.05210.14080.0004190.002520.01480.05170.13790.0004700.002450.01440.05080.142100.0004120.002550.01530.04890.126110.0004360.002470.01540.04970.124測定次數(shù)n1111111111平均值0.0004480.002510.01490.05080.130SD2.42E-053.85E-050.0004560.001180.00798RSD/%5.041.533.062.136.14Max0.0004930.002570.01540.05210.142Min0.0004120.002450.01420.04890.120Gmax1.8601.5581.0961.1021.504Gmin1.4881.5581.5351.6101.253G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-SEQ表\*ARABIC20試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#1210.000550.00260.0150.0520.1620.000520.00260.0150.0520.1630.000520.00250.0150.0530.1640.000530.00250.0160.0530.1650.000560.00250.0150.0520.1760.000510.00270.0160.0510.1670.000500.00260.0160.0510.1680.000540.00250.0160.0510.1690.000530.00240.0160.0510.16100.000540.00260.0170.0520.17110.000550.00250.0160.0520.17測定次數(shù)n1111111111平均值0.0005320.002550.01570.05180.163SD1.83E-058.20E-050.0006470.0007510.00467RSD/%3.443.224.121.452.87Max0.000560.00270.0170.0530.17Min0.000500.00240.0150.0510.16Gmax1.5301.8292.0091.5981.499Gmin1.7491.8291.0821.0650.642G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-SEQ表\*ARABIC21試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#1310.000480.00250.0150.0540.1620.000530.00280.0140.0520.1730.000470.00260.0140.0520.1640.000500.00240.0160.0510.1850.000510.00230.0150.0500.1760.000460.00270.0160.0520.1870.000520.00290.0170.0530.1680.000550.00280.0150.0540.1590.000460.00250.0130.0510.16100.000480.00260.0140.0500.17110.000490.00270.0160.0530.17測定次數(shù)n1111111111平均值0.0004950.002620.01500.05200.166SD2.94E-050.0001830.001180.001410.00924RSD/%5.946.987.872.715.57Max0.000530.00290.0170.0540.18Min0.000460.00230.0130.0500.15Gmax1.1901.5301.6951.4181.515Gmin1.1901.7491.6951.4181.732G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-SEQ表\*ARABIC22試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法1）實(shí)驗(yàn)室i測定結(jié)果5#6#7#8#9#1410.000560.00290.0170.0580.1720.000580.00290.0170.0570.1830.00060.00290.0180.0580.1840.000610.00290.0170.0580.1850.000540.00280.0160.0590.1860.000580.00270.0180.0570.1770.000570.00290.0170.0580.1880.000600.00290.0170.0570.1890.000590.00280.0180.0580.18100.000580.00280.0170.0570.17110.000570.00290.0170.0580.16測定次數(shù)n1111111111平均值0.0005800.002850.01720.05770.175SD2.00E-056.88E-050.0006030.0006470.00688RSD/%3.452.413.511.123.93Max0.000610.00290.0180.0590.18Min0.000540.00270.0160.0570.16Gmax1.5000.7271.3272.0090.727Gmin2.0002.1801.9901.0822.180G95(n)2.3552.3552.3552.3552.355G99(n)2.5642.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常無異常表2-23試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#1510.000120.00100.00250.05420.000130.00100.00260.05330.000150.00100.00270.05540.000130.00100.00270.05350.000140.00100.00260.05160.000150.00100.00270.05070.000160.00110.00250.05380.000150.00110.00270.05490.000130.00100.00260.053100.000140.00100.00280.052110.000140.00110.00270.056測定次數(shù)n11111111平均值0.0001400.001030.002650.0531SD1.18E-054.67E-059.34E-050.00170RSD/%8.434.533.523.20Max0.000160.00110.00280.056Min0.000120.00100.00250.050Gmax1.6951.4991.6061.706Gmin1.6950.6421.6061.824G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常無異常無異常無異常表2-24試驗(yàn)數(shù)據(jù)及Grubbs檢驗(yàn)（方法2）實(shí)驗(yàn)室i測定結(jié)果1#2#3#4#1610.000120.00110.00320.05620.000120.00110.00310.05630.000140.0013(**)0.00300.05540.000130.00110.00300.05750.000120.00110.00310.05660.000140.00110.00300.05770.000150.00110.00310.05580.000130.00100.00310.05690.000130.00110.00300.057100.000120.00110.00310.056110.000120.00100.00300.056測定次數(shù)n11111111平均值0.0001290.001100.003060.0561SD1.04E-057.75E-056.74E-050.000701RSD/%8.067.052.501.25Max0.000150.00130.00320.057Min0.000120.00100.00300.055Gmax2.0192.5812.0771.284Gmin0.8651.2900.8901.569G95(n)2.3552.3552.3552.355G99(n)2.5642.5642.5642.564檢驗(yàn)結(jié)果無異常0.0013為離群值(舍棄)無異常無異常3一致性和離群值檢查3.1曼德爾h-k檢驗(yàn)3.1.1方法1對各實(shí)驗(yàn)室方法1的試驗(yàn)數(shù)據(jù)進(jìn)行曼德爾h-k檢驗(yàn)，結(jié)果見表3和圖1：表3單元平均值一致性檢驗(yàn)--曼德爾統(tǒng)計(jì)量h（方法1）實(shí)驗(yàn)室pj5#6#7#8#9#1-0.240.51-0.91-0.390.442-0.42-1.46-1.02-2.04*-0.173-0.20-0.500.190.600.504-0.23-2.47**-1.77-1.68-2.15*5-0.690.51-0.15-0.27-0.5663.38**0.07-0.27-0.12-0.447-0.130.270.250.310.568-0.090.22-0.270.33-0.389-0.49-0.020.910.880.80100.090.172.33**1.461.1511-0.570.05-0.35-0.38-1.7912-0.170.220.19-0.100.3313-0.340.60-0.27-0.050.56140.061.85*1.121.461.15P=14h5%的臨界值為1.85，h1%的臨界值為2.30*為歧離值，**為離群值。從表3單元平均值曼德爾統(tǒng)計(jì)量h初步判定，實(shí)驗(yàn)室14的6#水平、實(shí)驗(yàn)室2的8#水平、實(shí)驗(yàn)室4的9#水平為歧離值，實(shí)驗(yàn)室6的5#水平、實(shí)驗(yàn)室4的6#水平、實(shí)驗(yàn)室10的7#水平為離群值。表4單元平均值一致性檢驗(yàn)--曼德爾統(tǒng)計(jì)量k（方法1）實(shí)驗(yàn)室pj5#6#7#8#9#10.801.031.111.081.2421.240.961.071.97**1.1630.310.820.670.930.9840.310.440.720.570.6250.150.550.580.820.9962.45**0.851.110.690.9971.231.47*1.070.781.2380.711.47*0.000.520.4890.220.000.660.511.31101.081.52**1.62**1.71**1.12110.790.330.650.900.95120.600.710.920.570.56130.961.59**1.69**1.081.10140.650.600.860.490.82P=14,n=11k5%的臨界值為1.35，k1%的臨界值為1.52*為歧離值，**為離群值。從表4單元平均值曼德爾統(tǒng)計(jì)量k初步判定，實(shí)驗(yàn)室7的6#水平、實(shí)驗(yàn)室8的6#水平為歧離值；實(shí)驗(yàn)室6的5#水平、實(shí)驗(yàn)室10的6#水平、實(shí)驗(yàn)室13的6#水平、實(shí)驗(yàn)室10的7#水平、實(shí)驗(yàn)室13的7#水平、實(shí)驗(yàn)室2的8#水平、實(shí)驗(yàn)室10的8#水平為離群值。3.1.2方法2對各實(shí)驗(yàn)室方法2的試驗(yàn)數(shù)據(jù)進(jìn)行曼德爾h-k檢驗(yàn)，結(jié)果見表5和圖3：表5單元平均值一致性檢驗(yàn)--曼德爾統(tǒng)計(jì)量h（方法2）實(shí)驗(yàn)室pj1#2#3#4#1-0.210.270.44-0.4520.25-1.82*-1.44-2.54**3-0.33-0.140.701.7741.02-0.08-0.310.4250.371.84*-0.54-0.0860.590.88-1.33-0.967-0.71-1.06-0.27-0.138-2.39**-0.280.970.29150.89-0.080.030.29160.520.471.761.40P=10h5%的臨界值為1.80，h1%的臨界值為2.18*為歧離值，**為離群值。從表5平均值曼德爾統(tǒng)計(jì)量h初步判定，實(shí)驗(yàn)室2的2#水平、實(shí)驗(yàn)室5的2#水平為歧離值，實(shí)驗(yàn)室8的1#、實(shí)驗(yàn)室2的4#水平水平離群值。表6單元平均值一致性檢驗(yàn)--曼德爾統(tǒng)計(jì)量k（方法2）實(shí)驗(yàn)室pj1#2#3#4#11.041.171.180.8821.200.731.201.58**30.580.731.321.1140.580.840.640.3550.601.35*0.890.4760.961.48*0.950.6870.760.430.421.69**81.270.001.000.56151.36*0.841.181.15161.201.40*0.850.47P=10,n=11k5%的臨界值為1.35，k1%的臨界值為1.50*為歧離值，**為離群值。從表6單元平均值曼德爾統(tǒng)計(jì)量k初步判定，實(shí)驗(yàn)室5的2#水平、實(shí)驗(yàn)室6的2#水平、實(shí)驗(yàn)室15的1#水平、實(shí)驗(yàn)室16的2#水平為歧離值，實(shí)驗(yàn)室2的4#、實(shí)驗(yàn)室7的4#為離群值。3.2科克倫檢驗(yàn)各實(shí)驗(yàn)室提供的精密度數(shù)據(jù)重復(fù)次數(shù)均為11次，根據(jù)GB/T6379.2-2004規(guī)定，n可取多數(shù)實(shí)驗(yàn)室的測定次數(shù)，同時GB/T6379.2-2004科克倫檢驗(yàn)臨界值表中單元重復(fù)測定數(shù)n最大為6，因此，本次柯克倫檢驗(yàn)采用P=20，n=6的臨界值：顯著性水平5%的臨界值為0.232，顯著性水平1%的臨界值為0.274。3.2.1方法1經(jīng)科克倫檢驗(yàn)，對5#水平，實(shí)驗(yàn)室6的科克倫統(tǒng)計(jì)量C=0.430，為離群值；舍棄后繼續(xù)進(jìn)行科克倫檢驗(yàn)，再無歧離值或者離群值。同理，對其它水平分別水平進(jìn)行科克倫檢驗(yàn)，檢驗(yàn)結(jié)果見表7：表7科克倫檢驗(yàn)統(tǒng)計(jì)量C（方法1）實(shí)驗(yàn)室pj5#6#7#8#9#10.00002450.0001180.0007750.001420.010420.00003810.000110.0007510.002580.0097330.000009340.00009440.00004670.001210.008240.000009440.00005050.0005050.0007510.0052250.000004670.00006320.0004050.001080.0083160.0000751**0.00009820.0007750.0009050.0083170.00003770.0001690.0007510.001030.010380.00002180.0001690.0003020.0006880.0040590.000006880.00003020.0004610.0006740.011100.00003290.0001750.001140.002240.00934110.00002420.00003850.0004560.001180.00798120.00001830.0000820.0006470.0007510.00467130.00002940.0001830.001180.001410.00924140.00002000.00006880.0006030.0006470.00688Smax0.00007510.0001830.001180.002580.011C0.4300.1810.2040.2770.122P=14顯著性水平5%的C臨界值為0.232，1%的C臨界值為0.274*為歧離值，**為離群值。科克倫檢驗(yàn)發(fā)現(xiàn)，實(shí)驗(yàn)室6在5#水平上的單元變異均超過顯著性水平1%的C臨界值，與3.1節(jié)曼德爾k檢驗(yàn)結(jié)果互相印證，進(jìn)一步說明這個實(shí)驗(yàn)室重復(fù)性相對較差，應(yīng)重點(diǎn)關(guān)注。3.2.2方法2經(jīng)科克倫檢驗(yàn)，無歧離值或者離群值。檢驗(yàn)結(jié)果見表8：表8科克倫檢驗(yàn)統(tǒng)計(jì)量C（方法2）實(shí)驗(yàn)室pj1#2#3#4#10.000009040.00006470.00009340.0013020.00001040.00004030.00009440.0024630.000005050.00004050.0001040.0016440.000005050.00004670.00005050.00052250.000005220.00007510.00007010.00070160.000008310.00008200.00007510.0010170.000006550.00002410.00003350.0025280.0000110.00003020.00007860.00083190.00001180.00004670.00009340.0017100.00001040.00007750.00006740.000701Smax0.00001180.00008200.0001040.00252C0.1860.2190.1750.287P=10顯著性水平5%的C臨界值為0.357，1%的C臨界值為0.303*為歧離值，保留參與精密度計(jì)算；**為離群值，舍棄。經(jīng)檢驗(yàn)，未發(fā)現(xiàn)歧離值或者離群值3.3格拉布斯檢驗(yàn)3.3.1方法1對方法1單元平均值分別進(jìn)行一個離群觀測值及兩個離群觀測值的格拉布斯檢驗(yàn)，結(jié)果分別見表9、表10。經(jīng)檢驗(yàn)，5#水平最大值有一離群，6#水平有一最小值歧離，9#水平有一最小值歧離，其他未發(fā)現(xiàn)歧離值或者離群值。表9單元平均值--Grubbs檢驗(yàn)統(tǒng)計(jì)量G(一個離群觀測值)（方法1）實(shí)驗(yàn)室pj5#6#7#8#9#10.0005170.002600.01400.05070.16520.0004790.002230.01380.04450.15530.0005250.002410.01570.05450.16540.0005190.002040.01260.04580.12550.0004230.002600.01520.05120.14960.00128**0.002520.01500.05170.15170.0005400.002550.01580.05340.16680.0005480.002510.01500.05350.15090.0004650.002510.01690.05550.170100.0005870.002540.01910.05770.175110