銅精礦化學分析方法 第5部分：氟含量的測定編制說明

銅精礦化學分析方法第5部分：氟含量的測定編制說明（討論稿）主編單位：江西銅業股份有限公司2026年7月銅精礦化學分析方法第5部分：氟含量的測定（編制說明）一、工作簡況一）任務來源根據2026年5月18日國家標準化管理委員會發布的《國家標準委關于下達2026年第四批推薦性國家標準計劃及相關標準外文版計劃的通知》（國標委發[2026]28號）的要求，國家標準《銅精礦化學分析方法第5部分：氟含量的測定離子選擇電極法》修訂項目由全國有色金屬標準化技術委員會負責歸口，由江西銅業股份有限公司負責起草，計劃號20262490-T-610，項目截止日期為2027年4月28日。二）制定背景銅精礦化學成分分析方法標準在有色領域標準體系中發揮著重要作用，該系列方法服務于銅精礦的生產、貿易和應用，為我國有色金屬行業高質量發展提供技術支撐，GB/T3884《銅精礦化學分析方法》目的在于描述銅精礦中銅、金、銀、硫、氟等不同化學元素成分的測定方法。隨著銅消費需求不斷地增加，銅精礦貿易也在不斷增加，銅產業的發展前景十分開闊。為滿足行業對銅精礦、銅渣精礦的生產、貿易以及資源回收利用的需求，增加檢測結果的可靠性和可比性，快速準確測定銅精礦、銅渣精礦中各元素的含量具有重要意義；在廣泛開展企業需求調研的基礎上，對GB/T3884《銅精礦化學分析方法》（共21部分）進行了整合修訂。原銅精礦標準標準于2012年發布實施已經近十年了，隨著近幾年銅精礦物料的變化，銅精礦的性質也發生了變化，樣品的復雜程度增加，原標準的檢測范圍對于部分銅精礦已經不適用了。本文件是對GB/T3884.5-2012《銅精礦化學分析方法第5部分：氟含量的測定離子選擇電極法》的修訂，在保留原離子選擇電極法（方法1）的基礎上，還整合了國際方法《Copperandzincsulfideconcentrates—DeterminationoffluorinecontentbysodiumhydroxidefusionandfluorideionselectiveelectrodedetectionISO/FDIS13548:2025(en)》（方法2）。方法1測定范圍是0.010%～1.00%，方法2測定范圍是0.008%～0.30%，適用于銅精礦和銅渣精礦。銅精礦、銅渣精礦標準整合修訂后，統一了溶樣方法、重復性和再現性的數值，能夠實現快速、準確地進行測定，對貿易結算和指導生產以及資源回收利用具有重要的現實性和必要性。三）起草過程3.1主要參加單位情況江西銅業股份有限公司主要從事銅冶煉工藝過程中的原料、中間產物、產品分析檢測、環保檢測等業務，擁有CNAS和CMA資質。參與起草的國際、國內和行業標準有：主持起草的國家標準涉及銅精礦分析方法、銅及銅合金化學分析方法、銀化學分析方法系列標準等多個大項；主持起草的行業陰極銅化學分析方法標準、銀精礦化學分析方法系列標準等大項；參加起草的分析檢測方面的標準達三十多項。公司擁有電感耦合等離子體原子發射光譜儀、直讀光譜儀、X熒光光譜儀、火焰原子吸收光譜儀、電感耦合等離子體質譜儀、原子熒光光譜儀、離子色譜儀、測汞儀等具備科學研究所需的儀器設備。實驗室擁有豐富工作經驗的技術人員和科研團隊，具有較強的檢測分析操作經驗和深入研究的能力，擁有制定該方法必需的環境、設備。3.2主要工作成員所負責的工作情況本文件由15家單位共同參與起草。主要起草人及工作職責見表1。表1本文件主要起草人及工作職責序號單位名稱人員分工1江西銅業股份有限公司榮莎莎、張千強、沈廣鑫、汪廷龍、楊師同、陳紅、康廣利負責調研、負責全過程的標準編制、標準起草、協調工作2銅陵有色金屬集團控股有限公司程曉瑩、鄭旭、張琦一驗單位，負責對主起草單位試驗報告中方法條件試驗、精密度、準確度試驗進行驗證3福建紫金礦冶測試技術有限公司陳祝海、張順娘、羅榮根一驗單位，負責對主起草單位試驗報告中方法條件試驗、精密度、準確度試驗進行驗證4山東中金嶺南銅業有限責任公司任民譚秀麗一驗單位，負責對主起草單位試驗報告中方法條件試驗、精密度、準確度試驗進行驗證5葫蘆島市鋅業股份有限公司高霞馬云飛一驗單位，負責對主起草單位試驗報告中方法條件試驗、精密度、準確度試驗進行驗證6北方銅業股份有限公司孫嘉瑩一驗單位，負責對主起草單位試驗報告中方法條件試驗、精密度、準確度試驗進行驗證證數據7山東恒邦冶煉股份有限公司王畯李昀姝一驗單位，負責對主起草單位試驗報告中方法條件試驗、精密度、準確度試驗進行驗證驗證數據8湖南有色金屬研究院有限責任公司張雪蓮陳涓一驗單位，負責對主起草單位試驗報告中方法條件試驗、精密度、準確度試驗進行驗證9金川集團股份有限公司任利華金亞楠二驗單位，負責對主起草單位試驗報告方法的精密度試驗進行驗證10五礦銅業(湖南)有限公司謝昆良陸莉二驗單位，負責對主起草單位試驗報告方法的精密度試驗進行驗證11防城海關綜合技術服務中心古建國、楊輝二驗單位，負責對主起草單位試驗報告方法的精密度試驗進行驗證12云南華聯鋅銦股份有限公司農樹懷楊紹輝二驗單位，負責對主起草單位試驗報告方法的精密度試驗進行驗證13昆明冶金研究院有限公司李瑾，李繼婷二驗單位，負責對主起草單位試驗報告方法的精密度試驗進行驗證14云南云銅鋅業股份有限公司保路華、王會玲二驗單位，負責對主起草單位試驗報告方法的精密度試驗進行驗證15梅特勒托利多科技（中國）黃斯慜二驗單位，負責對主起草單位試驗報告方法的精密度試驗進行驗證3.3主要工作過程3.3.1預研階段2025年，起草單位對GB/T3884.5-2012《銅精礦化學分析方法第5部分：氟含量的測定離子選擇電極法》的含量范圍及各企業所用方法以電話和書面問卷進行了全面調研，確定了含量范圍和初步方案，經過為期近1年的試驗和生產實際應用，最終向全國有色金屬標準化技術委員會提交了立項建議書。3.3.2立項階段2026年5月國標委下發的《國家標準委關于下達2026年第四批推薦性國家標準計劃及相關標準外文版計劃的通知（國標委發[2026]28號文件20262490-T-610）》，項目周期為11個月，項目計劃完成年限為2027年4月。3.3.3任務落實及起草階段2025年9月，全國有色金屬標準化技術委員會在陜西省西安市召開了《船用鋁合金擠壓管、棒、型材》等86項有色金屬標準工作會議，會議對標準計劃GB/T3884.5-2012《銅精礦化學分析方法第5部分：氟含量的測定離子選擇電極法》進行任務落實。會議確定了標準制定的起草單位和驗證單位，落實了標準制定項目的進度安排和分工。樣品由江西銅業股份有限公司單位提供，樣品情況如表2所示。表2驗證樣品情況分析方法分析元素樣品編號樣品種類方法1F1#、4#銅渣精礦2#、3#、5#、6#、7#銅精礦方法2F1#、4#銅渣精礦2#、3#、5#、銅精礦江西銅業股份有限公司在接到任務后立即組織技術人員成立了標準編制組，制定了該標準的研究內容、技術路線、任務分工和進度安排。在擬制定分析方法開展了多方調研、資料收集后進行試驗工作，包括熔融溫度的考察、各試劑用量的影響、共存元素干擾等的研究，形成了標準文本、試驗報告和編制說明的討論稿。2026年3月完成的試驗報告發至各驗證單位，各單位開始驗證工作，在此期間起草單位根據各單位反饋情況，不斷優化試驗，確定了最終試驗報告和方法文本。3.3.4征求意見階段（1）驗證單位反饋意見a、文中方法1測定部分，將4.5.4.1“將熔融物均勻搖動于坩堝內壁上，稍冷。”修改為“將熔融物搖勻，冷卻至室溫”。（銅陵有色金屬集團股份有限公司）。采納，已修改。b、文中方法1測定部分，4.5.4.2“將坩堝與熔融物置于250mL燒杯中，蓋上表面皿，吹入少量熱水，劇烈反應結束后，用熱水洗凈表面皿、坩堝”建議改成“將坩堝與熔融物置于250mL燒杯中加入80mL熱水，放置電熱板上溫和加熱至坩堝中熔融物完全溶解，低溫加熱蒸發試液并控制試液體積不超過100mL。”（銅陵有色金屬集團股份有限公司、紫金礦業集團股份有限公司）。采納，已修改。c、文中方法1測定部分，4.5.1-表1中分取體積數據，應該保留至小數點后兩位，如10.0mL修改為10.00mL。（銅陵有色金屬集團股份有限公司）。采納，已修改。d、文中方法1試劑部分，4.2.8三乙醇胺[N(CH2CH2OH)3]溶液：100mL三乙醇胺加64mL鹽酸(4.2.4)調至pH6.5～7.0，用水稀釋至500mL,混勻。因加入64ml鹽酸會變為強酸性，建議更改為“三乙醇胺[N(CH2CH2OH)3]-鹽酸溶液：100mL三乙醇胺置于干燥燒杯中，加入300ml純水，攪拌混勻，在攪拌下緩慢加入鹽酸(4.2.4)調至pH6.5～7.0，用水稀釋至500mL,混勻。”（山東中金嶺南銅業有限責任公司）。采納，已修改。e、文中方法2測定部分，5.5.4.3“用熱水洗滌塑料燒杯和沉淀物，完成后加熱濾液和洗滌液”建議改成“用熱水洗滌塑料燒杯和沉淀物3-4次，完成后加熱濾液和洗滌液”。（銅陵有色金屬集團股份有限公司）。不采納，限定洗滌次數的表述不夠嚴謹。f、文中方法2測定部分，5.2試劑中建議增加一個“硝酸（1+4）”用來調節pH，因為pH在臨近6.5-7.0時，硝酸（1+99）加多了會使待測液會超出100mL。（銅陵有色金屬集團股份有限公司）。不采納，5.5.4.4中已明確采用（1+1）和（1+99）2種濃度的硝酸調節pH。g、文中方法2測定部分，5.5.5.1-表5中，標準曲線最高點為10ug/mL，建議將最高點刪除，實際測定時，未達到該濃度，低于5ug/mL。（銅陵有色金屬集團股份有限公司）。不采納，不建議對國際標準的技術條款進行修改。h、文中方法2測定部分，5.5.4.2“將坩堝放入100mL塑料燒杯（5.3.7）中，向燒杯中倒入80mL熱水。將裝有坩堝的燒杯放在電熱板（5.3.5）上，溫和加熱（70°C至80°C）1小時以上”。建議修改為“將坩堝與熔融物置于250mL聚四氟乙烯燒杯中（5.3.7），加入80mL熱水，蓋上表面皿，置于電熱板加熱至微沸狀態20~30分鐘”。（紫金礦業集團股份有限公司）。采納，已修改。i、文中方法1中4.5.4.2和方法2中5.5.4.2測定部分，滴加3~5滴無水乙醇，通過無水乙醇消除高價錳的氧化干擾，破壞絡合物，釋放游離氟。（紫金礦業集團股份有限公司）。不采納，加入無水乙醇的作用沒有數據支撐。（2）發函征求意見：共發征求意見函14份，其中用戶單位10份，檢驗院所2份，海關1份，儀器制造公司1份，回函14份，回函有意見或建議的單位3份。根據征求意見稿的意見，編寫了《標準征求意見稿意見處理匯總表》。二、標準編制原則、主要內容及其確定依據一）標準編制原則符合性：本文件嚴格根據GB/T1.1-2020《標準化工作導則第1部分：標準化文件的結構和起草規則》和GB/T20001.4-2015《標準編寫規則第4部分：試驗方法標準》的要求進行編寫；并按照GB/T6379.2-2004《測量方法與結果的準確度》進行數理統計分析。二）標準主要內容及其確定依據主要內容：本文件整合GB/T3884.5-2012《銅精礦化學分析方法第5部分：氟含量的測定離子選擇電極法》和國際方法ISO/FDIS13548:2025《Copperandzincsulfideconcentrates—Determinationoffluorinecontentbysodiumhydroxidefusionandfluorideionselectiveelectrodedetection》后，擴大了標準適用范圍至銅渣精礦，統一了銅精礦和銅渣精礦的溶樣方法，修訂了重復性和再現性的數值。主要原理：方法1是試料以氫氧化鉀熔融，用水浸出熔融物后過濾，使氟與鐵、銅、鉛等分離，然后在pH6.5～7.0的檸檬酸鈉-三乙醇胺介質中，以飽和甘汞電極為參比電極，氟離子選擇電極為指示電極，用電極電位儀測定氟。方法2是試料以氫氧化鈉熔融，用水浸出熔融物后過濾，使氟與鐵、銅、鉛等分離，然后在pH6.5～7.0的檸檬酸鈉介質中，以飽和甘汞電極為參比電極，氟離子選擇電極為指示電極，用電極電位儀測定氟。三）修訂前后技術內容對比將本文件《銅精礦化學分析方法第5部分：氟含量的測定離子選擇電極法》與GB/T3884.5-2012《銅精礦化學分析方法第5部分：氟含量的測定離子選擇電極法》進行比對，結果見表3。表3修訂前后方法對比表比對項目修訂前修訂后說明對比情況更好or相當檢測方法只有一個檢測方法增加了方法2（采標國際標準）增加了檢測方法，更好適用范圍銅精礦銅精礦和銅渣精礦本文件擴大了適用范圍，更好測定范圍方法1測定范圍為氟0.010%～0.50%0.010%~0.60%方法1測定范圍為氟0.010%～1.00%。本文件擴展測定范圍，更好分取體積移取5.00mL或10.00mL濾液根據稱樣量規定了分取體積明確了不同稱樣量的分取體積，更好三、試驗驗證情況和預期效益3.1試驗驗證情況對銅精礦、銅渣精礦樣品溶解方法的選擇、分離和測定條件的選擇進行了條件試驗，具體結果見試驗報告。3.1.1方法1使用控制變量法，依次進行了試樣熔融溫度試驗、試樣熔融時長試驗、熔劑選擇試驗、熔劑加入方式試驗、熔劑加入量試驗、檸檬酸鈉和三乙醇胺加入量試驗。得出最佳的溶樣條件。具體結果見試驗報告。3.1.2方法2使用控制變量法，依次進行了試樣熔融溫度試驗、試樣熔融時長試驗、熔劑加入方式試驗、熔劑加入量試驗、檸檬酸鈉加入量試驗、PH試驗。得出最佳的溶樣條件。具體結果見試驗報告。3.2干擾及消除銅精礦中氟的測定采用離子選擇電極法，方法1的測定范圍是氟0.010%～1.00%，方法2的測定范圍是氟0.008%～0.30%。方法1離子選擇電極法主要考察了銅、鐵、硅、鈣、鎂、鋁等元素對氟的干擾。根據銅精礦和銅渣精礦中各元素的含量范圍上限，按方法1操作，計算出測定溶液中各元素的干擾量，單元素干擾試驗結果見表4，混合元素干擾試驗見表5。表4單元素干擾試驗測定結果（單位：mg）干擾元素F測得量（加入量0.10mg）干擾元素F測得量（加入量0.30mg）干擾元素F測得量（加入量1.00mg）干擾元素F測得量（加入量2.00mg）不加0.10不加0.31不加1.00不加2.01500mgCu0.105250mgCu0.30175mgCu1.02100mgCu2.07400mgFe0.095200mgFe0.29140mgFe0.9980mgFe2.0050mgCa0.10025mgCa0.3117.5mgCa0.9710mgCa2.0680mgMg0.10340mgMg0.2628mgMg1.0316mgMg1.99140mgSi0.09370mgSi0.2749mgSi1.0528mgSi1.98100mgAl0.10250mgAl0.2835mgAl1.0120mgAl2.04表5混合元素干擾試驗測定結果（單位：mg）共存雜質元素F測得量（加入量0.10mg）F測得量（加入量0.30mg）F測得量（加入量1.00mg）F測得量（加入量2.00mg）500mgCu、400mgFe、50mgCa、80mgMg、140mgSi、1000mgAl0.0950.301.012.00250mgCu、200mgFe、25mgCa、40mgMg、70mgSi、50mgAl0.1030.321.002.01175mgCu、140mgFe、17.5mgCa、28mgMg、49mgSi、35mgAl0.1000.281.031.98100mgCu、80mgFe、10mgCa、16mgMg、28mgSi、20mgAl0.1020.290.992.04從表4、表5結果可以看出，在方法1中，上述共存元素最大量的單元素及混合元素對氟的測定基本沒有干擾。方法2氫氧化鈉熔融-離子選擇電極法主要考察了銅、鐵、硅、鈣、鎂、鋁等元素對氟的干擾。根據銅精礦和銅渣精礦中各元素的含量范圍上限，按方法2操作，計算出測定溶液中各元素的干擾量，單元素干擾試驗結果見表6，混合元素干擾試驗見表7。表6共存元素對測定的影響（單位：mg）干擾元素F測得量（加入量0.10mg）干擾元素F測得量（加入量0.70mg）干擾元素F測得量（加入量1.50mg）不加0.10不加0.71不加1.48500mgCu0.095250mgCu0.70250mgCu1.45400mgFe0.102200mgFe0.68200mgFe1.5250mgCa0.09725mgCa0.7225mgCa1.5080mgMg0.10340mgMg0.6740mgMg1.49140mgSi0.10070mgSi0.6970mgSi1.47100mgAl0.09950mgAl0.7050mgAl1.54表7混合元素干擾試驗測定結果（單位：mg）共存雜質元素F測得量（加入量0.10mg）F測得量（加入量0.70mg）F測得量（加入量1.50mg）500mgCu、400mgFe、50mgCa、80mgMg、140mgSi、100mgAl0.0980.721.47250mgCu、200mgFe、25mgCa、40mgMg、70mgSi、50mgAl0.1040.701.49從表6、表7結果可以看出，在方法2中，上述共存元素最大量的單元素及混合元素對氟的測定基本沒有干擾。3.3樣品加標回收率方法1離子選擇電極法，選取一個模擬空白樣品，加入（250mgCu、200mgFe、25mgCa、40mgMg、70mgSi、50mgAl）和4個試驗樣品，加入一定量的氟標準溶液，按照方法1規定處理樣品，進行加標回收試驗。分析結果見表8。表8方法1離子選擇電極法加標回收試驗試樣編號次數加入氟量/mg試樣含氟量/mg加標后氟測定量/mg回收率/%模擬空白樣品10.2000.1995.020.200.20100.030.200.1995.01#10.070.140.2095.220.070.21100.030.070.2095.210.140.140.2796.420.140.29103.630.140.2796.410.210.140.3497.120.210.3510030.210.3497.13#10.1750.350.52199.220.1750.51397.730.1750.5310110.3500.350.6897.120.3500.71101.430.3500.6998.610.5250.350.88100.620.5250.8698.330.5250.87299.74#10.350.700.10398.120.350.10610130.350.10297.110.700.700.13898.620.700.13697.130.700.141100.711.050.700.17097.121.050.17298.331.050.176100.65#10.5351.070.15596.620.5350.15898.430.5350.162100.911.0701.070.21098.121.0700.20595.831.0700.21399.511.6051.070.26097.221.6050.26599.131.6050.268100.2從上述加標試驗可知，本試驗選擇的模擬空白樣品、2個銅精礦樣品、2個渣精礦樣品中氟是回收率為95%～103.6%，可作為行業標準方法推廣使用。方法2氫氧化鈉熔融-離子選擇電極法，選取一個模擬空白樣品，加入（500mgCu、400mgFe、50mgCa、80mgMg、140mgSi、100mgAl）和3個試驗樣品，加入一定量的氟標準溶液，按照本方法規定處理樣品，進行加標回收試驗。分析結果見表9。表9方法2氫氧化鈉熔融-離子選擇電極法加標回收實驗試樣編號次數加入氟量/mg試樣含氟量/mg加標后氟測定量/mg回收率/%模擬空白樣品10.5000.4896.020.500.5110230.500.501001#10.070.140.2095.220.070.2095.230.070.2095.210.140.140.2796.420.140.2810030.140.29103.610.210.140.36102.920.210.3497.130.210.3497.13#10.360.721.0496.320.361.0698.130.361.0810010.720.721.4298.620.721.45100.730.721.4097.211.080.721.7496.721.081.81100.631.081.7898.94#10.350.701.0196.220.351.06101.030.351.0398.110.700.701.42101.420.701.3596.430.701.3999.310.900.701.5295.020.901.61100.630.901.5898.8從上述加標試驗可知，本試驗選擇的模擬空白樣品、1個銅精礦樣品、2個渣精礦樣品中氟是回收率為95%～103.6%，回收率較好，表明該方法準確度較好，可作為行業標準方法推廣使用。3.4精密度試驗數據處理3.5.1方法1：離子選擇電極法1）各實驗室實驗數據見表10。表10方法1：離子選擇電極法F元素實驗室實驗數據實驗室次數水平j12345671、江西銅業股份有限公司（起草單位）10.0160.0320.0760.1390.3240.7461.06320.0120.0330.0680.1400.3160.7301.05630.0140.0310.0660.1400.2990.7121.04440.0130.0340.0750.1450.3100.7111.07050.0130.0310.0690.1460.2930.7001.03760.0120.0300.0720.1330.3030.7011.05870.0150.0290.0650.1370.2940.7281.08580.0120.0350.0760.1430.3080.7251.07690.0160.0300.0680.1350.2970.7051.058100.0130.0280.0670.1400.3170.7321.032110.0150.0290.0720.1420.3020.7101.070均值0.0140.0310.0700.1400.3060.7181.059標準偏差0.00150.00210.00380.00380.00970.01420.0156相對標準偏差10.806.785.462.713.171.971.472、銅陵有色金屬集團股份有限公司（一驗單位）10.0120.0330.0720.1450.3060.7121.06120.0100.0290.0710.1420.3050.7041.09130.0100.0300.0680.1410.3110.6921.07440.0100.0300.0720.1360.2950.6861.06950.0100.0350.0730.1400.3070.7081.08360.0110.0320.0700.1400.3100.7041.06270.0120.0280.0700.1420.3150.7161.05280.0110.0330.0740.1330.3120.6921.04590.0110.0320.0660.1370.3060.6881.080100.0110.0340.0670.1410.2970.6821.071110.0110.0310.0680.1380.3220.7101.065均值0.0110.0320.0700.1400.3080.6991.068標準偏差0.00070.00210.00250.00320.00730.01120.0129相對標準偏差6.626.533.522.272.361.601.203、紫金礦業集團股份有限公司（一驗單位）10.0130.0360.0730.140.330.721.120.0130.0340.0710.130.340.731.0830.0130.0350.0730.140.330.751.0940.0130.0350.0690.140.320.731.1150.0130.0350.0690.140.340.741.0860.0130.0340.070.130.320.731.0470.0120.0330.0690.140.310.711.0880.0130.0330.0680.140.330.71.0990.0130.0320.070.130.310.711.08100.0120.0320.0680.140.330.71.04110.0120.0330.0670.130.330.711.05均值0.0130.0340.0700.1360.3260.7211.076標準偏差0.00040.00130.00190.00480.00980.01560.0223相對標準偏差3.503.742.673.533.002.172.074、山東中金嶺南銅業有限責任公司（一驗單位））10.0130.0310.0760.1450.3110.6881.06320.0130.0330.0740.1470.3270.6751.0730.0120.030.070.1470.310.6731.07540.0140.0330.0680.1420.3160.6871.07950.0130.0310.0690.140.320.681.06760.0130.030.070.1390.330.6921.06870.0130.0320.0680.140.3210.6821.07180.0140.0310.0690.1420.3230.681.06190.0130.0340.070.1450.3150.6771.073100.0130.0330.0720.1390.320.6811.066110.0130.0320.0680.1440.3270.6871.077均值0.0130.0320.0700.1430.3200.6821.070標準偏差0.00050.00130.00250.00290.00630.00560.0054相對標準偏差3.933.983.552.031.950.830.515、葫蘆島鋅業股份有限公司（一驗單位））10.0120.0270.0670.120.280.681.0520.0110.0290.070.120.270.691.0430.0120.030.0680.120.270.711.0340.0120.0270.0710.130.280.721.0250.0130.0280.0690.130.280.681.0360.0130.030.0680.120.290.671.0270.0110.0290.0690.130.30.71.0280.0120.0280.0710.110.30.721.0290.010.0280.0710.120.30.711.02100.0110.030.070.120.310.671.03110.0120.0270.0670.120.30.691均值0.0120.0280.0690.1220.2890.6951.025標準偏差0.00090.00120.00150.00570.01310.01780.0123相對標準偏差7.354.072.124.724.542.561.206、昆明冶金研究院有限公司（二驗單位）10.0160.0280.0730.1380.310.7311.05820.0130.0340.0750.1440.3220.7521.06730.0140.0290.0720.1430.3160.761.06540.0160.030.0760.1370.3240.7431.06650.0150.0350.0730.1450.3180.7341.07260.0140.0320.0750.1420.320.7421.06470.0150.0330.0730.1390.3170.7581.06780.0160.0340.0740.1390.3180.7671.06890.0160.0350.0720.1440.3150.7451.066100.0150.0330.0740.1410.3160.7511.062110.0160.0310.0750.140.3180.7551.069均值0.0150.0320.0740.1410.3180.7491.066標準偏差0.00100.00230.00130.00260.00350.01060.0035相對標準偏差6.607.111.721.821.111.410.337、云南華聯鋅銦股份有限公司（二驗單位）10.01230.03320.07080.1490.3230.6761.10220.01250.03440.07370.1410.3320.7051.06930.01290.03410.07330.1390.3410.7121.07740.01270.03220.06510.1380.3010.7251.01550.01280.03660.06730.1430.3470.7551.09260.01270.03360.06620.1450.3460.7041.12970.01290.03450.06280.1330.3330.7041.07680.01250.03320.06930.1440.3250.6551.05990.01210.03420.07020.1410.3350.7121.082100.01350.03390.06890.1480.3280.6991.064110.0130.0340.0700.1350.3460.7351.071均值0.0130.0340.0690.1410.3320.7071.076標準偏差0.00030.00100.00320.00480.01280.02560.0270相對標準偏差2.753.084.603.393.863.622.518、北方銅業股份有限公司（二驗單位）10.0130.0350.0750.1450.3090.7111.05320.0120.0330.0690.1420.2940.7241.06930.0140.0310.0690.1390.3040.7061.06440.0140.0320.070.1410.310.7051.0550.0120.0310.0690.1450.3040.7071.06460.0160.0280.0720.1380.3110.7211.06370.0150.0320.0690.1370.3030.7031.05380.0130.0290.0710.1410.2940.7141.04490.0120.0290.0650.140.3120.7361.04100.0130.0300.0720.1440.2990.7201.044110.0150.030.0680.1430.3170.7281.052均值0.0140.0310.0700.1410.3050.7161.054標準偏差0.00130.00190.00250.00260.00710.01020.0092相對偏差9.636.243.531.842.321.430.879、山東恒邦冶煉股份有限公司（二驗單位）10.0140.0290.0660.140.360.731.0820.0110.0280.0670.150.330.751.0730.0130.0280.060.140.360.71.0440.0130.030.0640.130.340.711.0850.0110.030.0660.140.340.691.0960.0120.0270.0680.130.320.681.0770.0130.0290.0690.140.310.721.0880.0130.0280.0670.130.340.711.0990.0110.0300.0700.1400.3200.6901.050100.0110.0310.0670.130.310.681.04110.0120.0290.0670.140.330.711.05均值0.0120.0290.0660.1370.3330.7061.067標準偏差0.00100.00110.00250.00620.01660.02060.0181相對標準偏差8.443.893.824.494.982.911.7010、金川集團股份有限公司（二驗單位）10.01110.03310.07120.140.3070.6881.07720.01220.0330.07030.1430.3160.6691.04230.01180.03450.06970.140.3210.7051.05740.01120.03470.07150.1470.320.6761.04750.01160.03230.07220.1440.3180.7081.04760.01210.03080.070.1460.3210.7151.06170.01180.03420.06760.1440.3210.7081.07180.0120.0340.0700.1450.3210.6981.05290.01060.03190.07140.1420.3140.6921.071100.01170.03290.07020.1430.3080.6851.071110.01150.03370.0720.1450.3080.6921.067均值0.0120.0330.0710.1440.3160.6941.060標準偏差0.00050.00110.00120.00210.00550.01360.0114相對偏差3.923.361.751.501.741.961.0811.防城海關綜合技術服務中心（二驗單位）10.01040.03440.07220.140.330.721.0220.01170.03350.07390.140.330.711.0230.01180.03370.07060.150.340.721.0240.01140.03520.07210.140.330.711.0150.01120.03490.07210.140.340.721.0260.0120.0340.0710.1400.3300.7201.03070.01150.03480.07210.150.330.721.0180.01120.0350.07120.140.330.711.0290.01120.03390.07130.140.340.711.01100.0110.03360.07130.140.330.71.02110.0110.0340.0710.150.340.721.02均值0.0110.0340.0720.1430.3340.7151.018標準偏差0.00040.00060.00090.00450.00480.00660.0057相對偏差3.281.691.253.121.440.920.5612、梅特勒托利多科技（中國）有限公司（二驗單位）10.0130.0290.0660.140.360.731.0720.0110.0280.0670.150.330.751.0730.0140.0280.0650.140.360.721.0540.0130.0290.0640.130.340.721.0850.0110.0290.0660.1400.3400.7101.09060.0130.0280.0680.130.320.711.0770.0130.0290.0670.140.330.721.0880.0130.0280.0670.130.340.711.0990.0130.0290.070.140.320.691.05100.0130.030.0670.130.310.681.06110.0120.0290.0670.140.330.711.05均值0.0130.0290.0670.1370.3350.7141.069標準偏差0.00090.00060.00150.00620.01500.01770.0144相對標準偏差6.982.152.224.494.482.481.3513、五礦銅業（湖南）有限公司（二驗單位）10.0120.0360.0710.150.340.711.0820.0140.0370.0720.140.330.731.0530.0140.0380.0730.140.350.711.0740.0130.0370.0710.1300.3500.7101.05050.0140.0380.0710.140.360.71.0660.0140.0360.0720.150.350.721.0770.0140.0360.070.130.330.691.0680.0120.0380.0710.130.360.711.0590.0140.0380.0720.140.360.71.06100.0140.0380.070.150.330.731.05110.0130.0370.0690.130.350.71.05均值0.0130.0370.0710.1390.3460.7101.059標準偏差0.00080.00080.00110.00790.01150.01210.0100相對標準偏差5.812.241.525.703.321.700.9414、湖南有色金屬研究院有限責任公司（二驗單位）10.009110.03470.07370.150.320.711.0820.009110.03470.07460.150.320.731.0930.0090.0350.0770.1500.3300.7601.04040.009130.03480.07380.160.330.721.0750.008930.03790.07530.150.320.711.0960.01330.03550.07480.160.320.731.0770.008970.0340.07450.150.320.741.0980.009630.0340.07490.160.320.731.190.009720.0340.07680.150.330.731.06100.008930.03410.07460.170.340.710.98110.009360.03550.07470.150.340.731.08均值0.0100.0350.0750.1550.3260.7271.068標準偏差0.00120.00110.00100.00660.00770.01420.0321相對標準偏差12.743.111.274.242.361.953.0115.云南云銅鋅業股份有限公司（二驗單位）10.0100.0340.0740.1500.3300.7501.08020.00820.0370.0810.160.340.751.1230.00850.0350.0790.150.330.771.0940.00970.0340.0740.150.340.721.0850.00870.0380.0790.160.340.771.1260.00690.0350.0730.150.310.751.0970.00710.0370.080.150.320.721.1180.00840.0360.0760.150.330.741.0990.00890.0350.0740.150.340.731.12100.00920.0350.0780.160.320.761.1110.00780.0370.0770.150.340.751.11均值0.0080.0360.0770.1530.3310.7461.101標準偏差0.00090.00130.00270.00450.01000.01670.0150相對標準偏差10.353.603.462.923.012.231.372）單元平均值的計算由表10的數據，計算單元平均值見表11：表11方法1：離子選擇電極法F單元平均值統計實驗室i離子選擇電極法的F單元平均值w/%水平1水平2水平3水平4水平5水平6水平710.0140.0310.0700.1400.3060.7181.05920.0110.0360.0700.1400.3080.6991.06830.0130.0340.0700.1360.3260.7211.07640.0130.0320.0700.1430.3200.6821.07050.0120.0280.0690.1220.2890.6951.02560.0150.0320.0740.1410.3180.7491.06670.0130.0340.0690.1410.3320.7071.07680.0140.0310.0700.1410.3050.7161.05490.0120.0290.0660.1370.3330.7061.067100.0120.0330.0710.1440.3160.6941.060110.0110.0340.0720.1430.3340.7151.018120.0130.0290.0670.1370.3350.7141.069130.0130.0370.0710.1390.3460.7101.059140.0100.0350.0750.1550.3260.7271.068150.0080.0360.0770.1530.3310.7501.101總平均值0.0130.0320.0700.1390.3170.7091.0583）單元離散度的計算一致性和離群值的檢查，對各實驗室提供的數據進行曼德爾h-k檢驗，檢驗結果分別見表12、表13。表12方法1曼德爾h統計量的值實驗室i離子選擇電極法的F元素的單元離散度（曼德爾檢驗h值）w/%水平1水平2水平3水平4水平5水平6水平710.786-0.4240.0000.164-0.7790.5050.0522-1.5721.6960.0000.164-0.638-0.5610.51730.0000.8480.000-0.4910.6380.6740.93040.0000.0000.0000.6550.213-1.5160.6205-0.786-1.696-0.507-2.784**-1.984*-0.786-1.70561.5720.0002.028*0.3280.0712.246*0.41370.0000.848-0.5070.3281.063-0.1120.93080.786-0.4240.0000.328-0.8500.393-0.2079-0.786-1.272-2.028-0.3281.134-0.1680.46510-0.7860.4240.5070.819-0.071-0.8420.10311-1.5720.8481.0140.6551.2040.337-2.066*120.000-1.272-1.521-0.3281.2750.2810.568130.0002.1200.5070.0002.0550.0560.05214-2.358**1.2722.535**2.620**0.6381.0110.51715-3.931**1.6963.549**2.293*0.9922.302*2.221*h臨界值：p=15，顯著性水平為1%時h=2.32，顯著性水平為5%時，h=1.86結果表明：實驗室5的水平5、實驗室6的水平6；實驗室11的水平7；實驗室15的水平4、水平6和水平7的數據為歧離值（*標注），保留數據。實驗室5的水平4；實驗室14的水平1、水平3和水平4；實驗室15的水平1和水平3的數據為離群值（**標注），剔除離群值。表13方法1曼德爾k統計量的值實驗室i離子選擇電極法的F元素的單元離散度（曼德爾檢驗k值）w/%水平1水平2水平3水平4水平5水平6水平711.674**1.490*1.775**0.7830.9610.9430.95820.8081.456*1.1390.6550.7210.7470.79130.5020.8940.8600.9940.9711.0421.369*40.5800.8941.1520.5980.6200.3760.33450.9730.8170.6771.1881.3001.1840.75861.1241.617**0.5850.5320.3490.7030.22670.3940.7401.462*0.9901.2731.706**1.658**81.473*1.362*1.1390.5380.7040.6810.56391.1620.7971.1711.2741.643**1.370*1.115100.5140.7870.5710.4440.5460.9080.702110.4180.4100.3680.9200.4770.4370.353120.9950.4360.6851.2741.487*1.1800.887130.8830.5890.5001.637**1.1410.8030.612141.374*0.7670.4411.3540.7650.9461.975**150.9880.9091.2270.9200.9881.1100.925k臨界值：p=15，n=11，顯著性水平為1%時k=1.52，顯著性水平為5%時，k=1.36結果表明：實驗室1的水平2；實驗室2的水平2；實驗室3的水平7；實驗室7的水平3；實驗室8的水平1和水平2；實驗室9的水平6；實驗室12的水平5；實驗室14的水平1的數據為岐離值（*標注），保留數據。實驗室1的水平1和水平3；實驗室6的水平2；實驗室7的水平6和水平7；實驗室9的水平6；實驗室13的水平4；實驗室14的水平7的數據，為離群值（**標注），剔除離群值。4）柯克倫檢驗一致性檢驗剔除離群值后，方法1：離子選擇電極法F標準偏差的統計如表14。表14：方法1：離子選擇電極法F元素標準偏差統計實驗室i方法1：離子選擇電極法F元素標準偏差w/%水平1水平2水平3水平4水平5水平6水平710.00150.00210.00380.00380.00970.01420.015620.00070.00210.00250.00320.00730.01120.012930.00040.00130.00190.00480.00980.01560.022340.00050.00130.00250.00290.00630.00560.005450.00090.00120.00150.00580.01310.01780.012360.00100.00230.00130.00260.00350.01060.003570.00030.00100.00320.00480.01280.02560.027080.00130.00190.00250.00260.00710.01020.009290.00100.00110.00250.00620.01660.02060.0181100.00050.00110.00120.00210.00550.01360.0114110.00040.00060.00080.00450.00480.00660.0058120.00090.00060.00150.00620.01500.01770.0144130.00080.00080.00110.00790.01150.01210.0100140.00120.00110.00100.00660.00770.01420.0321150.00090.00130.00270.00450.01000.01670.0150根據GB/T6379.2-2004規定n可取為多數單元中的檢測結果數，同時查表GB/T6379.2-2004,C臨界值對n=11，P=15，柯克倫檢驗臨界值表中并未給出，采用n=6，p=15，科克倫檢驗5%臨界值為0.220，1%臨界值為0.259。詳見表15。表15方法1柯克倫檢驗結果水平1水平2水平3水平4水平5水平6水平7smaxP1，0.0015P6，0.0023P1，0.0038P14，0.0066P9，0.0166P7，0.0256P14，0.0321∑s20.00001180.00003010.00007040.00035150.00152460.00338040.0039694統計量C0.1870.1740.2100.1220.1800.1940.260**歧離值（Y/N）NNNNNNN離群值（Y/N）NNNNNNY柯克倫檢驗結果表明，無歧離值，有一個離群值（**標注）,為實驗室14水平7數據，舍棄離群值后進行第二次科克倫檢驗。根據GB/T6379.2-2004規定n可取為多數單元中的檢測結果數，同時查表GB/T6379.2-2004,C臨界值對n=11，P=15，柯克倫檢驗臨界值表中并未給出，采用n=6，p=15，科克倫檢驗5%臨界值為0.220，1%臨界值為0.259。詳見表16。表16方法1柯克倫檢驗結果水平1水平2水平3水平4水平5水平6水平7smaxP1，0.0015P6，0.0023P1，0.0038P14，0.0066P9，0.0166P7，0.0256P7，0.0270∑s20.00001180.00003010.00007040.00035150.00152460.00338040.0039694統計量C0.1870.1740.2100.1220.1800.1940.183歧離值（Y/N）NNNNNNN離群值（Y/N）NNNNNNN第二次柯克倫檢驗結果表明柯，無歧離值，無離群值，所有數據參與后續計算。5）格拉布斯檢驗將格拉布斯檢驗應用于單元平均值，當p=15時，格拉布斯單個值上1%臨界值為2.806，單個值上0.220，1%臨界值為0.259。詳見表17。表17方法1格拉布斯F檢驗結果實驗室水平水平1水平2水平3水平4水平5水平6水平7均值平均值0.0130.0320.0710.140.320.711.06均值標準差0.0016650.0026500.0026730.0079660.0148980.0181640.019870最大均值P6，0.015P13，0.037P5，0.074P14，0.16P13，0.35P6，0.75P15，1.10最小均值P15，0.008P5，0.028P6，0.066P5，0.12P5，0.29P4，0.68P11，1.02Gmax1.56121.76111.12251.85791.63311.96711.9426Gmin-2.6421*-2.4122-1.8708-2.2847-2.1929-1.7216-2.2345歧離值（Y/N）YNNNNNN離群值（Y/N）NNNNNNN經檢驗有1個岐離值，沒有離群值，所有數據參與后續計算。6）重復性及再現性剔除離群值后，重復性、再現性計算結果見表18。表18方法1：離子選擇電極法F元素重復性和再現性統計量水平1水平2水平3水平4水平5水平6水平7總平均值0.0130.0320.0700.140.320.711.06Sr20.000000610.00000170.0000400.0000180.0000890.000190.00020SL20.00000140.00000870.00000410.0000240.000230.000380.00040SR20.00000200.0000100.00000810.0000420.000330.000580.00060Sr0.000780.00130.00200.00420.0940.0140.013SR0.00140.00320.00280.00650.0180.0240.025r0.0020.0040.0030.010.030.040.04R0.0040.0090.0080.020.050.070.073.5.2方法2：氫氧化鈉熔融-離子選擇電極法1）各實驗室實驗數據各實驗室數據如表19：表19方法2：氫氧化鈉熔融-離子選擇電極法實驗室次數水平j123451、江西銅業股份有限公司（起草單位）10.0130.0320.0760.1390.32420.0120.0330.0680.140.31630.0140.0350.0660.140.29940.0130.0340.0750.1450.3150.0130.0310.0690.1460.29360.0130.030.0740.130.30370.0150.0330.070.1370.30580.0120.0350.0760.1430.30890.0160.030.0680.1350.32100.0130.0330.0670.1480.317110.0150.0290.0720.1420.31均值0.01350.03230.07100.1400.3102、銅陵有色金屬集團股份有限公司（一驗單位）10.0120.030.0670.140.30720.0120.0360.0750.140.29530.0130.0320.0720.1340.3140.0110.030.070.1390.29950.0110.030.0730.1370.32260.0120.0360.0720.1390.31670.0120.0350.0660.1370.31280.010.0350.0680.1420.30790.0110.0330.0730.1450.318100.010.0330.0720.1410.326110.010.0320.0750.1380.302均值0.01130.03290.07120.1390.3103、紫金礦業集團股份有限公司（一驗單位）10.0120.0330.0710.140.3320.0110.0340.0720.130.3230.0120.0330.070.130.3240.0120.0370.0670.140.3150.0110.0330.0660.140.3360.0120.0330.0710.130.3370.0120.0340.0690.140.3280.0110.0360.0680.130.3290.0110.0340.070.140.33100.0120.0320.0690.140.31110.010.0340.0670.140.31均值0.01150.03390.06910.1360.3214、山東中金嶺南銅業有限責任公司（一驗單位））10.0140.0320.0710.1370.31920.0140.0330.0720.1430.32230.0130.0310.0710.1450.32640.0140.0320.070.1410.31750.0140.0330.0730.1380.3260.0130.0340.0720.140.32270.0130.0320.0730.1420.31680.0140.0320.0720.1410.3390.0150.0310.070.1420.324100.0140.0330.0720.1430.309110.0140.0320.0710.1420.328均值0.01380.03230.07150.1410.3215、葫蘆島鋅業股份有限公司（一驗單位））10.0130.0280.0690.120.2920.0120.030.070.120.2930.0130.0290.0710.120.340.0110.0310.0680.130.3150.0120.0290.0680.110.2860.0120.030.070.120.3170.0110.0280.0710.130.2980.0130.030.0690.120.2890.0110.0290.070.130.3100.0110.0310.0680.120.29110.0110.030.0690.120.31均值0.01180.02950.06940.1220.2956、昆明冶金研究院有限公司（二驗單位）10.0110.0280.070.1410.31220.0150.0310.0710.140.32230.0120.0290.0750.1450.31640.0130.0280.0740.1410.3250.0140.0320.0720.1420.31860.0140.0290.0730.1410.31570.0130.0320.0710.1430.31780.0130.0310.0730.1420.21390.0120.030.0720.1410.318100.0140.0310.0710.1430.317110.0120.0280.070.1440.315均值0.0130.02990.07200.1420.3087、云南華聯鋅銦股份有限公司（二驗單位）10.01230.03320.07080.1490.32320.01250.03440.07370.1410.33230.01290.03410.07330.1390.34140.01270.03220.06510.1380.30150.01280.03660.06730.1430.34760.01270.03360.06620.1450.34670.01290.03450.06280.1330.33380.01250.03320.06930.1440.32590.01210.03420.07020.1410.335100.01350.03390.06890.1480.328110.01260.03440.06990.1350.346均值0.01270.03400.06890.1410.3328、北方銅業股份有限公司（二驗單位）10.0130.0310.0720.1420.3120.0160.0290.0680.1420.30330.0130.0330.070.1460.30640.0140.030.070.1420.350.0120.0310.070.140.360.0140.0320.0680.1370.29870.0120.0290.0720.140.31780.0150.030.0710.1390.30490.0130.0290.0680.1420.301100.0150.0330.0720.1440.333110.0120.0290.0680.1380.299均值0.01350.03050.06990.1410.3069、山東恒邦冶煉股份有限公司（二驗單位）10.0130.0290.0680.130.3220.0110.0290.0650.130.2930.0140.0310.0670.150.3440.0130.0290.0660.130.2950.0110.0320.0690.140.3560.0110.030.0670.130.3170.0120.0290.070.150.3280.0120.0320.0710.140.3390.0110.0330.0680.130.31100.0140.0310.070.130.32110.0120.0310.0710.140.33均值0.01220.03050.06840.1360.31910、金川集團股份有限公司（二驗單位）10.01210.03060.07270.1430.33520.01220.0330.07110.1460.32330.01080.02990.06930.1420.33340.01140.03080.06750.1440.33150.01180.03140.06720.1370.32460.0110.03060.06720.1440.32270.01160.03120.06840.1430.32180.01160.030.07020.1540.31890.01140.02970.0730.1520.314100.01140.03230.07010.1370.311110.01080.0330.07250.1350.319均值0.01150.03110.06990.1430.32311.防城海關綜合技術服務中心（二驗單位）10.0090.0340.0730.140.33420.0090.0360.0720.1410.33430.0090.0340.0720.1430.3340.010.0340.0720.1440.33150.0090.0340.0720.1450.33360.010.0360.070.1430.33570.010.0340.0710.1420.33180.0090.0350.0710.1420.33490.010.0340.0710.1430.334100.0090.0340.070.1420.331110.010.0360.0710.1440.331均值0.009450.03460.07140.1430.33312、梅特勒托利多科技（中國）有限公司（二驗單位）10.0110.0290.0680.130.3220.0110.0290.0650.130.2930.0130.0310.0670.150.3440.0130.0290.0660.130.2950.0110.0320.0690.140.3560.0110.030.0670.130.3170.0110.0290.070.150.3280.0110.0320.0710.140.3390.0120.0330.0680.130.31100.0130.0310.070.130.32110.0120.0310.0710.140.33均值0.01170.03050.06840.1360.31913、五礦銅業（湖南）有限公司（二驗單位）10.0120.0350.0690.150.3320.0130.0350.0680.150.330.0130.0360.0710.150.3240.0120.0350.070.160.3150.0140.0360.070.160.3260.0130.0360.070.140.3270.0130.0340.0710.150.3280.0130.0330.0690.160.3290.0140.