铜精矿化学分析方法 第5部分：氟含量的测定编制说明

铜精矿化学分析方法第5部分：氟含量的测定编制说明（讨论稿）主编单位：江西铜业股份有限公司2026年7月铜精矿化学分析方法第5部分：氟含量的测定（编制说明）一、工作简况一）任务来源根据2026年5月18日国家标准化管理委员会发布的《国家标准委关于下达2026年第四批推荐性国家标准计划及相关标准外文版计划的通知》（国标委发[2026]28号）的要求，国家标准《铜精矿化学分析方法第5部分：氟含量的测定离子选择电极法》修订项目由全国有色金属标准化技术委员会负责归口，由江西铜业股份有限公司负责起草，计划号20262490-T-610，项目截止日期为2027年4月28日。二）制定背景铜精矿化学成分分析方法标准在有色领域标准体系中发挥着重要作用，该系列方法服务于铜精矿的生产、贸易和应用，为我国有色金属行业高质量发展提供技术支撑，GB/T3884《铜精矿化学分析方法》目的在于描述铜精矿中铜、金、银、硫、氟等不同化学元素成分的测定方法。随着铜消费需求不断地增加，铜精矿贸易也在不断增加，铜产业的发展前景十分开阔。为满足行业对铜精矿、铜渣精矿的生产、贸易以及资源回收利用的需求，增加检测结果的可靠性和可比性，快速准确测定铜精矿、铜渣精矿中各元素的含量具有重要意义；在广泛开展企业需求调研的基础上，对GB/T3884《铜精矿化学分析方法》（共21部分）进行了整合修订。原铜精矿标准标准于2012年发布实施已经近十年了，随着近几年铜精矿物料的变化，铜精矿的性质也发生了变化，样品的复杂程度增加，原标准的检测范围对于部分铜精矿已经不适用了。本文件是对GB/T3884.5-2012《铜精矿化学分析方法第5部分：氟含量的测定离子选择电极法》的修订，在保留原离子选择电极法（方法1）的基础上，还整合了国际方法《Copperandzincsulfideconcentrates—DeterminationoffluorinecontentbysodiumhydroxidefusionandfluorideionselectiveelectrodedetectionISO/FDIS13548:2025(en)》（方法2）。方法1测定范围是0.010%～1.00%，方法2测定范围是0.008%～0.30%，适用于铜精矿和铜渣精矿。铜精矿、铜渣精矿标准整合修订后，统一了溶样方法、重复性和再现性的数值，能够实现快速、准确地进行测定，对贸易结算和指导生产以及资源回收利用具有重要的现实性和必要性。三）起草过程3.1主要参加单位情况江西铜业股份有限公司主要从事铜冶炼工艺过程中的原料、中间产物、产品分析检测、环保检测等业务，拥有CNAS和CMA资质。参与起草的国际、国内和行业标准有：主持起草的国家标准涉及铜精矿分析方法、铜及铜合金化学分析方法、银化学分析方法系列标准等多个大项；主持起草的行业阴极铜化学分析方法标准、银精矿化学分析方法系列标准等大项；参加起草的分析检测方面的标准达三十多项。公司拥有电感耦合等离子体原子发射光谱仪、直读光谱仪、X荧光光谱仪、火焰原子吸收光谱仪、电感耦合等离子体质谱仪、原子荧光光谱仪、离子色谱仪、测汞仪等具备科学研究所需的仪器设备。实验室拥有丰富工作经验的技术人员和科研团队，具有较强的检测分析操作经验和深入研究的能力，拥有制定该方法必需的环境、设备。3.2主要工作成员所负责的工作情况本文件由15家单位共同参与起草。主要起草人及工作职责见表1。表1本文件主要起草人及工作职责序号单位名称人员分工1江西铜业股份有限公司荣莎莎、张千强、沈广鑫、汪廷龙、杨师同、陈红、康广利负责调研、负责全过程的标准编制、标准起草、协调工作2铜陵有色金属集团控股有限公司程晓莹、郑旭、张琦一验单位，负责对主起草单位试验报告中方法条件试验、精密度、准确度试验进行验证3福建紫金矿冶测试技术有限公司陈祝海、张顺娘、罗荣根一验单位，负责对主起草单位试验报告中方法条件试验、精密度、准确度试验进行验证4山东中金岭南铜业有限责任公司任民谭秀丽一验单位，负责对主起草单位试验报告中方法条件试验、精密度、准确度试验进行验证5葫芦岛市锌业股份有限公司高霞马云飞一验单位，负责对主起草单位试验报告中方法条件试验、精密度、准确度试验进行验证6北方铜业股份有限公司孙嘉莹一验单位，负责对主起草单位试验报告中方法条件试验、精密度、准确度试验进行验证证数据7山东恒邦冶炼股份有限公司王畯李昀姝一验单位，负责对主起草单位试验报告中方法条件试验、精密度、准确度试验进行验证验证数据8湖南有色金属研究院有限责任公司张雪莲陈涓一验单位，负责对主起草单位试验报告中方法条件试验、精密度、准确度试验进行验证9金川集团股份有限公司任利华金亚楠二验单位，负责对主起草单位试验报告方法的精密度试验进行验证10五矿铜业(湖南)有限公司谢昆良陆莉二验单位，负责对主起草单位试验报告方法的精密度试验进行验证11防城海关综合技术服务中心古建国、杨辉二验单位，负责对主起草单位试验报告方法的精密度试验进行验证12云南华联锌铟股份有限公司农树怀杨绍辉二验单位，负责对主起草单位试验报告方法的精密度试验进行验证13昆明冶金研究院有限公司李瑾，李继婷二验单位，负责对主起草单位试验报告方法的精密度试验进行验证14云南云铜锌业股份有限公司保路华、王会玲二验单位，负责对主起草单位试验报告方法的精密度试验进行验证15梅特勒托利多科技（中国）黄斯慜二验单位，负责对主起草单位试验报告方法的精密度试验进行验证3.3主要工作过程3.3.1预研阶段2025年，起草单位对GB/T3884.5-2012《铜精矿化学分析方法第5部分：氟含量的测定离子选择电极法》的含量范围及各企业所用方法以电话和书面问卷进行了全面调研，确定了含量范围和初步方案，经过为期近1年的试验和生产实际应用，最终向全国有色金属标准化技术委员会提交了立项建议书。3.3.2立项阶段2026年5月国标委下发的《国家标准委关于下达2026年第四批推荐性国家标准计划及相关标准外文版计划的通知（国标委发[2026]28号文件20262490-T-610）》，项目周期为11个月，项目计划完成年限为2027年4月。3.3.3任务落实及起草阶段2025年9月，全国有色金属标准化技术委员会在陕西省西安市召开了《船用铝合金挤压管、棒、型材》等86项有色金属标准工作会议，会议对标准计划GB/T3884.5-2012《铜精矿化学分析方法第5部分：氟含量的测定离子选择电极法》进行任务落实。会议确定了标准制定的起草单位和验证单位，落实了标准制定项目的进度安排和分工。样品由江西铜业股份有限公司单位提供，样品情况如表2所示。表2验证样品情况分析方法分析元素样品编号样品种类方法1F1#、4#铜渣精矿2#、3#、5#、6#、7#铜精矿方法2F1#、4#铜渣精矿2#、3#、5#、铜精矿江西铜业股份有限公司在接到任务后立即组织技术人员成立了标准编制组，制定了该标准的研究内容、技术路线、任务分工和进度安排。在拟制定分析方法开展了多方调研、资料收集后进行试验工作，包括熔融温度的考察、各试剂用量的影响、共存元素干扰等的研究，形成了标准文本、试验报告和编制说明的讨论稿。2026年3月完成的试验报告发至各验证单位，各单位开始验证工作，在此期间起草单位根据各单位反馈情况，不断优化试验，确定了最终试验报告和方法文本。3.3.4征求意见阶段（1）验证单位反馈意见a、文中方法1测定部分，将4.5.4.1“将熔融物均匀摇动于坩埚内壁上，稍冷。”修改为“将熔融物摇匀，冷却至室温”。（铜陵有色金属集团股份有限公司）。采纳，已修改。b、文中方法1测定部分，4.5.4.2“将坩埚与熔融物置于250mL烧杯中，盖上表面皿，吹入少量热水，剧烈反应结束后，用热水洗净表面皿、坩埚”建议改成“将坩埚与熔融物置于250mL烧杯中加入80mL热水，放置电热板上温和加热至坩埚中熔融物完全溶解，低温加热蒸发试液并控制试液体积不超过100mL。”（铜陵有色金属集团股份有限公司、紫金矿业集团股份有限公司）。采纳，已修改。c、文中方法1测定部分，4.5.1-表1中分取体积数据，应该保留至小数点后两位，如10.0mL修改为10.00mL。（铜陵有色金属集团股份有限公司）。采纳，已修改。d、文中方法1试剂部分，4.2.8三乙醇胺[N(CH2CH2OH)3]溶液：100mL三乙醇胺加64mL盐酸(4.2.4)调至pH6.5～7.0，用水稀释至500mL,混匀。因加入64ml盐酸会变为强酸性，建议更改为“三乙醇胺[N(CH2CH2OH)3]-盐酸溶液：100mL三乙醇胺置于干燥烧杯中，加入300ml纯水，搅拌混匀，在搅拌下缓慢加入盐酸(4.2.4)调至pH6.5～7.0，用水稀释至500mL,混匀。”（山东中金岭南铜业有限责任公司）。采纳，已修改。e、文中方法2测定部分，5.5.4.3“用热水洗涤塑料烧杯和沉淀物，完成后加热滤液和洗涤液”建议改成“用热水洗涤塑料烧杯和沉淀物3-4次，完成后加热滤液和洗涤液”。（铜陵有色金属集团股份有限公司）。不采纳，限定洗涤次数的表述不够严谨。f、文中方法2测定部分，5.2试剂中建议增加一个“硝酸（1+4）”用来调节pH，因为pH在临近6.5-7.0时，硝酸（1+99）加多了会使待测液会超出100mL。（铜陵有色金属集团股份有限公司）。不采纳，5.5.4.4中已明确采用（1+1）和（1+99）2种浓度的硝酸调节pH。g、文中方法2测定部分，5.5.5.1-表5中，标准曲线最高点为10ug/mL，建议将最高点删除，实际测定时，未达到该浓度，低于5ug/mL。（铜陵有色金属集团股份有限公司）。不采纳，不建议对国际标准的技术条款进行修改。h、文中方法2测定部分，5.5.4.2“将坩埚放入100mL塑料烧杯（5.3.7）中，向烧杯中倒入80mL热水。将装有坩埚的烧杯放在电热板（5.3.5）上，温和加热（70°C至80°C）1小时以上”。建议修改为“将坩埚与熔融物置于250mL聚四氟乙烯烧杯中（5.3.7），加入80mL热水，盖上表面皿，置于电热板加热至微沸状态20~30分钟”。（紫金矿业集团股份有限公司）。采纳，已修改。i、文中方法1中4.5.4.2和方法2中5.5.4.2测定部分，滴加3~5滴无水乙醇，通过无水乙醇消除高价锰的氧化干扰，破坏络合物，释放游离氟。（紫金矿业集团股份有限公司）。不采纳，加入无水乙醇的作用没有数据支撑。（2）发函征求意见：共发征求意见函14份，其中用户单位10份，检验院所2份，海关1份，仪器制造公司1份，回函14份，回函有意见或建议的单位3份。根据征求意见稿的意见，编写了《标准征求意见稿意见处理汇总表》。二、标准编制原则、主要内容及其确定依据一）标准编制原则符合性：本文件严格根据GB/T1.1-2020《标准化工作导则第1部分：标准化文件的结构和起草规则》和GB/T20001.4-2015《标准编写规则第4部分：试验方法标准》的要求进行编写；并按照GB/T6379.2-2004《测量方法与结果的准确度》进行数理统计分析。二）标准主要内容及其确定依据主要内容：本文件整合GB/T3884.5-2012《铜精矿化学分析方法第5部分：氟含量的测定离子选择电极法》和国际方法ISO/FDIS13548:2025《Copperandzincsulfideconcentrates—Determinationoffluorinecontentbysodiumhydroxidefusionandfluorideionselectiveelectrodedetection》后，扩大了标准适用范围至铜渣精矿，统一了铜精矿和铜渣精矿的溶样方法，修订了重复性和再现性的数值。主要原理：方法1是试料以氢氧化钾熔融，用水浸出熔融物后过滤，使氟与铁、铜、铅等分离，然后在pH6.5～7.0的柠檬酸钠-三乙醇胺介质中，以饱和甘汞电极为参比电极，氟离子选择电极为指示电极，用电极电位仪测定氟。方法2是试料以氢氧化钠熔融，用水浸出熔融物后过滤，使氟与铁、铜、铅等分离，然后在pH6.5～7.0的柠檬酸钠介质中，以饱和甘汞电极为参比电极，氟离子选择电极为指示电极，用电极电位仪测定氟。三）修订前后技术内容对比将本文件《铜精矿化学分析方法第5部分：氟含量的测定离子选择电极法》与GB/T3884.5-2012《铜精矿化学分析方法第5部分：氟含量的测定离子选择电极法》进行比对，结果见表3。表3修订前后方法对比表比对项目修订前修订后说明对比情况更好or相当检测方法只有一个检测方法增加了方法2（采标国际标准）增加了检测方法，更好适用范围铜精矿铜精矿和铜渣精矿本文件扩大了适用范围，更好测定范围方法1测定范围为氟0.010%～0.50%0.010%~0.60%方法1测定范围为氟0.010%～1.00%。本文件扩展测定范围，更好分取体积移取5.00mL或10.00mL滤液根据称样量规定了分取体积明确了不同称样量的分取体积，更好三、试验验证情况和预期效益3.1试验验证情况对铜精矿、铜渣精矿样品溶解方法的选择、分离和测定条件的选择进行了条件试验，具体结果见试验报告。3.1.1方法1使用控制变量法，依次进行了试样熔融温度试验、试样熔融时长试验、熔剂选择试验、熔剂加入方式试验、熔剂加入量试验、柠檬酸钠和三乙醇胺加入量试验。得出最佳的溶样条件。具体结果见试验报告。3.1.2方法2使用控制变量法，依次进行了试样熔融温度试验、试样熔融时长试验、熔剂加入方式试验、熔剂加入量试验、柠檬酸钠加入量试验、PH试验。得出最佳的溶样条件。具体结果见试验报告。3.2干扰及消除铜精矿中氟的测定采用离子选择电极法，方法1的测定范围是氟0.010%～1.00%，方法2的测定范围是氟0.008%～0.30%。方法1离子选择电极法主要考察了铜、铁、硅、钙、镁、铝等元素对氟的干扰。根据铜精矿和铜渣精矿中各元素的含量范围上限，按方法1操作，计算出测定溶液中各元素的干扰量，单元素干扰试验结果见表4，混合元素干扰试验见表5。表4单元素干扰试验测定结果（单位：mg）干扰元素F测得量（加入量0.10mg）干扰元素F测得量（加入量0.30mg）干扰元素F测得量（加入量1.00mg）干扰元素F测得量（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混合元素干扰试验测定结果（单位：mg）共存杂质元素F测得量（加入量0.10mg）F测得量（加入量0.30mg）F测得量（加入量1.00mg）F测得量（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从表4、表5结果可以看出，在方法1中，上述共存元素最大量的单元素及混合元素对氟的测定基本没有干扰。方法2氢氧化钠熔融-离子选择电极法主要考察了铜、铁、硅、钙、镁、铝等元素对氟的干扰。根据铜精矿和铜渣精矿中各元素的含量范围上限，按方法2操作，计算出测定溶液中各元素的干扰量，单元素干扰试验结果见表6，混合元素干扰试验见表7。表6共存元素对测定的影响（单位：mg）干扰元素F测得量（加入量0.10mg）干扰元素F测得量（加入量0.70mg）干扰元素F测得量（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混合元素干扰试验测定结果（单位：mg）共存杂质元素F测得量（加入量0.10mg）F测得量（加入量0.70mg）F测得量（加入量1.50mg）500mgCu、400mgFe、50mgCa、80mgMg、140mgSi、100mgAl0.0980.721.47250mgCu、200mgFe、25mgCa、40mgMg、70mgSi、50mgAl0.1040.701.49从表6、表7结果可以看出，在方法2中，上述共存元素最大量的单元素及混合元素对氟的测定基本没有干扰。3.3样品加标回收率方法1离子选择电极法，选取一个模拟空白样品，加入（250mgCu、200mgFe、25mgCa、40mgMg、70mgSi、50mgAl）和4个试验样品，加入一定量的氟标准溶液，按照方法1规定处理样品，进行加标回收试验。分析结果见表8。表8方法1离子选择电极法加标回收试验试样编号次数加入氟量/mg试样含氟量/mg加标后氟测定量/mg回收率/%模拟空白样品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从上述加标试验可知，本试验选择的模拟空白样品、2个铜精矿样品、2个渣精矿样品中氟是回收率为95%～103.6%，可作为行业标准方法推广使用。方法2氢氧化钠熔融-离子选择电极法，选取一个模拟空白样品，加入（500mgCu、400mgFe、50mgCa、80mgMg、140mgSi、100mgAl）和3个试验样品，加入一定量的氟标准溶液，按照本方法规定处理样品，进行加标回收试验。分析结果见表9。表9方法2氢氧化钠熔融-离子选择电极法加标回收实验试样编号次数加入氟量/mg试样含氟量/mg加标后氟测定量/mg回收率/%模拟空白样品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从上述加标试验可知，本试验选择的模拟空白样品、1个铜精矿样品、2个渣精矿样品中氟是回收率为95%～103.6%，回收率较好，表明该方法准确度较好，可作为行业标准方法推广使用。3.4精密度试验数据处理3.5.1方法1：离子选择电极法1）各实验室实验数据见表10。表10方法1：离子选择电极法F元素实验室实验数据实验室次数水平j12345671、江西铜业股份有限公司（起草单位）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标准偏差0.00150.00210.00380.00380.00970.01420.0156相对标准偏差10.806.785.462.713.171.971.472、铜陵有色金属集团股份有限公司（一验单位）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标准偏差0.00070.00210.00250.00320.00730.01120.0129相对标准偏差6.626.533.522.272.361.601.203、紫金矿业集团股份有限公司（一验单位）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标准偏差0.00040.00130.00190.00480.00980.01560.0223相对标准偏差3.503.742.673.533.002.172.074、山东中金岭南铜业有限责任公司（一验单位））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标准偏差0.00050.00130.00250.00290.00630.00560.0054相对标准偏差3.933.983.552.031.950.830.515、葫芦岛锌业股份有限公司（一验单位））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标准偏差0.00090.00120.00150.00570.01310.01780.0123相对标准偏差7.354.072.124.724.542.561.206、昆明冶金研究院有限公司（二验单位）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标准偏差0.00100.00230.00130.00260.00350.01060.0035相对标准偏差6.607.111.721.821.111.410.337、云南华联锌铟股份有限公司（二验单位）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标准偏差0.00030.00100.00320.00480.01280.02560.0270相对标准偏差2.753.084.603.393.863.622.518、北方铜业股份有限公司（二验单位）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标准偏差0.00130.00190.00250.00260.00710.01020.0092相对偏差9.636.243.531.842.321.430.879、山东恒邦冶炼股份有限公司（二验单位）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标准偏差0.00100.00110.00250.00620.01660.02060.0181相对标准偏差8.443.893.824.494.982.911.7010、金川集团股份有限公司（二验单位）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标准偏差0.00050.00110.00120.00210.00550.01360.0114相对偏差3.923.361.751.501.741.961.0811.防城海关综合技术服务中心（二验单位）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标准偏差0.00040.00060.00090.00450.00480.00660.0057相对偏差3.281.691.253.121.440.920.5612、梅特勒托利多科技（中国）有限公司（二验单位）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标准偏差0.00090.00060.00150.00620.01500.01770.0144相对标准偏差6.982.152.224.494.482.481.3513、五矿铜业（湖南）有限公司（二验单位）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标准偏差0.00080.00080.00110.00790.01150.01210.0100相对标准偏差5.812.241.525.703.321.700.9414、湖南有色金属研究院有限责任公司（二验单位）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标准偏差0.00120.00110.00100.00660.00770.01420.0321相对标准偏差12.743.111.274.242.361.953.0115.云南云铜锌业股份有限公司（二验单位）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标准偏差0.00090.00130.00270.00450.01000.01670.0150相对标准偏差10.353.603.462.923.012.231.372）单元平均值的计算由表10的数据，计算单元平均值见表11：表11方法1：离子选择电极法F单元平均值统计实验室i离子选择电极法的F单元平均值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总平均值0.0130.0320.0700.1390.3170.7091.0583）单元离散度的计算一致性和离群值的检查，对各实验室提供的数据进行曼德尔h-k检验，检验结果分别见表12、表13。表12方法1曼德尔h统计量的值实验室i离子选择电极法的F元素的单元离散度（曼德尔检验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临界值：p=15，显著性水平为1%时h=2.32，显著性水平为5%时，h=1.86结果表明：实验室5的水平5、实验室6的水平6；实验室11的水平7；实验室15的水平4、水平6和水平7的数据为歧离值（*标注），保留数据。实验室5的水平4；实验室14的水平1、水平3和水平4；实验室15的水平1和水平3的数据为离群值（**标注），剔除离群值。表13方法1曼德尔k统计量的值实验室i离子选择电极法的F元素的单元离散度（曼德尔检验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临界值：p=15，n=11，显著性水平为1%时k=1.52，显著性水平为5%时，k=1.36结果表明：实验室1的水平2；实验室2的水平2；实验室3的水平7；实验室7的水平3；实验室8的水平1和水平2；实验室9的水平6；实验室12的水平5；实验室14的水平1的数据为岐离值（*标注），保留数据。实验室1的水平1和水平3；实验室6的水平2；实验室7的水平6和水平7；实验室9的水平6；实验室13的水平4；实验室14的水平7的数据，为离群值（**标注），剔除离群值。4）柯克伦检验一致性检验剔除离群值后，方法1：离子选择电极法F标准偏差的统计如表14。表14：方法1：离子选择电极法F元素标准偏差统计实验室i方法1：离子选择电极法F元素标准偏差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根据GB/T6379.2-2004规定n可取为多数单元中的检测结果数，同时查表GB/T6379.2-2004,C临界值对n=11，P=15，柯克伦检验临界值表中并未给出，采用n=6，p=15，科克伦检验5%临界值为0.220，1%临界值为0.259。详见表15。表15方法1柯克伦检验结果水平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统计量C0.1870.1740.2100.1220.1800.1940.260**歧离值（Y/N）NNNNNNN离群值（Y/N）NNNNNNY柯克伦检验结果表明，无歧离值，有一个离群值（**标注）,为实验室14水平7数据，舍弃离群值后进行第二次科克伦检验。根据GB/T6379.2-2004规定n可取为多数单元中的检测结果数，同时查表GB/T6379.2-2004,C临界值对n=11，P=15，柯克伦检验临界值表中并未给出，采用n=6，p=15，科克伦检验5%临界值为0.220，1%临界值为0.259。详见表16。表16方法1柯克伦检验结果水平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统计量C0.1870.1740.2100.1220.1800.1940.183歧离值（Y/N）NNNNNNN离群值（Y/N）NNNNNNN第二次柯克伦检验结果表明柯，无歧离值，无离群值，所有数据参与后续计算。5）格拉布斯检验将格拉布斯检验应用于单元平均值，当p=15时，格拉布斯单个值上1%临界值为2.806，单个值上0.220，1%临界值为0.259。详见表17。表17方法1格拉布斯F检验结果实验室水平水平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均值标准差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歧离值（Y/N）YNNNNNN离群值（Y/N）NNNNNNN经检验有1个岐离值，没有离群值，所有数据参与后续计算。6）重复性及再现性剔除离群值后，重复性、再现性计算结果见表18。表18方法1：离子选择电极法F元素重复性和再现性统计量水平1水平2水平3水平4水平5水平6水平7总平均值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：氢氧化钠熔融-离子选择电极法1）各实验室实验数据各实验室数据如表19：表19方法2：氢氧化钠熔融-离子选择电极法实验室次数水平j123451、江西铜业股份有限公司（起草单位）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、铜陵有色金属集团股份有限公司（一验单位）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、紫金矿业集团股份有限公司（一验单位）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、山东中金岭南铜业有限责任公司（一验单位））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、葫芦岛锌业股份有限公司（一验单位））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（二验单位）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、云南华联锌铟股份有限公司（二验单位）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、北方铜业股份有限公司（二验单位）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、山东恒邦冶炼股份有限公司（二验单位）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、金川集团股份有限公司（二验单位）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.防城海关综合技术服务中心（二验单位）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（中国）有限公司（二验单位）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、五矿铜业（湖南）有限公司（二验单位）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.