质子交换膜燃料电池汽车用氢气 含硫化合物、甲醛和有机卤化物的测定 气相色谱法 编制说明

1质子交换膜燃料电池汽车用氢气含硫化合物、甲醛和有机卤化物测定气相色谱法编制说明1工作概况对环境造成的污染亦越来越严重，因此迫切需要寻找一种作为替代品的清洁燃料。氢能作为一种高效、清洁、低碳环保、可持续发展的二次能源，被视为最具发展潜力的清洁能源。氢燃料电池车是氢能的重要应用载体，燃料电池器件的构成及工作原理从本质上要求作为反应原料的氢气要满足特定的质量指标，以保障燃料电池的长周期、可靠运行。在燃料电池用氢所需控制的杂质中，含硫化合物是严重的催化剂毒物，即使含量非常低也会导致燃料电池性能不可逆转的下降，甲醛和卤化物会吸附催化剂上，转化为CO和H₂,产生的CO在催化剂层上的吸附导致催化表面积的减小，致使痕量甲醛和卤化物的存在也会严重影响和卤化物(<0.05μmol/mol)是燃料电池车用氢气控制指标中限值要求最为严苛的参数，国内现有的检测方法均无法满足分析需求，因此建立一套有先进性，适用性强兼具经济性的燃料电池汽车用氢气中含硫化合物、甲醛和卤化物测定标准是十分必要的。本标准制定任务来源于国家标准化管理委员会国标委[2022]51号文件“国家标准化管理委员会关于下达2021年第四批推荐性国家标准计划标准由全国氢能标准化技术委员会提出并归口。1.2工作简要过程、协作单位、成员及主要工作2021年5月申请立项，2022年12月批准立项。2023年2月，参与单位征集，组建标准工作起草组。2用氢气中杂质种类及限值提出了明确技术指标要求。二是给出了相应技全产业链的多个环节都处于发展阶段，对于氢气质量指标和相应检测方定，而检测方法的制定则以采用国内现有标准为指导思想，所列检测方法基本来自国内工业（高纯）氢领域，高纯气领域、天然气领域及大气环境监测领域，方法整体所呈现的特点是来源多向、老旧，可靠性和实用性差，适用性方面更是无一方法针对质子交换膜燃料电池汽车关键杂质含硫化合物、甲醛和有机卤化物是质子交换膜燃料电池车用氢气产品中控制限值较低且对检测技术能力要求较高的项目。目前国内在气中含硫化合物分析领域没有方法可以达到限值要求。国内现有环境空气中甲醛检测的国家标准由于样品用量大，操作繁琐也不适用于现本标准方法借鉴ISO21087:2019推荐的分析技术原理，创新建立了3预浓缩气相色谱-硫化学发光及质谱检测平台，用于氢气中含硫化合物、甲醛和有机卤化物分析。3主要技术内容介绍及分析3.1标准主要内容及适用范围本文件规定了采用预浓缩/气相色谱-硫化学发光和质谱检测法测定质子交换膜燃料电池汽车用氢气中含硫化合物、甲醛和有机卤化物的试本文件适用于质子交换膜燃料电池汽车用氢气中含硫化合物、甲醛和有机卤化物的测定。本文件也可用于工业氢、高纯氢和超纯氢中含硫化合物、甲醛和有机卤化物的测定。1nmol/mol～400nmol/mol。有机卤化物测定范围1μmol/mol～100μmol/mol。硫化氢检出限值为0.01nmol/mol,甲醛检测出值为0.13.2主要内容的说明采用目前商用的气相色谱仪及检测器都无法满足GB/T37244对含硫化合物、甲醛、有机卤化物技术指标限值的检测要求，因此对样品进行浓缩处理是非常必要的。方法的分析流程如图1所示。其中预浓缩仪应具备有效去除样品基质、自动定量取样、样品捕集和解析功能。所有管路内壁和连接部件都须经过惰性化处理。浓缩后样品被引入带有非极性毛细管色谱柱的气相色谱仪，经特定色谱柱分离后的待测组分通过分流组件及连接柱，一路进入硫化学发光检测器对含硫化合物进行检测，另一路进入质谱检测器对甲醛和有机卤化物进行检测。47876141939对于含硫化合物，本方法以天然气制氢、轻烃制氢、煤制氢工艺中对于有机卤化物分析，根据在实际氯碱制氢工艺氢气样品中发现的本方法选用不同规格的内壁涂覆100%二甲基聚硅氧烷的毛细管色谱柱，对含硫化合物混合物、甲醛和有机卤化物混合物进行分离效果考5(b).图2不同规格色谱柱在GC-SCD对含硫化合物分(a)色谱柱规格：DB-1,长105m,内径0.53mm,液膜厚度5μm;当氢气中含有二氧化硫时，两种规格色谱柱对二氧化硫和羰基硫的分离度分别为1.4和0.6,其中105m的非极性色谱柱显示出了较好的分离能力，可达到基线分离。9-二氯甲烷；10-二硫化碳；11-顺-1,2-二氯乙烯；12-三氯甲烷；13-噻吩；14-二甲基二硫醚；15-图3显示，使用GC-MS时，较长的色谱柱对甲醛和硫化氢的分离显示出更优的分辨率。3.2.3浓缩仪条件参数确定目前商用气体浓缩仪多为液氮制冷型和电制冷吸附剂型两种模式。本方法分别对不同类型浓缩仪的分析流程的适用性、可靠性进行了考察，优化了包括捕集温度、解吸温度、捕集流速等参数，建立了适用于各类6浓缩系统的管线和阀温度(℃)2捕集温度(℃)解析温度(℃)捕集温度(℃)样品传输管线温度(℃)烘烤温度(℃)冷结合吸附剂模式浓缩仪的参数和操作条件进行优化，典型操作条件如浓缩系统的管线和阀温度(℃)27捕集温度(℃)解析温度(℃)130第三阶段：第三阶段：聚焦管升温速率(℃/s）50-100聚焦进样样品传输管线温度(℃)60-1502浓缩系统流路温度(℃)4采样冷阱低温(℃)41加热速率(℃/秒）解析高温(℃)3如下分析条件可保证低沸点组分的基线分离，高沸点组分洗脱并被8一阶升温速率：5℃/min一阶终温：128m/z-200m/z采用GC-SCD，对四川中测标物科技有限公司配制的气体标准物，组分峰面积响应值峰面积响应值9分析日期2023-7-4分析日期2023-10-10N2平衡气H2平衡气He平衡气N2平衡气H2平衡气He平衡气硫化氢721175417077562364763955228羰基硫760474807669598964934354157乙硫醇726477127075568054449653171853776578322584204848653008二硫化碳1504113972145579908610625291857592868360648508135455318759145211669112383196101109874注：不同分析日期的响应值差异是由于对仪器进行了维护，响应值有变化。使用氮气、氢气、氦气为平衡气的同浓度含硫化合物标准物质的响应值具有良好的一致性，说明使用不同类型平衡气并不会影响含硫化合物的定性和定量分析。因此，在日常使用中，可根据需要和实际情况选用平2554083注：不同分析日期的响应值差异是由于对仪器进行了维护，响应值有变化。数据显示，在标准物质配制完成初期，氮气、氢气为平衡气的同浓度甲醛标准物质响应值基本相同，存放约5个月后，氢气中甲醛与氮气中甲醛的响应值相比降低了85%。因此，在实际应用中，应将氮气用做为考察方法的可靠性，确定方法准确度。共有来自国内不同区域、验、精密度和正确度确定试验、检出限确定试验。参与单位及仪器设备实验室编号实验室名称色谱仪厂家及型号浓缩仪厂家及型号稀释装置厂家及型号L1中石化石油化工科学研究院有限公司安捷伦7890B-5977型气相色谱质谱仪，配8355型硫化学发光检Entech7200H型（液氮制冷型）Entech4700型L2四川中测标物科技有限公司测器岛津GCMS-QP2020NX型气相色谱质谱晟睿恒CED-S-2020（电子制冷吸附剂思创睿智TraceGasDilution-SFL3国）有限公司仪，NexisSCD-2030型硫化学发光检测器安捷伦8890GC-5977BMSD，配MarkesMultiGasUNITY-xr，MultiMarkesSD7000L4赛默飞世尔科8355型硫化学发光检测器赛默飞Trace1610，ISQ7610PACSeNse硫化学发光检测器（SCD）GasCIAadvantage-xr(电子制冷吸附剂型）MarkesMultiGasUNITY-xr，MultiGasCIAadvantage-xr(电子制冷吸附剂型）MarkesSD7000L5中国计量科学研究院安捷伦8890B-5977型气相色谱质谱仪，配氮制冷型）博赛德BCT-970DL6中国石化销售有限公司河北石油分公司8355型硫化学发光检测器安捷伦8890B-5977型气相色谱质谱仪，配8355型硫化学发光检测器博赛德BCT-990H型（液氮制冷型）博赛德BCT-970D号实验室名称色谱仪厂家及型号浓缩仪厂家及型号稀释装置厂家及型号L7北京博赛德科技有限公司岛津GCMS-QP2020NX型气相色谱质谱博赛德BCT-990H型（液氮制冷型）博赛德BCT-970DL8中国测试技术硫化学发光检测器岛津GCMS-QP2020晟睿恒CED-S-2020思创睿智TraceGasL9研究院中石化（大连）石油化工研究院有限公司NX型气相色谱质谱仪，配NexisSCD-2030型硫化学发光检测器岛津GC2030气相色谱质谱仪（GCMS-QP2020NX）（电子制冷吸附剂晟睿恒CED-S-2020（电子制冷吸附剂Dilution-SF思创睿智TraceGasDilutionSFL10岛津企业管理（中国）有限配SCD-2030型硫化学发光检测器GC-2030-QP2020NX型气相色谱质谱仪，配制冷吸附剂型）朋环SD6000L11广州能源检测研究院SCD-2030型硫化学发光检测器安捷伦8890B-5977型气相色谱质谱仪，配博赛德BCT-990H型（液氮制冷型）博赛德BCT-970DL12中国石化销售有限公司广东石油分公司8355型硫化学发光检测器安捷伦8890B气相色谱仪，配8355型硫化学发光检测器Entech7200H型（液氮制冷型）Entech4700型L13丰田汽车研发中心（中国）岛津GCMS-QP2020气相色谱质谱仪博赛德BCT-990H型（液氮制冷型）博赛德BCT-970DL14有限公司大连大特气体科技有限公司安捷伦8890B气相色谱仪，配8355型硫化学发光检测器博赛德BCT-990H型（液氮制冷型）博赛德BCT-970D各实验室所用气体标准物质均由四川中测标物科技有限公司配制，实验室组分名称及摩尔分数L1/L5/L6/L7/L110.999μmol/mol硫化氢、1.01μmol/mol羰基硫、1.01μmol/mol乙硫醇、1.00μmol/mol二甲基硫醚、1.01μmol/mol二硫化碳、1.00μmol/mol噻吩和1.01μmol/mol二甲基二硫醚混合气体，平衡气氮气L21.03μmol/mol硫化氢、1.01μmol/mol羰基硫、1.04μmol/mol乙硫醇、1.02μmol/mol二甲基硫醚、0.987μmol/mol二硫化碳、1.02μmol/mol噻吩、0.998实验室组分名称及摩尔分数L3μmol/mol二甲基二硫醚混合气体，平衡气氮气1.01μmol/mol硫化氢、1.01μmol/mol羰基硫、1.02μmol/mol乙硫醇、1.05μmol/mol二甲基硫醚、0.993μmol/mol二硫化碳、1.03μmol/mol噻吩、0.998μmol/mol二甲基二硫醚混合气体，平衡气氮气L40.980μmol/mol硫化氢、1.00μmol/mol羰基硫、0.995μmol/mol乙硫醇、0.993μmol/mol二甲基硫醚、0.998μmol/mol二硫化碳、0.992μmol/mol噻吩、1.00μmol/mol二甲基二硫醚混合气体，平衡气氮气L80.984μmol/mol硫化氢、0.995μmol/mol羰基硫、1.02μmol/mol乙硫醇、1.02μmol/mol二甲基硫醚、1.02μmol/mol二硫化碳、1.02μmol/mol噻吩、1.02μmol/mol二甲基二硫醚混合气体，平衡气氮气L91.02μmol/mol硫化氢、1.01μmol/mol羰基硫、1.02μmol/mol乙硫醇、1.04μmol/mol二甲基硫醚、0.992μmol/mol二硫化碳、1.03μmol/mol噻吩、0.991μmol/mol二甲基二硫醚混合气体，平衡气氮气L101.01μmol/mol硫化氢、1.01μmol/mol羰基硫、1.02μmol/mol乙硫醇、1.04μmol/mol二甲基硫醚、0.991μmol/mol二硫化碳、1.03μmol/mol噻吩、0.993μmol/mol二甲基二硫醚混合气体，平衡气氮气L120.969μmol/mol硫化氢、1.01μmol/mol羰基硫、0.986μmol/mol乙硫醇、0.982μmol/mol二甲基硫醚、1.05μmol/mol二硫化碳、1.02μmol/mol噻吩、0.996μmol/mol二甲基二硫醚混合气体，平衡气氮气L130.999μmol/mol硫化氢、0.969μmol/mol羰基硫、0.μmol/mol二甲基硫醚、0.991μmol/mol二硫化碳、0.992μmol/mol噻吩、1.02μmol/mol二甲基二硫醚混合气体，平衡气氮气L141.04μmol/mol硫化氢、1.04μmol/mol羰基硫、1.05μmol/mol乙硫醇、1.07μmol/mol二甲基硫醚、1.017μmol/mol二硫化碳、1.05μmol/mol噻吩、1.026μmol/mol二甲基二硫醚混合气体，平衡气氮气实验室组分名称及摩尔分数L1/L5/L6/0.980μmol/mol甲醛，0.977μmol/mol一氯甲烷，0.983μmol/mol二L7/L11μmol/mol三氯甲烷，1.00μmol/mol溴甲烷，1.01μmol/mol三氯一氟甲烷，1.01μmol/mol顺-1，2-二氯乙烯烷，1.01μmol/mol四氯乙烯，1.01μmol/mol氯苯混实验室组分名称及摩尔分数L2合标准气体，平衡气氮气1.00μmol/mol甲醛，0.98μmol/mol一氯甲烷，0.98μmol/mol二氯甲烷，0.99μmol/mol三氯甲烷，1.00μmol/mol溴甲烷，1.00μmol/mol三氯一氟甲烷，1.01μmol/mol顺-1，2-二氯乙烯烷，1.01μmol/mol四氯乙烯，1.01μmol/mol氯苯混合标准气体，平衡气氮气L31.01μmol/mol甲醛，0.978μmol/mol一氯甲烷，0.983μmol/mol二氯甲烷，0.996μmol/mol三氯甲烷，1.00μmol/mol溴甲烷，0.999μmol/mol三氯一氟甲烷，1.01μmol/mol顺-1，2-二氯乙烯烷，1.01μmol/mol四氯乙烯，1.01μmol/mol氯苯混合标准气体，平衡气氮气L40.960μmol/mol甲醛，0.977μmol/mol一氯甲烷，0.983μmol/mol二μmol/mol三氯甲烷，1.00μmol/mol溴甲烷，0.998μmol/mol三氯一氟甲烷，1.01μmol/mol顺-1，2-二氯乙烯烷，1.01μmol/mol四氯乙烯，1.01μmol/mol氯苯混合标准气体，平衡气氮气L81.05μmol/mol甲醛，0.96μmol/mol一氯甲烷，0.97μmol/mol二氯甲烷，0.98μmol/mol三氯甲烷，0.98μmol/mol溴甲烷，1.00μmol/mol三氯一氟甲烷，1.00μmol/mol顺-1，2-二氯乙烯烷，0.99μmol/mol四氯乙烯，0.99μmol/mol氯苯混合标准气体，平衡气氮气L91.00μmol/mol甲醛，0.978μmol/mol一氯甲烷，0.984μmol/mol二氯甲烷，0.996μmol/mol三氯甲烷，1.00μmol/mol溴甲烷，1.00μmol/mol三氯一氟甲烷，1.01μmol/mol顺-1，2-二氯乙烯烷，1.01μmol/mol四氯乙烯，1.01μmol/mol氯苯混合标准气体，平衡气氮气L101.04μmol/mol甲醛，0.975μmol/mol一氯甲烷，0.981μmol/mol二氯甲烷，0.993μmol/mol三氯甲烷，1.00μmol/mol溴甲烷，0.998μmol/mol三氯一氟甲烷，1.01μmol/mol顺-1，2-二氯乙烯烷，1.01μmol/mol四氯乙烯，1.01μmol/mol氯苯混合标准气体，平衡气氮气L120.98μmol/mol甲醛，1.03μmol/mol一氯甲烷，0.984μmol/mol二氯甲烷混合标准气体，平衡气氮气和电子制冷两种典型类型浓缩仪、三个不同公司气相色谱实验室L1采用Entech7200型液氮制冷型浓缩仪，搭配美国安捷伦公司7890B-5977型气相色谱质谱仪，配8355型硫化学发光检测器。通过Entech4700型高精度稀释仪加载不同体积的稀释气配制摩尔分数为10nmol/mol和1nmol/mol的校准样品。在浓缩仪控制程序中设置10浓缩仪控制程序中设置进样体积分别为200尔分数分别为10nmol/mol，4nmol/mol，2以各组分峰面积为纵坐标，以组分摩尔分数标称值为横坐标，建立各组分的校准曲线，斜率和截距依据最小二乘法并强制过原点计算。参/(mol/nmol)/(mol/nmol)88SCD响应与硫元素质量成正比，通过考察所有组分在校正范围内各浓度响应因子相对标准偏差以及各组分平均响应因子与二甲基硫醚的平校正范围内各组分的响应因子相对标准偏差应在不超过30%，各组标准气的降解、稀释仪和浓缩仪对含硫化物的选择性吸附、浓缩仪捕集组分实验室L1实验室L2实验室L3实验室L4RFRSD%RRF%RFRSD%RRF%RFRSD%RRF%RFRSD%RRF%硫化氢6.25×10-20.2312367.093.36%-9.870.22099.568.46羰基硫7.7×107.23-1.6913645.633.41%-0.562.69×105.769.250.25656.996.77乙硫醇7.06×107.30-9.8711567.846.29%-15.7010.845.240.23527.293.52二甲硫醚7.83×106.28-13722.085.67%-2.37×1014.25-0.27745.81-二硫化碳1.51×108.27-3.4813188.363.33%-3.895.61×105.4114.250.564310.008.72噻吩7.63×10-2.5913526.726.31%-1.422.74×104.880.27525.63二甲二硫醚1.40×107.26-10.8212704.747.50%-7.414.98×107.836.780.47036.596.40以使用液氮制冷和电子制冷两种典型类型浓缩仪、三个不同公司气实验室L1采用Entech7200型液氮制冷型浓缩仪，搭配美国安捷伦公司7890B-5977型气相色谱质谱仪，配8355型硫化学发光检测器。通过Entech4700型高精度稀释仪加载不同体积的稀释气配制摩尔分数为分，在浓缩仪控制程序中设置400nmol/mol校准样品取样量分别为500nmol/mol，40nmol/mol浓度点的系列校准样品；设置20nmol/mol校准卤化物组分，在浓缩仪控制程序中设置400nmol/mol校准样品取样量分甲醛和有机氯化物校准样品。对于甲醛组分，在浓缩仪控制程序中设置仪控制程序中设置400nmol/mol校准样品取样量分别为125mL和advantage-xr电子制冷吸附剂型浓缩仪，美国安捷伦公司7890B-5977型气相色谱质谱仪。对于甲醛组分，在浓缩仪控制程序中设置1μmol/mol标准气体进样体积分别为320mL，160mL，获得400nmol/mol，200准样品，在浓缩仪控制程序中设置进样体积分别为800mL，320mL，列校准样品。对于有机卤化物组分，通过气体稀释仪配制100nmol/mol配制摩尔分数分别为400nmol/mol，200nmol/mol，100nmol/mol，40以各组分峰面积为纵坐标，以组分摩尔分数标称值为横坐标，建立各组分的校正曲线，斜率和截距依据最小二乘法并强制过原点计算。参R2R2/(mol/nmol)45555355555结果表明，使用不同制冷方式浓缩仪、不同公司气相色谱，四家实验室甲醛和有机卤化物校准曲线均成线性，相关系数R2大于0.99，MS物质的保留时间比较进行样品中含硫化合物定性。甲醛使用MS检测，根据与所选甲醛特征离子比较，或与已知标准物质保留时间比较进行样品中甲醛定性。有机卤化物使用MS检测，根据与已知标准物质的保留1-硫化氢；2-羰基硫；3-乙硫醇；4-甲硫醚；5-二硫化碳；6-噻吩；7-二甲基二硫醚图41nmol/mol含硫化合物色谱图1-一氯甲烷；2-溴甲烷；3-三氯氟甲烷；4二氯甲烷；5-顺-1,2-二氯乙烯；6-三氯甲烷；7-四氯乙烯；8-氯苯可分别采用强制过原点校准曲线方程或平均响应因子(单点校准)模式进行定量分析。强制过原点校准曲线方程法选择3.2.6.2中5～7个不同浓度校准点，以组分校准点浓度为横坐标，以其对应的峰面积为纵坐标，建立强制过原点的多点校准曲线方程，则样品中目标化合物摩尔分φx=x——目标化合物x的摩尔分数，nmol/mol；Ax目标化合物x的峰面积；a——目标化合物x的校准曲线方程斜率。 =xRF=x RFx——目标化合物x的平均响应因子；xxxARF（3xxxx——目标化合物x的摩尔分数，nmol/mol；Ax目标化合物x的峰面积；——目标化合物x的平均响应因子。对于当天通过3.2.6.2.1线性相关性验证的系统，可采用校准曲线方程或平均响应因子进行定量分析，对已通过验证检验且7天内未关机的实际分析中，应先进行样品的预测定，当样品预测浓度值超过校准下限与方法检出限浓度之间时，采用单点校准，校准点浓度为方法规定因此本方法有必要对含硫化合物、甲醛、有机卤化物方法检出限进行考察，确定适宜的方法检出限。同时给出日常试验过程中，易于操作的检xMDL=3.143×（xixi,x——目标化合物测量结果和测量结果的平均值；本研究中，选用浓度为0.05nmol/mol的混合含硫化合物试样作为MDL计算用浓度点，按照公式（414个实验室得到的的含硫化合物单位：nmol/mol组分实验室L1实验室L2实验室L3实验室L4实验室L5实验室L6实验室L7硫化氢0.00790.00720.00850.00690.00740.00740.0057羰基硫0.00960.00710.00530.00850.00920.00730.0065乙硫醇0.00940.00740.00470.00580.01080.00900.00730.00800.01150.00410.00490.00960.00840.0046二硫化碳0.00600.00610.00250.00490.00970.00770.00650.00940.00690.00350.00330.01000.00770.0044二甲二硫醚0.00800.01090.00440.00500.00930.00870.0054单位：nmol/mol组分实验室L8实验室L9实验室L10实验室L11实验室L12实验室L13实验室L14硫化氢0.00850.00300.00260.00890.00300.00500.0035羰基硫0.01600.02000.00680.00890.01050.00440.0045乙硫醇0.00970.01640.00260.00860.01070.00380.00860.01350.00840.00220.00640.00620.00590.0046二硫化碳0.00660.00640.00380.00760.00650.00440.00270.01010.00740.00380.00970.00810.00460.00600.00850.00510.00180.00980.00760.00500.006814222534322343385786397786说明1：噪声采用ASTM算法说明2：L1、L3、L4实验室所用气相色谱为集成式GC-SCD-MS结果显示，在保证系统没有残存组分时，浓度为0.01nmol/mol含硫化合物的响应值与基线噪声有明显区别，各组分信噪比大于2。0.01nmol/mol含硫化合物均可通过目测被清晰识别，因此，本方法中含硫化合物能以99%置信度被检出的最低浓度为0.01nmol/mol。本研究中，选用甲醛测定范围中最低浓度点(1nmol/mol)作为MDL计算用浓度点，使用选择离子模式定性，定量离子定量。根据公式(4),13个实验室计算法MDL结果如表15所示。组分实验室L1实验室L2实验室L3实验室L4实验室L5实验室L6实验室L7组分实验室L8实验室L9实验室L10实验室L11实验室L12实验室L13甲醛0.06660.05970.0571表15显示，各实验室对甲醛MDL统计值均小于0.0836nmol/mol。根据计算法得到的MDL,使用稀释仪和浓缩仪，实验室L1、L3、L4分别对浓度相当于0.1nmol/mol的甲醛进行测试，谱图见图8,信噪比数据见表16。比数据见表16。说明1：噪声采用ASTM算法说明2：L1、L3、L4实验室所用气相色谱为集成式GC-SCD-MS谱图显示，浓度为0.1nmol/mol甲醛的响应值与基线噪声有明显区单位：nmol/mol组分实验室L1实验室L2实验室L3实验室L4实验室L5实验室L6一氯甲烷0.05580.08050.05780.09300.07920.0738溴甲烷0.04640.06540.05280.06370.04590.0582三氯一氟甲烷0.04100.06880.08490.08660.03920.0649二氯甲烷0.04920.08710.08770.07500.04950.0884顺-1,2-二氯乙烯0.03290.05470.04460.09190.13820.0951三氯甲烷0.03850.08740.03870.07950.05610.04340.03470.07350.07350.09620.11450.07160.05720.05190.04780.06210.08480.0627组分实验室L7实验室L8实验室L9实验室L11实验室L13一氯甲烷0.08540.08140.04950.07030.0443溴甲烷0.08830.09870.07890.05380.0330三氯一氟甲烷0.06060.05280.06350.07210.0288二氯甲烷0.10270.07040.03950.07240.0304顺-1,2-二氯乙烯0.07970.05560.05220.09220.0299三氯甲烷0.03080.04870.05000.05540.02550.11200.04750.04300.03820.03270.08800.04620.05180.06820.0299法规定采用全扫描模式测试样品中有机卤化物，而根据总离子图得到的使用稀释仪和浓缩仪，实验室L1、L3、L4分别对浓度相当于0.511122224324642455255636776说明说明1：噪声采用ASTM算法2：L1、L3、L4实验室所用气相色谱3为集成式GC-SCD-MS9谱图显示，随着化合物中氯原子数的增加，浓度为0.5nmol/mol有机卤化物响应值增大，信噪比提高，除一氯甲烷信噪比低于2以外，各有机卤化物均可通过目测被清晰识别，因此，本方法中有机卤化物能以99%置信度被检测的最低浓度为0.5nmol/mol。本方法含硫化合物检出限浓度为0.01nmol/mol,甲醛检出限浓度为0.1nmol/mol,有机卤化物检出限浓度为0.5nmol/mol。出限时，可使用适宜方法准备检出限浓度点样品并进行测试，当所检测组分通过目测均可以被清晰识别，90%以上组分信噪比大于2时，表明分析系统和分析方法具备测试方法检出限能力。实验室测定次数样品测定结果/(nmol/mol)L1110.06373.82291.99161.01340.42580.16440.0799210.04693.93771.92200.85830.42780.17010.0815L219.93503.98001.96600.93100.47000.19100.099429.73803.91501.98700.93600.46100.18600.0974L3110.58403.91181.91500.92840.41990.16910.0751210.17733.93591.90170.94050.42370.17330.0656L4111.02553.91661.92940.90280.47820.17200.0719210.63864.00281.94471.00820.48970.16290.0674L5110.04713.97281.83480.86330.47510.18410.0939210.45463.94041.87570.84770.49160.18590.0865L6110.08953.85081.82450.97010.44310.15840.078729.84593.80631.81600.96580.44080.14940.0754L719.74404.04001.98200.82600.42300.15400.0730210.02903.96101.98200.78700.40800.14800.0730L819.87503.93801.98300.92000.47100.18100.099029.86103.92101.95800.90700.44700.18800.0960L919.73703.93701.38500.68700.33400.14200.076029.81103.90901.36100.66400.32900.12900.0740L10110.38303.94701.93600.95100.38800.14500.0680210.07403.94601.93500.96500.38100.14300.0690L11110.08603.91601.82400.91500.42000.14700.0770210.22903.72201.73900.88400.39200.15200.0730L12110.28903.46101.63001.02500.49000.14500.076029.91804.22402.01600.90300.49300.15200.0740L13110.05203.90301.78901.16600.48900.23000.112029.87604.20402.05701.12000.61700.24900.1340L14110.62883.69161.67990.83910.39130.17100.0892210.72113.70431.67750.83970.40880.17260.0934实验室测定次数样品测定结果/(nmol/mol)L1110.92124.14862.16131.09970.46200.17840.0867211.09924.35012.12330.94820.47260.18790.0901L2110.53004.22002.08000.98600.49800.20200.0980210.32004.15002.11000.99100.48800.19700.1010L3112.00284.43622.17171.05290.47620.19180.0847211.54164.46352.15661.06660.48050.19660.0741L4111.91904.23402.08570.97590.51690.18590.0777211.50074.32722.10231.08990.52930.17610.0729L5110.66384.21671.94740.91620.50430.19540.0997211.09634.18231.99080.89980.52180.19730.0918L6111.16554.26142.01911.07350.49040.17530.0871210.89594.21232.00971.06880.48780.16540.0834L7111.07164.59032.25220.89390.48070.17520.0826211.39604.50102.25250.93820.46400.16810.0826L8110.23904.08402.05700.95400.48800.18800.1030210.22504.06502.03100.94000.46300.19500.0990L9112.87905.20741.83190.90870.44180.18780.1005212.97705.17041.80020.87830.43520.17060.0979L10110.95724.16452.04171.01830.40960.15140.0728210.63074.16502.04261.00380.40170.15260.0721L11111.51804.47202.08301.04500.48000.16700.0880211.68204.25101.98601.01000.44700.17300.0830L12111.61703.90801.84001.15700.55300.16300.0860210.77304.58802.19000.87100.53600.16500.0800L13110.25903.68001.68501.17800.46100.21900.106028.57403.64301.78200.97100.53500.22300.1230L14112.21324.24191.93030.96420.44960.19640.1024212.31934.25651.92750.96480.46980.19830.1073实验室测定次数样品测定结果/(nmol/mol)L1110.12633.88072.13311.16980.48380.19790.0976210.13283.97681.98610.99680.51010.21760.1005L219.81703.96701.98601.01000.49600.21000.111029.60703.90401.98701.03500.50900.21900.1070L3110.54663.97961.97410.97420.47740.18540.0974210.11204.04091.97400.99430.48330.18410.0869L4110.54824.08592.01690.97600.52080.18960.087629.99844.11932.06471.03530.52800.18390.0886L5110.10554.03971.98640.98480.56100.24060.1280210.42423.96432.00170.95120.59530.24600.1277L6110.17803.87651.88841.14020.51530.20550.1084210.43853.80491.84181.08760.53030.18970.1083L7110.27404.03801.91600.96200.46500.17700.0850210.13904.01201.91000.95800.46700.17800.0840L819.98603.94901.96901.01500.50500.20500.095029.93403.92801.95001.01400.50300.20700.0980L919.80704.24802.08801.06500.54500.22800.125029.62304.18902.05901.04500.54400.22100.1190L1019.84504.03702.03701.03200.50800.21200.111029.81704.05102.02601.03800.50300.21000.1090L11110.03204.07001.75901.05900.46900.18300.0970210.52003.63001.78600.90500.45500.19000.0990L12110.22803.72201.59100.73700.35300.16200.0950210.03204.04501.88800.78800.39700.15600.0780L1319.81303.64101.84500.92700.38900.15500.075029.79603.70201.85100.82400.40400.15900.0800L14110.30744.33881.93920.97910.47900.21680.1172210.08274.29831.95290.99320.49130.2097实验室测定次数样品测定结果/(nmol/mol)L1110.00983.83612.10861.15640.47820.19570.0965210.07553.95431.97480.99110.50720.21640.0999L219.75503.94201.97301.00300.49300.20800.111029.54603.88001.97501.02800.50600.21800.1060L3111.03234.16292.06501.01910.49940.19400.1019210.57774.22702.06491.04010.50560.19260.0909L4110.87934.21412.08031.00660.53720.19550.0904210.31234.24862.12961.06780.54460.18960.0914L519.39633.75621.84700.91570.52160.22370.119029.69263.68601.86120.88440.55350.22870.1187L619.97483.79911.85070.50500.20140.1063210.23013.72891.80511.06590.51970.18590.1062L7111.00584.32562.05281.02610.49790.18960.0909210.86204.29852.04561.03020.49990.19100.0895L819.88503.90901.95001.00500.50000.20200.094029.83403.88801.93101.00400.49800.20500.0970L919.45624.09602.01331.02690.52550.21980.120529.27874.03911.98531.00760.52450.21310.1147L1019.37033.85631.92810.98830.48410.19990.103929.34443.84211.93870.98230.47870.20140.1056L11110.59304.29801.85800.49500.19300.1030211.10903.83301.88600.95600.48100.20100.1040L12112.02304.37501.87100.86600.41500.19100.1120211.51404.64302.16600.90400.45600.17900.0890L13111.79804.07102.05101.03000.43200.16800.0800211.17504.14602.07300.92300.45300.17400.0890L14110.07034.23911.89460.95660.46800.21180.114529.85094.19951.90800.97040.48000.20490.1184实验室测定次数样品测定结果/(nmol/mol)L1110.16273.85392.09591.01270.44360.17790.0886210.12064.01781.95661.01760.50960.19900.1031L219.99203.93602.01200.90100.43700.18500.089029.84603.88202.01900.89100.44100.17100.0950L3110.47503.82471.86180.88970.38560.15520.0859210.32813.89681.86060.89670.40110.15250.0838L4110.71014.00351.91070.91110.48930.16280.0731210.17294.00991.99720.99640.47470.15650.0751L5110.11404.04981.95670.96060.50280.19500.0898210.55474.01141.82270.92160.52790.20090.0994L6110.18673.89381.85521.07620.49020.15460.0865210.29143.89941.85561.05150.50120.15640.0795L719.89504.12302.00100.88600.44300.16300.0770210.12504.02902.00100.86000.44500.16300.0760L8110.27604.03302.04700.89800.44200.18500.0910210.21204.02602.03900.91000.45300.17500.0890L919.94204.13901.93900.96600.45300.18700.100029.76104.11001.93500.96900.47600.20000.1100L10110.21903.97001.98600.99200.35700.14000.0680210.17503.97401.98201.00400.35900.13800.0690L11110.07603.90001.83501.01000.48100.18400.087029.78403.81001.60500.98200.48900.18100.0880L12110.03603.86002.06701.06200.52000.20100.070029.76804.46302.24800.99200.48400.16300.0770L1319.90803.93801.91301.22400.53300.25200.118029.76304.20602.09101.17400.66100.24800.1340L14110.67683.83751.73440.87020.42690.19630.1047211.05433.86221.76200.86530.43700.19200.1134实验室测定次数样品测定结果/(nmol/mol)L1110.71834.06462.21051.06800.46790.18760.0935210.13854.02491.96011.01940.51050.19930.1033L2110.86004.28002.18800.97900.47500.20100.0973210.71004.22102.19600.96800.47900.18600.1040L3111.99284.37902.13161.01860.44150.17770.0983211.82474.46152.13021.02670.45920.17460.0959L4111.45644.28242.04380.97460.52340.17410.0782210.88174.28932.13641.06580.50780.16740.0803L5110.45194.18512.02200.99270.51960.20150.0928210.90734.14531.88350.95240.54560.20770.1027L6110.88914.16231.98311.15040.52400.16530.092424.16831.98361.12400.53580.16720.0850L7110.96984.57052.21820.95330.49160.18100.0851211.22434.46712.21870.98200.49310.18090.0843L8110.91404.28302.17400.95300.46900.19600.0960210.84604.27602.16500.96600.48200.18600.0940L9110.24114.26351.99730.99510.46660.19260.1030210.05474.23371.99320.99820.49030.20600.1133L10110.58754.11762.05361.04010.37780.14320.0719210.54164.11302.05781.00400.37200.14520.0732L11110.62604.11301.93501.06500.50700.19400.0920210.31804.01801.69301.03600.51500.19100.0920L12110.32103.97002.12601.09100.53500.20600.072024.62102.32301.02700.50100.16900.0800L1319.64403.45701.67901.14700.46800.22200.119028.05103.50501.73800.98500.54500.23700.1360L14111.54204.14851.87490.94070.46150.21220.1131211.95014.17521.90480.93550.47250.20750.1225实验室测定次数样品测定结果/(nmol/mol)L1110.05803.81832.07211.03510.44190.18440.0922210.00363.97171.99661.06360.53880.20380.1026L219.83103.95402.02601.01000.50800.21500.115029.64803.90102.03101.00400.51000.20700.1140L3111.00253.94581.88420.91000.41030.14860.0899210.62504.01891.92900.93490.41910.14810.0756L4110.81744.03121.95490.97270.51700.16980.0872210.38483.95242.05991.05280.50060.17090.0912L5110.00864.00531.94630.98920.51040.22250.1189211.05073.86891.84700.97240.53050.22260.1168L6110.08333.82861.89981.05030.50330.20480.1052210.17813.84151.85911.06760.51660.19640.0973L7110.50404.04101.92400.97100.47800.17900.0850210.01404.01401.92800.98000.48100.18100.0850L8110.23404.04802.03701.03700.51800.21600.1170210.18004.03102.02201.03400.51700.21200.1120L9110.13704.22001.97700.98500.46200.19000.102029.95304.19001.97300.98800.48600.20400.1120L10110.71104.13502.09801.08100.54500.23100.1250210.28204.14702.10101.08600.54400.23600.1280L11110.09303.82801.84500.99200.54300.19000.100029.99303.69601.78901.04700.53900.20200.1080L12110.15103.76301.70600.99000.56800.21100.1120210.00004.05501.86601.02300.54900.19800.0980L1319.81503.84601.95001.04500.44900.19800.103029.83103.84401.92400.92000.49200.20600.1120L14110.87493.94271.74290.87350.43590.1997211.29303.93521.78030.87990.42730.1968实验室测定次数样品测定结果/(nmol/mol)L1110.41613.95422.14591.07200.45760.19100.095529.75563.87321.94711.03720.52550.19880.1000L219.98904.01702.05901.03000.51600.21800.114029.80303.96302.06301.02000.51800.21000.1170L3112.83264.60212.19761.06140.47850.17330.1048212.39234.68742.24981.09040.48880.17280.0882L4111.10234.13742.00640.99830.53070.17430.0895210.65834.05651.08050.51370.17540.0937L519.61473.84761.86970.95030.49030.2137210.61583.71671.77430.93410.50960.2138L6110.01453.80251.88691.04310.49990.20340.1045210.10873.81531.84651.06030.51310.19510.0966L7111.07194.25922.02811.03260.50390.18870.0898210.55554.23082.03271.02310.50650.19130.0891L8110.08903.99102.00801.02200.51100.21300.1150210.03503.97401.99301.01900.50900.20900.1110L919.94264.24182.07861.05190.49710.22650.110229.77184.14972.06461.02850.50800.20350.1100L10110.05913.89411.97271.01940.51820.21680.120029.65573.88281.97051.01530.51100.22130.1178L11110.12903.84101.85100.99500.54500.19100.1010210.02803.71001.79501.05100.54100.20200.1080L1219.99303.70401.68000.97500.55900.20800.110029.95004.03501.85601.01800.54600.19700.0970L13110.70903.77101.91201.02500.44000.19500.101029.68303.78601.89500.90600.48400.20300.1100L14111.69874.24141.87490.93970.46890.21480.1205212.14864.23331.91520.94650.45960.21170.1205实验室测定次数样品测定结果/(nmol/mol)L1110.08303.96942.16581.19340.45810.20510.1050210.11533.99752.02301.01070.51780.2152L219.80103.93702.01701.01500.50600.21800.114029.64903.88902.02701.01500.51600.21600.1140L3110.50743.79301.86880.90040.43810.17850.1172210.02083.83391.86350.91020.44540.18650.1041L4110.87884.17690.93650.52850.18310.1004210.59304.08542.09911.05680.49480.18020.1018L5110.09644.04351.99791.05210.53550.23290.1281210.20974.10661.94511.01880.55840.23410.1283L6110.14763.94161.91401.10910.56160.20660.1087210.66403.91441.85221.19650.57010.19290.1043L7110.29504.09001.91500.94200.45100.17100.0830210.14304.01001.89800.92700.45200.17100.0830L8110.24304.02202.02701.02600.53000.21800.1170210.15004.01002.01201.03100.51300.21700.1210L919.62404.07802.10201.09000.55400.23100.120029.44804.04802.03101.08800.56500.22500.1150L10110.13803.99202.00701.02600.52500.22700.122029.85803.98102.00501.02800.52500.22400.1240L11110.06203.96501.76701.07500.46000.18000.099029.93903.86701.86001.00900.44900.18400.0920L12110.27403.60201.60600.74900.38000.14000.0810210.08703.96501.82200.74900.37600.14200.0730L13110.00403.78101.91700.96700.40800.17200.083029.95703.90201.93700.89200.44900.18100.0960L14110.34493.74061.63830.80700.39680.17740.1004210.67623.73461.68000.82710.39760.17940.0996实验室测定次数样品测定结果/(nmol/mol)L119.80793.86112.10681.16080.44560.19950.102129.84303.88991.96850.98350.50390.20940.1090L219.32603.74601.91900.96600.48100.20800.108029.18203.70101.92900.96600.49100.20500.1090L3110.95443.95441.94830.93870.45670.1861210.44703.99691.94280.94900.46430.19450.1086L4110.58094.06251.91710.91090.51400.17810.0977210.30303.97352.04161.02790.48130.17530.0990L519.40673.76731.86140.98030.49890.21700.119429.51233.82611.81220.94920.52030.21810.1195L619.81523.81251.85131.07280.54320.19980.1051210.31473.78621.79151.15730.55140.18660.1009L7111.19594.44772.08301.00870.49000.18550.0904211.03164.36072.06381.02400.49120.18600.0901L819.84403.86501.94800.98600.50900.21000.112029.75403.85301.93300.99100.49300.20800.1160L918.84263.74691.93131.00150.50900.21220.110328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