固定污染源废气酞酸酯类的测定气相色谱法

中华人民共和国国家环境保护标准HJ869—2017固定污染源废气酞酸酯类的测定气相色谱法Stationarysourceemission—Determinationofphthalateesters—Gaschromatography（发布稿）本电子版为发布稿。请以中国环境出版社出版的正式标准文本为准。2017—11—28发布2018—01—01实施环境保护部发布i目次前言····························································································································ii1适用范围·····················································································································12规范性引用文件············································································································13方法原理·····················································································································14干扰和消除··················································································································15试剂和材料··················································································································16仪器和设备··················································································································37样品···························································································································48分析步骤·····················································································································69结果计算与表示············································································································610精密度和准确度··········································································································711质量保证和质量控制····································································································712废物处理···················································································································813注意事项···················································································································8附录A（规范性附录）方法的检出限和测定下限···································································9附录B（资料性附录）方法的精密度和准确度····································································10附录C（资料性附录）标准色谱图····················································································12ii前言为贯彻《中华人民共和国环境保护法》和《中华人民共和国大气污染防治法》，保护环境，保障人体健康，规范固定污染源废气中酞酸酯类化合物的测定方法，制定本标准。本标准规定了测定固定污染源废气中酞酸酯类化合物的气相色谱法。本标准的附录A为规范性附录，附录B和附录C为资料性附录。本标准为首次发布。本标准由环境保护部环境监测司和科技标准司组织制订。本标准起草单位：沈阳市环境监测中心站。本标准验证单位：辽宁省环境监测实验中心、大连市环境监测中心、鞍山市环境监测中心站、抚顺市环境监测中心站、沈阳市疾病预防控制中心和沈阳市环境保护局铁西分局环境监测站。本标准环境保护部于2017年11月28日批准。本标准自2018年1月1日起实施。本标准由环境保护部解释。1固定污染源废气酞酸酯类的测定气相色谱法警告：本方法所用的溶剂和试剂具有一定毒性，样品前处理过程应在通风橱中进行，并按规定佩戴防护用具，避免接触皮肤和衣物。1适用范围本标准规定了测定固定污染源有组织排放废气中酞酸酯类化合物的气相色谱法。本标准适用于固定污染源有组织排放废气中邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁苄酯、邻苯二甲酸二（2-乙基己基）酯和邻苯二甲酸二正辛酯共6种酞酸酯的测定。若通过验证，本标准也适用于其他酞酸酯类的测定。当采样体积为1m3（标准状态下干采样体积）时，方法的检出限为0.4µg/m3～0.8µg/m3，测定下限为1.6µg/m3～3.2µg/m3。详见附录A。2规范性引用文件本标准内容引用了下列文件中的条款。凡是不注明日期的引用文件，其有效版本适用于本标准。GB/T16157固定污染源排气中颗粒物测定与气态污染物采样方法HJ/T48烟尘采样器技术条件HJ/T373固定污染源监测质量保证与质量控制技术规范（试行）HJ/T397固定源废气监测技术规范3方法原理以等速采样方式，使固定污染源排气依次通过加热的采样管、冷却装置和树脂柱，颗粒物和气相中的酞酸酯类分别被收集到玻璃（或石英）纤维滤膜（或滤筒）和XAD-2树脂上，同时冷凝液被收集。滤膜（或滤筒）和XAD-2树脂用乙醚-正己烷混合溶液提取，冷凝液用正己烷提取，提取液经浓缩、净化后，用具有氢火焰离子化检测器的气相色谱分离检测，根据保留时间定性，内标法或外标法定量。4干扰和消除采用硅酸镁柱净化可去除或减少干扰，详见7.3.3。5试剂和材料除非另有说明，分析时均使用符合国家标准的分析纯化学试剂，实验用水为新鲜制备的纯水。25.1二氯甲烷（CH2Cl2）：色谱纯。5.2正己烷（C6H14）：色谱纯。5.3乙醚（C4H10O）：色谱纯。5.4丙酮（C3H6O）：色谱纯。5.5无水硫酸钠（Na2SO4）：使用前在马弗炉中于450℃烘烤4h，冷却，于磨口玻璃瓶中密封保存。5.6乙醚-正己烷混合溶液：1+9，临用现配。5.7乙醚-正己烷混合溶液：2+8，临用现配。5.8丙酮-正己烷混合溶液：1+9，临用现配。5.9二氯甲烷-正己烷混合溶液：2+8，临用现配。5.10邻苯二甲酸二苯酯（C20H14O4）：纯度98%以上。替代物，亦可使用其他类似物。5.11替代物贮备液：ρ=2000µg/ml。称取邻苯二甲酸二苯酯（5.10）0.1g（准确至0.1mg），于50ml容量瓶中，加入少许丙酮（5.4）溶解并用正己烷（5.2）定容，混匀。4℃以下密封保存。5.12替代物使用液：ρ=80.0µg/ml。移取1.00ml替代物贮备液（5.11）于25ml容量瓶中，用正己烷（5.2）定容，混匀。4℃以下密封保存。5.13苯甲酸苄酯（C14H12O2）：纯度98%以上。内标，亦可使用其他类似物。5.14内标使用液：ρ=2000µg/ml。称取苯甲酸苄酯（5.13）0.1g（准确至0.1mg），于50ml容量瓶中，加入少许二氯甲烷（5.1）溶解并用正己烷（5.2）定容，混匀。4℃以下密封保存。5.15酞酸酯类标准贮备液：ρ=2000µg/ml。直接购买市售有证标准溶液，包括邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁苄酯、邻苯二甲酸二（2-乙基己基）酯和邻苯二甲酸二正辛酯，溶剂为正己烷，4℃以下密封保存，或参考标准溶液证书保存。5.16酞酸酯类混合标准使用液：ρ=80.0µg/ml。分别移取酞酸酯类标准贮备液（5.15）和替代物贮备液（5.11）1.00ml于25ml容量瓶中，用正己烷（5.2）定容，混匀。4℃以下密封保存。5.17硅酸镁：150µm～250µm（100目～60目）。使用前，称取100g±10g放入蒸发皿中，于140℃加热16h，趁热转移至500ml磨口试剂瓶中，加盖，冷却至室温后，加入3.0ml±0.1ml实验用水，密封，充分振摇混合10min，静置2h后使用。5.18硅酸镁固相萃取柱：1000mg/6ml，亦可根据杂质含量选择适宜容量的商业化硅酸镁固相萃取柱。5.19玻璃（或石英）纤维滤膜（或无胶滤筒）：对0.3µm标准粒子的截留效率不低于99%。使用前在马弗炉中于500℃加热6h以上，冷却，避免与塑料直接接触，密封保存，使用前保证没3有折痕。5.20XAD-2树脂（苯乙烯-二乙烯基苯聚合物）：250µm～840µm（60目～20目）。使用前用二氯甲烷（5.1）回流提取16h后，更换二氯甲烷继续回流提取16h，再用乙醚-正己烷混合溶液（5.6）回流提取16h，室温下真空干燥2h～3h，于玻璃瓶中密封保存。5.21氮气：纯度≥99.999%。5.22玻璃棉：使用前用二氯甲烷（5.1）回流提取2h～4h，干燥后密封保存。5.23变色硅胶：1180µm～3350µm（16目～6目）。6仪器和设备6.1气相色谱仪：具有分流/不分流进样口、程序升温功能和氢火焰离子化检测器。6.2色谱柱：石英毛细管色谱柱，30m（长）×0.25mm（内径）×0.25µm（膜厚)，固定相为5%苯基95%二甲基聚硅氧烷、35%苯基65%二甲基聚硅氧烷或14%氰丙基苯基86%二甲基聚硅氧烷，或其他等效色谱柱。6.3采样设备：包括组合采样管、滤膜（或滤筒）托架、冷却装置、树脂柱和冷凝液接收瓶、流量计量和控制装置及采样泵等部分，见图1。测定固定污染源排气颗粒物中的酞酸酯类，应采用符合HJ/T48的烟尘采样器。6.3.1组合采样管：包括采样管、S型皮托管和热电阻（或热电偶）。采样管带有加热装置，加热温度为105℃～125℃。如果排气温度超过500℃，应使用带冷却水套的采样管。采样管外管材质为不锈钢，内管材质为硼硅酸盐玻璃、石英玻璃或钛合金金属，内表面平滑。6.3.2滤膜（或滤筒）托架：材质为聚四氟乙烯、不锈钢或钛合金等，带有加热装置，加热温度为105℃～125℃。6.3.3冷却装置、树脂柱和冷凝液接收瓶：冷却装置包括冷凝器（具有冷却水循环泵或电子冷却装置）和冷却水箱。冷凝器用