动物源性食品中94种激素残留量的测定 液相色谱-串联质谱法

ICS号中国标准文献分类号T/SZNB团体标准T/SZNBXXXXX-XXXX动物源性食品中94种激素残留量的测定液相色谱-串联质谱法Determinationof94hormoneresiduesinanimalderivedfoodsbyliquidchromatography-tandemmassspectrometryXXXX-XX-XX发布XXXX-XX-XX实施深圳市农业产业化龙头企业协会发布T/SZNBXXXXX-XXXX目录TOC\o"1-1"\h\u30506前言 T/SZNBXXXXX-XXXX前言本文件按照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》的规定起T/SZNBXXXXX-XXXX动物源性食品中94种激素残留量的测定液相色谱-串联质谱法1范围本标准规定了畜禽产品、水产品、奶、禽蛋、蜂蜜等食品中皮质激素、雄激素、孕激素、雌激素的液相色谱-串联质谱法。本标准适用于畜禽产品、水产品、乳、禽蛋、蜂蜜等食品中皮质激素、雄激素、孕激素、雌激素的测定。2规范性引用文件下列文件中的内容通过文中的规范性引用而构成本文件必不可少的条款。其中，注日期的引用文件，仅该日期对应的版本适用于本文件；不注日期的引用文件，其最新版本（包括所有的修改单）适用于本文件。GB/T6682分析实验室用水规格和试验方法3术语和定义本文件没有需要界定的术语和定义。4原理试样经β葡萄榶醛苷酶/芳基硫酸酯酶水解后,残留的激素用乙腈提取,增强型除脂固相萃取柱净化，液相色谱-串联质谱测定,基质匹配外标法定量。5试剂和材料除另有规定外，在分析中仅使用分析纯的试剂，水为GB/T6682规定的一级水。5.1试剂5.1.1乙腈（CH3CN，CAS号：75-05-8）：色谱纯。5.1.2甲醇（CH3OH，CAS号：67-56-1）：色谱纯。5.1.3乙酸铵（CH3COONH4，CAS号：631-61-8）。5.1.4氯化钠（NaCl，CAS号：7647-14-5）。5.1.5氟化铵（NH4F，CAS号：12125-01-8）。5.1.6β-葡萄糖醛苷酶/芳基硫酸酯酶(β-Glucuronidase/arylsulfatase)，100000units/20000units/mL。5.2溶液配制T/SZNBXXXXX-XXXX5.2.150%乙腈水溶液：取乙腈50mL，用水稀释至100mL，混匀。5.2.20.2mol/L乙酸铵溶液：取乙酸铵1.54g，用水溶解并稀释至100mL，混匀。5.2.30.1%甲酸水溶液：取1mL甲酸，用水稀释至1000mL，混匀。5.2.41mmol/L氟化铵：取0.037g氟化铵，用水稀释至1000mL，混匀。5.2.5乙腈：甲醇（8：2）（含0.1%甲酸）溶液：取200mL甲醇和1mL甲酸，用乙腈稀释至1000mL，混匀。5.3标准品5.3.1雄激素：脱氢表雄酮、群勃龙、去甲雄烯二酮、诺龙、勃地酮、雄烯二酮、睾酮、表睾酮、炔诺酮、美雄酮、甲基睾酮、美替诺龙、司坦唑醇、丙酸诺龙、氟甲睾酮、达那唑、丙酸睾酮、美替诺龙醋酸酯、苯丙酸诺龙，参见附录A表A，纯度≥95%，或经国家认证并授予标准物质证书的标准品。5.3.2雌激素：己烯雌酚、己烷雌酚、雌三醇、雌酮、炔雌醇、17α-雌二醇、17β-雌二醇、己二烯雌酚，参见附录A表A，纯度≥95%，或经国家认证并授予标准物质证书的标准品。5.3.3孕激素：孕三烯酮、左炔诺孕酮、17α-羟基孕酮、21α-羟基孕酮、甲地孕酮、甲羟孕酮、氯地孕酮、醋酸甲地孕酮、醋酸甲羟孕酮、醋酸美仑孕酮、醋酸氯地孕酮、己酸羟孕酮、醋酸环丙氯地孕酮，参见附录A表A，纯度≥95%，或经国家认证并授予标准物质证书的标准品。5.3.4皮质激素：醛固酮、保泰松、脱氧可的松、泼尼松、可的松、泼尼松龙、氢化可的松、醋酸去氧皮质酮、非那雄胺、甲基泼尼松龙、6α-甲基氢化可的松、氟米龙、氟氢可的松、倍他米松、地塞米松、曲安西龙、6α-氟-异氟泼尼龙、泼尼松醋酸酯、可的松醋酸酯、泼尼松龙醋酸酯、氢化可的松醋酸酯、倍氯米松、氟米松、甲基泼尼松龙醋酸酯、16α-羟基泼尼松龙醋酸酯、氟米龙醋酸酯、异氟泼尼松醋酸酯、氟氢可的松醋酸酯、布地奈德、氢化可的松丁酸酯、地塞米松醋酸酯、曲安奈德、醋酸倍他米松、地夫可特、泼尼松龙戊酸酯、氢化可的松戊酸酯、倍他米松丙酸酯、哈西奈德、丁乙酸泼尼松龙、氢化可的松琥珀酸酯水合物、曲安奈德醋酸酯、倍他米松戊酸酯、地塞米松戊酸酯、曲安西龙双醋酸酯、丁酸氯倍他松、醋酸氟轻松22-甲基同系物、泼尼卡酯、丁酸丙酸氢可的松、二氟拉松双醋酸酯、氟替卡松丙酸酯、安西奈德、倍他米松双丙酸酯、16α-羟基泼尼松龙、氟轻松，参见附录A表A，纯度≥95%，或经国家认证并授予标准物质证书的标准品。5.4标准溶液配制5.4.1标准储备液：精密称取脱氢表雄酮等标准品约10mg，用甲醇溶解并定容至100mL容量瓶中，配制成浓度为100μg/mL的标准储备液。-18℃以下保存，有效期6个月。5.4.2混合标准中间液：分别精密量取标准储备液（3.4.1）适量，按照各项激素不同检出限，确定其在混合标准溶液中的浓度，具体信息参见附录D。-18℃下保存，有效期3个月。5.4.3混合标准工作液：精密量取标准中间液（3.4.2）1.0mL，于10mL容量瓶中，用甲醇稀释至刻度。-18℃下保存，有效期1个月。5.5材料5.5.1尼龙滤膜：0.22μm。5.5.2EMR固相萃取小柱：600mg/6mL，或相当者。T/SZNBXXXXX-XXXX6仪器6.1超高效液相色谱-质谱/质谱仪：配电喷雾离子源（ESI）。6.2分析天平：感量0.1mg和0.01g。6.3高速离心机：转速不低于9500r/min。6.4组织捣碎机。6.5微量移液器：量程10μL~100μL，100μL~1000μL。6.6氮吹仪：可控温。6.7涡旋混合器。7试样制备与贮存7.1试样制备7.1.1畜禽产品、水产品从原始样品取出代表性样品约500g，用组织捣碎机充分捣碎混匀，均分成两份，分别装入洁净容器作为试样，密封，并标明标记。7.1.2蛋从原始样品取出代表性样品约500g，蛋去壳后用匀浆机充分搅拌均匀，均分成两份，分别装入洁净容器作为试样，密封，并标明标记。7.1.3乳、蜂蜜样品搅拌均匀，均分成两份，分别装入洁净容器作为试样，密封，并标明标记。7.2试样贮存将制备好的动物源性试样冷冻-20℃保存；将制备好的奶和蜂蜜试样置于4℃冷藏避光保存。8测定步骤8.1酶解和提取准确称取试样5g（准确至±0.05g），置于50mL离心管中，加入β-盐酸葡萄糖醛苷酶/芳基硫酸酯酶溶液100µL，再加10mL0.2mol/L的乙酸铵溶液（3.2.2）涡旋混匀，于37℃下恒温水浴16h。取出后放置至室温，加入10

mL乙腈（3.1.1），加入5g氯化钠（3.1.4），振荡提取20min，9500r/min条件下离心4min，取上清液于另一离心管中，再用5mL乙腈（3.1.1）重复提取一次，合并上清液，待净化。8.2净化取6.1的待净化液通过EMR固相萃取小柱（3.5.2）净化，用15mL离心管接收流出液，再用3mL乙腈（3.1.1）洗脱，抽干，合并流出液，氮吹至剩1滴左右，先用0.5mL乙腈（3.1.1）涡旋溶解后，再加0.5mL水，涡旋混匀，过尼龙滤膜（3.5.1），供液相色谱-串联质谱仪测定。8.3基质匹配标准曲线的制备T/SZNBXXXXX-XXXX精密量取混合标准工作溶液（3.4.3）适量，分别加入6份经提取和净化的空白试液残渣中，水浴氮吹至近干，先用0.5mL乙腈（3.1.1）涡旋溶解后，再加0.5mL水，涡旋混匀，配置成适当浓度的基质匹配系列混合标准溶液，过尼龙滤膜（3.5.1），供液相色谱-串联质谱测定。以特征离子质量色谱峰面积为纵坐标、对应的基质匹配标准溶液浓度为横坐标，绘制标准曲线。求回归方程和相关系数。8.4测定8.4.1皮质激素、雄激素、孕激素的测定8.4.1.1皮质激素、雄激素、孕激素液相色谱参考条件a)色谱柱:含ADME(金刚烷键合相)的C18(100mmx2.1mm，2.0μm)，或相当者；b)柱温：40℃；c)进样量：4μL；d)流速：0.300mL/min；e)流动相：A相为0.1%甲酸水溶液，B相为乙腈：甲醇（8：2）（含0.1%甲酸）溶液；f)梯度洗脱条件见表1。表1流动相梯度洗脱条件时间/minA/%B/%0.0095.05.01.5095.05.02.0080.020.06.0060.040.08.0050.050.012.05.095.014.05.095.014.595.05.016.095.05.08.4.1.2皮质激素、雄激素、孕激素质谱参考条件a)离子源：电喷雾离子源（ESI）；b)扫描方式：正离子扫描；c)检测方式：多反应监测(MRM)，分段扫描；d)离子源温度：500℃；e)喷雾电压(IS)：5500V；f)气帘气压力（CUR）：40psi；g）雾化气压力（GS1）：55psi；h）辅助气压力（GS2）55psi；i）定性定量离子对及锥孔电压（DP）、碰撞能量（CE）见附录B，典型谱图见附录C。8.4.2氟轻松、雌激素的测定T/SZNBXXXXX-XXXX8.4.2.1氟轻松、雌激素液相色谱参考条件色谱柱：C18(100mmx2.1mm，1.8μm)，或相当者；b)柱温：35℃；c)进样量：4μL；d)流速：0.250mL/min；e)流动相：A相为1mmol/L氟化铵溶液，B相为甲醇；f)梯度洗脱条件见表2。表2氟轻松、雌激素流动相梯度洗脱条件时间/minA/%B/%0.0040.060.00.5040.060.02.5025.075.03.0020.080.05.002.098.05.5040.060.06.0040.060.08.4.2.2氟轻松、雌激素质谱参考条件离子源：电喷雾离子源（ESI）；扫描方式：负离子扫描；检测方式：多反应监测(MRM)，分段扫描；离子源温度：550℃；喷雾电压(IS)：-4500V；气帘气压力(CUR)：40psi；雾化气压力(GS1)：55psi；辅助气压力(GS2)：60psi；定性定量离子对及锥孔电压(DP)、碰撞能量(CE)见附录B。8.5定性及定量8.5.1定性测定在同样测试条件下，试料溶液中目标物的保留时间与标准工作液中目标物的保留时间，偏差在±2.5%以内，且检测到的离子的相对丰度，应当与浓度相当的校正标准溶液相对丰度一致。其允许偏差应符合表3要求。表3定性确证时相对离子丰度的允许偏差相对离子丰度>50%20%～50%10%～20%≤10%允许偏差±20%±25%±30%±50%8.5.2定量测定取试料溶液和相应的标准溶液，作单点或多点校准，按外标法以色谱峰面积定量。基质匹配标准工作液及试样溶T/SZNBXXXXX-XXXX液中目标物响应值均应在仪器检测的线性范围内。对于试料中目标药物残留量超过仪器测定线性范围的,在提取时根据药物浓度稀释试样,使试样溶液稀释后目标药物的响应在仪器线性范围内。在上述色谱-质谱条件下，标准溶液特征离子质量色谱图见附录C。8.6平行试验按以上步骤对同一试样进行平行试验测定。8.7空白试验取空白试料,除不加药物外,采用完全相同的测定步骤进行平行操作。9结果计算试样中激素的残留量按标准曲线或公式(1)计算。X=Cs×式中： X——试样中激素的数值，单位为微克每千克(μg/kg)；Cs——标准溶液中激素的数值，单位为微克每升(μg/L)；Ai——试样溶液中激素As——标准溶液中激素V——溶解最终残余物体积的数值，单位为毫升(mL)；m——试样质量的数值，单位为克(g)。计算结果保留三位有效数字。10灵敏度化合物的检出限（LOD）和定量限（LOQ）见附录A。11精密度本方法批内相对标准偏差≤15%，批间相对标准偏差≤20%。12准确度本方法添加水平为2×LOD、5×LOD、10×LOD时，添加浓度水平上的回收率为60%~120%。

T/SZNBXXXXX-XXXX附录A(资料性附录）94种激素中英文名称、化学分子式、CAS号、检出限、定量限94种激素中英文名称、化学分子式、CAS号、检出限、定量限见表A。表A94种激素中英文名称、化学分子式、CAS号、检出限、定量限序号中文名称英文名称化学分子式CAS号检出限（μg/kg）定量限（μg/kg）药物类别1醛固酮AdosteroneC21H28O552-39-11.02.0皮质激素2保泰松PhenylbutazoneC19H20N2O250-33-92.04.03脱氧可的松CortexoloneC21H30O4152-58-90.20.44泼尼松PrednisoneC21H26O553-03-20.40.85可的松CortisoneC21H28O553-06-50.40.86泼尼松龙PrednisoloneC21H28O550-24-80.40.87氢化可的松HydrocortisoneC21H30O550-23-70.20.48醋酸去氧皮质酮DeoxycorticosteroneacetateC23H32O456-47-30.40.89非那雄胺FinasterideC23H36N2O298319-26-70.20.410甲基泼尼松龙MethylprednisoloneC22H30O583-43-20.40.8116α-甲基氢化可的松6α-MethylHydrocortisoneC22H32O51625-39-41.02.012氟米龙FluorometholoneC22H29FO4426-13-10.20.413氟氢可的松FludrocortisoneC21H29FO5127-31-10.20.414倍他米松BetamethasoneC22H29FO5378-44-90.20.415地塞米松DexamethasoneC22H29FO550-02-20.20.416曲安西龙TriamcinoloneC21H27FO6124-94-70.20.4176α-氟-异氟泼尼龙6-alpha-Fluoro-isoflupredoneC21H26F2O5806-29-10.20.418泼尼松醋酸酯Prednisone21-acetateC23H28O6125-10-00.20.419可的松醋酸酯CortisoneacetateC23H30O650-04-40.20.420泼尼松龙醋酸酯Prednisolone-21-acetateC23H30O652-21-10.40.821氢化可的松醋酸酯HydrocortisoneacetateC23H32O650-03-30.20.422倍氯米松BeclomethasoneC22H29ClO54419-39-00.40.823氟米松FlumethasoneC22H28F2O52135-17-30.40.824甲基泼尼松龙醋酸酯MethylprednisoloneacetateC24H32O653-36-11.02.02516α-羟基泼尼松龙醋酸酯16alpha-HydroxyprednisonloneacetateC23H30O786401-80-10.40.826氟米龙醋酸酯EfloneC24H31FO53801-06-70.20.427异氟泼尼松醋酸酯IsoflupredoneAcetateC23H29FO6338-98-71.02.028氟氢可的松醋酸酯FludrocortisoneacetateC23H31FO6514-36-30.20.429布地奈德BudesonideC25H34O651333-22-30.20.430氢化可的松丁酸酯Hydrocortisone-17-butyrateC25H36O613609-67-11.02.031地塞米松醋酸酯Dexamethasone-17-acetateC24H31FO61177-87-31.02.032曲安奈德TriamcinoloneacetonideC24H31FO676-25-50.20.433醋酸倍他米松Betamethasone21-acetateC24H31FO6987-24-60.40.834地夫可特DeflazacortC25H31NO614484-47-00.20.435泼尼松龙戊酸酯Prednisolone21-trimethylacetateC26H36O61107-99-90.40.836氢化可的松戊酸酯Cortisol17-valerateC26H38O657524-89-70.40.837倍他米松丙酸酯Betamethasone17,21-dipropionateC28H37FO75593-20-40.40.838哈西奈德HalcinonideC24H32ClFO53093-35-41.02.039丁乙酸泼尼松龙PrednisolonetebutateC27H38O67681-14-30.20.440氢化可的松琥珀酸酯水合物Hydrocortisone21-hemisuccinateC25H34O82203-97-60.20.441曲安奈德醋酸酯Triamcinoloneacetonide21-acetateC26H33FO73870-07-30.20.442倍他米松戊酸酯Betamethasone17-valerateC27H37FO62152-44-50.20.443地塞米松戊酸酯9-Fluoro-11b,17,21-trihydroxy-16a-methylpregna-1,4-diene-3,20-dione17-valerateC27H37FO633755-46-30.20.444曲安西龙双醋酸酯TriamcinolonediacetateC25H31FO867-78-70.20.445丁酸氯倍他松ClobetasonebutyrateC26H32ClFO525122-57-00.20.446醋酸氟轻松22-甲基同系物Fluocinonide22MethylHomologueC25H30F2O751333-59-60.40.847泼尼卡酯PrednicarbateC27H36O873771-04-70.20.448丁酸丙酸氢可的松HydrocortisoneButyratePropionateC28H40O772590-77-30.40.849二氟拉松双醋酸酯DiflorasonediacetateC26H32F2O733564-31-70.40.850氟替卡松丙酸酯FluticasonepropionateC25H31F3O5S80474-14-20.20.451安西奈德AmcinonideC28H35FO751022-69-60.20.452倍他米松双丙酸酯Betamethasone17,21-dipropionateC28H37FO75593-20-40.20.45316α-羟基泼尼松龙11β,16α,17,21-tetrahydroxypregna-1,4-diene-3,20-dioneC21H28O613951-70-70.40.854氟轻松FluocinonideC26H32F2O7356-12-71.02.055脱氢表雄酮DehydroepiandrosteroneC19H28O253-43-01.02.0雄激素56群勃龙TrenboloneC18H22O210161-33-80.20.457去甲雄烯二酮NorandrostenedioneC18H24O2734-32-70.40.858诺龙NandroloneC18H26O2434-22-00.20.459勃地酮BoldenoneC19H26O2846-48-00.20.460雄烯二酮AndrostenedioneC19H26O263-05-80.40.861睾酮TestosteroneC19H28O258-22-00.40.862表睾酮EpitestosteroneC19H28O2481-30-10.40.863炔诺酮NorethindroneC20H26O268-22-40.20.464美雄酮MetandienoneC20H28O272-63-90.20.465甲基睾酮17-MethyltestosteroneC20H30O258-18-41.02.066美替诺龙MetenoloneC20H30O2153-00-41.02.067司坦唑醇StanozololC21H32N2O10418-03-80.40.868丙酸诺龙Nandrolone17-propionateC21H30O37207-92-30.40.869氟甲睾酮FluoxymesteroneC20H29FO376-43-70.40.870达那唑DanazolC22H27NO217230-88-50.40.871丙酸睾酮TestosteronepropionateC22H32O357-85-20.40.872美替诺龙醋酸酯MethenoloneacetateC22H32O3434-05-90.40.873苯丙酸诺龙NandrolonephenylpropionateC27H34O362-90-80.40.874孕三烯酮GestrinoneC21H24O216320-04-00.20.475左炔诺孕酮LevonorgestrelC21H28O2797-63-70.20.47617α-羟基孕酮17α-HydroxyprogesteroneC21H30O368-96-20.20.47721α-羟基孕酮DesoxycorticosteroneC21H30O364-85-70.20.478甲地孕酮MegestrolC22H30O33562-63-80.40.879甲羟孕酮PremarinC18H19NaO5S12126-59-90.40.880氯地孕酮ChlormadinonC21H27ClO31961-77-92.04.081醋酸甲地孕酮MegestrolacetateC24H32O4595-33-50.40.882醋酸甲羟孕酮MedroxyprogesteroneacetateC24H34O471-58-90.40.883醋酸美仑孕酮MelengestrolacetateC25H32O42919-66-60.20.484醋酸氯地孕酮ChlormadinoneacetateC23H29ClO4302-22-70.20.485己酸羟孕酮HydroxyprogesteronecaproateC27H40O4630-56-80.20.486醋酸环丙氯地孕酮CyproteroneacetateC24H29ClO4427-51-00.40.887己烯雌酚DiethylstilbestrolC18H20O256-53-10.20.4雌激素88己烷雌酚HexestrolC18H22O284-16-20.20.489雌三醇EstriolC18H24O350-27-11.02.090雌酮EstroneC18H22O253-16-70.20.491炔雌醇EthinylestradiolC20H24O257-63-60.40.89217α-雌二醇EstradiolC18H24O257-91-00.40.89317β-雌二醇β-EstradiolC18H24O250-28-20.40.894己二烯雌酚DienestrolC18H18O284-17-30.20.4

T/SZNBXXXXX-XXXX附录B(资料性附录）94种激素保留时间、定性离子对、定量离子对、锥孔电压及碰撞能量94种激素保留时间、定性离子对、定量离子对、锥孔电压及碰撞能量见表B。表B94种激素保留时间、定性离子对、定量离子对、锥孔电压及碰撞能量序号中文名称保留时间(min)母离子(m/z)子离子(m/z)CE(eV)DP(eV)1醛固酮7.75361.4343.1a23.680361.4315.429802保泰松11.62309160a314030914630403脱氧可的松9.74347.3108.9a47120347.397451204泼尼松8.22359.2341.1a2080359.3313.417805可的松8.37361.2163.2a3480361.2121.147806泼尼松龙8.29361.2343.2a1480361.2147.234807氢化可的松8.34363.2121.1a3180363.210568808醋酸去氧皮质酮11.76373109.1a4812037397.1541209非那雄胺10.93373.3317.2a31138373.3305.34113810甲基泼尼松龙9.26375.2339.2a1466375.2161.22866116α-甲基氢化可的松9.38377.2135.1a30110377.2341.22411012氟米龙10.11377.2279.3a2280377.2321.3188013氟氢可的松8.36381.5181.1a4080381.5239.3248014倍他米松9.14393.1373.3a1460393.1355.3166015地塞米松9.29393.3373.3a1460393.3355.3166016曲安西龙7.02395.2357.2a1780395.2225.12680176α-氟-异氟泼尼龙7.10397.2253.1a2480397.2263.1298018泼尼松醋酸酯10.26401.2295a17.171401.2341.2188019可的松醋酸酯10.36403.2163.2a3480403.2343.2258020泼尼松龙醋酸酯10.11403.2384.9a1380403.2147.1358021氢化可的松醋酸酯10.17405.3327.2a2480405.3309.2258022倍氯米松9.66409.2391.2a1580409.2279.3298023氟米松9.18411.3253.2a2280411.3121508024甲基泼尼松龙醋酸酯10.73417.2399.2a1797417.2253.228972516α-羟基泼尼松龙醋酸酯8.99419.2401.2a1790419.2323.1189026氟米龙醋酸酯11.02419.3279.2a2080419.3321.2198027异氟泼尼松醋酸酯9.98421.2277.1a3040421.2147.1354028氟氢可的松醋酸酯10.17423.2238.9a34.8116423.2343.2318029布地奈德11.29431.2413a1790431.2146.9399030氢化可的松丁酸酯11.13433.3345a1992433.3120.8409231地塞米松醋酸酯10.73435.2309.1a2284435.2415.2158432曲安奈德9.86435.2415.2a1580435.2397.2158033醋酸倍他米松10.55435.3397.2a1580435.31415.2158034地夫可特10.56442.3142.1a4580442.3124.1658035泼尼松龙戊酸酯11.73445.3427.2a1890445.3307.2259036氢化可的松戊酸酯11.58447.3345.2a1993447.3120.8399337倍他米松丙酸酯10.90449.2279.2a2490449.2355.2169038哈西奈德11.71455.3104.9a81.485455.3359.2278039丁乙酸泼尼松龙12.04459.3441.2a1690459.3307.2279040氢化可的松琥珀酸酯水合物9.65463.2309.2a2530463.2327.2323041曲安奈德醋酸酯11.30477.2339.2a2280477.2321.2238042倍他米松戊酸酯11.75477.3354.9a16.490477.3278.823.59043地塞米松戊酸酯11.64477.3279.2a2690477.3355.2169044曲安西龙双醋酸酯9.94479.2440.9a1575479.232123.37545丁酸氯倍他松12.35479.3343.2a1980479.3279.2228046醋酸氟轻松22-甲基同系物10.95481.2253.1a3090481.2441.2219047泼尼卡酯12.08489.2381.3a1680489.2115.1258048丁酸丙酸氢可的松12.33489.3345.2a25110489.3401.21711049二氟拉松双醋酸酯11.24495.2316.8a1990495.2278.8229050氟替卡松丙酸酯11.92501.2293.2a2282501.2313.1208251安西奈德11.99503.2338.9a2480503.2321288052倍他米松双丙酸酯12.13505.3318.9a22.980505.3411.215805316α-羟基泼尼松龙7.15377.2359.2a1770377.2147.1307054氟轻松3.17497.4431.5a-20-25497.4355.4-20-2555脱氢表雄酮10.75271253.2a2240271197.1314056群勃龙9.97271.1199.3a3550271.1253.2285057去甲雄烯二酮10.35273.1109.1a3284273.4197.1248458诺龙10.15275.1109.1a3170275.1239.1257059勃地酮10.08287.1121.1a3150287.1135265060雄烯二酮10.76287.297.1a2080287.2109.1248061睾酮10.5428997.1a2890289109.2309062表睾酮10.98289.197a36120289.11093512063炔诺酮10.63299.3109.1a3460299.3231.2276064美雄酮10.58301.2121.1a3580301.2149.1228065甲基睾酮10.94303.1109.1a37106303.197.13910666美替诺龙10.94303.1187.2a33100303.1201.12512067司坦唑醇10.68329.195.1a5260329.1121.4526068丙酸诺龙12.59331.1257.2a2270331.1239.2277069氟甲睾酮9.53337.1241.2a32120337.1131.14012070达那唑11.98338.7148a31120338.7310.12712071丙酸睾酮12.78345.197.1a2960345.1109276072美替诺龙醋酸酯12.55345.183.1a2560345.1187.2276073苯丙酸诺龙13.36407.3105.1a3360407.3257.1256074孕三烯酮11.05309.1241.1a29120309.1199.24312075左炔诺孕酮11.3313.2245.2a24115313.2109.1331157617α-羟基孕酮10.95331.597a4350331.5108.921507721α-羟基孕酮10.71331.5108.9a21100331.597.13010078甲地孕酮11.32343.2187.1a3240343.2267.2294079甲羟孕酮11.50345.597.1a32126345.5123.12512680氯地孕酮11.42363.2309.1a23105363.2345.12010581醋酸甲地孕酮12.12385.5267.3a2090385.5325.6269082醋酸甲羟孕酮12.14387.2327.3a1180387.2123.1198083醋酸美仑孕酮12.25397.3279.1a28100397.3337.21910084醋酸氯地孕酮12.18405.2309.2a21100405.2345.21710085己酸羟孕酮13.06429.1313.2a2076429.1271.3277686醋酸环丙氯地孕酮12.16417357a2060417279306087己烯雌酚3.65267.1251.1a-34-90267.1237.1-39-9088己烷雌酚3.89269.1119a-51-90269.1133-21-9089雌三醇1.96287.3145.2a-56-97287.3171.1-45-9790雌酮3.73269.3145.1a-45-83269.3158.9-45-8391炔雌醇3.67295.4145.2a-41-48295.4159.2-35-489217α-雌二醇3.85271.4145.2a-53-90271.4183.1-53-909317β-雌二醇3.72271.4145.2a-53-90271.4183.1-53-9094己二烯雌酚3.78265249.1a-29-90265236.1-29-90注：a为定量离子对。T/SZNBXXXXX-XXXX附录C(资料性附录）94种激素多反应监测（MRM）色谱图94种激素多反应监测（MRM）色谱图见图C醛固酮11.000361.4/343.1醛固酮20.373361.4/315.4保泰松11.000309.0/160.0保泰松20.428309.0/146.0脱氧可的松11.000347.3/108.9脱氧可的松20.964347.3/97.0泼尼松11.000359.2/341.1泼尼松20.608359.3/313.4可的松11.000361.2/163.2可的松20.726361.2/121.1泼尼松龙11.000361.2/343.2泼尼松龙20.409361.2/147.2氢化可的松11.000363.2/121.1氢化可的松20.287363.2/105.0醋酸去氧皮质酮11.000373.0/109.1醋酸去氧皮质酮20.967373.0/97.1非那雄胺11.000373.3/317.2非那雄胺20.539373.3/305.3甲基泼尼松龙11.000375.2/339.2甲基泼尼松龙20.682375.2/161.26α-甲基氢化可的松11.000377.2/135.16α-甲基氢化可的松20.877377.2/341.2氟米龙11.000377.2/279.3氟米龙20.742377.2/321.3氟氢可的松11.000381.5/181.1氟氢可的松20.695381.5/239.3醛固酮11.000361.4/343.1醛固酮20.373361.4/315.4保泰松11.000309.0/160.0保泰松20.428309.0/146.0脱氧可的松11.000347.3/108.9脱氧可的松20.964347.3/97.0泼尼松11.000359.2/341.1泼尼松20.608359.3/313.4可的松11.000361.2/163.2可的松20.726361.2/121.1泼尼松龙11.000361.2/343.2泼尼松龙20.409361.2/147.2氢化可的松11.000363.2/121.1氢化可的松20.287363.2/105.0醋酸去氧皮质酮11.000373.0/109.1醋酸去氧皮质酮20.967373.0/97.1非那雄胺11.000373.3/317.2非那雄胺20.539373.3/305.3甲基泼尼松龙11.000375.2/339.2甲基泼尼松龙20.682375.2/161.26α-甲基氢化可的松11.000377.2/135.16α-甲基氢化可的松20.877377.2/341.2氟米龙11.000377.2/279.3氟米龙20.742377.2/321.3氟氢可的松11.000381.5/181.1氟氢可的松20.695381.5/239.3倍他米松11.000393.1/373.3倍他米松20.468393.1/355.3地塞米松11.000393.3/373.3地塞米松20.576393.3/355.3曲安西龙11.000395.2/357.2曲安西龙20.441395.2/225.16α-氟-异氟泼尼龙11.000397.2/253.16α-氟-异氟泼尼龙20.406397.2/263.1泼尼松醋酸酯11.000401.2/295.0泼尼松醋酸酯21.471401.2/341.2可的松醋酸酯11.000403.2/163.2可的松醋酸酯20.819403.2/343.2泼尼松龙醋酸酯11.000403.2/384.9泼尼松龙醋酸酯20.436403.2/147.1氢化可的松醋酸酯11.000405.3/327.2氢化可的松醋酸酯21.081405.3/309.2倍氯米松11.000409.2/391.2倍氯米松20.157409.2/279.3氟米松11.000411.3/253.2氟米松20.421411.3/121.0甲基泼尼松龙醋酸酯11.000417.2/399.2甲基泼尼松龙醋酸酯20.262417.2/253.216α-羟基泼尼松龙醋酸酯11.000419.2/401.216α-羟基泼尼松龙醋酸酯20.385419.2/323.1氟米龙醋酸酯11.000419.3/279.2氟米龙醋酸酯20.548419.3/321.2异氟泼尼松醋酸酯11.000421.2/277.1异氟泼尼松醋酸酯20.747421.2/147.1氟氢可的松醋酸酯11.000423.2/238.9氟氢可的松醋酸酯20.975423.2/343.2布地奈德11.000431.2/413.0布地奈德20.324431.2/146.9氢化可的松丁酸酯11.000433.3/345.0氢化可的松丁酸酯20.382433.3/120.8地塞米松醋酸酯11.000435.2/415.2地塞米松醋酸酯20.443435.2/309.1曲安奈德11.000435.2/415.2曲安奈德20.249435.2/397.2醋酸倍他米松11.000435.3/415.2醋酸倍他米松20.789435.3/397.2地夫可特11.000442.3/142.1地夫可特20.705442.3/124.1泼尼松龙戊酸酯11.000445.3/427.2泼尼松龙戊酸酯20.363445.3/307.2氢化可的松戊酸酯11.000447.3/345.2氢化可的松戊酸酯20.301447.3/120.8倍他米松丙酸酯11.000449.2/279.2倍他米松丙酸酯21.547449.2/355.2哈西奈德11.000455.3/359.2哈西奈德20.467455.3/104.9丁乙酸泼尼松龙11.000459.3/441.2丁乙酸泼尼松龙20.310459.3/307.2氢化可的松琥珀酸酯水合物11.000463.2/309.2氢化可的松琥珀酸酯水合物20.512463.2/327.2曲安奈德醋酸酯11.000477.2/339.2曲安奈德醋酸酯20.684477.2/321.2倍他米松戊酸酯11.000477.3/354.9倍他米松戊酸酯20.465477.3/278.8地塞米松戊酸酯11.000477.3/279.2地塞米松戊酸酯21.548477.3/355.2曲安西龙双醋酸酯11.000479.2/440.9曲安西龙双醋酸酯20.821479.2/321.0丁酸氯倍他松11.000479.3/343.2丁酸氯倍他松20.891479.3/279.2醋酸氟轻松22-甲基同系物11.000481.2/253.1醋酸氟轻松22-甲基同系物21.554481.2/441.2泼尼卡酯11.000489.2/381.3泼尼卡酯20.344489.2/115.1丁酸丙酸氢可的松11.000489.3/345.2丁酸丙酸氢可的松21.151489.3/401.2二氟拉松双醋酸酯11.000495.2/316.8二氟拉松双醋酸酯20.584495.2/278.8氟替卡松丙酸酯11.000501.2/293.2氟替卡松丙酸酯21.119501.2/313.1安西奈德11.000503.2/338.9安西奈德20.810503.2/321.0倍他米松双丙酸酯11.000505.3/318.9倍他米松双丙酸酯22.216505.3/411.216α-羟基泼尼松龙11.000377.2/359.216α-羟基泼尼松龙20.329377.2/147.1氟轻松11.000497.4/431.5氟轻松20.422497.4/355.4脱氢表雄酮11.000271.0/253.2脱氢表雄酮20.272271.0/197.1群勃龙11.000271.1/199.3群勃龙21.677271.1/253.2去甲雄烯二酮11.000273.1/109.1去甲雄烯二酮20.628273.4/197.1诺龙11.000275.1/109.1诺龙20.692275.1/239.1勃地酮11.000287.1/121.1勃地酮20.509287.1/135.0雄烯二酮11.000287.2/97.1雄烯二酮21.036287.2/109.1睾酮11.000289.0/97.1睾酮20.834289.0/109.2表睾酮11.000289.1/97.0表睾酮21.039289.1/109.0炔诺酮11.000299.3/109.1炔诺酮20.672299.3/231.2美雄酮11.000301.2/121.1美雄酮20.844301.2/149.1甲基睾酮11.000303.1/109.1甲基睾酮20.852303.1/97.1美替诺龙11.000303.1/201.1美替诺龙27.175303.1/187.2司坦唑醇11.000329.1/95.1司坦唑醇20.774329.1/121.4丙酸诺龙11.000331.1/257.2丙酸诺龙20.379331.1/239.2泼尼松龙醋酸酯20.436403.2/147.1氢化可的松醋酸酯11.000405.3/327.2氢化可的松醋酸酯21.081405.3/309.2倍氯米松11.000409.2/391.2倍氯米松20.157409.2/279.3氟米松11.000411.3/253.2氟米松20.421411.3/121.0甲基泼尼松龙醋酸酯11.000417.2/399.2甲基泼尼松龙醋酸酯20.262417.2/253.216α-羟基泼尼松龙醋酸酯11.000419.2/401.216α-羟基泼尼松龙醋酸酯20.385419.2/323.1氟米龙醋酸酯11.000419.3/279.2氟米龙醋酸酯20.548419.3/321.2异氟泼尼松醋酸酯11.000421.2/277.1异氟泼尼松醋酸酯20.747421.2/147.1氟氢可的松醋酸酯11.000423.2/238.9氟氢可的松醋酸酯20.975423.2/343.2布地奈德11.000431.2/413.0布地奈德20.324431.2/146.9氢化可的松丁酸酯11.000433.3/345.0氢化可的松丁酸酯20.382433.3/120.8地塞米松醋酸酯11.000435.2/415.2地塞米松醋酸酯20.443435.2/309.1曲安奈德11.000435.2/415.2曲安奈德20.249435.2/397.2醋酸倍他米松11.000435.3/415.2醋酸倍他米松20.789435.3/397.2地夫可特11.000442.3/142.1地夫可特20.705442.3/124.1泼尼松龙戊酸酯11.000445.3/427.2泼尼松龙戊酸酯20.363445.3/307.2氢化可的松戊酸酯11.000447.3/345.2氢化可的松戊酸酯20.301447.3/120.8倍他米松丙酸酯11.000449.2/279.2倍他米松丙酸酯21.547449.2/355.2哈西奈德11.000455.3/359.2哈西奈德20.467455.3/104.9丁乙酸泼尼松龙11.000459.3/441.2丁乙酸泼尼松龙20.310459.3/307.2氢化可的松琥珀酸酯水合物11.000463.2/309.2氢化可的松琥珀酸酯水合物20.512463.2/327.2曲安奈德醋酸酯11.000477.2/339.2曲安奈德醋酸酯20.684477.2/321.2倍他米松戊酸酯11.000477.3/354.9倍他米松戊酸酯20.465477.3/278.8地塞米松戊酸酯11.000477.3/279.2地塞米松戊酸酯21.548477.3/355.2曲安西龙双醋酸酯11.000479.2/440.9曲安西龙双醋酸酯20.821479.2/321.0丁酸氯倍他松11.000479.3/343.2丁酸氯倍他松20.891479.3/279.2醋酸氟轻松22-甲基同系物11.000481.2/253.1醋酸氟轻松22-甲基同系物21.554481.2/441.2泼尼卡酯11.000489.2/381.3泼尼卡酯20.344489.2/115.1丁酸丙酸氢可的松11.000489.3/345.2丁酸丙酸氢可的松21.151489.3/401.2二氟拉松双醋酸酯11.000495.2/316.8二氟拉松双醋酸酯20.584495.2/278.8氟替卡松丙酸酯11.000501.2/293.2氟替卡松丙酸酯21.119501.2/313.1安西奈德11.000503.2/338.9安西奈德20.810503.2/321.0倍他米松双丙酸酯11.000505.3/318.9倍他米松双丙酸酯22.216505.3/411.216α-羟基泼尼松龙11.000377.2/359.216α-羟基泼尼松龙20.329377.2/147.1氟轻松11.000497.4/431.5氟轻松20.422497.4/355.4脱氢表雄酮11.000271.0/253.2脱氢表雄酮20.272271.0/197.1群勃龙11.000271.1/199.3群勃龙21.677271.1/253.2去甲雄烯二酮11.000273.1/109.1去甲雄烯二酮20.628273.4/197.1诺龙11.000275.1/109.1诺龙20.692275.1/239.1勃地酮11.000287.1/121.1勃地酮20.509287.1/135.0雄烯二酮11.000287.2/97.1雄烯二酮21.036287.2/109.1睾酮11.000289.0/97.1睾酮20.834289.0/109.2表睾酮11.000289.1/97.0表睾酮21.039289.1/109.0炔诺酮11.000299.3/109.1炔诺酮20.672299.3/231.2美雄酮11.000301.2/121.1美雄酮20.844301.2/149.1甲基睾酮11.000303.1/109.1甲基睾酮20.852303.1/97.1美替诺龙11.000303.1/201.1美替诺龙27.175303.1/187.2司坦唑醇11.000329.1/95.1司坦唑醇20.774329.1/121.4丙酸诺龙11.000331.1/257.2丙酸诺龙20.379331.1/239.2氟甲睾酮11.000337.1/241.2氟甲睾酮20.658337.1/131.1达那唑11.000338.7/148.0达那唑21.063338.7/310.1丙酸睾酮11.000345.1/97.1丙酸睾酮20.710345.1/109.0美替诺龙醋酸酯11.000345.1/83.1美替诺龙醋酸酯21.491345.1/187.2苯丙酸诺龙11.000407.3/105.1苯丙酸诺龙20.420407.3/257.1孕三烯酮11.000309.1/241.1孕三烯酮20.934309.1/199.2左炔诺孕酮11.000313.2/245.2左炔诺孕酮20.888313.2/109.117α-羟基孕酮11.000331.5/97.017α-羟基孕酮20.373331.5/108.921α-羟基孕酮11.000331.5/108.921α-羟基孕酮23.661331.2/97.1甲地孕酮11.000343.2/187.1甲地孕酮21.081343.2/267.2甲羟孕酮11.000345.5/97.1甲羟孕酮22.372345.5/123.1氯地孕酮11.000363.2/309.1氯地孕酮20.616363.2/345.1醋酸甲地孕酮11.000385.5/267.3醋酸甲地孕酮20.562385.5/325.6醋酸甲羟孕酮11.000387.2/327.3醋酸甲羟孕酮20.306387.2/123.1醋酸美仑孕酮11.000397.3/279.1醋酸美仑孕酮21.464397.3/337.2醋酸氯地孕酮11.000405.2/309.2醋酸氯地孕酮20.969405.2/345.2己酸羟孕酮11.000429.1/313.2己酸羟孕酮20.313429.1/271.3醋酸环丙氯地孕酮11.000417.0/357.0醋酸环丙氯地孕酮20.606417.0/279.0己烯雌酚11.000267.1/251.1己烯雌酚21.112267.1/237.1己烷雌酚11.000269.1/119.0己烷雌酚20.732269.1/133.0雌三醇11.000287.3/145.2雌三醇21.151287.3/171.1雌酮11.000269.3/145.1雌酮20.134269.3/158.9炔雌醇11.000295.4/145.2炔雌醇20.359295.4/159.217β-雌二醇11.000271.4/145.217β-雌二醇21.000271.4/183.117α-雌二醇11.000271.4/145.217α-雌二醇20.292271.4/183.1己二烯雌酚11.000265.0/249.1己二烯雌酚2己二烯雌酚11.000265.0/249.1己二烯雌酚21.144265.0/236.1图C94种激素多反应监测（MRM）色谱图

T/SZNBXXXXX-XXXX附录D(资料性附录）94种激素中英文名称、方法检出限、溶剂选择和混合标准中间液浓度表94种激素化学品中英文名称、方法检出限、溶剂选择和混合标准中间液浓度见表D。表D94种激素化学品中英文名称、方法检出限、分组、溶剂选择和混合标准中间液浓度表序号中文名称英文名称检出限（μg/kg）溶剂混合标准中间液浓度/(μg/mL)1醛固酮Adosterone1.0甲醇5.02保泰松Phenylbutazone2.0甲醇10.03脱氧可的松Cortexolone0.2甲醇1.04泼尼松Prednisone0.4甲醇2.05可的松Cortisone0.4甲醇2.06泼尼松龙Prednisolone0.4甲醇2.07氢化可的松Hydrocortisone0.2甲醇1.08醋酸去氧皮质酮Deoxycorticosteroneacetate0.4甲醇2.09非那雄胺Finasteride0.2甲醇1.010甲基泼尼松龙Methylprednisolone0.4甲醇2.0116α-甲基氢化可的松6α-MethylHydrocortisone1.0甲醇5.012氟米龙Fluorometholone0.2甲醇1.013氟氢可的松Fludrocortisone0.2甲醇1.014倍他米松Betamethasone0.2甲醇1.015地塞米松Dexamethasone0.2甲醇1.016曲安西龙Triamcinolone0.2甲醇1.0176α-氟-异氟泼尼龙6-alpha-Fluoro-isoflupredone0.2甲醇1.018泼尼松醋酸酯Prednisone21-acetate0.2甲醇1.019可的松醋酸酯Cortisoneacetate0.2甲醇1.02