饲料包括单一饲料、添加剂预混合饲料、浓缩饲料、配合饲料和精料补充料等[1]。在饲料中合理添加一些重金属元素能够促进畜禽的生长，但是超剂量的添加会损害畜禽健康，导致重金属在畜禽体内富集，部分重金属元素通过代谢物排出进入生态系统，对环境和畜禽造成危害[2-9]。因此，饲料中重金属元素的监控格外重要。目前，检测重金属元素的方法主要有原子吸收分光光度法、原子荧光光度法、电感耦合等离子体发射光谱法等。原子吸收分光光度法和原子荧光光度法具有较强的选择性与较小的光谱干扰性，但不能同时检测多元素。电感耦合等离子体发射光谱法可以同时检测多元素，但较适合含量为毫克每千克的元素，对含量为微克每千克的元素检测准确度较差。电感耦合等离子体质谱法以离子体为离子源，具有低检出限、高灵敏度、高准确度、干扰少、可多元素同时分析等优点[10-17]。本研究旨在建立微波消解-电感耦合等离子体质谱法，同时测定饲料中21种元素，为饲料中多元素的定量分析提供参考。1材料与方法1.1仪器设备电感耦合等离子体质谱仪（ICP-MS）（赛默飞世尔iCAP Qc ICP-MS）；TOPEX+全能型微波化学工作平台（上海屹尧仪器科技发展有限公司）；G-400智能控温电加热器（上海屹尧仪器科技发展有限公司）；BSA224S电子天平（Sartorius）；Milli-Q超纯水仪（Millipore）；移液器（Eppendorf）。1.2试剂与材料硝酸（UP级，苏州晶锐化学股份有限公司）；高纯氩气（纯度≥99.999%）；高纯氦气（纯度≥99.999%）；Li、Be、Ti、V、Cr、Co、Ni、Ga、As、Se、Rb、Sr、Mo、Ag、Cd、Sb、Cs、Ba、Tl、Pb、Bi单元素标准溶液（国家有色金属及电子材料分析测试中心），浓度为1 000 mg/L；Ge、Rh、Re内标元素标准溶液（国家有色金属及电子材料分析测试中心），浓度为1 000 mg/L；Li、Co、In、U调谐液（国赛默飞世尔公司），浓度为1.00 μg/L；40批次饲料样品（市场中随机购买）。元素标准工作溶液配制：使用2%硝酸溶液配制0.10~20.00 μg/L的Li、Be、V、Cr、Co、Ni、Ga、As、Se、Mo、Ag、Cd、Sb、Cs、Ba、Pb、Bi混合标准工作溶液；1.00~100.0 μg/L的Ti、Rb、Sr、Ba混合标准工作溶液；0.10~10.00 μg/L的Ag标准工作溶液。元素标准工作溶液浓度见表1。10.13557/j.cnki.issn1002-2813.2021.18.025.T001表1元素标准工作溶液浓度序号123456789Li0.100.250.501.002.004.008.0010.0020.00Be0.100.250.501.002.004.008.0010.0020.00Ti1.002.004.008.0010.0020.0040.0080.00100.00V0.100.250.501.002.004.008.0010.0020.00Cr0.100.250.501.002.004.008.0010.0020.00Co0.100.250.501.002.004.008.0010.0020.00Ni0.100.250.501.002.004.008.0010.0020.00Ga0.100.250.501.002.004.008.0010.0020.00As0.100.250.501.002.004.008.0010.0020.00Se0.100.250.501.002.004.008.0010.0020.00Rb1.002.004.008.0010.0020.0040.0080.00100.00Sr1.002.004.008.0010.0020.0040.0080.00100.00Mo0.100.250.501.002.004.008.0010.0020.00Ag0.050.100.250.501.002.004.005.0010.00Cd0.100.250.501.002.004.008.0010.0020.00Sb0.100.250.501.002.004.008.0010.0020.00Cs0.100.250.501.002.004.008.0010.0020.00Ba1.002.004.008.0010.0020.0040.0080.00100.00Tl0.100.250.501.002.004.008.0010.0020.00Pb0.100.250.501.002.004.008.0010.0020.00Bi0.100.250.501.002.004.008.0010.0020.00μg/L1.3样品处理微波消解法：称取0.2 g（精确至0.1 mg）饲料样品于微波消解罐中，加入5.00 mL硝酸，按微波消解仪步骤消解试样（微波消解程序为：140 ℃升温8 min，保温5 min；190 ℃升温6 min，保温20 min），冷却后取出消解罐，在智能控温电加热器上设置赶酸温度为140 ~160 ℃，赶酸至试样剩余量约1.00 mL。待消解罐冷却后将消解液转移至50.00 mL容量瓶中，用适量一级水冲洗消解罐2~3次，并将冲洗液合并于容量瓶中，使用一级水定容至刻度，混匀备用。同时做试剂空白。1.4仪器工作条件使用1.00 μg/L Li、Co、In、U调谐液对ICP-MS的状态进行调谐，调谐至Li、Co、In、U信号强度为Li：57 063 cps≥50 000 cps；Co：110 046 cps≥100 000 cps；In：221 035 cps≥220 000 cps；U：307 810 cps≥300 000 cps；双电荷（138Ba++/137Ba+）：2.9%≤3.0%；氧化物（156CeO/140Ce）：1.7%≤1.9%；59Co/51ClO：30≥28。21种待测目标同位素及内标元素选择见表2。10.13557/j.cnki.issn1002-2813.2021.18.025.T002表221种待测目标同位素及内标元素选择序号元素内标元素序号元素内标元素17Li72Ge1288Sr72Ge29Be72Ge1395Mo103Rh348Ti72Ge14107Ag103Rh451V72Ge15111Cd103Rh552Cr72Ge16121Sb103Rh659Co72Ge17133Cs103Rh760Ni72Ge18138Ba103Rh869Ga72Ge19205Tl185Re975As72Ge20208Pb185Re1078Se72Ge21209Bi185Re1185Rb72Ge优化后的仪器各项参数为：射频功率1 548.6 W；等离子体冷却气流量14.02 L/min；辅助气流量0.80 L/min；雾化气流量1.16 L/min；雾化室温度2.70 ℃；采样深度5.00 mm；泵速40.0 rpm；采用He碰撞气模式（KED），碰撞气流量4.864 L/min；镍锥、同心雾化室。2结果与分析2.1检出限在上述优化的仪器条件下，按照试验方法分析标准工作溶液中的Li、Be、Ti、V、Cr、Co、Ni、Ga、As、Se、Rb、Sr、Mo、Ag、Cd、Sb、Cs、Ba、Tl、Pb、Bi，以所分析元素的质量浓度为横坐标，信号强度为纵坐标，绘制标准工作曲线。并对空白溶液进行11次分析测定，取信号强度的3倍标准偏差所对应质量浓度为该元素的检出限，10倍标准偏差所对应质量浓度为该元素的定量限。21种元素的线性范围、标准工作曲线方程、线性相关系数、检出限、定量限见表3。10.13557/j.cnki.issn1002-2813.2021.18.025.T003表321种元素的线性范围、标准工作曲线方程、线性相关系数、检出限、定量限元素线性范围/(μg/L)标准工作曲线线性相关系数检出限/(mg/kg)定量限/(mg/kg)7Li0.10~20.00y=221.109 1x+3.009 80.999 70.022 90.076 49Be0.10~20.00y=168.607 5x+1.009 60.999 60.008 00.026 748Ti1.00~100.00y=2 251.158 6x+376.003 30.999 80.025 20.083 951V0.10~20.00y=8 875.300 1x+66.844 80.999 70.006 80.022 552Cr0.10~20.00y=13 426.596 5x+299.136 20.999 90.003 20.010 859Co0.10~20.00y=23 380.491 9x+168.036 10.999 60.002 40.007 960Ni0.10~20.00y=6 499.059 5x+1 652.703 40.999 80.009 40.031 369Ga0.10~20.00y=7 419.082 7x+159.082 60.999 80.008 60.028 875As0.10~20.00y=1 626.769 3x+12.972 70.999 70.010 90.036 278Se0.10~20.00y=164.502 3x+2.990 80.999 90.012 80.042 885Rb1.00~100.00y=5 587.441 9x+215.946 21.000 00.005 60.018 688Sr1.00~100.00y=7 567.082 3x+680.120 40.999 80.002 80.009 495Mo0.10~20.00y=8 975.382 0x+69.911 70.999 90.002 70.009 0107Ag0.05~10.00y=50 215.633 7x+180.085 10.999 80.004 90.016 4111Cd0.10~20.00y=9 039.436 0x+26.958 80.999 70.002 00.006 5121Sb0.10~20.00y=1 430.431 3x+71.084 00.999 80.014 00.046 7133Cs0.10~20.00y=30 130.377 3x+56.074 10.999 90.000 40.001 3138Ba1.00~100.00y=39 795.044 1x+2 836.426 30.999 80.004 00.013 3205Tl0.10~20.00y=198 329.230 4x+603.305 70.999 70.004 50.015 0208Pb0.10~20.00y=148 812.202 1x+5 111.367 60.999 90.021 30.071 1209Bi0.10~20.00y=203 344.236 7x+1 086.366 20.999 90.006 90.022 92.2回收率和精密度试验为验证本研究方法的可行性，分别选取5种饲料各1批次作为加标本底样品，对所选取饲料样品进行加标回收验证，每个饲料样品及加标回收样品做3个平行处理。其中单一饲料、添加剂预混合饲料、精料补充料各元素加标浓度为：Li、V、Cr、Co、Ni、Ga、As、Se、Mo、Pb加标浓度低、中、高为1.00、5.00、10.00 mg/kg，Ti、Rb、Sr、Ba加标浓度低、中、高为5.00、10.00、20.00 mg/kg，Be、Ag、Cd、Sb、Cs、Tl、Bi加标浓度低、中、高为0.50、1.00、2.00 mg/kg；配合饲料各元素加标浓度为：Li、Be、V、Cr、Co、Ni、Ga、As、Se、Mo、Cd、Cs、Pb加标浓度低、中、高为1.00、5.00、10.00 mg/kg，Ti、Rb、Sr、Ba加标浓度低、中、高为5.00、10.00、20.00 mg/kg，Ag、Sb、Cs、Tl、Bi加标浓度低、中、高为0.50、1.00、2.00 mg/kg；浓缩饲料各元素加标浓度为：Li、Be、Co、Ni、Ga、As、Se、Mo、Cd、Cs、Pb加标浓度低、中、高为1.00、5.00、10.00 mg/kg，Ti、V、Cr 、Rb、Sr、Ba加标浓度低、中、高为5.00、10.0、20.00 mg/kg，Ag、Sb、Cs、Tl、Bi加标浓度低、中、高为0.50、1.00、2.00 mg/kg。5种类型饲料21种元素加标量、回收率及相对标准偏差见表4~表8。10.13557/j.cnki.issn1002-2813.2021.18.025.T004表4单一饲料21种元素加标量、回收率及相对标准偏差（n=3）元素本底值/（mg/kg）加标1加标2加标3加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%7Li0.5061.0098.6~103.02.45.0094.1~102.04.010.00104.0~105.00.79Be0.0840.5095.3~97.93.21.0087.3~95.54.52.00105.0~106.00.848Ti24.2005.0092.7~96.11.810.0091.9~95.01.720.0094.6~103.04.751V0.8991.00100.0~102.00.95.00102.0~103.01.110.00102.0~104.01.552Cr1.2101.0086.8~92.33.45.0091.3~95.72.710.00104.0~108.01.859Co0.5131.0095.7~102.03.55.0099.1~101.00.910.00105.0~107.00.860Ni1.5901.0091.2~97.13.25.0090.4~94.02.010.0099.7~102.01.469Ga1.7901.0091.9~95.82.15.0095.8~99.11.910.00102.0~105.01.775As0.3411.0091.9~97.63.05.0085.0~91.43.710.00104.0~107.01.778Se0.4291.0088.6~99.26.25.0085.5~88.92.010.0084.7~91.43.985Rb9.8505.0093.9~103.04.810.00101.0~105.02.220.0099.7~101.00.988Sr13.1005.0096.4~112.07.610.0094.9~99.07.320.0094.9~104.04.895Mo0.8311.0097.2~105.04.15.00102.0~105.01.310.0099.9~102.01.1107Ag0.0800.5085.6~89.74.11.0087.6~90.61.82.0087.1~89.41.3111Cd0.0680.5090.9~94.62.21.0084.7~90.23.12.00101.0~106.02.5121Sb0.0670.5084.6~92.24.41.0085.7~88.53.42.0088.2~98.45.7133Cs0.2110.5084.7~88.32.31.0091.5~98.63.92.0099.6~100.00.4138Ba6.2905.0098.0~103.02.310.00102.0~108.02.820.00103.0~104.00.5205Tl0.0100.50101.0~108.03.41.0099.4~105.02.52.0097.3~99.31.1208Pb0.2330.5091.7~96.72.71.0091.9~93.71.02.00100.0~104.01.8209Bi0.0070.5096.4~106.04.81.0097.6~100.01.52.0095.2~101.03.110.13557/j.cnki.issn1002-2813.2021.18.025.T005表5添加剂预混合饲料21种元素加标量、回收率及相对标准偏差（n=3）元素本底值/（mg/kg）加标1加标2加标3加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%7Li0.4181.0098.0~102.02.45.0097.5~104.03.210.0099.8~104.02.69Be0.0400.5097.9~99.00.61.0089.5~97.34.52.00101.0~105.02.548Ti19.6005.0093.9~99.63.110.0094.0~98.02.420.0090.0~95.93.551V0.7961.0089.2~95.23.35.0094.1~100.03.210.00103.0~107.02.152Cr2.5601.0085.6~94.05.65.0089.4~99.25.310.0098.7~104.02.759Co0.7491.0092.2~99.43.85.0089.3~98.24.910.00101.0~109.03.360Ni2.0201.0098.0~106.03.95.0093.6~99.73.610.0095.5~99.72.169Ga1.0601.00100.0~104.01.65.0094.9~101.03.110.0098.7~101.01.375As0.2570.5091.9~102.05.41.0094.8~104.04.32.0096.0~101.02.778Se0.4071.0099.7~104.02.45.0093.0~99.53.65.0089.2~99.15.585Rb9.9705.0094.6~108.06.710.0095.9~109.06.720.0099.7~102.01.188Sr9.8605.0092.7~101.05.110.0093.6~101.04.220.0098.2~100.01.295Mo0.5541.0092.1~93.60.85.0096.0~99.84.810.0096.9~108.05.9107Ag0.0030.5081.6~86.22.85.0094.4~97.82.02.0091.0~96.43.1111Cd0.0800.5094.7~101.03.21.0097.3~107.04.42.0097.2~104.03.7121Sb0.0200.5081.0~85.83.01.0099.5~105.02.72.0089.2~97.04.4133Cs0.0930.5083.0~90.84.61.0083.9~90.14.02.0090.6~100.05.6138Ba4.1205.0091.2~94.51.810.0098.5~104.02.520.0085.4~88.11.6205Tl0.0200.50100.0~108.03.51.0099.8~107.03.72.0094.2~98.02.2208Pb0.2701.00102.0~109.03.25.0097.8~103.02.65.0096.5~104.03.8209Bi0.0160.50106.0~110.02.21.00102.0~110.04.42.0096.6~102.02.710.13557/j.cnki.issn1002-2813.2021.18.025.T006表6配合饲料21种元素加标量、回收率及相对标准偏差（n=3）元素本底值/（mg/kg）加标1加标2加标3加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%7Li0.5871.0086.6~92.73.45.0093.2~102.04.710.00102.0~106.02.69Be0.0380.5088.3~96.14.21.0089.7~91.40.82.0092.7~95.71.948Ti50.5005.0090.5~97.54.210.0089.8~91.20.820.0092.7~95.71.951V1.1001.0099.0~101.00.95.0098.5~99.30.410.0098.0~102.02.452Cr4.7001.0086.9~98.86.45.0087.8~101.07.110.0098.5~103.02.159Co0.5651.0099.7~103.01.75.00102.0~106.02.310.00101.0~105.02.460Ni2.3301.0089.2~94.13.05.0093.7~107.06.710.00102.0~106.02.469Ga8.5905.0090.9~95.52.710.0083.5~90.44.020.0099.6~102.01.175As2.1101.0092.1~98.63.85.0096.4~104.04.210.0097.5~98.80.878Se1.1101.0092.2~99.43.85.0096.7~99.51.510.00101.0~102.00.485Rb19.1005.0098.3~105.03.310.0093.8~99.93.320.0096.1~100.02.488Sr16.1005.0089.8~100.06.010.0090.0~102.06.120.0097.2~98.80.995Mo1.3501.0096.5~98.81.25.0098.0~102.02.210.0090.1~93.82.0107Ag0.0520.5082.2~89.04.01.0083.6~87.42.02.0095.1~101.03.2111Cd1.5801.0093.3~100.03.85.0095.5~96.70.610.0096.7~99.41.4121Sb0.0480.5085.8~95.45.41.0089.5~94.12.52.0093.0~95.01.1133Cs0.2250.5098.3~103.02.71.0099.7~99.90.52.0099.8~100.00.1138Ba44.2005.0094.7~101.03.210.0090.5~99.93.120.0095.4~101.03.1205Tl0.0290.5099.7~102.00.91.0099.7~104.02.02.0096.3~99.01.4208Pb0.5021.0093.9~102.04.25.00101.0~102.00.910.0099.9~101.00.9209Bi0.0090.50103.0~105.00.91.0098.7~101.01.22.0096.6~99.21.310.13557/j.cnki.issn1002-2813.2021.18.025.T007表7浓缩饲料21种元素加标量、回收率及相对标准偏差（n=3）元素本底值/（mg/kg）加标1加标2加标3加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%7Li3.1301.0096.5~98.81.45.0096.2~99.51.710.0090.2~93.41.89Be0.3711.0095.0~102.03.65.0095.3~103.03.910.0093.2~101.04.148Ti207.0005.0086.8~91.62.910.0086.1~98.26.620.0090.1~93.92.251V22.9005.0092.9~93.70.510.0091.3~93.21.120.0091.8~100.04.752Cr9.2205.0089.3~101.06.510.0091.0~105.07.320.0098.5~103.02.259Co2.0801.0085.2~97.87.25.0086.3~97.47.010.0091.1~97.63.560Ni6.3601.0097.8~109.06.45.0085.6~99.67.510.0088.3~94.03.169Ga5.0001.0090.1~96.93.75.0089.3~95.93.710.0086.2~98.06.975As2.4501.0086.0~90.82.85.0082.2~90.34.710.0086.6~92.13.478Se4.9501.0086.1~98.37.45.0084.5~97.17.210.0099.0~103.02.385Rb16.0005.0088.5~90.10.910.0093.6~101.03.720.0091.3~96.53.288Sr83.0005.0084.9~92.04.010.0088.8~99.46.020.00101.0~104.01.995Mo1.1301.0094.6~96.30.95.0098.0~101.01.510.0091.8~98.23.7107Ag0.0080.5088.8~98.05.21.0094.5~107.07.12.0096.3~105.04.4111Cd0.2851.0093.3~104.05.75.0095.9~100.02.310.0086.0~92.03.9121Sb0.0730.5085.0~96.06.61.0083.5~88.12.62.0091.5~97.53.3133Cs0.6231.0088.2~103.07.75.0097.7~98.20.310.0098.1~99.60.7138Ba28.8005.0084.9~98.78.810.0095.9~98.41.320.0090.4~104.07.0205Tl0.1270.5097.5~98.90.71.0097.5~100.00.92.0093.1~103.04.9208Pb2.2301.0091.1~104.06.75.0097.5~100.01.410.0089.4~96.33.8209Bi0.0290.5098.5~101.01.61.0095.9~100.02.42.0089.0~101.07.110.13557/j.cnki.issn1002-2813.2021.18.025.T008表8精料补充料21种元素加标量、回收率及相对标准偏差（n=3）元素本底值/（mg/kg）加标1加标2加标3加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%加标浓度/（mg/kg）回收率/%相对标准偏差/%7Li0.1271.0092.1~97.62.95.0092.1~96.72.410.0090.6~98.34.19Be0.0090.5097.8~101.01.61.0096.3~97.60.72.0094.9~98.82.348Ti11.8005.0084.8~90.63.610.0082.3~88.43.620.0084.8~90.13.251V0.6931.0084.5~96.21.05.0094.8~95.90.610.0094.0~99.64.352Cr2.1901.0096.2~105.04.45.0094.8~96.00.610.0094.0~102.04.359Co1.0301.0097.4~103.03.25.00103.0~107.02.010.00102.0~103.00.560Ni1.3501.0089.1~97.04.45.0096.5~106.04.710.00100.0~103.01.569Ga2.3801.0083.8~92.55.25.0096.2~100.02.010.0098.1~104.02.975As0.3531.0092.5~103.05.95.0096.7~103.03.210.0096.7~99.03.178Se0.3431.0085.9~92.43.75.0097.1~98.90.910.0098.6~102.01.885Rb10.8005.0089.0~94.93.310.0094.6~100.03.320.0097.0~100.01.688Sr42.6005.0088.6~92.01.910.0098.5~104.02.820.0093.6~100.03.895Mo0.7461.0097.8~105.04.15.0095.2~99.62.410.0095.2~101.03.2107Ag0.0050.5086.0~98.06.91.0095.6~104.04.42.0094.4~103.04.3111Cd0.0250.5090.0~101.05.61.00101.0~105.02.02.0099.7~103.01.6121Sb0.0120.5088.2~96.65.11.0091.6~97.93.42.0092.1~99.04.0133Cs0.0840.5086.0~89.82.41.0093.4~94.20.52.0091.4~93.81.3138Ba12.6005.0091.9~95.62.210.0088.8~97.74.920.0094.4~103.04.4205Tl0.0090.5098.6~99.40.41.00101.0~103.01.22.0099.6~104.02.0208Pb0.3931.0094.1~99.02.55.0095.4~99.92.410.0096.7~102.02.7209Bi0.0160.5088.8~92.82.31.0094.7~103.04.22.0099.4~102.01.5由表4~表8可知，单一饲料加标回收率结果为84.6%~112%，RSD为0.4%~7.6%；添加剂预混合饲料加标回收率结果为81.0%~110%，RSD为0.6%~6.7%；配合饲料加标回收率结果为82.2%~107.0%，RSD为0.1%~7.1%；浓缩饲料加标回收率结果为82.2%~109%，RSD为0.3%~8.8%；精料补充料加标回收率结果为82.3%~107%，RSD为0.4%~6.9%。5种饲料各元素加标回收率结果及RSD均符合GB/T 27404—2008《实验室质量控制规范 食品理化检测》的要求。结果表明，微波消解-ICP-MS法可以用于饲料中Li、Be、Ti、V、Cr、Co、Ni、Ga、As、Se、Rb、Sr、Mo、Ag、Cd、Sb、Cs、Ba、Tl、Pb、Bi共21种元素的同时检测。在市场中随机购买饲料样品共40批次，编号为Y1~Y40，其中Y1~Y9为单一饲料，Y10~Y18为添加剂预混合饲料，Y19~Y28为配合饲料，Y29~Y37为浓缩饲料，Y38~Y40为精料补充料。使用本研究所建立方法进行定量分析。40批次饲料样品21种元素定量分析结果及相对标准偏差范围见表9。由表9可知，40批次饲料样品的21种元素定量分析结果RSD均小于10%，RSD符合GB/T 27404—2008《实验室质量控制规范食品理化检测》的要求。10.13557/j.cnki.issn1002-2813.2021.18.025.T009表940批次饲料样品21种元素定量分析结果及相对标准偏差范围 （n=3）元素7Li9Be48Ti51V52Cr59Co60Ni69Ga75As78Se85Rb88Sr95Mo107Ag111Cd121Sb133Cs138Ba205Tl208Pb209BiRSD/%0.9~4.52.2~4.91.4~6.10.5~5.60.8~5.90.6~4.70.8~6.70.6~4.61.0~7.41.4~6.50.3~3.50.9~4.21.7~6.80~8.70.7~5.40~5.01.0~6.00.6~5.00~3.62.0~6.20~6.4Y10.0780.01557.00.1860.8660.0591.530.5860.0840.1876.2419.21.460.0070.0540.0480.0422.140.0150.1510.041Y20.3450.02138.10.3883.1800.2591.081.0201.0900.9787.3433.81.040.0070.4230.0380.3183.610.0290.2600.032Y30.2070.04323.90.7260.8330.3641.742.7900.2460.6278.4012.50.910.0160.0410.0250.09610.100.0240.3060.018Y40.1960.03822.60.7010.9990.4101.701.1600.3280.7196.6512.30.830.0070.0940.0440.0834.060.0250.1850.016Y50.1760.04227.70.9600.9510.2520.980.9100.6400.5266.7412.81.030.0120.0290.0260.1053.200.0080.1960.012Y60.1950.04631.80.9051.2300.2641.070.9790.2400.5126.7213.41.010.0070.0300.0240.1193.460.0080.1710.008Y70.2070.04129.50.9110.3330.3071.111.0600.2740.6247.1012.60.930.0110.0310.0190.1873.800.0070.1680.007Y80.5060.08424.20.8991.2100.5131.591.7900.3410.4299.8513.10.830.0800.0680.0670.2116.290.0100.2330.007Y90.1100.01115.00.2691.5400.4831.531.2300.1590.34411.8011.31.010.0110.048ND0.0705.44ND0.162NDY100.4180.04019.60.7962.5600.7492.021.0600.2570.4079.979.90.55ND0.0800.0200.0934.120.0200.2700.016Y115.3901.010317.022.6006.1402.8405.958.5203.6009.42024.50128.00.290.0210.4500.02016.40053.100.39014.4000.332Y1211.6000.22270.52.8209.1001.1103.182.7403.7904.3505.5320.80.250.0060.0820.0340.85112.200.0591.8000.035Y133.2101.380239.05.76010.60023.7007.578.5402.7706.06024.0048.50.400.0200.2330.1742.14055.100.8946.8900.174Y146.5300.850166.04.78028.400117.00028.103.9402.54029.80010.305.10.960.0530.1490.0092.32033.607.0106.6201.390Y1510.8001.140276.013.50022.80027.5007.834.7706.76011.40030.4079.00.690.1160.4670.0534.54027.800.2445.7402.650Y165.8801.530333.08.75019.60025.0003.788.21038.8009.00023.80103.00.420.0120.1990.1212.87045.800.1405.2700.199Y1721.4000.915225.011.20021.0002.0505.329.5202.9403.46010.8081.30.160.0120.2640.0171.31055.900.0854.4000.086Y184.6101.020347.013.3006.43021.30012.603.0309.5609.77016.30137.00.350.0250.5800.0681.89016.800.6074.2800.450Y190.8890.05387.61.5704.5700.5082.052.2601.5100.5619.9131.00.980.0370.2680.1200.34111.000.0461.2000.009Y200.9680.07632.81.1705.1400.8973.651.9104.4301.62010.1052.91.640.0451.1500.0710.5348.540.0280.6040.009Y210.4300.04814.50.6411.6000.3642.453.4000.2320.44620.6013.50.960.0410.062ND0.33015.500.0090.215NDY220.6000.03924.80.9223.7300.3231.343.6200.2500.68821.2019.31.960.0120.0680.0530.26116.900.1240.4040.015Y230.3470.02267.40.6371.7400.3011.082.5101.5901.0508.64229.00.910.0290.2240.0270.17712.000.0100.613NDY240.8870.04052.21.0604.4400.4241.173.3603.6801.24010.50107.00.920.0470.4260.0420.22616.200.0130.5380.008Y250.5870.03850.51.1004.7000.5652.338.5902.1101.11019.10159.01.350.0521.5800.0480.22544.200.0290.5020.009Y260.9120.08960.31.5505.0000.5462.603.9503.4901.8009.18273.00.790.0391.4700.0181.08020.300.0351.7000.018Y270.8620.04525.81.1804.0600.7982.484.7901.9500.92717.6052.21.820.0310.7570.0320.14823.900.0870.6570.008Y280.1830.05027.00.6612.6500.3092.133.2400.2150.43621.5016.11.36ND0.0570.0190.42416.400.0160.2780.015Y290.1360.06611.70.4611.1200.5852.212.5300.1561.90024.8021.54.430.0480.0700.0370.19612.700.0340.1430.037Y300.5370.07036.20.3700.6091.5003.833.2000.5281.27021.1032.72.54ND0.1250.0220.24616.600.0130.2570.036Y315.0200.19024.70.6650.8541.4402.304.4800.2780.42225.4020.52.80ND0.1780.0950.49522.200.0140.7740.008Y321.7900.04166.02.0604.5403.5203.062.5100.6431.29014.7073.43.030.0050.162ND0.19012.800.0400.5450.017Y333.1300.371207.022.9009.2102.0806.365.0002.4504.92016.0083.11.130.0080.2850.0730.62328.800.1272.2300.029Y341.0100.16046.62.3601.7601.7005.701.4600.5432.15013.3034.62.590.0050.0850.0250.3667.660.0220.7320.041Y352.2300.204214.025.2008.3601.6105.311.4402.4503.98011.2096.31.600.0090.4580.0580.3197.890.0180.7780.027Y360.7210.04150.71.6601.2601.2005.973.7500.7541.97040.7038.41.770.0050.1800.0730.24421.000.0240.4580.008Y370.4790.226102.04.3603.1207.5505.442.5301.2103.66020.4071.32.160.0030.4580.1140.31214.900.0290.6090.007Y380.1680.08313.40.6072.0001.1301.382.2500.3530.37014.1049.70.770.0050.027ND0.10812.000.0110.3730.013Y390.2380.02318.90.5414.2400.9892.461.9400.4941.11016.3052.91.670.0050.0420.0460.43510.200.0150.515NDY400.1990.0108.20.4706.0002.7305.281.7300.2576.32017.5013.51.170.0060.0400.0180.1929.110.2200.462ND注：ND表示未检出。mg/kg3讨论本研究用微波消解-电感耦合等离子体质谱法对饲料中锂、铍、钛、钒、铬、钴、镍、镓、砷、硒、铷、锶、钼、银、镉、锑、铯、钡、铊、铅、铋21种元素进行定量分析，并从线性方程、相关系数、检出限、定量限、精密度及准确度等方面验证了本研究方法的可行性。分别对5种类型饲料的21种元素进行加标回收试验，回收率及RSD结果为单一饲料84.6%~112.0%、0.4%~7.6%；添加剂预混合饲料81.0%~110.0%、0.6%~6.7%；配合饲料82.2%~107.0%、0.1%~7.1%；浓缩饲料82.2%~109%、0.3%~8.8%；精料补充料82.3%~107.0%、0.4%~6.9%。对市场中随机购买的40批次不同类型饲料样品进行定量分析，40批次饲料样品21种元素结果RSD均小于10%，均符合GB/T 27404—2008《实验室质量控制规范食品理化检测》的要求。本研究方法不仅具有原子吸收分光光度法、原子荧光光度法等多元素同时分析的特点，还具有分析效率高、节省人力的优势。与电感耦合等离子体发射光谱法相比，本方法具有更低的检出限，更高的灵敏度和准确度。由于本研究方法前处理称样量较少，为减少样品不均匀引起的分析误差，对样品的均匀性有比较高的要求，同时对制样提出较高的要求。4结论本研究建立微波消解-ICP-MS法同时检测饲料中锂、铍、钛、钒、铬、钴、镍、镓、砷、硒、铷、锶、钼、银、镉、锑、铯、钡、铊、铅、铋21种元素含量。该方法样品前处理操作简单、安全、效率高；检测结果准确度高、灵敏度高、稳定性好。微波消解-ICP-MS法可以实现5种类型饲料21种元素的通量检测，为饲料的生产和加工以及相应检测标准的制定提供参考。