TZNZ 221-2023 水產(chǎn)品中37 種農(nóng)藥殘留量的測(cè)定 氣相色譜-串聯(lián)質(zhì)譜法

ICS67.120.30CCSB50

T/ZNZT/ZNZ221—202337Determinationof37pesticidesresiduesinaquaticproductbygaschromatography-tandemmassspectrometricmethod2023-10-13發(fā)布 2023-11-13實(shí)施浙江省農(nóng)產(chǎn)品質(zhì)量安全學(xué)會(huì)??發(fā)布T/ZNZ221T/ZNZ221—2023II前??言本文件按照GB/T1.1—20201草。請(qǐng)注意本文件的某些內(nèi)容可能涉及專利。本文件的發(fā)布機(jī)構(gòu)不承擔(dān)識(shí)別專利的責(zé)任。本文件由浙江省農(nóng)產(chǎn)品質(zhì)量安全學(xué)會(huì)提出并歸口。本文件起草單位：綠城農(nóng)科檢測(cè)技術(shù)有限公司。本文件主要起草人：趙月鈞、俞璐萍、倪娟楨、徐冰潔、姜亞琴、王偉、桑力青、王馨瑜、馬曉瑩、陶楊勻、黃榮博、吳丹虹、李聞潔、童曉玲、梁黎明、徐巧。T/ZNZ221T/ZNZ221—2023PAGEPAGE1水產(chǎn)品中37種農(nóng)藥殘留量的測(cè)定氣相色譜—串聯(lián)質(zhì)譜法范圍本文件規(guī)定了水產(chǎn)品中37種農(nóng)藥殘留量的氣相色譜—串聯(lián)質(zhì)譜測(cè)定方法。本文件適用于魚(yú)類、蝦類、蟹類、鱉類等水產(chǎn)品中37種農(nóng)藥的測(cè)定。規(guī)范性引用文件（包括所有的修改單適用于本文件。GB/T6682分析實(shí)驗(yàn)室用水規(guī)格和試驗(yàn)方法術(shù)語(yǔ)和定義本文件沒(méi)有需要界定的術(shù)語(yǔ)和定義。原理試劑和材料除非另有說(shuō)明，本方法所用試劑均為分析純，水為GB/T6682規(guī)定的一級(jí)水。5.1 乙腈CHCNCAS號(hào)：7505-）色譜純。5.2 丙酮CHCOC，CAS號(hào)：11-543）色譜純。5.3 （H，CAS號(hào)：11054-）色譜純。（A3）200目～300目。（MgO）650℃灼燒4h，置于干燥器內(nèi)冷卻后備用。氯化鈉（NaCl）500℃灼燒4h，置于干燥器內(nèi)冷卻后備用。N-丙基乙二胺（PSA）粒徑范圍40μm～60μm，平均孔徑100?。C8吸附劑）粒徑范圍40μm～60μm，平均孔徑60?。微孔濾膜0.22μm，有機(jī)膜。5.10 丙酮-正己烷溶液（10:90）量取10mL丙酮加入90mL正己烷中，混勻。標(biāo)準(zhǔn)品37種農(nóng)藥及環(huán)氧七氯的中文名稱、英文名稱、CAS號(hào)、分子式、相對(duì)分子量見(jiàn)附錄A，純度應(yīng)≥95%。標(biāo)準(zhǔn)溶液配制標(biāo)準(zhǔn)儲(chǔ)備溶液：分別準(zhǔn)確稱取標(biāo)準(zhǔn)品（5.11）10mg10mL，此溶液濃1000mg/L。2℃~8℃6個(gè)月。1.00mL5.121100mL10m/L的混合標(biāo)準(zhǔn)中間溶液，2℃~8℃避光密封保存，有效期1個(gè)月。10mg100100mg/L。儀器和設(shè)備氣相色譜—串聯(lián)質(zhì)譜儀：配有電子轟擊源。0.01mg0.01g。低溫離心機(jī)：轉(zhuǎn)速≥8000r/min。渦旋振蕩器：轉(zhuǎn)速≥2000r/min。40kHz200W。分析步驟試樣制備與保存-18℃以下冷凍保存；-18℃以下冷凍保存；蟹類取可食部分，絞碎混合均勻后備用，制好后將試樣于-18℃以下冷凍保存；龜鱉類取可食部分，絞碎混合均勻后備用，制好后將試樣于-18℃以下冷凍保存；提取稱取5g（精確至于50mL10mL1min10.0mL乙腈（5.1），渦旋振蕩1min，超聲提取20min，4℃條件下8000r/min離心5min，取上清液于裝有5g氯化鈉（5.6）的50mL離心管中，再加10.0mL乙腈（5.1），混勻1min，4℃條件下8000r/min離心5min，合并上清液。凈化和濃縮將6.00mL提取液置于裝有100mgPSA（5.7）、100mgC18（5.8），500mg中性氧化鋁（5.4）和300mg無(wú)水硫酸鎂（5.5）的15mL離心管中，渦旋混勻3min，4℃下8000r/min離心3min。取4.00mL上清液氮吹近干，準(zhǔn)確加入0.500mL丙酮—正己烷溶液（5.10），加入內(nèi)標(biāo)溶液（5.12.3）15μL，渦旋混勻10s，過(guò)0.22μm微孔濾膜（5.9），供氣相色譜—串聯(lián)質(zhì)譜聯(lián)用儀分析。測(cè)定色譜參考條件色譜柱：（5%-苯基）-甲基聚硅氧烷石英毛細(xì)管柱（30m0.25mm0.25μm），或性能相當(dāng)者。進(jìn)樣量：1.0μL。進(jìn)樣口溫度：250℃。進(jìn)樣方式：不分流進(jìn)樣。7.4.1.5 載氣：高純氮?dú)?，純度?9.999%。7.4.1.6柱流速：1.41mL/min。7.4.1.7柱溫程序：80℃，保持1min40℃/min升至170℃，保持1min20℃/min升至290℃，保持7min。質(zhì)譜參考條件離子源：電子轟擊源（EI），70eV。接口溫度：280℃。離子源溫度：230℃。溶劑延遲時(shí)間：3.2min。標(biāo)準(zhǔn)工作曲線精確吸取一定量的混合標(biāo)準(zhǔn)溶液，逐級(jí)用丙酮—正己烷溶液（5.10）稀釋成質(zhì)量濃度為0.005mg/L、0.01mg/L、0.05mg/L、0.1mg/L、0.5mg/L和0.8mg/L的標(biāo)準(zhǔn)工作溶液?？瞻谆|(zhì)溶液氮?dú)獯蹈?，加?5μL1mL配置成系列基質(zhì)混合標(biāo)準(zhǔn)工—定性測(cè)定2.5之內(nèi)；表1定性確證時(shí)相對(duì)離子豐度的最大允許偏差相對(duì)豐度（%）＞50＞20-50＞10-20≤10允許偏差（%）±20±25±30±50試樣溶液的測(cè)定將基質(zhì)混合標(biāo)準(zhǔn)工作溶液和試樣溶液依次注入氣相色譜—質(zhì)譜聯(lián)用儀中，保留時(shí)間和定性離子定平行試驗(yàn)按7.2~7.3的規(guī)定對(duì)同一試樣進(jìn)行平行試驗(yàn)測(cè)定?？瞻自囼?yàn)除不加試樣外，均按7.2~7.3的規(guī)定進(jìn)行平行操作。結(jié)果計(jì)算和表述8.1 定量測(cè)定采用標(biāo)準(zhǔn)曲線法或單點(diǎn)內(nèi)標(biāo)法定量。按式（1）或儀器數(shù)據(jù)處理軟件計(jì)算獲得：············（1）式中：——試樣中被測(cè)物質(zhì)的殘留量，單位為毫克每千克（mg/kg）；——可從標(biāo)準(zhǔn)曲線上或儀器上直接得到被測(cè)物質(zhì)的濃度，單位為毫克每升（mg/L）；f——稀釋因子；——溶解殘余物所用定容溶液體積，單位為毫升（mL）；——試樣質(zhì)量，單位為克（g）；F——最終分取體積/提取液體積。計(jì)算結(jié)果應(yīng)扣除空白值，保留3位有效數(shù)字。定量限本方法的定量限為0.01mg/kg~0.03mg/kg（參見(jiàn)附錄A）。準(zhǔn)確度本方法在0.03mg/kg~0.3mg/kg添加濃度水平上的回收率在70%~120%之間，見(jiàn)附錄D。精密度在重復(fù)性條件下獲得的兩次獨(dú)立測(cè)定結(jié)果的絕對(duì)差值不得超過(guò)算術(shù)平均值的15%，見(jiàn)附錄D。T/ZNZ221T/ZNZ221—2023PAGEPAGE1附 錄 A（資料性）37種農(nóng)藥及內(nèi)標(biāo)的中英文名稱、CAS號(hào)、分子式、相對(duì)分子量、定量限表A.1給出了37種農(nóng)藥及內(nèi)標(biāo)的中英文名稱、CAS號(hào)、分子式、相對(duì)分子量、定量限。表A.137種農(nóng)藥及內(nèi)標(biāo)的中文名稱、英文名稱、CAS號(hào)、分子式、相對(duì)分子量、定量限序號(hào)中文名稱英文名稱CAS號(hào)分子式相對(duì)分子量定量限/mg·kg-11α-六六六Alpha-BHC319-84-6C6H6Cl6290.830.032β-六六六Beta-BHC319-85-7C6H6Cl6290.830.033γ-六六六Gamma-BHC58-89-9C6H6Cl6290.830.034δ-六六六Delta-BHC319-86-8C6H6Cl6290.830.035苯醚甲環(huán)唑Difenoconazole119446-68-3C19H17Cl2N3O3406.260.026吡唑醚菌酯Pyraclostrobin175013-18-0C19H18ClN3O4387.820.037丙環(huán)唑Propiconazole60207-90-1C15H17Cl2N3O2342.220.038蟲(chóng)螨腈Chlorfenapyr122453-73-0C15H11BrClF3N2O407.610.039敵敵畏Dichlorvos62-73-7C4H7Cl2O4P220.980.0310丁草胺Butachlor23184-66-9C17H26ClNO2311.850.0211毒死蜱Chlorpyrifos2921-88-2C9H11Cl3NO3PS350.590.0112二甲戊靈Pendimethalin40487-42-1C13H19N3O4281.310.0213氟蟲(chóng)腈Fipronil120068-37-3C12H4Cl2F6N4OS437.150.0314氟蟲(chóng)腈砜Fipronil-sulfone120068-36-2C12H4Cl2F6N4O2S453.150.0215氟蟲(chóng)腈硫醚Fipronil-sulfide120067-83-6C12H4Cl2F6N4S421.150.0316氟甲腈Fipronil-desulfinyl205650-65-3C12H4Cl2F6N4389.080.0217環(huán)氧七氯Hcptachlor-epoxideB17498-34-9C12H14O5238.24/18甲氰菊酯Fenpropathrin64257-84-7C22H23NO3349.420.0319聯(lián)苯菊酯Bifenthrin82657-04-3C23H22ClF3O2422.870.0120氯氟氰菊酯和高效氯氟氰菊酯CyhalothrinandIambda-cyhalothrin68085-85-891465-08-6C23H19ClF3NO3449.850.0321氯菊酯Permethrin52645-53-1C21H20Cl2O3391.290.03表A.1（續(xù)）序號(hào)中文名稱英文名稱CAS號(hào)分子式相對(duì)分子量定量限/mg·kg-122氯氰菊酯和高效氯氰菊酯Cypermethrinandbeta-cypermethrin52315-07-886752-99-0C22H19Cl2NO3416.30.0323馬拉硫磷Malathion121-75-5C10H19O6PS2330.360.0224醚菊酯Etofenprox80844-07-1C25H28O3376.490.0225醚菌酯Kresoxim-methyl143390-89-0C18H19NO4313.850.0226嘧菌酯Azoxystrobin131860-33-8C22H17N3O5403.390.0327氰戊菊酯和FenvalerateandEsfenvalerate51630-58-166230-04-4C25H22ClNO3419.90.0228噻蟲(chóng)嗪Thiamethoxam153719-23-4C8H10ClN5O3S291.710.0329噻呋酰胺Thifluzamide130000-40-7C13H6Br2F6N2O2S528.060.0230三環(huán)唑Tricyclazole41814-78-2C9H7N3S189.240.0331三唑醇Triadimenol55219-65-3C14H18ClN3O2295.760.0232三唑磷Triazophos24017-47-8C12H16N3O3PS313.310.0233三唑酮Triadimefon43121-43-3C14H16ClN3O2293.750.0234水胺硫磷Isocarbophos24353-61-5C11H16NO4PS289.290.0235肟菌酯Trifloxystrobin141517-21-7C20H19F3N2O4408.370.0236戊唑醇Tebuconazole107534-96-3C16H22ClN3O307.820.0237溴氰菊酯Deltamethrin52918-63-5C22H19Br2NO3505.20.0338乙酰甲胺磷Acephate30560-19-1C4H10NO3PS183.170.03附 錄 B（資料性）37種農(nóng)藥及環(huán)氧七氯監(jiān)測(cè)離子對(duì)和碰撞能量表B.1給出了37種農(nóng)藥及環(huán)氧七氯和保留時(shí)間、監(jiān)測(cè)離子對(duì)、碰撞能量。表B.1 37種農(nóng)藥及環(huán)氧七氯和保留時(shí)間、監(jiān)測(cè)離子對(duì)、碰撞能量序號(hào)化合物保留時(shí)/min定量離子對(duì)（m/z）碰撞電壓V定性離子對(duì)（m/z）碰撞電壓V1α-六六六6.915218.90>182.908218.90>144.90202β-六六六7.184218.90>182.908218.90>144.90203γ-六六六7.301218.90>182.908218.90>144.90204δ-六六六7.604218.90>182.9010218.90>144.90205苯醚甲環(huán)唑14.643322.80>264.8015264.90>202.00206吡唑醚菌酯14.098132.00>77.0020132.00>51.00307丙環(huán)唑10.173259.00>69.0014259.00>191.0088蟲(chóng)螨腈9.579247.10>227.0016247.10>200.00249敵敵畏3.984185.00>93.0014185.00>109.001410丁草胺9.144188.10>160.2010176.10>147.102211毒死蜱8.364196.90>169.0015198.90>171.001512二甲戊靈8.745252.10>162.1010252.10>191.10813氟蟲(chóng)腈8.739366.80>212.8025368.80>214.802514氟蟲(chóng)腈砜9.343382.90>255.9024382.95>213.003615氟蟲(chóng)腈硫醚8.623350.90>255.9018419.95>350.901516氟甲腈7.843387.95>332.9018383.00>231.002717環(huán)氧七氯8.783352.80>262.9015352.80>281.901518甲氰菊酯10.821207.90>181.005264.90>210.001019聯(lián)苯菊酯10.686181.20>165.2025181.20>166.201020氯氟氰菊酯和高效氯氟氰菊酯11.304197.00>141.0010197.00>161.005表B.1（續(xù)）序號(hào)化合物保留時(shí)間定量離子對(duì)（m/z）碰撞電壓V定性離子對(duì)（m/z）碰撞電壓V21氯菊酯12.104183.10>168.1014183.10>165.101422氯氰菊酯和高效氯氰菊酯12.987181.10>152.1022181.10>127.102223馬拉硫磷8.293173.10>99.0014173.10>127.00624醚菊酯13.21206.10>116.106206.10>131.101425醚菌酯9.48206.10>131.1014206.10>116.10626嘧菌酯15.383344.10>329.1016344.10>183.102427氰戊菊酯和S-氰戊菊酯13.955167.00>125.105224.90>119.001528噻蟲(chóng)嗪8.731247.00>212.004247.00>182.001229噻呋酰胺9.415448.90>428.9020448.90>402.003430三環(huán)唑9.501189.00>161.9012189.00>135.001831三唑醇8.963168.00>70.0010128.00>65.002532三唑磷10.009161.20>134.205161.20>106.101033三唑酮8.513208.00>181.105208.00>111.002034水胺硫磷8.528135.9>108.0015135.90>69.003035肟菌酯10.059222.10>190.104222.10>162.101036戊唑醇10.416250.10>125.1022250.10>153.101237溴氰菊酯15.113252.90>93.0015250.70>172.00538乙酰甲胺磷5.106136.00>42.005136.00>94.0010T/ZNZ221T/ZNZ221—202311附 錄 C（資料性）37種農(nóng)藥及環(huán)氧七氯的多反應(yīng)監(jiān)測(cè)（MRM）色譜圖37種農(nóng)藥及環(huán)氧七氯的多反應(yīng)監(jiān)測(cè)（MRM）色譜圖見(jiàn)圖C.1。2.5(x10,000)2.01.51.00.5

0.0

3.80 3.85 3.90 3.95 4.00 4.05 4.10 4.15

0.0

4.95 5.00 5.05 5.10 5.15 5.20

0.00

6.75 6.80 6.85 6.90 6.95 7.00 7.05 7.10敵敵畏

乙酰甲胺磷α-六六六2.5

2.5

(x1,000)

7.5

5.01.0

1.0

2.50.5 0.50.0

7.00 7.05 7.10 7.15 7.20 7.25 7.30 7.35

0.0

7.15 7.20 7.25 7.30 7.35 7.40 7.45

0.0

7.45 7.50 7.55 7.60 7.65 7.70 7.75 7.80β-六六六γ-六六六δ-六六六7.5

1.25

(x100,000)

4.0

(x10,000)

3.01.00.0

7.65 7.70 7.75 7.80

7.90

8.00

0.00

8.10 8.15 8.20 8.25 8.30 8.35 8.40 8.45

0.0

8.40 8.45

8.60 8.65 8.70氟甲腈

馬拉硫磷

三唑酮

0.00

8.35 8.40 8.45 8.50 8.55 8.60 8.65 8.70

0.0

8.20 8.25 8.30 8.35 8.40 8.45 8.50 8.55

0.00

8.45 8.50

8.60

8.70 8.75 8.80水胺硫磷

毒死蜱

氟蟲(chóng)腈硫醚圖C.1 37種農(nóng)藥及環(huán)氧七氯的多反應(yīng)監(jiān)測(cè)（MRM）色譜圖（50μg/L）

(x1,000)

(x10,000)

(x10,000)噻蟲(chóng)嗪

氟蟲(chóng)腈

二甲戊靈

(x10,000)

2.5

2.01.00.0

8.75 8.80 8.85 8.90

9.00 9.05 9.10

0.0

8.80 8.85 8.90 8.95 9.00

9.10 9.15

0.0

8.95 9.00 9.05 9.10 9.15 9.20 9.25 9.30環(huán)氧七氯

三唑醇

丁草胺

(x10,000)

0.0

9.15 9.20 9.25 9.30 9.35

9.45 9.50

0.0

9.25 9.30 9.35 9.40 9.45 9.50 9.55 9.60

0.0

9.30 9.35 9.40 9.45 9.50

9.60 9.65氟蟲(chóng)腈砜

噻呋酰胺

醚菌酯

(x1,000)

(x10,000)9.85 9.90 9.9510.00三環(huán)唑

蟲(chóng)螨腈

三唑磷圖C.1（續(xù)）

(x10,000)

(x10,000)

(x10,000)

9.90 9.9510.0010.05

10.1010.1510.20

0.0

10.0510.1010.1510.2010.2510.3010.35

10.2510.3010.3510.4010.4510.5010.5510.607.0(x100,000)6.05.04.03.02.01.0

25肟菌酯

26丙環(huán)唑

(x10,000)

27戊唑醇0.0

10.5010.5510.6010.6510.7010.75

10.8010.85

0.0

10.6510.7010.7510.8010.8510.90

10.9511.00

0.0

11.3511.4011.4511.50聯(lián)苯菊酯

甲氰菊酯

氯氟氰菊酯和高效氯氟氰菊酯

(x10,000)

1.0

0.25

0.50.0

11.9512.0012.0512.10

12.1512.2012.2512.30

0.00

13.25

0.0

13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3(x1,000)7.55.0

31氯菊酯

32氯氰菊酯和高效氯氰菊酯1.000.75

33氰戊菊酯和S-氰戊菊酯

0.500.25

1.00.50.013.9013.9514.0014.0514.1014.1514.20

14.25

0.00

14.4514.5014.5514.6014.6514.7014.7514.80

0.0

13.0513.1013.1513.2013.25

13.3013.3513.40吡唑醚菌酯

苯醚甲環(huán)唑圖C.1（續(xù)）

醚菊酯(x1,000) (x1,000)4.03.0 5.0

2.50.0

14.75 15.00

15.25 15.50

0.0

15.2015.2515.3015.3515.4015.4515.5015.5537溴氰菊酯

38嘧菌酯圖C.1（續(xù)）T/ZNZ221T/ZNZ221—2023PAGEPAGE1附 錄 D（資料性）37種農(nóng)藥在不同基質(zhì)樣品中添加濃度及回收率與精密度范圍表D.1給出了37中農(nóng)藥實(shí)際在不同基質(zhì)樣品中添加濃度及回收率與精密度范圍。表D.1 37種農(nóng)藥在不同基質(zhì)樣品中添加濃度及回收率與精密度范圍（n=24）序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范1α-六六六0.0382.0~108.02.5~8.876.7~1072.2~7.875.0~103.72.0~6.084.0~109.01.2~6.674.3~101.32.2~6.374.0~102.32.6~7.40.0982.2~100.31.8~5.381.2~99.91.9~5.579.4~98.90.7~4.280.6~100.11.4~4.873.6~100.42.1~7.579.6~99.91.8~4.70.3082.0~98.31.1~4.176.3~1001.2~5.183.0~100.71.4~4.381.0~99.30.4~5.779.7~99.01.6~4.479.3~101.02.6~3.22β-六六六0.0378.0~103.04.1~6.074.3~107.02.2~6.173.0~100.03.8~5.979.0~106.31.3~8.572.3~101.31.8~7.572.0~101.32.1~7.90.0981.4~96.01.7~5.678.2~98.71.2~4.373.2~96.40.9~7.174.3~99.20.7~4.475.8~100.61.8~4.373.9~99.41.4~6.20.3090.3~100.71.6~3.980.7~99.71.5~4.879.7~1001.0~6.278.3~110.01.0~5.577.0~100.71.2~5.272.3~100.31.7~2.83γ-六六六0.0382.0~101.02.5~5.874.0~99.72.2~4.475.7~98.03.9~4.378.3~112.04.4~5.170.7~100.74.2~7.871.7~100.01.6~5.90.0984.0~99.92.9~6.278.2~99.43.2~5.175.3~99.00.9~8.479.3~109.31.6~4.574.9~99.91.2~4.671.8~101.71.5~6.90.3086.7~100.71.9~4.681.3~100.30.9~4.381.7~100.00.7~4.681.3~108.01.2~5.473.0~100.71.2~3.871.3~98.71.0~2.44δ-六六六0.0379.3~107.02.6~7.875.0~105.32.8~8.473.7~101.72.8~7.780.0~108.03.4~4.575.3~99.72.4~6.175.3~100.02.2~6.20.0977.8~95.81.6~4.579.6~98.81.8~6.672.0~96.61.4~8.078.4~100.33.3~4.875.1~99.61.8~7.472.3~101.42.1~7.70.3087.0~99.31.4~4.581.7~98.70.9~3.676.0~101.72.2~4.878.7~99.30.5~4.378.7~100.01.5~5.574.0~97.31.0~5.8T/ZNZ221—T/ZNZ221—2023表D.1（續(xù)）PAGEPAGE2序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范5苯醚甲環(huán)唑0.0376.0~103.32.3~6.378.0~97.72.8~5.677.3~102.70.8~6.482.7~99.73.4~4.574.7~103.03.0~7.481.7~100.32.0~7.00.0976.3~97.72.3~3.475.1~99.33.5~5.475.3~108.71.7~7.574.0~98.41.8~4.375.1~100.03.1~6.177.1~96.32.1~5.00.3080.3~97.71.3~5.478.3~1012.4~5.680.3~105.34.4~6.575.7~100.32.9~7.173.0~100.01.8~4.773.3~99.32.3~4.96吡唑醚菌酯0.0374.0~104.02.6~4.474.3~108.72.3~5.084.0~110.73.0~7.281.3~112.73.0~6.977.7~108.72.7~7.385.0~106.71.9~4.20.0972.9~92.91.8~4.275.0~103.91.6~6.076.9~107.61.7~6.474.2~111.12.5~5.378.9~96.11.7~4.777.7~99.82.8~3.90.3091.3~95.72.2~3.378.3~102.32.5~6.884.3~101.02.1~5.174.3~101.71.5~5.774.3~105.32.0~3.379.3~102.74.0~5.87丙環(huán)唑0.0377.7~106.71.1~9.582.0~98.02.9~4.782.0~101.32.0~5.285.0~104.31.2~7.773.7~101.32.6~9.376.7~98.04.8~7.70.0977.4~99.01.3~6.786.1~101.71.9~5.983.0~101.70.7~6.784.8~107.81.2~5.176.9~100.71.3~7.579.4~99.62.9~4.80.3085.0~100.71.9~2.983.7~102.02.3~3.877.0~104.71.4~7.282.3~102.71.1~5.277.0~103.31.7~4.577.3~104.02.5~3.98蟲(chóng)螨腈0.0376.3~102.02.7~6.573.7~98.03.3~7.572.7~101.71.7~8.175.3~110.03.1~8.480.3~100.72.3~7.575.0~102.33.3~5.70.0982.7~95.71.7~4.970.7~101.12.2~7.579.4~101.31.1~7.480.2~113.92.0~7.780.9~100.01.8~8.280.3~105.63.5~9.80.3078.7~102.73.0~4.974.3~104.34.7~6.576.3~109.32.7~5.175.7~106.31.7~7.277.0~107.31.8·8.577.0~102.71.5~5.89敵敵畏0.0374.7~100.71.4~7.874.3~101.32.3~8.174.3~102.02.2~7.378.3~101.31.6~7.674.3~99.31.4~7.277.3~101.01.9~6.90.0982.4~97.91.8~4.681.3~97.61.6~6.080.8~97.11.9~5.983.9~108.62.4~4.080.0~103.41.5~4.280.2~101.61.0~5.00.3083.7~99.02.0~3.881.7~100.02.0~4.379.0~98.32.1~4.381.0~103.01.4~5.476.7~100.01.1~3.577.7~104.02.3~3.6序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范10丁草胺0.0380.7~107.32.3~5.177.0~102.33.0~6.073.0~102.32.2~7.582.7~101.01.5~4.776.3~108.01.1~8.676.0~100.01.9~7.60.0980.2~95.41.8~3.582.1~100.11.2~4.180.7~98.61.0~5.681.9~100.92.0~7.783.1~103.02.0~8.178.4~103.22.5~4.90.3084.7~98.31.5~3.982.7~98.31.8~3.281.3~95.71.9~5.784.3~97.71.2~4.380.3~101.31.7~3.880.3~100.31.9~3.211毒死蜱0.0381.3~103.31.3~5.075.0~105.32.7~5.580.0~100.31.7~7.881.7~101.71.5~4.272.0~104.31.4~6.878.7~102.02.9~4.60.0979.0~89.91.4~3.183.0~98.91.6~4.281.0~101.00.8~6.582.0~100.62.2~3.674.4~100.12.6`7.880.6~98.41.3~6.80.3080.0~98.71.7~3.080.3~100.32.3~2.680.0~100.30.6~8.079.0~99.30.5~5.179.7~104.02.4~4.278.7~101.01.9~4.712二甲戊靈0.0377.3~105.72.4~3.776.0~110.01.8~7.477.0~108.74.6~8.677.7~118.02.1~7.176.7~104.72.1~5.872.3~109.73.3~9.60.0979.4~91.32.0~5.175.9~102.72.7~6.372.7~98.72.2~7.473.7~101.61.8~6.274.2~91.22.7~5.677.2~93.32.1~5.80.3080.7~99.71.8~3.377.3~101.30.8~3.478.7~105.30.9~8.477.7~112.01.6~6.482.3~98.72.3~5.077.0~100.01.8~2.913氟蟲(chóng)腈0.0376.7~107.31.2~9.479.7~108.73.6~7.179.3~115.31.9~7.780.0~107.02.6~6.774.7~102.02.8~7.584.3~107.32.3~8.00.0984.0~96.02.5~4.180.9~99.32.8~4.280.7~98.10.7~5.981.8~101.72.5~3.980.0~99.72.1~7.383.7~107.01.9~5.80.3083.0~104.32.3~5.079.0~104.72.5~7.875.3~103.02.8~8.278.7~101.01.5~5.681.7~105.31.6~5.683.3~103.01.3~5.614氟蟲(chóng)腈砜0.0379.3~111.32.7~7.280.0~116.03.9~7.776.3~110.33.9~8.776.0~109.04.8~8.974.7~109.74.1~7.479.3~112.73.1~6.40.0979.9~88.91.2~3.482.9~94.82.1~5.380.9~101.41.0~7.978.7~106.44.1~7.378.7~100.92.4~7.083.4~99.41.4~4.70.3085.0~101.71.5~3.983.0~102.31.9~3.381.0~106.03.9~6.776.0~102.02.3~4.879.7~102.32.3~4.478.7~99.02.5~4.115氟蟲(chóng)腈硫醚0.0377.3~107.72.7~8.873.7~1114.3~8.575.3~111.04.7~7.780.3~99.72.8~6.775.0~109.33.3~6.083.3~112.71.5~5.90.0978.3~98.83.1~7.585.2~99.12.2~3.479.8~99.03.3~6.482.0~98.61.5~4.377.9~99.71.4~7.283.2~99.82.6~6.20.3073.7~97.32.5~5.573.7~90.01.9~4.876.7~99.02.9~7.274.7~101.01.8~6.476.7~96.32.7~4.873.7~95.71.2~5.2序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范16氟甲腈0.0375.3~110.02.3~6.676.0~107.71.9~6.977.0~108.72.0~5.479.0~106.02.3~9.373.3~109.73.1~6.781.0~107.31.9~5.80.0982.1~98.41.7~5.684.3~99.32.0~3.882.0~98.71.1~6.283.9~101.84.4~4.875.1~97.31.4~8.682.9~102.32.2~6.40.3075.7~98.30.8~3.372.7~98.01.5~3.975.0~98.01.5~6.671.7~97.71.1~5.575.0~96.01.6~4.173.7~102.32.0~3.517甲氰菊酯0.0381.3~102.31.7~5.673.3~109.31.9~8.176.3~109.31.8~6.675.3~103.72.0~8.075.0~114.01.9~8.678.0~106.02.0~6.80.0976.1~99.91.9~6.375.3~99.10.7~8.778.2~99.21.3~8.581.4~99.71.6~6.675.4~106.31.7~8.179.1~100.81.6~7.50.3080.0~104.32.7~4.877.3~103.71.5~4.578.3~110.31.9~7.481.0~102.00.9~5.475.0~105.71.3~5.778.0~103.71.3~3.918聯(lián)苯菊酯0.0376.3~101.72.4~6.281.0~98.32.9~5.980.0~103.32.8~5.276.7~100.71.9~6.479.0~101.30.9~6.477.7~97.01.8~5.00.0981.9~104.31.5~5.287.6~103.31.6~4.180.9~100.21.2~5.787.6~101.90.8~5.082.0~102.41.7~7.184.2~100.31.7~3.80.3088.7~101.31.0~3.682.0~102.33.1~4.579.0~105.02.0~7.378.3~103.01.1~5.779.0~103.70.5~3.478.3~101.01.0~4.2序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范19氯氟氰菊酯和高效氯氟氰菊酯0.0377.7~103.32.1~5.575.3~101.03.1~7.475.7~103.35.4~7.078.7~102.03.1~8.771.0~115.72.3~7.775.3~98.01.9~6.40.0972.1~94.91.4~4.076.9~100.62.1~6.477.9~105.62.3~8.776.6~100.62.2~6.176.3~99.61.5~5.481.1~101.41.4~3.80.3078.0~100.01.3~3.378.7~101.31.8~5.176.3~104.32.2~6.775.3~100.30.8~5.774.7~103.71.8~4.978.0~99.32.7~3.720氯菊酯0.0377.3~98.02.5~5.479.0~98.31.2~7.776.0~99.32.7~8.977.0~99.32.6~9.375.7~104.01.7~6.875.7~100.03.9~8.00.0977.2~95.41.8~6.378.8~98.81.7~7.074.3~99.22.1~9.476.7~99.82.0~5.477.2~103.31.2~7.178.1~102.21.6~6.00.3083.0~103.01.8~3.077.0~102.33.8~5.173.0~107.71.6~8.378.0~102.31.5~6.575.0~113.72.5~4.178.0~106.72.5~4.1序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范21氯氰菊酯和高效氯氰菊酯0.0377.7~100.32.4~5.979.3~101.32.6~8.972.7~99.31.5~6.774.7~100.03.9~6.474.0~97.31.9~8.274.0~94.32.9~6.00.0975.3~91.91.8~5.280.7~109.02.4~6.675.7~110.21.6·8.076.1~94.12.4~7.872.1~96.60.6~5.875.8~98.41.9~6.60.3075.3~95.32.1~5.181.0~104.72.4~7.275.3~106.02.5~7.476.3~97.31.2~5.976.0~101.31.1~8.074.0~100.71.3~4.722馬拉硫磷0.0374.3~102.31.1~6.975.0~103.73.1~8.373.3~97.71.7~6.875.3~101.32.7~7.975.3~100.02.1~5.773.3~100.32.0~6.70.0979.0~94.92.2~4.579.8~98.91.8~5.179.1~103.11.3~8.679.8~101.20.7~6.277.3~100.61.0·5.978.7~101.21.7~6.10.3076.3~99.31.8~3.975.0~98.32.5~3.679.7~103.71.5~6.074.3~98.30.8~6.377.7~100.02.3~4.478.0~98.31.1~3.023醚菊酯0.0380.3~100.02.1~4.376.3~97.31.7~6.979.3~98.72.8~5.476.0~103.02.7~7.072.3~101.72.6~7.177.3~99.02.1~5.60.0975.3~90.32.3~3.583.1~98.62.5~5.480.1~100.12.4~6.678.1~98.21.8~5.876.4~97.01.9~5.781.8~95.31.0~4.20.3078.7~96.71.5~3.182.3~99.02.3~4.573.0~101.32.4~8.376.7~99.01.8~6.478.3~99.72.7~3.881.3~99.71.8~4.424醚菌酯0.0382.3~103.32.0~6.381.3~105.01.7·6.875.0~106.71.0~6.578.7~101.71.5~5.473.7~106.00.8~7.376.0~108.33.3~5.90.0980.6~118.21.8~8.388.4~1012.0~2.674.7~99.60.5~5.385.2~101.20.9~5.781.4~99.81.8~7.381.4~99.72.6~5.00.3084.3~101.32.9~5.183.7~102.72.5~5.173.0~104.71.8~6.085.7~101.71.1~5.680.0~101.70.6~3.481.7~102.30.9~2.8序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范25嘧菌酯0.0378.7~100.71.9~7.275.0~105.03.2~8.071.3~100.33.8~11.482.0~98.71.6~4.874.0~108.34.2~8.077.7~99.32.1~7.70.0973.3~89.71.4~4.175.2~102.72.2~5.473.3~102.13.4~8.574.2~96.12.2~6.072.9~101.02.0~7.277.0~99.03.3~6.00.3076.3~96.72.0~4.973.7~96.02.2~5.880.3~97.01.7~5.876.3~102.01.6~8.177.3~97.01.2~4.577.7~104.02.9~5.826氰戊菊酯和S-氰戊菊酯0.0378.0~101.02.5~4.478.0~98.72.2~8.474.7~100.04.5~8.075.3~98.72.7~7.871.0~98.02.1~7.775.3~99.73.5~8.50.0978.2~97.71.6~6.776.6~103.32.1~8.276.6~98.42.8~5.376.4~99.63.5~5.974.8~100.01.5~7.177.6~99.91.6~4.10.3080.0~98.30.8~5.476.3~100.03.4~4.878.7~100.71.4~7.974.0~1021.9~5.478.3~100.32.6~3.476.7~100.01.8~4.827噻蟲(chóng)嗪0.0378.3~101.32.7~4.171.3~97.33.1~6.671.0~1032.3~8.080.3~108.71.4~8.677.7~109.02.5~8.472.0~100.31.2~6.00.0976.4~95.31.8~5.175.0~101.93.6~6.476.8~95.61.2~8.376.0~103.92.4~6.275.6~110.02.8~7.971.7~98.90.9~6.70.3084.3~102.73.5~6.178.0~1052.4~5.276.7~100.32.3~9.474.3~112.32.5~5.679.7~109.30.7~7.671.0~102.32.6~7.028噻呋酰胺0.0374.0~104.32.8~6.780.7~104.31.9~7.578.0~105.73.6~4.982.7~97.72.6~5.873.7~104.31.6~5.383.7~106.72.2~6.20.0972.4~91.70.7~5.170.6~102.01.1~5.472.6~98.11.9~5.973.4~107.01.7~6.370.1~97.92.3~7.878.1~98.83.0~4.40.3084.3~103.31.6~4.681.0~101.01.4~4.072.3~104.02.2~7.482.7~104.02.5~4.882.7~104.02.4~3.880.0~102.02.0~3.5序號(hào)參數(shù)添加濃度（mg/kg）中華鱉梭子蟹青蟹大黃魚(yú)沼蝦草魚(yú)回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范回收率范精密度范圍（%）回收率范精密度范29三環(huán)唑0.0376.3~100.33.0~3.975.0~103.34.1~9.370.7~102.03.8~8.575.3~100.71.6~7.073.0~111.33.1~6.680.7~111.02.5~5.90.0977.1~97.41.2~4.275.9~101.81.0~3.878.2~100.21.6~7.274.1~101.21.5~3.873.7~107.81.5~8.575.0~100.22.3~4.80.3085.3~107.02.0~3.676.7~109.32.4~4.779.3~108.31.7~6.774.7~105.71.4~4.878.3~113.31.8~4.874.3~108.02.5~4.530三唑醇0.0376.3~100.73.0~5.277.3~103.34.5~7.672.3~102.03.0~5.680.3~99.73.4~5.874.3~100.02.8~6.578.0~105.03.9~8.70.0980.4~94.42.1~5.980.8~95.31.2~4.373.3~98.61.8~9.380.6~106.42.3~7.777.3~99.42.4~8.178.9~98.71.9~6.80.3082.3~104.32.0~5.683.7~103.71.3~6.176.0~108.31.2~6.479.7~103.32.2~5.481.7~103.31.8~4.977.0~101.72.1~4.531三唑磷0.0381.0~102.01.8~5.270.3~102.31.2~8.976.0~103.03.9~6.278.0~100.01.2~7.075.3~103.01.5~7.875.7~100.72.3~5.10.0976.1~96.71.3~2.475.9~107.82.4~9.384.9~102