TCIQA-養(yǎng)殖用水中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物殘留量的測(cè)定 高效液相色譜-串聯(lián)質(zhì)譜法編制說(shuō)明

P/CIQA-104-2022PAGE5中國(guó)出入境檢驗(yàn)檢疫協(xié)會(huì)團(tuán)體標(biāo)準(zhǔn)《養(yǎng)殖用水中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物殘留量的測(cè)定高效液相色譜-串聯(lián)質(zhì)譜法》編制說(shuō)明（征求意見(jiàn)稿）標(biāo)準(zhǔn)起草組二〇二四年二月《養(yǎng)殖用水中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物殘留量的測(cè)定高效液相色譜-串聯(lián)質(zhì)譜法》編制說(shuō)明標(biāo)準(zhǔn)起草的基本情況（一）任務(wù)來(lái)源2022年9月15日,根據(jù)中國(guó)出入境檢驗(yàn)檢疫協(xié)會(huì)綜合質(zhì)量服務(wù)標(biāo)準(zhǔn)化技術(shù)委員（CIQA/TC12）立項(xiàng)審查結(jié)果，由中國(guó)檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司牽頭，自然資源部第四海洋研究所、北海海關(guān)綜合技術(shù)服務(wù)中心參與《養(yǎng)殖用水中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物殘留量的測(cè)定高效液相色譜-串聯(lián)質(zhì)譜法》的項(xiàng)目制定工作，項(xiàng)目編號(hào)為P/CIQA-104-2022。為保證標(biāo)準(zhǔn)制訂的科學(xué)性、適用性，中國(guó)檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司和自然資源部第四海洋研究所、北海海關(guān)綜合技術(shù)服務(wù)中心成立標(biāo)準(zhǔn)起草工作組，制定工作方案、明確職責(zé)分工、時(shí)間進(jìn)度和有關(guān)工作要求。（二）主要起草單位、起草人及分工主要起草單位：中國(guó)檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司、自然資源部第四海洋研究所、北海海關(guān)綜合技術(shù)服務(wù)中心。主要起草人：梁光纖、張麗、梁任佳、劉冬靈、黃芯語(yǔ)、金其揚(yáng)、陸媛苑、樊春燕、劉丹（三）簡(jiǎn)要起草過(guò)程2022年9月，由中國(guó)檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司牽頭，自然資源部第四海洋研究所、北海海關(guān)綜合技術(shù)服務(wù)中心參與《養(yǎng)殖用水中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物殘留量的測(cè)定高效液相色譜-串聯(lián)質(zhì)譜法》的項(xiàng)目制定工作。2022年10月，中國(guó)檢驗(yàn)認(rèn)證集團(tuán)廣西有限公司和自然資源部第四海洋研究所、北海海關(guān)綜合技術(shù)服務(wù)中心成立標(biāo)準(zhǔn)起草工作組，開(kāi)始制定實(shí)驗(yàn)方案，經(jīng)過(guò)前期大量文獻(xiàn)調(diào)查和在實(shí)驗(yàn)室研究工作的基礎(chǔ)上探索研究了檢測(cè)方法條件。2022年11月-2023年9月，開(kāi)始開(kāi)展儀器條件研究、前處理步驟、線性范圍、方法回收率、準(zhǔn)確度、精密度等一系列技術(shù)內(nèi)容的確定研究。2023年10月形成標(biāo)準(zhǔn)檢測(cè)方法草案。2023年11月-12月，在完成實(shí)驗(yàn)室內(nèi)方法學(xué)驗(yàn)證的基礎(chǔ)上，組織了自然資源部第四海洋研究所、北海海關(guān)綜合技術(shù)服務(wù)中心、青島海關(guān)技術(shù)中心對(duì)本標(biāo)準(zhǔn)進(jìn)行了實(shí)驗(yàn)室間驗(yàn)證，驗(yàn)證結(jié)果表明方法的各項(xiàng)技術(shù)指標(biāo)滿足養(yǎng)殖用水中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物殘留量的測(cè)定的要求。2024年1月-2月針對(duì)各家分析實(shí)際操作時(shí)標(biāo)準(zhǔn)文本中存在的問(wèn)題及建議，對(duì)標(biāo)準(zhǔn)進(jìn)行了修改，得到標(biāo)準(zhǔn)起草小組的一致認(rèn)可，形成該標(biāo)準(zhǔn)征求意見(jiàn)稿和標(biāo)準(zhǔn)編寫(xiě)報(bào)告。三、標(biāo)準(zhǔn)的重要內(nèi)容本文件對(duì)標(biāo)準(zhǔn)方法的原理、檢測(cè)項(xiàng)目、分析步驟、線性范圍、試劑和材料、儀器分析條件的優(yōu)化和選擇、方法檢出限及定量限、回收率、正確度和精密度等重要內(nèi)容進(jìn)行了規(guī)定和說(shuō)明。原理水樣中的硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物經(jīng)親水親脂平衡型固相萃取柱直接富集凈化后，用高效液相色譜-串聯(lián)質(zhì)譜法測(cè)定，三苯甲烷類采用內(nèi)標(biāo)法定量，其他藥物采用外標(biāo)法定量。檢測(cè)項(xiàng)目本標(biāo)準(zhǔn)起草小組根據(jù)常見(jiàn)的監(jiān)測(cè)檢測(cè)獸藥類別，參考GB31658.17-2021《食品安全國(guó)家標(biāo)準(zhǔn)動(dòng)物性食品中四環(huán)素類、磺胺類和喹諾酮類藥物殘留量的測(cè)定液相色譜－串聯(lián)質(zhì)譜法》、GB31660.1-2019《食品安全國(guó)家標(biāo)準(zhǔn)水產(chǎn)品中大環(huán)內(nèi)酯類藥物殘留量的測(cè)定液相色譜-串聯(lián)質(zhì)譜法》等相關(guān)獸藥殘留檢測(cè)食品安全國(guó)家標(biāo)準(zhǔn)，對(duì)硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物等7類獸藥的檢測(cè)項(xiàng)目進(jìn)行了預(yù)先設(shè)定，結(jié)合儀器檢測(cè)條件參數(shù)研究中對(duì)混合標(biāo)準(zhǔn)物質(zhì)進(jìn)行測(cè)定，重點(diǎn)對(duì)流動(dòng)相、色譜柱、洗脫梯度進(jìn)行了選擇優(yōu)化，確認(rèn)最終的目標(biāo)獸藥檢測(cè)項(xiàng)目為硝基呋喃類(呋喃唑酮、呋喃它酮)、氯霉素類（氯霉素、氟苯尼考）、三苯甲烷類（孔雀石綠、隱性孔雀石綠）、喹諾酮類（環(huán)丙沙星、二氟沙星、依諾沙星、恩諾沙星、氟甲喹、洛美沙星、諾氟沙星、氧氟沙星、培氟沙星、沙拉沙星、噁喹酸）、磺胺類（磺胺苯酰、乙酰磺胺、磺胺氯噠嗪、磺胺嘧啶、磺胺甲噁唑、磺胺間二甲氧嘧啶、磺胺鄰二甲氧嘧啶、磺胺甲嘧啶、磺胺二甲嘧啶、磺胺甲噻二唑、磺胺苯吡唑、磺胺吡啶、磺胺噻唑、磺胺二甲異噁唑）、四環(huán)素類（四環(huán)素、金霉素、多西環(huán)素）和大環(huán)內(nèi)酯類（紅霉素、克拉霉素、阿奇霉素、吉他霉素、交沙霉素、替米考星、泰樂(lè)菌素）。試劑純度和級(jí)別的選擇除非另有規(guī)定，本方法所使用試劑均為優(yōu)級(jí)純，水為GB/T6682規(guī)定的一級(jí)水。7類獸藥的養(yǎng)殖用水前處理和儀器檢測(cè)條件的優(yōu)化4.1、前處理?xiàng)l件本標(biāo)準(zhǔn)起草小組對(duì)根據(jù)既有參考文獻(xiàn)及相關(guān)獸藥檢測(cè)的食品安全國(guó)家標(biāo)準(zhǔn)的研究，前處理關(guān)鍵在于樣品的濃縮富集，本標(biāo)準(zhǔn)采用加標(biāo)回收的方式直接比較了HBL、C18、中性氧化鋁柱等3種固相萃取小柱，以及甲醇、1%0.1%甲酸乙睛、0.1%甲酸酸乙睛+甲醇等3種洗脫液的洗脫能力。結(jié)果表明，三種的洗脫能力順序?yàn)椋?.1%甲酸乙睛+甲醇＞0.1%甲酸乙睛＞甲醇；采用C18固相萃取小柱，7類獸殘的回收率基本＜20%；采用中性氧化鋁柱，僅有孔雀石綠可富集洗脫;采用HLB作固相萃取小柱時(shí)，7類獸藥基本能有效的富集洗脫，且大部分物質(zhì)滿足回收率在60%-120%。故采用HBL固相萃取小柱作進(jìn)行濃縮富集，并以0.1%甲酸乙睛+甲醇經(jīng)行洗脫。并最終建立了以下分析步驟：水樣經(jīng)0.45μm濾膜過(guò)濾后，移取50mL水樣，加入100μL混合內(nèi)標(biāo)工作溶液(5.4.5)，超聲2min，吸取全部液體過(guò)固相萃取柱（預(yù)先用6mL甲醇，6mL水活化），待試樣完全流出后用6mL0.1%甲酸水淋洗，棄去水淋液，抽干，再依次用6mL甲醇、6mL0.1%

甲酸乙睛洗脫，收集洗脫液于15mL

玻璃試管中，45℃水浴氮?dú)獯蹈桑儆?.00mL0.1%甲酸水+乙睛(95+5)溶液溶解殘?jiān)?，?jīng)0.22μm濾膜過(guò)濾，待上機(jī)測(cè)定。4.2、測(cè)定條件的優(yōu)化和選擇液相色譜串聯(lián)質(zhì)譜分析條件，是養(yǎng)殖用水中多種類型獸藥實(shí)現(xiàn)統(tǒng)一分析檢測(cè)的關(guān)鍵，綜合考慮響應(yīng)值、峰形、穩(wěn)定性、準(zhǔn)確度、儀器分析時(shí)間等因素，排除在同時(shí)測(cè)定過(guò)程中被干擾影響的物質(zhì)，在對(duì)測(cè)定條件反復(fù)試驗(yàn)與優(yōu)化的基礎(chǔ)之上，本標(biāo)準(zhǔn)對(duì)養(yǎng)殖用水中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物殘留量的測(cè)定條件詳細(xì)了規(guī)定，確立了可以進(jìn)行統(tǒng)一分析檢測(cè)的檢測(cè)項(xiàng)目，給出了高效液相色譜-串聯(lián)質(zhì)譜的參考條件。4.2.1、液相色譜工作條件本標(biāo)準(zhǔn)參考既往研究選用安捷倫的EclipseXDB-C18、EclipsePlusC18（100mm×2.1mm，1.8μm）作為色譜柱，選用0.1%甲酸水溶液與乙腈作為流動(dòng)相，并采用梯度洗脫的方法，可以實(shí)現(xiàn)7類目標(biāo)獸藥物質(zhì)的有效分離，并將儀器分析檢測(cè)時(shí)間控制在15分鐘，保留時(shí)間詳見(jiàn)表3。建立的液相色譜工作條件如下：色譜柱：C18(100mm×2.1mm，1.8μm）；柱溫：35℃；進(jìn)樣量：10μL；流速：0.5mL/min；流動(dòng)相：A為0.1%甲酸水溶液，B為乙腈，梯度洗脫條件見(jiàn)表1。流動(dòng)相洗脫條件時(shí)間min0.1%甲酸水溶液%乙腈%09820.598228020470307595959511010013.5010015982169824.2.2、質(zhì)譜工作條件本標(biāo)準(zhǔn)為實(shí)現(xiàn)7類獸藥物質(zhì)的統(tǒng)一分析，采用正離子、負(fù)離子同時(shí)掃描的方式，質(zhì)譜分析條件主要為定性離子對(duì)、定量離子對(duì)、碰撞能量等分析參數(shù)的優(yōu)化與建立。根據(jù)本實(shí)驗(yàn)室的儀器特性，利用儀器自帶的優(yōu)化軟件，建立了7類獸藥目標(biāo)物質(zhì)的質(zhì)譜分析參數(shù)。建立的質(zhì)譜工作條件如下：離子源：電噴霧離子源；掃描方式：正離子、負(fù)離子掃描；檢測(cè)方式：多反應(yīng)檢測(cè)；氣體溫度：300℃；霧化器壓力：45psi；干燥氣流量：氮?dú)?1L/min；鞘流氣溫度：350°C；鞘流氣流量：氮?dú)?1L/min；毛細(xì)管電壓：3500V（正離子）；4000V（負(fù)離子）；定性離子對(duì)、定量離子對(duì)、碰撞能量見(jiàn)表2。定性離子對(duì)、定量離子對(duì)、碰撞能量、掃描方式藥物名稱母離子m/z子離子m/z碰撞能量eV掃描方式呋喃它酮325.1281.216+325.1252.2*20+呋喃唑酮226.113915+226.1122*20+氯霉素3212574-321152*12-氟苯尼考356336*4-35618514-孔雀石綠329313.2*36+329208.132+孔雀石綠-D5334318.1*38+隱色孔雀石綠331315.228+331239.2*28+隱色孔雀石綠-D6337240.1*30+環(huán)丙沙星332314.2*17+332288.213+二氟沙星400356.1*17+400299.129+依諾沙星321.4303.3*19+321.4233.922+恩諾沙星360342.217+360316.2*17+氟甲喹262.3244.2*16+262.3202.136+洛美沙星351.933430+351.9265*36+諾氟沙星320302.2*17+320276.213+氧氟沙星362.4318.2*17+362.4261.125+培氟沙星334316.2*17+334290.213+沙拉沙星386342.213+386299.2*25+噁喹酸262.2244*12+262.221628+磺胺苯酰276.9156*12+276.910828+乙?；前?15156*8+21510812+磺胺氯噠嗪285156*12+28510820+磺胺嘧啶251156*12+25110820+磺胺甲噁唑254156.19+254108.1*21+磺胺間二甲氧嘧啶311156*16+31110828+磺胺鄰二甲氧嘧啶311156*16+31110824+磺胺甲嘧啶265156*15+26510828+磺胺二甲嘧啶27918613+279124.1*25+磺胺甲噻二唑271156*12+27110816+磺胺苯吡唑31522220+315158*24+磺胺吡啶250156*16+25010824+磺胺噻唑256156*12+25610824+磺胺二甲異噁唑268156*12+268112.716+金霉素47946215+479444*22+多西環(huán)素445428*15+44515415+四環(huán)素44542725+445410*20+阿奇霉素749.5591.427+749.5158*36+克拉霉素748.5590.118+748.5158.1*28+紅霉素734.4576.218+734.4158.2*28+交沙霉素828.3174.129+828.3109*40+吉他霉素772.4174.329+772.4109*40+替米考星869.569636+869.5174*48+泰樂(lè)菌素916.4174.2*37+916.4772.225+*為定量離子。線性范圍在選定的儀器工作條件下，以各目標(biāo)藥物的特征離子的峰面積（響應(yīng)值）為縱坐標(biāo)，以為各目標(biāo)藥物的濃度為橫坐標(biāo)，繪制標(biāo)準(zhǔn)曲線。由于各類獸藥物質(zhì)在液相色譜-串聯(lián)質(zhì)譜儀器上的響應(yīng)值不同，故根據(jù)響應(yīng)值大小，將7類獸藥物質(zhì)分成兩組濃度，建立一條由兩個(gè)濃度系列組成的標(biāo)準(zhǔn)曲線，即硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、大環(huán)內(nèi)酯類濃度為0.5ng/mL、1ng/mL、2ng/mL、5ng/mL、10ng/mL，四環(huán)素類濃度為5ng/mL、10ng/mL、20ng/mL、50ng/mL、100ng/mL，并最終含1ng/mL同位素內(nèi)標(biāo)物（氘代孔雀石綠、氘代隱性孔雀石綠）的標(biāo)準(zhǔn)曲線。結(jié)果表明，硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、大環(huán)內(nèi)酯濃度在0.5ng/mL~10ng/mL，四環(huán)素類濃度在5ng/mL~100ng/mL，各種藥物的濃度與響應(yīng)值具有良好的相關(guān)性，各相關(guān)系數(shù)R>0.99，詳見(jiàn)表3。保留時(shí)間與線性匯總表保留時(shí)間（min）線性相關(guān)系數(shù)r4.661y=3077.472792x-253.725982r=0.9976.865y=2920.813587x-123.364344r=0.9967.104y=2111.791346x86.004207r=0.9987.044y=8299.103293x-246.884952r=0.9997.233y=1.567939x-0.028941r=0.9999.984y=1.023069x-0.055921r=0.9994.917y=7751.071543x-1431.335655r=0.9965.765y=9595.421883x-2068.825708r=0.9964.701y=17671.83483x-3468.002853r=0.9985.212y=15308.715468x-5235.501012r=0.9977.832y=117424.797445x-3834.332653r=0.9995.074y=9381.764916x-766.955054r=0.9994.800y=7308.815379x-1291.903384r=0.9984.836y=28035.357253x-3366.366036r=0.9984.877y=7535.130526x-870.717865r=0.9975.666y=6991.751259x-670.253443r=0.9997.179y=149425.795711x-391.376508r=0.9987.316y=10124.81345x-441.121977r=0.9995.143y=6413.579497x-480.937027r=0.9986.900y=4096.417382x+120.419946r=0.9985.380y=3662.993981x+109.287917r=0.9997.022y=3647.64154x307.139741r=0.9986.998y=28035.438512x-1724.747113r=0.9997.334y=17169.444386x-2442.135847r=0.9975.971y=3812.841688x-122.442869r=0.9984.604y=22679.409322x-1100.460791r=0.9996.307y=4526.088191x-314.44665r=0.9977.373y=8360.187454x-343.749898r=0.9995.637y=4776.75244x+10.12838r=0.9995.359y=6901.824674x-139.639756r=0.9997.119y=5693.445727x-729.508177r=0.9975.803y=1425.152673x-123.345843r=0.9996.457y=6736.851749x-804.813481r=0.9974.992y=5268.053472x-1041.623093r=0.9976.910y=13474.528854x-1484.029963r=0.9986.910y=45362.79034x-5414.125109r=0.9986.673y=1442.965261x-89.0611r=0.9997.048y=23096.372957x-3258.18317r=0.9996.870y=11123.97815x-693.525122r=0.9996.275y=4421.565992x-19.053743r=0.9996.710y=7687.802923x+1050.344595r=0.997結(jié)果的計(jì)算和表述水樣中硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、四環(huán)素類和大環(huán)內(nèi)酯類藥物的殘留量按式（1）計(jì)算。

Xi=Ci×VV0式中：Xi——水樣中待測(cè)藥物殘留量的含量，單位為微克每升(μg/L)；Ci——試樣液中待測(cè)藥物殘留量的濃度，單位為微克每升(μg/L)；V——最終定容體積，單位為毫升(mL)；V0——測(cè)定水樣品的體積，單位為毫升(mL)。方法檢出限及定量限的確定本標(biāo)準(zhǔn)采用3倍信噪比計(jì)算儀器的檢出限，將儀器檢出限帶入結(jié)果公式計(jì)算得到方法檢出限詳見(jiàn)表4，采用2倍檢出限計(jì)算方法的定量限。經(jīng)綜合評(píng)定，取硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、大環(huán)內(nèi)酯類的檢出限為0.01μg/mL，定量限為0.02μg/mL；四環(huán)素類的檢出限為0.10μg/mL，定量限為0.20μg/mL。方法檢出限計(jì)算結(jié)果表藥物名稱信噪比測(cè)試濃度μg/L計(jì)算方法檢出限μg/L呋喃它酮30.70.50.0010呋喃唑酮76.00.50.0004氯霉素487.20.50.0001氟苯尼考77.50.50.0004孔雀石綠444.90.50.0001隱色孔雀石綠318.60.50.0001環(huán)丙沙星16.60.50.0019二氟沙星43.90.50.0007依諾沙星51.50.50.0006恩諾沙星51.20.50.0006氟甲喹78.40.50.0004洛美沙星49.60.50.0007諾氟沙星28.80.50.0011氧氟沙星136.90.50.0003培氟沙星29.30.50.0011沙拉沙星75.30.50.0004噁喹酸56.20.50.0006磺胺苯酰/苯甲?；前?6.40.50.0007乙酰磺胺85.60.50.0004磺胺氯噠嗪34.10.50.0009磺胺嘧啶713.30.50.0001磺胺甲噁唑389.90.50.0001磺胺間二甲氧嘧啶112.60.50.0003磺胺鄰二甲氧嘧啶107.90.50.0003磺胺甲嘧啶69.20.50.0005磺胺二甲嘧啶1566.40.50.0001磺胺甲噻二唑23.50.50.0013磺胺苯吡唑680.50.0005磺胺吡啶90.90.50.0004磺胺噻唑65.50.50.0005磺胺二甲異惡唑56.40.50.0006金霉素15.550.0194多西環(huán)素31.550.0096四環(huán)素1350.0231阿奇霉素91.70.50.0004克拉霉素703.50.50.0001紅霉素186.20.50.0002交沙霉素192.90.50.0002吉他霉素72.10.50.0005替米考星37.40.50.0009泰樂(lè)菌素136.20.50.0003回收率和精密度按試驗(yàn)方法，將3個(gè)梯度濃度的混合標(biāo)準(zhǔn)溶液加入空白養(yǎng)殖淡水和空白養(yǎng)殖海水樣品中進(jìn)行回收試驗(yàn)和精密度實(shí)驗(yàn)，每個(gè)加標(biāo)做7個(gè)平行，計(jì)算回收率和精密度。硝基呋喃類、氯霉素類、三苯甲烷類、喹諾酮類、磺胺類、大環(huán)內(nèi)酯類標(biāo)準(zhǔn)物質(zhì)加入水平為0.5ng/mL、1.0ng/mL、5.0ng/mL；四環(huán)素類標(biāo)準(zhǔn)物質(zhì)加入水平為5ng/mL、10ng/mL、50ng/mL。得到回收率均在60%~120%之間，RSD≦20%，滿足檢測(cè)要求。結(jié)果見(jiàn)表5、表6。淡水養(yǎng)殖用水回收率和精密度實(shí)驗(yàn)結(jié)果藥物名稱加入量ng測(cè)得量ng回收率%RSD%加入量ng測(cè)得量ng回收率%RSD%加入量ng測(cè)得量ng回收率%RSD%呋喃它酮0.50.4~0.5780.94~113.2810.2910.69~1.0369.2~102.9712.1253.72~4.1474.37~82.724.12呋喃唑酮0.50.37~0.5674.81~111.1914.7910.64~0.8864.13~88.079.6553.58~4.1771.51~83.435.33氯霉素0.50.36~0.5171.33~101.1113.3810.6~0.9160.04~91.1113.2253.9~4.2378.09~84.63.39氟苯尼考0.50.36~0.4972.86~98.2410.2910.7~0.9670.31~96.1310.4953.82~4.476.38~87.995.09孔雀石綠0.50.46~0.5191.29~101.114.0110.83~0.8782.52~87.162.2953.84~4.1176.7~82.292.27隱色孔雀石綠0.50.35~0.3970.84~77.782.9810.69~0.7368.88~73.152.2054.2~4.3283.9~86.451.05環(huán)丙沙星0.50.49~0.5998.08~117.766.4610.74~0.8874.22~87.835.9955.45~5.78108.99~115.572.24二氟沙星0.50.47~0.5594.45~109.956.8410.67~0.8466.77~83.578.1854.92~5.3798.49~107.363.22依諾沙星0.50.47~0.5494.27~107.624.2410.69~0.7968.65~78.594.5155.46~5.89109.27~117.92.59恩諾沙星0.50.42~0.5183.08~102.667.2610.61~0.6961.17~69.384.7855.73~5.98114.53~119.551.44氟甲喹0.50.4~0.4580.73~90.994.2510.74~0.874.07~80.022.7354.85~5.0896.91~101.61.75洛美沙星0.50.52~0.57103.89~1132.6310.79~0.8479.33~83.651.9454.89~5.1997.73~103.891.98諾氟沙星0.50.49~0.5798.84~114.195.3710.78~0.8778.16~86.844.0655.58~5.91111.58~118.272.24氧氟沙星0.50.38~0.4476.93~87.534.5210.6~0.6960.11~69.234.1655.69~5.96113.88~119.121.68培氟沙星0.50.38~0.4976.44~98.159.9010.61~0.6860.74~67.713.9255.82~5.95116.42~119.070.78沙拉沙星0.50.46~0.5491.9~107.396.5410.75~0.8975.42~89.425.2854.68~5.0893.61~101.513.10噁喹酸0.50.58~0.6115.78~119.731.2110.92~0.9691.97~95.71.5654.92~5.1598.46~103.091.92磺胺苯酰/苯甲酰磺胺0.50.4~0.4580.95~90.013.7710.68~0.8168.07~81.196.0853.68~3.9173.66~78.252.02乙?；前?.50.47~0.5794.25~114.36.3410.78~0.977.94~90.345.1854.03~4.3780.69~87.362.68磺胺氯噠嗪0.50.36~0.4672.76~92.987.9010.72~0.9272.12~91.778.8453.83~4.1476.53~82.892.67磺胺嘧啶0.50.41~0.5882.36~116.7811.1610.7~0.9369.81~92.669.2653.57~4.0671.32~81.244.12磺胺甲噁唑0.50.4~0.5279.55~103.158.6910.76~0.9375.94~93.378.5253.73~3.9974.59~79.762.71磺胺間二甲氧嘧啶0.50.34~0.5268.53~104.0314.8410.75~0.975.29~90.086.7154.09~4.3881.88~87.572.58磺胺鄰二甲氧嘧啶0.50.38~0.4276.28~84.794.6410.74~0.8573.78~84.754.4454.11~4.2382.29~84.541.03磺胺甲嘧啶0.50.4~0.4479.99~88.653.6510.76~0.8476.13~83.843.9553.87~4.1577.35~82.932.29磺胺二甲嘧啶0.50.44~0.5687.08~112.778.3010.62~0.9361.87~92.8712.6253.84~4.1376.83~82.583.02磺胺甲噻二唑0.50.48~0.5295.33~104.23.4010.88~0.9387.56~92.642.1253.97~4.1479.45~82.711.64磺胺苯吡唑0.50.5~0.699.39~119.597.3410.91~1.0691.49~106.035.0354.23~4.684.57~92.093.340.50.45~0.5190.64~101.354.2510.77~0.9177.11~90.575.6953.61~4.1572.12~83.065.130.50.33~0.4465.62~87.8410.3710.73~0.8872.54~88.257.7353.91~4.2278.15~84.393.06磺胺二甲異惡唑0.50.37~0.5474.94~108.0512.6510.73~0.8773.35~86.935.4453.7~4.0374.08~80.523.38金霉素50.39~0.5478.79~107.6910.49100.64~0.8363.83~82.79.44503.96~4.9379.1~98.628.40多西環(huán)素50.39~0.5877.21~115.611.96100.64~0.6964.25~68.892.77505.48~5.96109.58~119.253.03四環(huán)素50.45~0.5289.53~103.965.59100.53~0.6553.42~65.366.94504.26~4.4485.23~88.721.74阿奇霉素0.50.4~0.4679.32~91.245.0710.65~0.7765.15~77.355.5953.02~3.2760.47~65.462.86克拉霉素0.50.39~0.4477.72~88.434.2410.7~0.7870.07~78.494.0453~3.1560.06~63.11.86紅霉素0.50.43~0.5586.86~109.19.1810.76~1.0976.01~108.7612.3453.72~4.674.31~92.027.20交沙霉素0.50.45~0.4890.3~96.82.4510.8~0.8679.86~86.32.5653.91~4.1678.28~83.192.15吉他霉素0.50.48~0.5995.98~117.557.3610.83~0.9583.47~95.334.5654.1~4.3881.95~87.662.32替米考星0.50.47~0.5794.4~114.757.4810.82~0.9582.3~95.35.8654.16~4.8583.23~96.925.58泰樂(lè)菌素0.50.43~0.4785.15~93.934.0110.7~0.7970.28~78.74.6653.43~3.6268.55~72.392.06海水養(yǎng)殖用水回收率和精密度實(shí)驗(yàn)結(jié)果藥物名稱加入量ng測(cè)得量ng回收率%RSD%加入量ng測(cè)得量ng回收率%RSD%加入量ng測(cè)得量ng回收率%RSD%呋喃它酮0.50.43~0.5485.86~108.838.8710.79~0.9478.67~97.528.2453.66~4.3973.26~87.745.60呋喃唑酮0.50.36~0.5371.4~106.9812.2810.75~1.0274.67~102.0510.1553.69~4.273.86~83.944.42氯霉素0.50.33~0.5466.99~108.2216.6310.64~0.9863.61~98.3718.7853.52~4.5270.49~90.348.56氟苯尼考0.50.38~0.4576.68~90.697.0610.69~0.977.56~90.095.7253.85~4.4977.01~89.835.33孔雀石綠0.50.49~0.5397.27~105.632.8810.89~0.9689.03~96.872.9854.12~4.3782.34~87.422.11隱色孔雀石綠0.50.46~0.4891.34~96.812.1810.77~0.876.74~80.181.4653.69~3.8773.71~77.421.64環(huán)丙沙星0.50.4~0.5179.72~102.867.8210.76~0.9675.97~89.386.6753.15~3.5863~71.625.31二氟沙星0.50.46~0.5291.37~103.734.4910.75~0.975.36~92.016.5253.18~3.5363.6~70.573.97依諾沙星0.50.42~0.5284.44~103.826.2610.81~0.9281.43~91.725.0553.28~3.4965.63~69.822.22恩諾沙星0.50.52~0.58103.47~115.373.5310.81~0.9281.29~93.174.2853.07~3.1761.32~63.461.25氟甲喹0.50.39~0.4378.64~85.73.3710.77~0.8477.36~82.742.6453.72~4.0274.45~80.322.89洛美沙星0.50.34~0.4168.42~82.026.5210.73~0.8573.37~84.65.2453.31~3.7266.12~74.443.83諾氟沙星0.50.44~0.5188.44~102.515.7810.81~181.46~99.827.2453.21~3.6764.24~73.485.51氧氟沙星0.50.39~0.4378.53~86.823.5410.77~0.8777.15~87.463.9153.34~3.4866.72~69.541.45培氟沙星0.50.34~0.4168.39~82.667.7510.71~0.8670.75~85.536.0453.08~3.4561.62~68.923.83沙拉沙星0.50.36~0.4872.21~95.829.4610.77~0.8578.99~87.63.4553.62~3.7672.36~75.191.38噁喹酸0.50.36~0.3971.41~77.22.9910.76~0.8375.82~80.442.3453.69~3.8673.78~77.221.95磺胺苯酰/苯甲?；前?.50.41~0.4481.43~87.512.9310.73~0.8773.12~86.715.9653.78~3.9575.65~78.931.67乙?；前?.50.43~0.586.04~100.235.6010.71~0.9170.76~91.358.0553.97~4.3379.46~86.53.37磺胺氯噠嗪0.50.32~0.4964.51~97.2715.1610.61~0.8460.87~84.0610.5953.89~4.3177.87~86.184.00磺胺嘧啶0.50.32~0.4764.31~93.3713.8010.66~0.8265.82~82.096.6953.86~4.2477.11~84.824.09磺胺甲噁唑0.50.42~0.684.04~119.3511.4610.81~0.9674.25~95.778.0754.04~4.4380.81~88.563.08磺胺間二甲氧嘧啶0.50.43~0.5586.98~110.179.4010.79~0.9779.42~978.6753.76~4.2175.16~84.283.90磺胺鄰二甲氧嘧啶0.50.43~0.4986.64~97.033.9610.79~0.8678.91~86.082.9153.94~4.2578.88~84.922.25磺胺甲嘧啶0.50.51~0.57101.37~113.094.1110.83~0.9183.22~90.763.0353.9~4.2278.09~84.332.55磺胺二甲嘧啶0.50.41~0.5181.32~102.088.8910.72~0.8773.73~86.666.6753.74~4.374.73~85.995.05磺胺甲噻二唑0.50.4~0.4779.93~94.016.3010.8~0.8376.82~82.912.4154.04~4.2480.83~84.91.78磺胺苯吡唑0.50.42~0.4683.38~91.933.6110.73~0.8673.47~85.545.2354.01~4.280.16~83.971.690.50.33~0.4865.82~95.0713.1810.68~0.8267.63~82.336.0353.75~4.0475.02~80.752.580.50.35~0.4769.26~93.8511.3910.72~0.8572.96~84.956.1253.97~4.1979.34~83.832.04磺胺二甲異惡唑0.50.46~0.5592.25~110.056.7710.77~0.976.55~89.766.0853.67~4.3473.43~86.75.48金霉素50.31~0.3961.55~77.567.61100.64~0.9363.87~93.0118.07503.03~3.260.61~63.952.09多西環(huán)素50.36~0.5172.98~101.9713.09100.79~0.9477.96~93.887.92503~3.1860.04~63.692.35四環(huán)素50.3~0.3860.51~75.857.71100.61~0.6460.53~64.392.25503.02~3.9460.41~78.8610.56阿奇霉素0.50.43~0.4886.42~96.853.8110.65~0.7265.4~72.13.3653.05~3.261.06~64.091.68克拉霉素0.50.44~0.4987.26~97.063.6510.66~0.7364.92~72.534.0453.02~3.260.47~63.941.94紅霉素0.50.42~0.5783.48~114.3812.8910.65~0.9365.44~92.3612.5453.62~4.1572.45~82.945.02交沙霉素0.5