中空纤维液相微萃取-高效液相色谱法测定水中残留的氨基甲酸酯类农药

应用中空纤维液相微萃取(HP-LPME)技术建立了水样中呋喃丹、西维因、异丙威和乙霉威的高效液相色谱分析方法。对影响HP-LPME的实验条件进行了优化。采用Accurel Q3/2聚丙烯中空纤维,以甲苯为萃取溶剂,于室温、搅拌速度为720 r/min条件下在4.5 mL样品溶液中萃取20 min,萃取物在室温下经氮气流吹干后用流动相溶解进样。采用Baseline C18分离柱(4.6 mm×250 mm,5.0 μm),以甲醇-水(体积比为60∶40) 为流动相,流速为1.0 mL/min。呋喃丹、西维因、异丙威和乙霉威的检测波长分别为200,223,200和208 nm。该方法对4种氨基甲酸酯类农药的富集倍数均大于45倍;4种氨基甲酸酯类农药在10~100 μg/L质量浓度范围内,其质量浓度与峰面积之间有良好的线性关系,相关系数均大于0.99;呋喃丹、西维因、异丙威和乙霉威的检出限(S/N=3)分别为5,1,5和3 μg/L;实际水样中的加标回收率为82.0%~102.2%,相对标准偏差为2.0%～6.2%(n=6)。     

QuEChERS提取与高效液相色谱-电喷雾电离串联质谱联用法检测茶叶中的19种农药残留

建立了高效液相色谱-电喷雾电离串联质谱同时检测茶叶中阿维菌素、啶虫脒、涕灭威、甲萘威、克百威、萎锈灵、除虫脲、烯酰吗啉、唑螨酯、吡虫啉、茚虫威、甲霜灵、灭多威、腈菌唑、咪酰胺、丙环唑、鱼藤酮、西玛津、戊唑醇19种农药残留的方法.试样经QuEChERS方法进行前处理,超高效液相色谱-电喷雾电离串联质谱法测定,外标法定量....     

QuEChERS净化超高效液相色谱-串联质谱法检测莲雾中4种杀菌剂

建立了超高效液相色谱-串联质谱法同时检测莲雾中氟硅唑、戊唑醇、抑霉唑和烯唑醇4种杀菌剂的分析方法。莲雾样品经改进的QuEChERS方法进行前处理,超高效液相色谱-串联质谱法(UPLC-MS/MS)测定。氟硅唑、戊唑醇、抑霉唑和烯唑醇的质量浓度在5.0~500.0ng/mL范围内线性良好,相关系数均大于0.99;检出限在0.30~0.80μg/kg之间;平均加标回收率在79.2%~122%之间;相对标准偏差(RSD)在1.4%~9.6%之间。该方法简便、快速、准确度高,可用于莲雾中氟硅唑等四种杀菌剂的检测。     

海产品、底泥、海水中扑草净药物残留量的液相色谱-串联质谱检测

建立了海产品、底泥、海水中扑草净药物残留量的液相色谱-串联质谱检测方法。对海产品、底泥样品,采用快速溶剂提取仪(ASE)乙腈提取,凝胶渗透色谱(GPC)净化,液质联用仪(LC-MS/MS)分析;对海水样品采用酸化乙腈提取,氨基固相萃取柱净化,LC-MS/MS分析。实验结果显示,扑草净在浓度0.025～8.0ng/mL时,线性关系良好(R2=0.9999);海产品、底泥样品的方法测定低限为0.25μg/kg,3个加标水平下的平均回收率为90.0%～105.4%,相对标准偏差(RSD)为2.9%～5.3%;海水样品的方法测定低限为0.50μg/L,3个加标水平下的平均回收率为79.5%～99.6%,RSD为3.4%～11.9%。该方法简单、快速、准确,可用于海产品、底泥、海水样品中扑草净的筛选和测定。     

超高效液相色谱串联质谱法测定茶叶、茶汤和土壤中氟环唑、茚虫威和苯醚甲环唑残留

建立了绿茶、红茶、普洱茶、茶鲜叶、红茶汤和土壤中氟环唑、茚虫威、苯醚甲环唑残留分析方法。采用Florisil与GCB混合柱净化茶叶和土壤,BondElut C18固相萃取柱富集净化茶汤,超高效液相色谱串联质谱法测定,并对3种农药的质谱裂解和基质效应进行了研究探讨。在0.005～4.0 mg/L浓度范围内均满足线性关系,r>0.9997,仪器检出限LOD<0.002 mg/L;在高、中、低3个添加浓度水平下,不同基质样品(绿茶、红茶、普洱茶、红茶汤、茶鲜叶和土壤)中平均回收率为66.3%～111.5%;相对标准偏差为0.85%～17.6%(n=6);方法定量限LOQ分别为0.005 mg/kg(成茶)、0.002 mg/kg(茶鲜叶、土壤)和0.10!g/L(茶汤)。采用此方法检测40份红茶、绿茶出口样品,1份检出茚虫威残留量为0.014 mg/kg;4份检出苯醚甲环唑残留量为0.012～0.040mg/kg,均未检出氟环唑残留。采用此方法进行茚虫威在茶鲜叶-绿茶加工过程中的消解率、茶叶-茶汤冲泡过程中的浸出率研究,表明茚虫威在绿茶加工过程中的平均消解率为24.8%,3次冲泡的总浸出率平均值为5.2%。     

两种叶菜中5种典型手性农药对映体的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法研究

基于手性固定相/超高效液相色谱-串联质谱技术建立了同时拆分2种叶菜类蔬菜(菜心、油麦菜)中5种典型手性农药(多效唑、腈菌唑、甲霜灵、三唑酮和唑菌酮)对映体的分析方法。样品用乙腈提取,N-丙基乙二胺(PSA)粉和石墨化碳黑(GCB)粉净化,经手性色谱柱CHIRALCEL OD-RH拆分后,超高效液相色谱-串联质谱(UPLC-MS/MS)检测。结果表明,5种手性农药在0.005~1.0 mg·L-1范围内均呈良好线性关系;在0.01、0.1、0.5 mg·kg-1加标水平下的平均回收率为68.8%~104%,相对标准偏差(n=6)为1.0%~13.7%。该方法准确、简单、可靠,可以满足叶菜类蔬菜中多种手性农药残留的检测要求,并为这5种手性农药对映体在蔬菜中的残留及消解规律研究提供技术支持。     

荔枝中抑霉唑和嘧霉胺残留量的超高效液相色谱-串联质谱法同时测定

建立了超高效液相色谱-串联质谱法同时测定荔枝中抑霉唑和嘧霉胺的方法,对提取试剂、流动相、质谱条件进行了研究,并对抑霉唑和嘧霉胺可能的断裂机理进行了推测。待测样品直接用乙腈提取,采用电喷雾离子源(ESI)、多反应监测正离子模式扫描,外标法定量。抑霉唑、嘧霉胺的质量浓度在1.00～20.0μg/L范围内与峰面积呈良好线性,方法的检出限为0.005mg/kg;添加水平为0.005、0.010、0.020mg/kg时抑霉唑和嘧霉胺的平均回收率分别为91%～96%和83%～90%,相对标准偏差分别为6.5%～8.4%和9.5%～11.1%。该方法快速、简便、准确,可用于荔枝中抑霉唑和嘧霉胺残留量的定性与定量检测。     

分散液相微萃取-气相色谱联用测定葡萄中百菌清、克菌丹和灭菌丹残留

采用分散液相微萃取与气相色谱-电子捕获检测联用技术建立了测定葡萄样品中百菌清、克菌丹和灭菌丹农药残留的新方法.对影响萃取和富集效率的因素进行了优化.萃取条件选定为在10 mL带塞离心试管中加入 5.0 mL葡萄样品溶液,并加入1.0 mL丙酮(分散剂),振荡摇匀后以5000 r/min离心5 min,然后将上层清液转移至另一离心试管中,加10.0 μL氯苯(萃取剂),分散混匀后再以5000 r/min离心5 min,萃取剂氯苯相沉积到试管底部,吸取1.0 μL萃取相直接进样分析.在优化的实验条件下,3种杀菌剂的富集倍数可达788～876倍;检出限在6.0～8.0 μg/kg(S/N=3∶ 1)范围内.以α-六六六为内标,测定3种杀菌剂的线性范围为10～150 μg/kg,线性相关系数在0.9990～0.9995范围内.本方法已成功应用于葡萄样品中百菌清、克菌丹和灭菌丹残留的测定,平均加标回收率在92.3%～106.1%范围内;相对标准偏差在4.5%～7.2%之间,结果令人满意.     

QuEChERS–气相色谱–三重四级杆质谱法监测地表水中5种有机氯农药残留

建立QuEChERS–气相色谱–三重四级杆质谱法监测地表水中5种常见有机氯类农药如七氯、艾氏剂、百菌清、腐霉利、三唑酮残留的方法。用乙腈对地表水样品萃取,以无水硫酸镁盐析,萃取液用N-丙基乙二胺(PSA)和C_(18)柱进行净化。净化液经氮气吹至近干后用正己烷定容至1 mL,经0.2μm滤膜过滤后进样检测,外标法定量。七氯、艾氏剂、百菌清、腐霉利、三唑酮的检出限分别为0.009,0.008,0.010,0.006,0.012μg/L。5种有机氯农药的质量浓度在0.02～2.0μg/mL范围内与其色谱峰面积呈良好的线性关系,相关系数均大于0.995,平均加标回收率为72.9%～92.1%,检测结果的相对标准偏差均小于5%(n=6)。该方法样品前处理简单,检测灵敏度高,可用于地表水中多种农药残留的同时检测。     

高效液相色谱–串联质谱法同时测定土壤中8种杀菌剂残留

建立高效液相色谱-串联质谱法同时测定土壤中戊唑醇、腈菌唑、腈苯唑、氟硅唑、三唑酮、丙环唑、烯唑醇、苯醚甲环唑8种杀菌剂残留量的方法。采用QuEChERS样品前处理方法对土壤样品进行提取、净化和富集,用电喷雾离子源、正负离子扫描,以多反应监测(MRM)模式进行定性和定量分析。在优化的实验条件下,8种杀菌剂的质量浓度在0.01~0.50 mg/L范围内与色谱峰面积均成良好的线性关系,相关系数均大于0.995,方法检出限为0.005~0.010 mg/kg。样品平均加标回收率为85.6%~102.2%,测定结果的相对标准偏差为4.6%~13.2%(n=5)。该方法操作简便,灵敏度和准确度高,满足土壤中戊唑醇等8种杀菌剂残留量的测定要求。     

Silica Microspheres for SPE and Determination of Fungicides in Water by LC

A new method has been developed for the determination of metalaxyl, myclobutanil, and tebuconazole in environmental water samples with preconcentration by cartridges packed with SiO₂ microspheres prior to LC. Several parameters such as the volume and composition of eluent, sample flow rate, sample pH, and sample volume were optimized. Under the optimal conditions, excellent detection limits (S/N = 3) and precision (RSD, n = 6) were 0.02 ng mL^?1, 1.3% for metalaxyl, 0.02 ng mL^?1, and 2.4% for myclobutanil and 0.08 ng mL^?1 and 4.3% for tebuconazole, respectively. The method was applied to the analysis of real-water samples, and satisfactory results were obtained. The average spiked recoveries were in the range of 86.3–97.5%. These results indicate that SiO₂ microspheres have great potential to be used as a novel solid phase extraction adsorbent that could have wide applications in the environmental field.     

Temperature‐controlled ionic liquid dispersive liquid‐phase microextraction combined with HPLC with ultraviolet detector for the determination of fungicides

Present study described a simple, environmental benign, easy to operate, and determination method for fungicides including thiram, metalaxyl, diethofencarb, myclobutanil, and tebuconazole. The method is based on temperature‐controlled ionic liquid dispersive liquid phase microextraction coupled to HPLC with ultraviolet detector. In the enrichment procedure, ionic liquid 1‐octyl‐3‐methylimidazolium hexafluorophosphate [C₈MIM][PF₆] was used as the extraction solvent. Variable affecting parameters such as the volume of [C₈MIM][PF₆], temperature, extraction time, centrifuging time, and salting‐out effect have been optimized in detail. Under the optimal conditions, this method has been found to have good linear relationship in the concentration range of 1.0–100 μg/L and excellent detection sensitivity with LODs (S/N = 3) in the range of 0.32–0.79 μg/L. Precisions of proposed method were in the range of 3.7–5.9% for intraday and 7.8–11.0% for interday (RSDs, n = 6). The proposed method was used for the analysis of real water samples and good spiked recoveries at two different spiked levels were achieved in the range of 84.6–102%.     

固相萃取-高效液相色谱法测定环境水样中的三嗪类化合物

建立了固相萃取-高效液相色谱法(SPE-HPLC)测定地表水中三嗪类化合物的方法。考察了4种不同固相萃取柱对三嗪类化合物的吸附效果,最终选择ENVI-18固相萃取柱用于萃取地表水中的三嗪类化合物;系统研究了环境水样中三嗪类化合物的最佳固相萃取条件,选择洗脱溶剂为甲醇,洗脱溶剂用量5 mL,水样在萃取前不需要添加甲醇,不调节pH值。测定了方法的检测限,结果表明,扑草净、莠去津、西玛津、脱乙基莠去津、羟基化莠去津和脱异丙基莠去津的最低检测限依次为0.14 μg/L,0.12 μg/L,0.08 μg/L,0.08 μg/L,0.10 μg/L和0.18 μg/L。将该法应用于实际环境水样的分析测定,结果表明某湖水中扑草净的含量为（9.33±0.27） μg/L,某江水中莠去津和扑草净的含量分别为（5.28±0.43） μg/L和（7.12±0.54） μg/L。     

Fabric phase sorptive extraction for the determination of 17 multiclass fungicides in environmental water by gas chromatography‐tandem mass spectrometry

A rapid environmental pollution screening and monitoring workflow based on fabric phase sorptive extraction‐gas chromatography‐tandem mass spectrometry (FPSE‐GC‐MS/MS) is proposed for the first time for the analysis of 17 widespread used fungicides (metalaxyl, cyprodinil, tolylfluanid, procymidone, folpet, fludioxonil, myclobutanil, kresoxim methyl, iprovalicarb, benalaxyl, trifloxystrobin, fenhexamid, tebuconazole, iprodione, pyraclostrobin, azoxystrobin and dimethomorph) in environmental waters. The most critical parameters affecting FPSE, such as sample volume, matrix pH, desorption solvent and time, and ionic strength were optimized by statistical design of experiment to obtain the highest extraction efficiency. Under the optimized conditions, the proposed FPSE‐GC‐MS/MS method was validated in terms of linearity, repeatability, reproducibility, accuracy and precision. To assess matrix effects, recovery studies were performed employing different water matrices including ultrapure, fountain, river, spring, and tap water at 4 different concentration levels (0.1, 0.5, 1 and 5 µg/L). Recoveries were quantitative with values ranging between 70–115%, and relative standard deviation values lower than 14%. Limits of quantification were at the low ng/L for all the target fungicides. Finally, the validated FPSE‐GC‐MS/MS method was applied to real water samples, revealing the presence of 11 out of the 17 target fungicides.     

Determination of fungicides in wine by mixed-mode solid phase extraction and liquid chromatography coupled to tandem mass spectrometry

A novel procedure for the determination of nine selected fungicides (metalaxyl-M, azoxystrobin, myclobutanil, flusilazole, penconazole, tebuconazole, propiconazole, diniconazole and difenoconazole) in wine samples is presented. Sample enrichment and purification is simultaneously performed using mixed-mode, anion exchange and reversed-phase, OASIS MAX solid-phase extraction (SPE) cartridges. Analytes were determined by liquid chromatography coupled to tandem mass spectrometry using atmospheric pressure electrospray ionization (LC-ESI-MS/MS). Parameters affecting the chromatographic determination and the extraction-purification processes were thoroughly investigated. Under optimized conditions, 10 mL of wine were firstly diluted 1:1 with ultrapure water and then passed through the mixed-mode SPE cartridge at a flow of ca. 5 mLmin(-1). After a washing step with 5 mL of an aqueous NH(4)OH solution (5%, w:v), analytes were recovered with just 1 mL of methanol and injected in the LC-MS/MS system without any additional purification. The selective extraction process avoided significant changes in the ionization efficiency for red and white wine extracts in comparison with pure standards in methanol. Performance of the method was good in terms of precision (RSDs<11%) and accuracy (absolute recoveries>72%, determined against pure standards in methanol) reporting method LOQs in the range of 0.01-0.79 ngmL(-1) for target compounds, which are far below the EU maxima residue levels (MRLs) for fungicides in vinification grapes and wine. Several commercial wines from different geographic areas in Spain were analyzed. In most samples, metalaxyl-M and azoxystrobin were found at concentrations up to several ngmL(-1).     

固相萃取-分散液液微萃取-柱前衍生法测定水样中痕量雌激素

建立了碳纳米管的固相萃取-分散液液微萃取-柱前荧光衍生化(SPE-DLLME-PFD)测定水体中痕量雌三醇(E3)、双酚A(BPA)、17α-乙炔基雌二醇(EE2)及17β-雌二醇(E2)的高效液相色谱方法.采用中心复合设计和响应曲面法分析并优化SPE、DLLME及PLD条件,最佳条件为210 mL水样以2.0 mL/min的流速过固相萃取柱(碳纳米管量30 mg),甲醇洗脱,氮气浓缩并定容至0.6 mL(分散剂),将100 μL C6MIM[PF6]与分散剂的混合液注入到NaCl含量为25％的2.0 mL去离子水中,离心,移取20 μL下层有机相于样品瓶中,与4.0 mg衍生剂混合,在40℃水浴中衍生25 min;用0.1mL甲醇溶解过量的衍生剂颗粒,取20 μL进样分析.在优化条件下.4种雌激素的线性范围为0.05～5.00 μg/L,相关系数R2=0.9966～0.9999;,检出限介于0.13～6.33 ng/L(S/N=3)之间.不同加标浓度条件下,雌激素的加标回收率在83.1％～122.4％范围内(RSD=1.7％～9.6％).在实际水样中E3和BPA检出率较高.与其它方法相比,本方法虽然萃取时间长、水样量大、步骤多,但具有检出限低、操作简便、环境友好等优点.     

Highly sensitive determination of tetrabromobisphenol A and bisphenol A in environmental water samples by solid‐phase extraction and liquid chromatography‐tandem mass spectrometry

Using bamboo‐activated charcoal as SPE adsorbent, a novel SPE method was developed for the sensitive determination of tetrabromobisphenol A and bisphenol A in environmental water samples by rapid‐resolution LC‐ESI‐MS/MS. Important parameters influencing extraction efficiency, including type of eluent, eluent volume, sample pH, volume and flow rate, were investigated and optimized. Under the optimal extraction conditions (eluent: 8 mL methanol, pH: 7; flow rate: 4 mL/min; sample volume: 100 mL), low LODs (0.01–0.02 ng/mL), good repeatability (6.2–8.3%) and wide linearity range (0.10–10 ng/mL) were obtained. Satisfied results were achieved when the proposed method was applied to determine the two target compounds in real‐world environmental water samples with spiked recoveries over the range of 80.5–119.8%. All these facts indicate that trace determination of tetrabromobisphenol A and bisphenol A in real‐world environmental water samples can be realized by bamboo‐activated charcoal SPE‐rapid resolution‐LC‐ESI‐MS/MS.     

Combination of solid-phase extraction-hollow fiber for ultra-preconcentration of some triazole pesticides followed by gas chromatography-flame ionization detection

In this study, an extraction and preconcentration technique using solid-phase extraction (SPE) along with hollow fiber (HF) has been developed as an ultra-preconcentration technique for some triazole pesticides in aqueous samples. Triazole pesticides were employed as model compounds to assess the method and were monitored by gas chromatography-flame ionization detection (GC-FID). Initially, an aqueous solution of target analytes was passed through an RP-8 SPE cartridge and then the adsorbed analytes were eluted with μL amounts of toluene. The collected elute was slowly introduced into an HF that had one end blocked. This allowed precipitation inside the lumen and pores of the HF. Finally, the obtained HF was mounted on a home-made solid-phase microextraction syringe and entered into the GC injection port for thermal desorption-GC analysis. The effect of various experimental parameters including injection port temperature, desorption time, state of HF, washing solvent, elution solvent and its volume, sample volume, etc. were investigated for finding the optimum conditions. The calibration graphs were linear in the ranges of 2-1000 ng/mL (penconazole and hexaconazole), 5-1000 ng/mL (tebuconazole), 15-1000 ng/mL (triticonazole) and the detection limits (LODs) ranged from 0.6 to 4.5 ng/mL. The enhancement factors were in the range of 870-950. The relative standard deviations (RSD%) for five repeated experiments (C=250 ng/mL of each pesticide) varied from 4.5 to 8.7%. The relative recoveries obtained for analytes in grape juice samples, spiked with different levels of each pesticide, were in the range of 87-119%.     

无胶筛分毛细管电泳法测定猕猴血浆中的反义寡核苷酸药物癌泰得

采用两步固相萃取(SPE)法结合无胶筛分毛细管电泳(NGCE)技术建立了猕猴血浆中的反义寡核苷酸药物癌泰得的定量分析方法。优化并确定了SPE的相关条件(阴离子交换柱,上样缓冲液pH值为9.0,上样体积及洗脱体积分别为5 mL和3 mL)和NGCE的分析条件(灌胶时间为30 min,分离电压为24 kV)。在优化的条件下,猕猴血浆中癌泰得在1.95～250 mg/L范围内呈良好的线性关系,定量限(LOQ)为1.95 mg/L。批内准确度为93.38%～100.71%,批内相对标准偏差＜11%;批间准确度为89.46%～103.46%,批间相对标准偏差＜9%。在不同条件(室温下存放4 h; 4 ℃下存放24 h;反复冻融（-80 ℃至室温）2次;-80 ℃下保存1个月)下癌泰得在猕猴血浆中的稳定性良好。已将该方法成功地应用于癌泰得的猕猴药代动力学研究。     

Sensitive determination of amide herbicides in environmental water samples by a combination of solid‐phase extraction and dispersive liquid–liquid microextraction prior to GC–MS

In this paper, solid‐phase extraction (SPE) in combination with dispersive liquid–liquid microextraction (DLLME) has been developed as a sample pretreatment method with high enrichment factors for the sensitive determination of amide herbicides in water samples. In SPE–DLLME, amide herbicides were adsorbed quantitatively from a large volume of aqueous samples (100 mL) onto a multiwalled carbon nanotube adsorbent (100 mg). After elution of the target compounds from the adsorbent with acetone, the DLLME technique was performed on the resulting solution. Finally, the analytes in the extraction solvent were determined by gas chromatography–mass spectrometry. Some important extraction parameters, such as flow rate of sample, breakthrough volume, sample pH, type and volume of the elution solvent, as well as salt addition, were studied and optimized in detail. Under optimum conditions, high enrichment factors ranging from 6593 to 7873 were achieved in less than 10 min. There was linearity over the range of 0.01–10 μg/L with relative standard deviations of 2.6–8.7%. The limits of detection ranged from 0.002 to 0.006 μg/L. The proposed method was used for the analysis of water samples, and satisfactory results were achieved.