改进的QuEChERS-高效液相色谱法测定水产品中16种多环芳烃

采用改进的QuEChERS,对水产样品进行提取、净化,用高效液相色谱仪-荧光/紫外检测器串联检测,建立了同时测定水产品中16种多环芳烃的高效液相色谱分析方法.样品经乙腈提取,Florisil+C18小柱净化,Waters PAH色谱柱分离,以乙腈-水为流动相进行梯度洗脱,外标法定量.本方法中,16种多环芳烃在各自相应浓度范围内线性关系良好,相关系数不低于0.999,检出限为0.1—3.6μg·kg-1.采用该方法在鲤鱼、对虾和牡蛎中进行加标回收实验,回收率在75.0%—118.2%范围内,相对标准偏差(RSD)为2.6%—13.7%.应用本方法对环渤海湾的水产样品进行了调查分析,发现部分样品中含有PAHs,含量为2.11—147μg·kg-1,为下一步开展相关风险评估工作打下了良好工作基础.     

中空纤维膜辅助离子液体液相微萃取-高效液相色谱法测定环境水体中的水杨酸

分别以l-辛基-3-甲基咪唑六氟磷酸离子液体([C8MIM][PF6])和三辛基氧化膦(TOPO)作为萃取剂与辅助萃取剂,建立了中空纤维膜辅助的两相液液微萃取-高效液相色谱测定环境水体中水杨酸(Salicylicacid,SA)的新方法.通过对中空纤维膜种类、萃取剂、供体相体积、供体相pH、离子强度和萃取时间相关参数进行优化,获得了较高的富集倍数(1653倍).方法的检出限为0.1μg.L-1,线性范围为0.5—1000μg.L-1.方法对实际样品的加标回收率为89.6%—102.4%,可应用于环境水体中痕量SA的测定.     

High performance liquid chromatographic determination of pesticides in soluble phase and suspended phase in river water

A high performance liquid chromatographic method has been developed to determine pesticides in river water as both dissolved phase and suspended phase. The target pesticides were eight herbicides, asulam, diuron, flazasulfuron, linuron, MCPB, mecoprop, pyrazosulfuron‐ethyl and siduron, and two fungicides, oxine‐copper and thiram. The pesticides in filtered river water were extracted with styrene‐divinylbenzene copolymer and were eluted with acetonitrile. The pesticides on suspended solids were extracted ultrasonically with acetonitrile. Each eluate was concentrated and analyzed by HPLC with multiwavelength detector. Recoveries of the pesticides in the overall procedure of this method were 78–114% for filtered river water and 75–107% for suspended solids. The limits of detection in water and suspended solids ranged from 0.1 to 0.9 μg/L and 1 to 7 μg/g, respectively. Pesticide distribution between soluble phase and suspended phase in river water was measured by this method.     

A rapid determination of histamine and 3-methylhistamine in human plasma by high performance liquid chromatography

Histamine plays an important pathophysiological role in allergy, inflammation, gastric acid secretion, microcirculation and neurotransmission. 3-Methylhistamine is a prominent metabolite of histamine. Different methods for determination of histamine in biological fluids have been developed. In the present study, a simple, simultaneous determination of histamine and 3-methylhistamine by HPLC (precolumn derivatization with fluorescamine) was developed in human plasma using fluorescence detection with 1-methylhistamine as the internal standard. Linear regression analysis of the ratios of the concentrations of histamine and 3-methylhistamine (X) against peak height ratios (Y) yielded the following: y = 0.0073x ? 0.0096 (R ² = 0.990) and y = 0.0077x ? 0.0111 (R ² = 0.989). In conclusion, it was possible to detect histamine and 3-methylhistamine below 5 ng mL^?1 in 1 mL plasma.     

高效液相色谱-质谱联用法测定饮用水中的五氯苯酚

建立了高效液相色谱-质谱联用法检测饮用水中五氯苯酚(PCP)。选用ZORBAXXDB-C18柱(50mm×2.1mm,3.5μm)为分析柱,流动相为V(甲醇):V(纯水)=88:12,流量为200μL·min-1;质谱条件选用气动辅助电喷雾离子源(ESI),检测方式为负离子多离子反应检测(MRM);PCP标准曲线线形范围为0.1～100μg·L-1;方法加标回收率达到90%以上;相对标准偏差为2.31%～2.92%(n=5);方法检测低限为0.1μg·L-1。结果表明该方法快速、简便、准确、灵敏、特异,适用于饮用水中PCP残留的测定。     

基于液相色谱法分析水环境中大环内酯类抗生素污染的研究进展

大环内酯抗生素广泛使用,在水环境中的残留越来越引起世界关注.本文综述了国内外基于液相色谱技术分析水环境中大环内酯的方法,比较不同预处理法以及分析方法的灵敏度和检出限.固相萃取法可以同时富集和净化,消耗试剂少,方便,野外操作可行,是理想的预处理技术.液相色谱串联质谱技术选择性好、特异性高、灵敏度高,可以检测浓度低于ng.L-1的目标物,是一种可靠理想的分析方法.最后对大环内酯分析研究进行了展望.     

高效液相色谱-质谱联用法测定饮用水中的五氯苯酚

建立了高效液相色谱-质谱联用法检测饮用水中五氯苯酚（PCP）。选用ZORBAXXDB-C18柱（50mm×2．1mm,3．5μm）为分析柱,流动相为V（甲醇）：V（纯水）=88：12,流量为200μL·min-1;质谱条件选用气动辅助电喷雾离子源（ESI）,检测方式为负离子多离子反应检测（MRM）;PCP标准曲线线形范围为0．1～100μg·L-1;方法加标回收率达到90％以上;相对标准偏差为2-31％-2．92％（n=5）;方法检测低限为0．1μg·L-1。结果表明该方法快速、简便、准确、灵敏、特异,适用于饮用水中PCP残留的测定。     

固相萃取-液相色谱法测定食品废水中8种色素残留

建立了食品工业废水中8种合成色素残留的固相萃取-液相色谱测定方法.水样经固相萃取柱富集,氮吹浓缩定容后直接进样.采用C18色谱柱分离,以甲醇-乙酸铵(0.01 mol·L-1)溶液为流动相,进行梯度洗脱,最后利用二极管阵列检测器(DAD)进行可变波长分析,外标法定量.结果表明,8种合成色素在1.0-50 mg·L-1的...     

在线柱浓缩-液相色谱法测定水体中痕量敌草快和百草枯

采用在线柱浓缩-超快速液相色谱联用技术测定水体中痕量百草枯和敌草快.水样无需样品前处理,过滤后即可进样.采用固相萃取小柱富集待测物,以色谱梯度泵完成样品的净化后,利用阀切换技术将待测物反冲至分析柱进行分离,以二极管阵列检测器定量.方法在1.0—20.0μg.L-1范围内线性良好,百草枯和敌草快的线性相关系数分别为0.9997和0.9989.百草枯和敌草快的检出限(S/N=3)分别为0.10、0.12μg.L-1,加标回收率在96.0%—98.0%之间.用所建立的方法测定了水中痕量的百草枯与敌草快的含量,结果令人满意.     

在线固相萃取-超高效液相色谱法检测水中14种有机磷酸酯

与传统固相萃取耗时长、工作量大、有机溶剂使用量多相比,本文建立了一种在线固相萃取-超高效液相色谱串联质谱方法同时测定地表水中14种有机磷酸酯的新方法.地表水样过膜后,直接注入在线固相萃取净化装置,经净化后进入分离柱分离,用乙腈和0.1%的甲酸水溶液梯度洗脱,采用电喷雾离子源正离子多反应监测模式,对14种有机磷酸酯类化合物进行检测,内标法定量.该方法分析时长13.0 min,方法的线性相关系数R~20.98,地表水和自来水样品的加标回收率在64.8%—113%,相对标准偏差RSD在1.2%—9.3%,检出限为0.1—2.7 ng·L~(-1).与常规方法相比,该方法提高了分析通量和灵敏度,准确度好,操作简便,适用于地表水和自来水中有机磷酸酯的检测.     

中空纤维膜萃取-液相色谱法测定印染废水中芳香胺

建立了一种中空纤维膜液相微萃取的样品前处理技术,结合液相色谱法测定印染废水中芳香胺,并且优化了萃取溶剂、供体相、接收相、搅拌速度、萃取时间等前处理条件.实验结果表明,以正辛醇为萃取溶剂,0.1 mol·L-1Na OH为供体相,0.1 mol·L-1HCl为接收相时,400 r·min-1作为搅拌速度,30 min萃取后的芳香胺富集倍数可达到101—193倍,萃取效率达20.2%—38.6%.结合液相色谱检测芳香胺的线性范围为0.01—0.25 mg·L-1,检出限为1.0—2.0μg·L-1,回收率为95.2%—105.2%.表明该方法可用于检测印染废水中的芳香胺类物质.     

微波辅助萃取-气相色谱法检测裙带菜中的多氯联苯和有机氯农药残留

建立微波辅助萃取-气相色谱法同时检测裙带菜中多氯联苯和有机氯农药残留的方法.裙带菜风干、粉碎后,采用微波辅助萃取仪提取粗提液,经净化、脱酸、脱水、浓缩后,用气相色谱-电子捕获检测器进行分析检测.结果表明,本方法多氯联苯和有机氯农药的检出限分别在0.008—0.044 ng.g-1和0.029—0.273 ng.g-1之间,各组分线性相关系数均大于0.996,加标回收率为72%—131%,相对标准偏差在2%—16%之间(n=3).因此,本方法具有节省时间、减少污染、操作简单便捷等特点,可用于裙带菜等海洋藻类中多氯联苯和有机氯农药残留量的检测.     

分散固相萃取-超高效液相色谱-串联质谱法测定城市污水中2种溴代阻燃剂

建立了分散固相萃取-超高效液相色谱-串联质谱法准确测定城市污水中六溴环十二烷(HBCD)和三-(2,3-二溴丙基)异氰脲酸酯(TBC)的方法.对萃取剂用量、萃取时间、淋洗剂、洗脱剂及色谱分离和质谱测定等条件进行了优化.优化后方法为:待测水样加入同位素标记的回收率内标,用0.4 g Silica、C18和HLB(1∶1∶1)混合填料分散固相萃取,回收萃取剂后用5 m L的10%的甲醇水溶液淋洗,8 m L甲醇洗脱,氮吹浓缩,加入同位素标记的进样内标测定.方法在1—200μg·L-1范围线性关系良好,HBCD和TBC的线性相关系数R20.9986,检出限为0.6—1.2 ng·L-1.应用该方法在某大型污水处理厂各工艺段污水中检测出了α-HBCD,浓度水平为1.3—5.4 ng·L-1.该方法操作简单、灵敏度高,尤其适合城市污水复杂基质中HBCD和TBC的分析.     

Determination of pesticides in apples,grapes and apple juice from a Kosovo market by gradient liquid chromatography with tandem mass spectrometry

Apple, grape, and apple juice were analyzed for pesticides using a multireaction mode (MRM) method in samples taken from a Kosovo market. With this method it was possible to analyze about 100 pesticides in the ESI mode. In these samples some types of pesticides were found, but most of them did not exceed the maximum tolerance levels. In apple samples, six pesticides were detected but only three of them were in sufficient quantitites. Dimethoat was below the limit, while acephate and imazalil exceeded the limit. In grape and apple juice samples, all of pesticides which were found did not exceed the maximum tolerable limits.     

基于改性石墨烯固相萃取-液相色谱法测定联苯菊酯

以石墨粉末为原料通过Hummers法逐步合成磁性胺基化石墨烯(Fe3O4-NH2-G),分别用扫描电镜和FTIR对其表面形貌和化学结构进行表征,并对Fe3O4-NH2-G用于实际样品中联苯菊酯的吸附性能进行了研究.以高效液相色谱为检测手段,对洗脱液和淋洗液的选择、萃取时间和洗脱时间、离子强度、溶液p H、吸附剂总量等相关参数进行优化.实验结果表明,用1%乙酸乙腈溶液做洗脱液,50%甲醇水溶液作为淋洗液,吸附时间洗脱时间都是20 min,溶液p H值为7,不加Na Cl时吸附效果最好.在293 K下改性石墨烯的平衡吸附量136 mg·g-1.实验表明最优条件下检出限达到1.7 ng·m L-1,线性范围为0.005—10μg·m L-1,方法对实际样品的加标回收率91.8%—101.6%,可应用于痕量联苯菊酯的测定.该实验研究表明Fe3O4-NH2-G对联苯菊酯有很好的吸附能力.     

超高效液相色谱-串联质谱法测定污水中14种有机磷酸酯阻燃剂

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)联用法同时测定污水中14种有机磷酸酯阻燃剂(OPEs)的分析方法.样品采集后,经GF/C膜过滤,HLB固相萃取小柱净化后进样分析.以BEH C18色谱柱为分离柱,乙腈和水混合液为流动相(0.2 mL min-1)梯度洗脱,15 min内可完成14种OPEs的分离.在电喷雾正离子模式下,采用多反应监测模式(MRM)进行质谱测定.在加标浓度为1.0μg·L-1时,14种OPEs在污水处理厂进水和出水中的回收率分别为52.1%—119%、43.6%—114%,相对标准偏差(RSD)分别为1.2%—16.2%、0.4%—9.2%,方法的检出限(LOD)在0.3—6.0 ng·L-1间.方法精密度好,准确度高,可满足同时对污水样品中的14种OPEs进行定性及定量分析的要求.     

加速溶剂萃取(ASE)-固相萃取(SPE)-高效液相色谱法(HPLC)测定土壤中青霉素钠

建立了一种加速溶剂萃取(ASE)-固相萃取(SPE)-高效液相色谱(HPLC)测定土壤中青霉素钠的简单、快速的方法.样品以超纯水为提取溶剂,50℃提取温度为ASE提取条件参数;HLB型固相萃取柱富集净化:6.0mL 5%甲醇淋洗、4.0mL乙腈-甲醇(1∶1)洗脱;高效液相色谱-紫外检测器(HPLC-PDA)测定,检测波长λ=191.1nm,柱温30℃,流动相为乙腈-0.1%甲酸/水(1∶1),采用等梯度洗脱程序,取得较好的检测分离效果.对0.5、2.0、8.0mg·kg-1等3个不同添加浓度水平的青霉素钠平均加标回收率范围为73.1%—89.7%,回收率相对标准偏差RSD范围为1.1%—2.9%(n=5),检出限可达235.0μg·L-1.结果表明,该方法操作简单,快速,准确度和精密度均符合质量控制要求,能够满足环境土壤样本中痕量青霉素钠检测分析的要求.     

Green chemistry approach to analysis of formic acid and acetic acid in aquatic environment by headspace water-based liquid-phase microextraction and high-performance liquid chromatography

A simple and totally organic-free (green) method, viz. headspace water-based liquid-phase microextraction combined with high-performance liquid chromatography-ultraviolet detection has been successfully developed for analysis of formic acid and acetic acid in environmental water samples. A microdrop of an aqueous solution of sodium hydroxide was suspended from the tip of a microsyringe needle over the headspace of the stirred sample solution containing the analytes at pH 1.0 for a given time. The microdrop was then retracted into the microsyringe, diluted with HPLC mobile phase, and injected to HPLC. Optimum efficiency has been achieved for: 3.0 µL NaOH microdrop (0.1 mol L^?1) exposed for 15 min over the headspace of an aqueous sample of 6.5 mL at 55 °C, containing 15% w/v of Na₂SO₄, adjusted to pH = 1.0 and stirred at 750 rpm. Under these conditions, enrichment factors of 162 and 187, limits of detection of 0.3 and 0.1 µg L^?1 (S/N = 3) with dynamic linear ranges of 1–500 and 0.5–500 µg L^?1 were obtained for formic acid and acetic acid, respectively. A reasonable repeatability (5.8% ≤ RSD ≤ 8.8%, n = 6) and satisfactory linearity (r² ≥ 0.997) illustrated the performance of the method.     

Trace analysis of airborne toluene diisocyanate as a pentafluorobenzyl derivative by gas chromatography with electron capture detection

Trace analysis of airborne toluene diisocyanate (TDI) vapor was accomplished by measuring the derivative using gas chromatography with electron‐capture detector after collecting gas samples with a microimpinger containing 2 ml toluene, 1 μl pentafluorobenzyl alcohol, and 1 μl triethylamine. The sampling efficiency was determined to be 99.4% for short‐term exposure level of TDI and the 2,4‐ and 2,6‐isomers of TDI were well separated. The derivative was identified to be a new compound with a molecular weight of 570 by mass spectrometry in fast atomic bombardment mode and nuclear magnetic resonance spectrometry. This method is convenient and can be applied in the field where airborne TDI is in vapor form.     

Validation of QuEChERS-based method for determination of flusilazole residues in grape by high-performance liquid chromatography with photodiode array detector

A high-performance liquid chromatography with photodiode array detector analytical method was developed to determine the residue levels of flusilazole in grape and investigate the dissipation pattern and safety. The results showed that the mean recoveries were in the range of 86%–90%. Limits of detection and quantification were 0.008 and 0.02 mg/kg, respectively. The residue levels of flusilazole were best described by first-order rate kinetics and with half-lives ranging from 4.2 days (recommended dose) to 4.6 days (double the recommended dose). In conclusion, flusilazole at the recommended or even at double the recommended doses does not pose any apparent hazards to consumers.