微波提取-高压液相色谱-原子荧光光谱联用(HPLC-AFS)法分析稻米样品中砷形态

建立了液相色谱-原子荧光光谱联用(LC-AFS)法测定稻米中4种砷形态的方法。稻米样品用硝酸溶液(0.15mol/L)微波提取50min,消解溶液经离心分离后,采用Hamilton PRP-X100色谱柱,KH_2PO_4(45mmol/L)-Na_2HPO_4(5mmol/L)缓冲液为流动相,砷形态4个组分能够在7min内达到基线分离,且无需调节pH值。优化了氢化物发生条件,使用了更低浓度的载流和还原剂。实验结果表明,各组分在2～10ng/mL范围内线性关系良好,相关系数为0.998 8～0.999 8,各组分的检出限分别为0.29、0.47、0.62和1.16ng/mL;各组分峰面积的相对标准偏差均低于3.1%;加标回收率为85.3%～113%;对稻米标准物质的分析测定结果表明方法定值准确。最后,与GB 5009.11—2014中使用的提取及测定条件进行对比,表明方法具备快速、环保、高效的特点。     

高效液相色谱-氢化物发生-原子荧光光谱在线联用系统分析中成药中砷化合物形态

建立了高效液相色谱-氢化物发生-原子荧光光谱砷形态分析在线联用系统,考察了不同实验条件对4种砷形态化合物（As^Ⅲ,DMA^Ⅴ,MMA^Ⅴ和As^Ⅴ）分离分析的影响,优化了实验条件.在优化的实验条件下,采用pH 5.8的磷酸盐缓冲溶液为流动相,梯度洗脱,10 min之内4种砷形态达到基线分离.进样20μL,测定4种形态的检出限分别为：As^Ⅲ2.76 ng/mL,DMA^Ⅴ7.37 ng/mL,MMA^Ⅴ2.86 ng/mL和As^Ⅴ5.22 ng/mL,相对标准偏差RSD在2.9%～4.2%之间.该联用系统灵敏度高,准确性好,分离分析了部分市售中成药中的不同砷形态化合物.     

液相色谱-电感耦合等离子体质谱法测定稻米中的5种砷形态

建立了稻米中砷酸根[As（Ⅴ）]、亚砷酸根[As（Ⅲ）]、砷甜菜碱（AsB）、一甲基砷（MMA）和二甲基砷（DMA）的液相色谱-电感耦合等离子体质谱（LC-ICP-MS）检测方法。以0.3 mol/L硝酸水溶液为提取试剂,样品在石墨消解仪中于95 ℃消解1.5 h,上清液供LC-ICP-MS分析。5种砷形态采用Dionex IonPac AS19阴离子交换柱（250 mm×4 mm）分离,经ICP-MS检测。比较了4种提取液对稻米中5种砷形态的提取效率,并对提取溶剂的浓度、提取温度和提取时间等条件进行了优化。通过加标回收试验结合测定标准物质考察了方法准确度及精密度,在2个加标水平上各形态的回收率为89.6%~99.5%,RSD（n=5）不大于3.6%,大米标准物质中各形态之和的测定结果与其标准值吻合,5种砷形态的线性范围AsB和DMA为0.05~200 μg/L,As（Ⅲ）和MMA为0.10~400 μg/L,As（V）为0.15~600 μg/L,方法检出限为0.15~0.45 μg/kg。结果表明,本方法简单、灵敏、耐用,可用于稻米中5种砷形态的准确定量和风险评估。     

离子色谱-双阳极电化学氢化物发生-原子荧光光谱法测定Ⅰ型牙髓失活材料中的砷形态

将自制的双阳极电化学氢化物发生器作为离子色谱与原子荧光光谱的联用接口,建立了离子色谱-双阳极电化学氢化物发生-原子荧光光谱法在线分析砷形态系统.最佳实验条件为淋洗液6.0 mmol/L NH4H2PO4(pH 6.20),电解液0.40 mol/L H2SO4,电解液流量为阳极4.0 mL/min,阴极 1.5 mL/min,电解电流密度0.50 A/cm.2,载气流量300 mL/min,屏蔽气流量500 mL/min,氢气流量80 mL/min.在优化的实验条件下,As(Ⅲ)、DMA、MMA的线性范围为5～200 μg/L、As(Ⅴ)的线性范围为10～200 μg/L,As(Ⅲ)、DMA、MMA和As(Ⅴ)检出限分别为3.04、4.27、3.97和9.30 μg/L(信噪比S/N=3).50 μg/L的As(Ⅲ)、DMA、MMA和As(Ⅴ)混合标准溶液平行进样7次,得到的色谱峰面积的相对标准偏差(RSD)分别为415%、3.08%、519%和3.62%.将该方法用于牙髓失活材料中的砷形态分析.     

高灵敏度原子荧光光谱系统应用于砷、硒形态分析的研究

将实验室自制的高灵敏度原子荧光光谱系统与色谱分离、在线紫外光前处理装置联用,实现了元素形态的液相色谱分离、在线紫外消解、蒸气发生及原子荧光光谱测定,并以砷、硒两元素为例对系统的分析性能进行研究。样品通过加热混旋提取、离心、过滤,使用反相色谱柱并以5.0 mmol/L磷酸氢二铵缓冲溶液(pH 5.7)-0.5 mmol/L四丁基溴化铵(TBAB)-1%甲醇为流动相进行分离;三价砷(AsO3-3)、二甲基砷(DMA)、一甲基砷(MMA)、五价砷(AsO3-4)可在7 min内进行分离和测定,硒代胱氨酸(SeCys)、硒代蛋氨酸(SeMet)、四价硒(SeO2-3)、六价硒(SeO2-4)的测定约需11 min。在优化实验条件下,方法检出限(DLs,S/N=3)为0.08~0.74μg/L;相对标准偏差(RSD,n=7)为1.4%~7.9%,实际样品的加标回收率为82.5%~116.5%;砷、硒各形态在0.28~40.0μg/L和0.38~80.0μg/L范围内线性良好。建立的联用系统稳定性好、检出限低,可实现样品中低浓度砷、硒形态的准确测定。     

高效液相色谱-电感耦合等离子体质谱同时测定虾类中6种砷形态

建立了高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)同时测定虾类中6种砷形态的方法。研究了不同流动相、梯度洗脱方法对6种砷形态化合物的分离效果。在优化的质谱条件下,采用pH=8.5的50 mmol/L(NH4)2CO3-甲醇(99∶1,V/V)溶液及pH=8.5的0.5mmol/L(NH4)2CO3-甲醇(99∶1,V/V)溶液为流动相进行梯度洗脱,10 min之内6种砷形态达到基线分离。同时采用0.5 mmol/L(NH4)2CO3-甲醇(99∶1,V/V)溶液(pH=8.5)作为提取剂能较好地提取养殖虾样品中的砷形态。该联用技术重现性好,能快速地同时测定养殖虾中6种砷形态化合物。     

离子色谱-电感耦合等离子体质谱同步分离测定环境水中砷、铬、溴、碘的10种形态

建立了离子色谱-电感耦合等离子体质谱(IC-ICP-MS)联用技术，用于测定环境水中亚砷酸根、砷酸根、一甲基砷(MMA)、二甲基砷(DMA)、三价铬、铬酸根、溴离子、溴酸根离子、碘离子、碘酸根离子。使用Hamilton PRP-X100阴离子交换色谱柱，在流速1.4 mL/min、5%甲醇-40 mmol/L NH₄NO₃流动相(pH=8.6)等度洗脱条件下，20 min内实现了砷、铬、溴、碘4种元素10种形态的分离检测。10种元素形态检出限在0.1～2μg/L之间，定量限在0.5～6μg/L之间，平均加标回收率在75.4%～104.7%之间，相对标准偏差(RSD,n=3)在0.91%～4.96%之间。该方法可以用于环境水样中砷、铬、溴、碘4种元素10种形态的常规分析检测。     

高效液相色谱-电感耦合等离子体串联质谱法同时测定土壤中的阿散酸、洛克沙胂及其降解产物

建立了高效液相色谱-电感耦合等离子体串联质谱(HPLC-ICP-MS/MS)同时测定土壤中阿散酸(p-ASA)、洛克沙胂(ROX)及其降解产物无机砷(i-As)(亚砷酸(As(Ⅲ))和砷酸(As(Ⅴ)))、一甲基砷(MMA)和二甲基砷(DMA)等5种砷形态的分析方法。以0.1 mol/L NaH_2PO_4-0.1 mol/L H_3PO_4(体积比9∶1)为提取剂,液固比为50 mL/g,样品经微波辅助提取(80℃,30 min)后,采用Hamilton PRP-X100阴离子交换柱(250 mm×4.1 mm,10μm),以60 mmol/L(NH_4)_2HPO_4-5%甲醇(pH 6.0)和水为流动相进行梯度洗脱,在15 min内实现了5种砷形态的良好分离。在优化条件下,各砷形态在0～500μg/L范围内线性良好(r~2≥0.999 1),检出限为0.043～0.080μg/kg(以As计),相对标准偏差为1.7%～3.8%。将该方法用于分析3种土壤样品,各砷形态的加标回收率为71.6%～106%。该方法简单、快速、准确、可靠,适用于土壤中阿散酸、洛克沙胂和常规砷形态的检测。     

HPLC-HG-AFS测定大气颗粒物中砷的形态

采用高效液相色谱-氢化物发生原子荧光光谱联用测定了北京大气颗粒物中As(III),As(Ⅴ),二甲基砷酸(DMA)和一甲基砷酸(MMA)的含量。研究了仪器条件、流动相组成和梯度洗脱程序对砷形态分离的影响。实验结果显示,在优化的色谱与氢化原子荧光检测条件下,采用pH6.0,浓度为10 mmol/L和200 mmol/L NH4H2PO4为流动相A和B,在1~3 min内用60%的A和40%的B洗脱使砷的4种形态达到最佳分离效。As(III),As(Ⅴ),DMA和MMA的检出限为1.45,1.22,1.91和1.64 mg/L,回收率为90.5%~93.2%,相对标准偏差为0.38%~1.7%。方法适用于大气颗粒物中砷的形态分析研究。     

捕集阱顶空-气相色谱法测定水中低浓度苯系物

建立了捕集阱顶空-气相色谱检测水中低浓度苯系物的方法。在捕集阱顶空平衡温度70℃,10 min平衡时间,色谱温度70℃(2 min),10℃/min升温至学20℃,保持2 min,载气流量2.5 mL/min的条件下,6种苯系物分离效果良好,在0.16~40μg/L范围内,苯系物浓度与色谱峰面积呈良好的线性关系,相关系数为0.9994~0.9999;使用捕集阱极大地提高了苯系物分析的灵敏度,方法检出限分别为:苯0.025 ng/L、甲苯0.025 ng/L、乙苯0.023 ng/L、对,间二甲苯0.025 ng/L、邻二甲苯0.027 ng/L、异丙苯0.022 ng/L;本法测定苯系物RSD≤5.1%,加标回收率为79.1%~104.9%。本方法应用于自来水中低浓度苯系物的分析,效果良好。     

Determination of 'arsenosugars' in algae with anion-exchange chromatography and an inductively coupled plasma mass spectrometer as element-specific detector

The retention behavior of four naturally occurring dimethylarsinoylribosides with -CH2-CHOH-CH2X (X = OH, HO3POCH2CHOHCH2OH, SO3H, OSO3H) as aglycones, of arsenous acid, arsenic acid, methylarsonic acid, and dimethylarsinic acid was investigated on a Hamilton PRP-X100 anion-exchange column with aqueous solutions of ammonium dihydrogen phosphate (20 mmol/L) in the pH range of 3.8-9.0 as mobile phase. A HP 4500 inductively coupled plasma mass spectrometer (ICP-MS) served as arsenic-specific detector. The influence of pH, temperature, and the concentration of methanol in the mobile phase on the retention times of these arsenic compounds was explored. An aqueous 20 mM ammonium dihydrogen phosphate solution at pH 5.6 at a column temperature of 40 degrees C was considered optimal as it allowed the separation of seven of the arsenic compounds within 16 min. Only arsenous acid and the ribose with the glycerol aglycone have overlapping signals with both migrating almost with the solvent front. At a concentration of 0.50 ng As mL(-1) the relative standard deviations (n = 3) of the signal areas of the eight arsenic compounds was in the range from 3.5 to 8.1%. The linear calibration curves (peak areas) from 0.5 to 10 ng/mL had correlation coefficients > 0.997. Extracts obtained from the brown algae Fucus spiralis and Halidrys siliquosa were chromatographed under the optimized conditions. Both species contained the sulfate riboside as the major arsenic compound (approximately 55% of total extractable arsenic) together with the sulfonate- and phosphate riboside. Arsenic acid was a significant constituent of Halidrys siliquosa (approximately 6.5%), but was not detected in Fucus spiralis.     

液相色谱-串联质谱法测定食品中甜味剂和抗氧化剂

建立了液相色谱-四级杆飞行时间串联质谱联用技术同时测定4种甜味剂(安赛蜜、糖精钠、甜蜜素、阿斯巴甜)及2种抗氧化剂(叔丁基对苯二酚、丁基羟基茴香醚)的方法.试验采用Extend-C18色谱柱分离与ESI(-)检测,以乙腈-1 mmol/L乙酸铵为流动相梯度洗脱,在6 min内实现6种目标物的快速分离,检测限为0.250 0~5.00 0 ng/m L,日间精密度小于10.71%(n=3),液态样品平均回收率为83.24%~118.3%.方法准确、灵敏,可快速检测食品中的甜味剂和抗氧化剂.     

Speciation of Arsenic in Rice by Ion Chromatography with Online Anion Suppression and Inductively Coupled Plasma Mass Spectrometry

Arsenic speciation in rice has received attention due to its impact on food safety and human health. In this study, a sensitive method was developed for the determination of inorganic arsenic in rice using online anion suppression with ion chromatography and inductively coupled plasma mass spectrometry. HCl of 0.01?mol/L was the optimal extracting agent, and 38?mmol/L sodium carbonate and 15?mmol/L sodium acetate were used as the mobile phase to separate dimethylarsinic acid (DMA), arsenite, monomethylarsonic acid (MMA), and arsenate. The results showed that there were no significant losses or transformations with the anion suppressor and an improvement in sensitivity. The limits of quantification were 0.1?µg/L for DMA, As(III) and MMA, and 0.2?µg/L for As(V). The procedure was used to determine inorganic arsenic in rice; As(III) and DMA were the primary forms present. The reproducibility from seven measurements showed that the relative standard deviation was less than 1.68%. The recoveries were from 99.76 to 110.42%. The present work offers a new approach for the determination of inorganic arsenic in rice.     

化学蒸气发生-四通道原子荧光光谱法同时测定高纯金中的痕量As,Sb,Bi,Te

采用化学蒸气发生-四通道原子荧光光谱法测定了高纯金中的痕量砷、锑、铋和碲。用乙酸乙脂萃取分离金,水相还原后采用化学蒸气发生-四通道原子荧光光谱法测定高纯金中的痕量砷、锑、铋和碲。在最佳条件下,方法对As,Sb,Bi,Te的检出限分别为0.04,0.05,0.04,0.03 ng/mL(3σ);测定精密度分别为0.98,0.89,0.94,0.99%(对10 ng/mL As,Sb,Bi和Te混合标准,n=7)。方法对实际样品中的As,Sb,Bi,Te进行了同时测定,测定结果与标准方法无明显差异,各元素的加标回收率为95%～105%。     

Determination of arsenic species in Solanum Lyratum Thunb using capillary electrophoresis with inductively coupled plasma mass spectrometry

A simple and highly efficient interface to couple capillary electrophoresis with inductively coupled plasma mass spectrometry by a microflow polyfluoroalkoxy nebulizer and a quadruple ion deflector was developed in this study. By using this interface, six arsenic species, including arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, were baseline‐separated and determined in a single run within 11 min under the optimized separation conditions. The instrumental detection limit was in the range of 0.02–0.06 ng/mL for the six arsenic compounds. Repeatability expressed as the relative standard deviation (n = 5) of both migration time and peak area were better than 2.5 and 4.3% for six arsenic compounds. The proposed method, combined with a closed‐vessel microwave‐assisted extraction procedure, was successfully applied for the determination of arsenic species in the Solanum Lyratum Thunb samples from Anhui province in China with the relative standard deviations (n = 5) ≤4%, method detection limits of 0.2–0.6 ng As/g and a recovery of 98–104%. The experimental results showed that arsenobetaine was the main speciation of arsenic in the Solanum Lyratum Thunb samples from different provinces in China, with a concentration of 0.42–1.30 μg/g.     

Sensitive Determination of Five Priority Haloacetic Acids by Electromembrane Extraction with Capillary Electrophoresis

A method for sensitive determination of five priority haloacetic acids in drinking water has been developed for the first time based on electromembrane extraction (EME) prior to CZE with capacitively coupled contactless conductivity detection (CZE‐C⁴D). The target analytes were extracted from 10 mL of the sample solution (donor phase), through the supported liquid membrane (using a polypropylene membrane supporting 1‐octanol), and into 10 µL of 50 mmol/L NaAc solution (acceptor phase). The extracted solution was directly analyzed by CZE‐C⁴D without derivatization. Several factors that affect separation, detection and extraction efficiency were investigated. Under the optimum conditions, five haloacetic acids (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid) could be well separated from other components coexisting in water samples within 23 min, exhibiting a linear calibration over two orders of magnitude (r?0.9943); the enrichment factors at 430–671 were obtained in a 30 min of extraction, and the limits of detection were in the range of 0.17–0.61 ng/mL. The intraday relative standard deviations for peak areas investigated at 10 ng/mL were between 1.2% and 9.7% for the combined EME‐CZE‐C⁴D procedure. This approach offers an attractive alternative to the officially proposed method for purified drinking water analysis, which requires derivatization procedure prior to gas chromatography analysis.     

固相萃取–高效液相色谱法测定地表水中4种磺胺类抗生素

建立固相萃取–高效液相色谱法测定地表水中磺胺嘧啶、磺胺二甲嘧啶、磺胺氯哒嗪、醋磺胺甲恶唑4种磺胺类抗生素。样品采用HLB柱进行萃取富集,流动相为甲醇–水(体积比为20∶80),流量为0.5 m L/min,用SPD检测器检测,检测波长为270 nm;采用外标法定量。4种磺胺类抗生素质量浓度在4~160 ng/L范围内与色谱峰面积的线性关系良好,相关系数不低于0.998 2,方法检出限为1.0~1.7 ng/L,样品加标回收率为75.2%~97.4%,测定结果的相对标准偏差为2.8%~6.1%(n=7)。该方法操作简便,灵敏度高,可用于地表水中磺胺类抗生素的检测。     

固相萃取-超高效液相色谱-电喷雾串联质谱法同时测定地表水中16种全氟有机化合物

建立了固相萃取-超高效液相色谱-电喷雾串联三重四极杆质谱联用技术分析水中16种全氟有机化合物的高通量检测方法。样品经WAX固相萃取柱富集和净化后,采用Waters ACQUITY UPLC^TM BEH C₁₈色谱柱,含2 mmol/L乙酸铵的甲醇和含2 mmol/L乙酸铵的水作为流动相进行梯度洗脱,质谱采用电喷雾负离子电离,多反应监测模式检测。16种全氟有机化合物在0.5~100 μg/L或1.0~100 μg/L浓度范围内线性关系良好,相关系数为0.9987~0.9999,方法的检出限为0.06~0.46 ng/L;高、中、低3个添加水平的回收率为67.6%~103%,相对标准偏差为2.94%~12.0%。结果表明,该方法灵敏、准确且检测范围广,分析速度快,是一种适于实际水样中全氟有机化合物检测分析的方法。     

临床干血斑样本中12种抗凝血鼠药的液相色谱-串联质谱法同时定量检测

为应对临床中毒快检的需求,建立了干血斑样本中12种抗凝血鼠药的液相色谱-串联质谱定性定量方法。针对全打孔的干血斑样本,考察了滤纸卡种类、润湿步骤、提取溶剂种类对提取效果的影响。采用C18色谱柱进行分离,以乙酸铵(5 mmol/L)水溶液-乙酸铵(5 mmol/L)甲醇溶液为流动相进行梯度洗脱,在电喷雾负离子电离方式下使用三重四极多反应监测模式检测。结果表明,采用Whatman903滤纸卡为基底,以水为溶剂充分润湿,再以含内标的甲醇溶液提取5 min,各鼠药的提取率为66%~115%,且结果稳定(日内RSD小于15%)。除杀鼠酮的线性范围为20~500 ng/m L(r2=0.998 7)外,其它11种鼠药的线性范围为5~500 ng/m L(r2=0.998 8~0.999 6);12种鼠药的回收率为61%~105%,基质效应为71%~193%(日内RSD小于15%)。该方法准确、灵敏、快速且操作简便,成功应用于3例临床鼠药中毒病人样本的快速检测,为临床毒物检测和法医毒物分析的快速筛查和准确定量提供了新的技术方法。