气相色谱-质谱法测定富硒酵母中的硒蛋氨酸

建立了气相色谱-质谱（GC-MS）测定富硒酵母中硒蛋氨酸含量的方法。比较了3种从样品中提取硒蛋氨酸方法的效果。样品在三羟甲基氨基甲烷（Tris）缓冲液中酶解24 h后,以丁醇及三氟乙酸酐为衍生化试剂对硒蛋氨酸进行衍生化,采用选择离子模式对衍生物进行GC-MS测定。硒蛋氨酸的回收率为98.5%~103.7%,相对标准偏差为0.9%~2.4%,检出限为0.5 mg/L（S/N=3）。对实际样品进行测定,得到样品中硒蛋氨酸的含量结果。该法简便快速,准确可靠,灵敏度高。     

液相色谱-氢化物发生原子荧光光谱法测定富硒酵母中硒的形态

建立了富硒酵母中硒酸Se(Ⅵ)、亚硒酸Se(Ⅵ)、硒代蛋氨酸(SeMet)和硒甲基硒代半胱氨酸(SeMeCys)4种硒形态的高效液相色谱-氢化物发生原子荧光光谱(HPLC-HG-AFS)分析方法。样品采用蛋白酶和胰蛋白酶酶解提取,20 mmol/L(NH4)2HPO4为流动相,经PRP-X100阴离子交换色谱柱分离后HG-AFS测定。结果显示,4种硒形态标准曲线的线性关系良好(R2≥0.9995),方法检出限为0.5~5.0μg/kg,平均回收率为82.5%~101.2%,日内相对标准偏差≤8.6%,日间相对标准偏差≤14.5%。本方法前处理简单、灵敏度高、设备便宜、运行费用低廉,适用于富硒饲料产品中硒的形态分析。     

氢化物发生-原子吸收法测定饮用水中的砷、硒

建立了测定饮用水中砷、硒的氢化物发生－原子吸收法，探讨了盐酸、硼氢化钠溶液的浓度以及样品还原处理对测定结果的影响，测定结果的相对标准偏差（n=7)小于3％，回收率为89．1％－110．7％，测定砷的线性范围为0－40ug/L(r=0.9990)，测定硒的线性范围为0－50ug/L(r=0.9990)，砷、硒的检出限分别为1．06，0．78ug/L。     

高效液相色谱-原子荧光光谱联用技术测定富硒鸡蛋中的硒形态

为监测市场上富硒鸡蛋中蛋清及蛋黄中硒形态的种类及分布规律,优化建立了一种高效液相色谱-氢化物发生-原子荧光光谱联用技术测定富硒鸡蛋蛋清及蛋黄粉中硒形态的方法。随机选取富硒鸡蛋样品,进行蛋清蛋黄分离、冷冻干燥及蛋黄脱脂处理,处理后样品经Tris-HCl缓冲液（5 mmol/L, pH=7.5）55 oC恒温振荡、酶解提取,高速离心机（10000 r/min）离心10 min,上清液过0.22 μm有机滤膜后采用高效液相色谱-氢化物发生-原子荧光光谱联用技术进行测定,外标法定量。结果表明,该方法能在11 分钟内实现5种硒形态的基线分离,且各种硒形态的线性相关系数(r)均大于0.9994,其检出限在0.5-3.0 μg/L之间,回收率在81.6%~110.4%之间,可以满足检测需求,按照该实验方法测定市场上富硒鸡蛋中的硒形态,方法灵敏度高、准确性好,且测得的富硒鸡蛋蛋清样品中硒形态主要成分为硒代蛋氨酸,而蛋黄样品主要成分为硒代半胱氨酸,还有少量的硒代蛋氨酸,同时,一些鸡蛋还含有极少量的亚硒酸根,但蛋清及蛋黄中硒代氨基酸的含量总和占总硒含量的83.3-98.4%,适用于富硒鸡蛋中的硒形态提取。由此可见,市场上富硒鸡蛋中的硒主要以硒代氨基酸的形式存在,比较适合日常补硒,且该方法可以对市场上富硒食品起到一定监测作用。     

气相色谱-质谱联用测定紫花苜蓿中的硒蛋氨酸

建立了气相色谱质谱联用(GC—MS)测定紫花苜蓿中硒蛋氨酸含量的方法。将紫花苜蓿中提取的叶蛋白样品在6 mol/L HCl溶液中,超声处理20 min。离心分离后,以丁醇及三氟乙酸酐为衍生化试剂对硒蛋氨酸进行衍生化,采用选择离子监测模式对衍生物进行GC—MS测定。硒蛋氨酸的回收率为97.6%~105.2%,相对标准偏差为1.7%~3.6%,检出限为0.3 mg/L。该法样品前处理简单,测定快速,结果准确,灵敏度高,可用于植物样品中硒蛋氨酸含量的测定。     

气相色谱串联四极杆质谱法对富硒包菜汁中硒甲基硒半胱氨酸与硒蛋氨酸的测定

建立了一种快速分析富硒包菜汁中硒甲基硒半胱氨酸和硒蛋氨酸含量的方法。以氯甲酸乙酯作衍生化试剂,利用串联质谱技术在多离子监测模式下对衍生物进行GC-MS/MS测定。方法的线性范围为0.01～25 mg/L,线性相关系数r≥0.9988;方法检出限分别为硒甲基硒半胱氨酸（met-Se-cys）4μg/L、硒蛋氨酸（Se-met）2μg/L;met-Se-cys的方法回收率为82%～97%,RSD小于6.3%,Se-met的方法回收率为100%～109%,RSD小于7.5%。结果表明该方法简单、快速、准确,并能有效排除基质的干扰,适合于食品中硒甲基硒半胱氨酸和硒蛋氨酸的定性定量分析。     

超声辅助酶法提取-原子荧光光谱法测定富硒黑木耳中硒形态

建立了富硒黑木耳中硒代胱氨酸、硒代半胱氨酸、亚硒酸、硒蛋氨酸、硒酸5种硒形态的液相色谱-原子荧光光谱分析方法。通过链酶蛋白酶E酶解,结合超声提取后,选取Hamilton PRP-X100离子交换色谱柱(250 mm×4.1 mm,10μm),40 mmol/L的磷酸氢二铵为流动相,在16 min内,5种硒形态完全达到基线分离。5种硒形态在线性范围内相关系数R为0.9990~0.9999;加标回收率为76.1%~108%;检出限分别为硒代胱氨酸0.35μg/L、甲基-硒代半胱氨酸0.46μg/L、亚硒酸0.26μg/L、硒代蛋氨酸0.64μg/L、硒酸3.06μg/L;方法应用于富硒黑木耳中硒形态的分析,精密度高、重现性好、方法稳定、准确可靠,是测定富硒黑木耳中硒形态含量的有效方法。     

柱前衍生化-HPLC法测定恩施3种富硒蔬菜中硒氨基酸

采用HPLC与ICP-MS间隙联用的方法,以柱前衍生化-HPLC法进行定性定量分析,使用ICP-MS鉴定,建立一种富硒蔬菜中硒氨基酸的分离检测方法。结果表明:所测定的硒代氨基酸在其线性范围内呈现良好的线性关系(R2>0.999)。该方法中硒代蛋氨酸和硒代胱氨酸的检出限分别为0.204 mg/L和0.680 mg/L,加标回收率分别为97.4%和94.0%,RSD分别为2.1%和0.69%。检测恩施富硒蔬菜样品,白菜、萝卜叶和苋菜含有硒代蛋氨酸和硒代胱氨酸。此方法可用于富硒蔬菜中硒代氨基酸的含量检测。     

高效液相色谱-电感耦合等离子体质谱（HPLC-ICP-MS）联用测定富硒小麦中硒代氨基酸

为科学补硒和促进富硒小麦的种植推广,建立了高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)检测富硒小麦中硒代氨基酸的方法。用蛋白酶XIV辅助微波振荡提取富硒小麦中硒代氨基酸,采用C18 分离柱分离,以30.0mmol/L磷酸氢二铵+1.0%甲醇+2.0mmol/L四丁基溴化铵溶液(pH=6.5)为流动相,能在10min内实现5种硒代氨基酸的分离。在高能氦气模式（HEHe）下,用78Se的色谱峰积分面积作为定量依据,5种硒代氨基酸在1.0～200.0μg/L范围内线性相关性良好,检出限在 0.11~0.29μg/L之间。以富硒小麦为基体进行加标回收试验,除硒代胱氨酸（SeCys2）可能不稳定,易分解造成回收率偏低外,其他4种硒代氨基酸的加标回收率在92.34～102.46%之间,相对标准偏差为 1.6 %~4.2 %（n=7）。用该方法测定了农业科技工作者种植推广的富硒小麦,结果发现小麦中的硒赋存形态多为硒代蛋氨酸（SeMet）,此外,小麦中还含有少量硒代胱氨酸（SeCys2）、硒代半胱氨酸（SeCys）、甲基硒代半胱氨酸（MeSeCys）和硒代乙硫氨酸（SeEt)。该方法具有良好的精密度和准确度,适用于富硒小麦中硒代氨基酸的形态分析。     

氢化物发生-原子荧光光谱法测定富硒酵母中的有机硒和无机硒

建立了氢化物发生-原子荧光光谱法测定富硒酵母中硒的分析方法。研究了仪器的工作条件、试剂对硒测定的影响;探讨了消化试剂对样品消化的影响和共存离子的干扰及消除。在优化的工作条件下,硒的检出限为0.078μg/L,相对标准偏差为0.45%,线性范围为0~100μg/L。应用该方法检测了不同富硒酵母中的总硒含量为1.40~3.20 mg/g;其中,有机硒含量为1.30~2.97 mg/g,加标回收率为95.4%~104.3%。     

Optimization of a chemical modifier in the determination of selenium by graphite furnace atomic absorption spectrometry and its application to wheat and wheat flour analysis.

A method for the determination of total selenium in wheat and wheat flour using graphite furnace atomic absorption spectrometry (GFAAS) with palladium/ascorbic acid as a chemical modifier was studied. The effects of nickel nitrate, palladium/ascorbic acid, and palladium/magnesium nitrate as chemical modifiers on the sensitivity in the determination of selenite, selenate and selenomethionine by GFAAS were compared. The palladium/ascorbic acid modifier was used for the determination of total selenium in wheat and wheat flour, because the oxidation states of the selenium ion are not important in the determination. The detection limit was estimated to be 1 microg L(-1) (calculated as 3sigma of the blank); the calibration curve was linear for the concentration range 5 - 50 microg L(-1) and the recovery range was 96.66 - 101.80%. The optimal ashing and atomizing temperatures were 1300 degrees C and 2250 degrees C, respectively. The proposed method was successfully applied to the determination of total selenium in wheat and wheat flour.     

Selenium speciation by coupling vesicle mediated HPLC with off-line ETAAS and on-line focused microwave digestion HG-AAS detection

A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C(18) reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 microg/L of Se. The detection limit using HPLC-"on line" focused microwave digestion-HG-AAS has been found to be 1 microg/L of Se, with a precision (repeatability) better than +/- 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes.     

石墨炉原子吸收光谱法测定生活饮用水中砷的方法优化

建立了石墨炉原子吸收光谱(GFAAS)法测定生活饮用水中砷的方法。升压放电空心阴极灯的使用,降低了基线噪声水平和检出限。对温度程序、化学基体改进剂和热稳定剂进行了优化并用于GFAAS测定砷,无需进行初步处理。研究结果显示,线性方程为y=0.005 62x+0.000 04,相关系数R为0.998 3,样品体积为16μL时的检出限为0.26μg/L。加标回收率为98.1%～99.2%,相对标准偏差5%。取实际饮用水样验证了其适用性。     

石墨炉原子吸收光谱法测定生活饮用水中砷的方法优化

建立了石墨炉原子吸收光谱(GFAAS)法测定生活饮用水中砷的方法。升压放电空心阴极灯的使用,降低了基线噪声水平和检出限。对温度程序、化学基体改进剂和热稳定剂进行了优化并用于GFAAS测定砷,无需进行初步处理。研究结果显示,线性方程为y=0.005 62x+0.000 04,相关系数R为0.998 3,样品体积为16μL时的检出限为0.26μg/L。加标回收率为98.1%～99.2%,相对标准偏差<5%。取实际饮用水样验证了其适用性。     

Classical analysis including trace-matrix separation versus solid state mass spectrometry: A comparative study for the analysis of high purity Mo,W and Cr

The applicability of GDMS, SIMS, SSMS, NAA and TMS with AAS, ICP-OES and ICP-MS end determination for routine bulk ultratrace analysis of high purity refractory metals was investigated. Due to the heterogeneous distribution of trace elements in the sub-ppm range, sample consumption and analysis time have a tremendous influence on quantification with procedures of low sample consumption. As an example, GDMS, which is commonly used for ultrapure material certification by most of the manufacturers in Europe and the USA, exhibits discrepancies by more than one order of magnitude for repetitive analyses of a series of trace components in the same sample. Furthermore, results of different laboratories using the same instrument are frequently not comparable. Due to easy standardization and large sample consumption TMS procedures combined with FAAS, GFAAS, ICP-AES and ICP-MS as methods of end determination exhibit better precision and accuracy than GDMS and SIMS. Detection limits are comparably low or even better in case of ICP-MS end determination. TMS procedures are less expensive and less time consuming than highly sophisticated analytical techniques like GDMS, SIMS or NAA. Additionally, they can be easily applied by experienced personnel in a well equipped industrial analytical laboratory.List of Acronyms Used AAS Atomic Absorption Spectrometry - FAAS Flame Atomic Absorption Spectrometry - GDMB Gesellschaft Deutscher Metallhütten- und Bergleute - GDMS Glow Discharge Mass Spectrometry - GFAAS Graphite Furnace Atomic Absorption Spectrometry - ICP-AES Inductively Coupled Plasma Atomic Emission Spectrometry - ICP-MS Inductively Coupled Plasma Mass Spectrometry - IDMS Isotope Dilution Mass Spectrometry - NAA Neutron Activation Analysis - SIMS Secondary Ion Mass Spectrometry - SSMS Spark Source Mass Spectrometry - TMS Trace-Matrix Separation - VLSI Very Large Scale Integration - XRFS X-Ray fluorescence Spectroscopy Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Selenium speciation by coupling vesicle mediated HPLC with off-line ETAAS and on-line focused microwave digestion HG-AAS detection

A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C₁₈ reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 g/L of Se. The detection limit using HPLC-on line focused microwave digestion-HG-AAS has been found to be 1 g/L of Se, with a precision (repeatability) better than ± 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes.     

原子荧光光谱法测定铜合金中铋元素含量方法改进

基于原子荧光光谱法测定铋元素时检出限低、测定结果稳定且准确等优点,研究原子荧光光谱法测定铜合金中铋元素含量的方法。在标准系列中加入相近浓度的铜元素标准溶液,原子荧光光谱法测定铜合金中铋元素含量。称取0.1 g样品,加入10 mL硝酸溶解,10%硫脲-5%抗坏血酸溶液7.5 mL预处理样品。在20μg/L的铋标准溶液中加入6 mL浓度为1000μg/mL的铜元素标准溶液。结果表明:在0~20μg/L范围内,该方法线性关系良好,线性方程为I=138.1670c+43.8572,相关系数为0.9996,所测定的样品中铋元素含量的相对误差在-4.3%~7.7%之间,精密度在0.4%~4.7%之间。原子荧光光谱法可作为铜合金中铋元素含量测定的方法。     

催化裂解-冷原子吸收法测定固体生物质中汞含量

为开展汞的污染监测和环境治理,本文以我国能源用散状固体生物质为研究对象,建立了催化裂解-冷原子吸收测定汞含量方法。通过试验确定了样品称样量、分解温度和分解时间,方法线性关系良好,线性系数>0.999,检出限0.045ug/kg,方法重复性符合要求,标准样品汞含量在标准值不确定度内,经过F检验和t检验,催化裂解-冷原子吸收法与电感耦合等离子体质谱法不存在显著性差异。试验结果表明催化裂解-冷原子吸收法测定汞含量具备良好的精密度和准确度,可应用于固体生物质中汞的检测     

Flow injection determination of Pb and Cd traces with graphite furnace atomic absorption spectrometry

The preconcentration and recovery of lead and cadmium traces at ng l(-1) level were evaluated in standard solutions and natural aqueous samples using a FIAS (Flow Injection Atomic Spectrometry) apparatus. The method is based on retention of the complex formed between Pb or Cd and 1,2-dihydroxy-3,5-benzendisulphonic acid (Tiron) on a macroporous anion-exchange resin. The recovery of the analytes was obtained by elution with 0.1 M HCl and their determination was performed by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). The detection limits were 9 and 7 ng l(-1) for Pb and Cd respectively. The effects of sample solution pH and composition and of interfering agents as well as reagent purity are discussed. The technique was applied to the analysis of natural waters.     

Determination of cadmium in coal fly ash, soil and sediment samples by GFAAS with evaluation of different matrix modifiers

The determination of cadmium in different samples such as coal fly ashes, soils and sediments by Graphite Furnace Atomic Absorption Spectrometry (GFAAS) was studied. The best analytical conditions and instrumental parameters were deduced. Different types of matrix modifiers were tested and an optimization of several conditions (pyrolysis and atomization temperatures, heating rate, use of L’vov platform, etc.) was carried out. A mixture of 2% NH₄H₂PO₄ + 0.4% Mg(NO₃)₂ in 0.5 mol L^–1 HNO₃ as matrix modifier provided the highest sensitivity and an efficient behaviour for the three types of samples. A detection limit of 26 ng g^–1 was achieved and other figures of merit are shown. Analytical results obtained by direct calibration using standard samples prepared in the laboratory and by standard addition method were comparable.