优化高效液相色谱-电感耦合等离子体质谱联用测定汞化合物形态条件的研究

通过建立并优化了高效液相色谱一电感耦合等离子体质谱联用技术（HPLC—ICP—MS）测定化合物形态的条件,该方法采用8mmol／L醋酸铵／0.01％L一半胱氨酸,pH=7．0缓冲溶液及甲醇体系组成的流动相按一定比例进行梯度洗脱,以二价汞、甲基汞、乙基汞、苯基汞为标准物,其检出限分别为16μg／mL,18μg／mL,24μg／mL和40ug／mL,并连续测定10次,重复性能好。     

微波消解-氢化物原子荧光光谱法同时测定金华火腿中砷和汞研究

为提高金华火腿中砷和汞的检测水平，建立了微波消解-氢化物原子荧光光度法同时测定火腿中砷和汞的方法。确定了微波消解样品的条件，优化了仪器的最佳工作参数。在最佳的试验条件下，0～10．0μg．L^-1砷和0～2．0μg．L^-1汞标准溶液，标准曲线具有良好的线性，砷、汞的检出限分别为：砷0．073μg．L^-，汞0．0055μg．L^-1；回收率砷在90．0％。110．0％之间、汞在95．0％～1．10．0％之间；相对标准偏差砷为1．26％，汞为3．08％。     

应用电感耦合等离子体发射光谱法测定岩矿中的金

用电感耦合等离子体发射光谱法测定锑金精矿中金量解决了样品在烧样除炭过程中因锑的熔解而结块、在溶解实验过程中因大量锑的水解包裹使金的溶解变得较为困难的问题。采用电感耦合等离子体发射光谱法测定金，克服了原子吸收法测定的线性范围小，而稀释倍率大，造成分析误差偏大的不足。方法的检出限为0．1μg／g。金加标回收率96％～104％，精密度（RSD，n=6）〈3．0％。适宜于锑金精矿中金的测定。     

HPLC-ICP-MS法测定水样中的甲基汞、乙基汞和无机汞

建立了高效液相色谱(HPLC)和电感耦合等离子体质谱(ICP-MS)联用测定环境水样中的甲基汞、乙基汞和无机汞的方法。实验使用的高效液相色谱流动相为含有0.06mol/L乙酸氨,20μg/LBi,0.1%(V/V)2-巯基乙醇的5%(V/V)甲醇-水溶液,色谱柱为C18反相柱(5μm,2.1mm×50mm),经前处理的水样在液相色谱中分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞和无机汞的浓度。甲基汞、乙基汞和无机汞检出限分别为0.05μg/L、0.10μg/L和0.10μg/L。     

高效液相色谱法定量分析化妆品中对羟基苯甲酸酯

建立了用高效液相色谱测定化妆品中对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯和对羟基苯甲酸丁酯4种防腐剂的方法。以甲醇与水作为流动相,DAD检测器的检测波长254nm,流速为1．0mL／min,柱温30℃。方法检出限分别为对羟基苯甲酸甲酯0．18μg、对羟基苯甲酸乙酯0．20μg、对羟基苯甲酸丙酯0．20μg、对羟基苯甲酸丁酯0．21μg。4种防腐剂在0～100mg／L呈现良好的线性关系。样品的加标回收率为101.3％～102.5％,相对标准偏差为0．13％～O．21％     

优化注射用头孢西丁钠含量测定方法研究

目的采用离子对色谱法测定注射用头孢西丁钠的含量,为完善注射用头孢西丁钠质量标准提供依据。方法采用离子对色谱法,色谱柱为Agilent ZORBAX 80A Extend C18柱（150mm×4．6mm,5μm）;流动相为5mmol·L^-1氢氧化四丁基铵溶液乙腈（体积比750：250）;检测波长254nm,流速为1mL.min^-1。结果头孢西丁的质量在0．3101～3．1010μg范围内与峰面积线性关系良好,r=0．99998;平均回收率为100．2％,RSD为1．05％。结论本文方法简单、准确、重复性好,为完善注射用头孢西丁钠含量测定方法提供了依据。     

锌酸盐镀锌液中杂质元素的质谱分析

利用带八极杆碰撞／反应池（ORS）和屏蔽炬技术的电感耦合等离子体质谱（ICP-MS）可同时直接测定锌酸盐镀锌液中Mg，V，Cr，Mn，Co，Ni，Cu，Cd，Sb，Pb杂质元素。通过向碰撞池中引入氢气和氦气消除多元素分子、离子的干扰，以50μg／Lsc，Ge，In，Tb为内标元素校正基体干扰和漂移，确定了仪器的最佳工作参数。结果表明：各元素在0～500．0μg／L内均有良好的线性关系，相关系数均在0．9995以上；10种杂质元素的检出限在0．001～0．034μg／L，回收率为95．2％～107．4％，相对标准偏差（R肋）小于2．90％。     

二羟二丁基醚及其手性杂质的毛细管GC法分离

采用毛细管气相色谱法(CGC)分别对二羟二丁基醚(DHDB)及手性杂质的分离条件进行考察,建立二羟二丁基醚(DHDB)含量的测定方法。PEG-20M(30 m×0.53 mm×1.0μm)毛细管柱为色谱柱,FID为检测器,正辛醇作为内标,DHDB手性杂质程序升温条件为初温120℃,以0.5℃/min升温至180℃,保持40 min;DHDB含量测定程序升温条件为140℃保持1 min,以20℃/min升至200℃。DHDB及其手性异构体得到完全分离;DHDB在66.70~800.1μg/m L的范围具有良好的线性关系(y=0.007 0x+0.055 4;r2=0.999 6);平均回收率为99.54%,重复性RSD为0.68%,中间精密度RSD为0.95%,样品的平均含量为77.92%(RSD=0.25%)。该方法快速、简便,适于DHDB手性杂质分析和含量测定。     

牡蛎粉中砷、铅、汞、镉有害金属含量的测定研究

采用微波消解法处理的样品,用原子荧光法来分析测定样品中的痕量Hg,用等离子原子发射光谱法来分析测定样品中As、Pb、Cd的含量。研究了测定不同金属元素的最佳仪器的工作条件,并对方法的准确度和精密度进行考察。结果表明,牡蛎粉中的砷、铅、镉、汞含量分别为9．65μg／g,1．00μg/g,11．1μg/g,0．0511μg/g,加标回收率为89．0％～106．9％,相对标准差为0．50％～4．76％。测定方法简单易行,方便快捷。     

微波消解-ICP-AES／ICP—MS测定大米中微量元素

采用微波消解技术,电感耦合等离子体光谱（ICP-AES）和电感耦合等离子体质谱（ICP—MS）测定了分别产自辽宁、四川、湖南三地的大米中21种元素B、Ba、Ca、Cd、Cu、Fe、K、Mg、Mn、Na、P、S、Sr、Zn、Co、Ni、Cr、Mo、Pb、Li、Cs。所有元素标准曲线回归方程线形系数均大于0．999,各元素相对标准偏差（RSD）均小于5．31％（测定次数n=4）,加标回收率为96．6％-110．6％,方法检出限：ICP-AES为0．0048-0．33μg·mL-1,ICP-MS为0．022-0．192ng·mL-1。用国家一级标准物质大米（GBW10010）验证了方法的准确性,测定值与推荐值相符,实验表明,P、S、K、Mg、Ca、Na、Zn、Mn、Fe、Cu在大米中含量较高。此方法简便、快速,适用于大米等粮食作物中微量元素的测定。     

顶空气相色谱/质谱法分析大豆油中正己醛含量

建立大豆油中正己醛含量的顶空气质分析方法。将大豆油试样放入密封的气化瓶中,在55℃温度下,使正己醛气化达到平衡时,取液上气体注入GC/MS,经非极性毛细管柱HP-5ms分离,质谱选择离子监测对正己醛进行定量测定。该方法在0.05~1.00μg/mL范围内线性关系良好,相关系数0.9997;最小检测限为3.15ng/mL,方法回收率在90.0~107%之间,相对标准偏差3.4%。该方法前处理简单、快速,定量准确,灵敏度高,可用于实验室检测大豆油中正己醛含量。     

Investigation of antimony,cobalt, and acetaldehyde migration into the drinking water in Turkey

Polyethylene terephthalate (PET) is a widely used material for the packaging of drinking water. The development of this research arises from the demand of a popular Turkish drinking water company, which has reported odour problems in their PET bottled products. Acetaldehyde, cobalt, and antimony contents were determined in bottled water of different volumes (0.5, 1.5, and 5 L), PET bottles, plastic blue closures, and preform material by gas chromatography mass spectrometry (GC‐MS) and inductively coupled plasma mass spectrometry (ICP‐MS). Antimony, cobalt, and acetaldehyde migration into the drinking water (PET bottled) was tracked for every 2 months through a year. Migration of these compounds rose with increased storage time at 20°C. The highest amounts of migrated compounds were observed in 0.5 L (smallest) of PET bottles. All migration results were found to be under the migration limit at the end of storage period. In addition to these findings, nonintentionally added substances (NIASs) analyses were performed by headspace (HS)/GC‐MS. Odour‐active compounds were identified using the library database. Off‐odours in the drinking water were due to the migration of various compounds such as acetaldehyde and other NIASs from PET bottle into the drinking water. In addition, acetaldehyde amounts were ranged from 0 to 140 μg/L in all drinking waters, and some acetaldehyde values were above the taste threshold of 15 μg/L.     

Two trace analytical methods for determination of hydroxylated PCBs and other halogenated phenolic compounds in eggs from Norwegian birds of prey

Two new trace analytical methods are presented for identification and quantification of phenolic compounds in complex biological matrixes such as bird of prey eggs. One method is based on derivatization with methyl chloroformate prior to GC/high-resolution MS (HRMS) analysis in electron impact ionization mode. Alternatively, the underivatized phenolic analytes were separated and detected by HPLC coupled to time-of-flight MS (TOF-MS) in the negative ion electrospray ionization mode. For both methods, the egg samples were homogenized and dried with acidified sodium sulfate, cold column-extracted, and cleaned up by gel permeation chromatography and subsequently a Florisil column. Recovery rates for pentachlorophenol (PCP), tetrabromobisphenol A (TBBPA), and selected hydroxylated PCBs (HO-PCBs) from spiked hen's eggs (spiking level 1 ng/g of wet weight (ww)) were in the range of 56-98% for the HPLC/MS method and 57-108% for GC/MS including derivatization. Typical detection limits of the HPLC/TOF-MS method were 5 pg/g ww (1-2 pg injected) for HO-PCBs and PCP and 20 pg/g ww (3 pg injected) for TBBPA. The GC/HRMS method achieved detection limits of approximately 1 pg/g ww in predatory bird eggs for all analytes (0.2 pg injected for derivatized TBBPA and 0.05 pg injected for derivatized HO-PCBs and PCP). Eight eggs from four different Norwegian predatory bird species were analyzed. The concentrations determined with the two different quantification methods corresponded well with each other. PCP and TBBPA were found in all samples at concentrations up to 1350 and 13 pg/g ww, respectively (GC/HRMS values). A total of 55 penta- to nonachloro-HO-PCB congeners were detected in the eight eggs, 10 of those could be structurally identified. The maximum HO-PCB congener concentration was found for 4-HO-CB 187 in a peregrine falcon egg with estimated 388 pg/g ww. Another peregrine falcon egg was highest contaminated with sum HO-PCBs (estimated 2.1 ng/g ww). This level was 1.2 per thousand of the sum PCBs value for the same egg. Furthermore, indications were found that the HO-PCB congener distribution pattern could be species specific for predatory birds.     

水产品中四环素类抗生素残留量的高效液相色谱测定方法

本文建立了高效液相色谱(HPLC)检测水产品中3种四环素类抗生素残留量的方法。采用4%高氯酸溶液提取样品中的残留抗生素,经浓缩处理,以乙氰和0.01mol·L-1NaH2PO4(18∶82,v/v)为流动相,流速1mL·min-1,3种抗生素组分峰能与杂质峰完全分开,检测波长为355mm。在50~1000μg·mL-1范围内,峰面积与抗生素浓度呈良好的线性关系(r2>0.99),以测量的3倍标准偏差计算方法的检出限分别为0.045μg·g-1(土霉素)、0.041μg·g-1(四环素)和0.080μg·g-1(金霉素)。平均加标加收率分别为96.5%(土霉素)、87%(四环素)和73.2(金霉素)。精密度(RSD)小于5%。实验检测了几种常见水产品样品的四环素类抗生素残留量,发现在本检出水平下被检测的几种鱼和虾样品均未能检出。     

固相萃取-气相色谱-质谱联用法检测进出口蔬菜产品中百菌清残留

建立了固相萃取-气相色谱-质谱法检测蔬菜中百菌清残留的分析方法。样品用乙腈-水-磷酸混合液提取,经液液分配、Florisil/Na2SO4柱净化后过滤膜上机。采用选择离子扫描方式,外标法定量。通过优化前处理和上机条件,在最优条件下进行测试,实验结果百菌清的定量检出限为0.001mg/kg,在加标水平0.005～0.1mg/kg范围内,回收率为78.65%～90.67%,相对标准偏差为3.5%～5.8%。该方法简便、快速、净化效果理想,能满足残留分析的要求,可用于进出口蔬菜中百菌清残留的检测。     

分散固相萃取-高效液相色谱-串联质谱快速测定鸡肉中盐霉素残留

建立了分散固相萃取-超高效色谱-电喷雾串联质谱快速测定鸡肉中盐霉素残留的方法。样品经乙腈提取后,采用QuEChERS方法净化,氮吹转换溶剂后,采用Acquity BEH C18柱进行分离,0.3%甲酸水溶液-甲醇体系为流动相,梯度洗脱,电喷雾质谱正离子多反应监测模式测定,外标法定量。结果表明,在优化的条件下对样品进行分析检测,盐霉素的检出限为0.03μg·kg-1,添加水平为5.5~31.4μg·kg-1时,加标回收率为78.2-97.8%,RSD<2.0%(n=6),在0.630~25.2μg·L-1质量浓度范围内呈良好线性,相关系数R2>0.9989。该方法前处理步骤简单,具有较高灵敏度,可用于大批量样品的快速筛查检测。     

水浮莲叶挥发性化学成分的GC/MS法分析

采用气相色谱-质谱联用方法(GC/MS)分析了水浮莲叶中挥发性化学成分。以水蒸气蒸馏法从水浮莲叶中提取挥发油,以毛细管柱为分离柱,在最佳分析条件下共分离出30个化合物,用归一化法测定其相对含量,并用气相色谱-质谱法对分离出的化学成分进行鉴定,共鉴定了26个成分,占挥发油总成分的95·20%。该法对挥发油化学成分的分离效果满意。     

P&T-GC/MS法分析地表水中的挥发性有机化合物

建立了P&T-GC/MS联用分析地表水中的挥发性有机化合物的方法,并对实际水样进行了分析。各目标物的线性回归R值均大于0.999,MDL为0.02-0.11μg/L,RSD为1.3%-6.0%,回收率为90.5%-106%。     

Simultaneous derivatization and quantification of the nitric oxide metabolites nitrite and nitrate in biological fluids by gas chromatography/mass spectrometry

Simultaneous quantification of nitrite and nitrate, the major oxidative metabolites of L-arginine-derived nitric oxide (NO), in biological fluids by GC or GC/MS methods is currently impossible. The separate analysis of these anions is associated with severe methodological problems. Therefore, a GC/MS method was developed which allows, for the first time, simultaneous quantification of nitrite and nitrate in various biological fluids. The method involves a single derivatization procedure, by which endogenous nitrite and nitrate and their externally added 15N-labeled analogues are simultaneously converted in aqueous acetone by pentafluorobenzyl bromide to the nitro and nitric acid ester pentafluorobenzyl derivatives, respectively, and a single GC/MS analysis. Nitrite and nitrate concentrations measured in plasma and urine of humans by this method correlated excellently with those from quantification of nitrite and nitrate in these matrixes using a previously reported GC/MS method that, however, requires reduction of nitrate to nitrite. Also, the present method enables discrimination between S-nitro- and S-nitroso-glutathione, which have identical chromatographic and spectrophotometric properties. The method is very useful to routinely study metabolism and reactions of NO and its metabolites in vitro and in vivo. It is accurate, interference-free, sensitive-50 fmol of [15N]-nitrite and [15N]nitrate were detected at signal-to-noise ratios of 870:1 and 95:1, respectively-and should be a reference method for nitrite and nitrate measurements.     

气相色谱法快速测定油脂及加工食品中的BHA、BHT、TBHQ

本文研究了用毛细管气相色谱快速测定油脂及其加工食品中BHA、BHT、TBHQ含量的方法。样品用无水乙醇提取、过滤、浓缩后直接进样测定。结果三种组分加标回收率在94.6%~109.1%之间,相对偏差均小于5.2%,线性范围在10~500μg/ml之间,相关系数均大于0.999,最低检测浓度(以3N计)均小于0.5μg/ml。