凝胶渗透色谱-气相色谱串联质谱法测定动物脂肪中164种农药残留

建立了气相色谱-串联质谱法(GC-MS-MS)同时测定动物脂肪中164种农药的多残留分析方法。样品经乙腈均质提取2次,合并提取液并在45℃水浴中旋转浓缩至1 mL,加入5 mLV(环己烷)∶V(乙酸乙酯)=1∶1进行溶剂交换2次后,用V(环己烷)∶V(乙酸乙酯)=1∶1稀释至10 mL,用凝胶渗透色谱(GPC)净化,GC-MS-MS多反应监测模式(MRM)测定,内标法定量。本方法研究的164种农药的线性相关系数为0.9438~1.0000,其中有154种在0.9900以上,占总数的93.9%。方法检出限(S/N≥3)为0.1~360.0μg/kg,其中在10.0μg/kg以下的有121种,占研究农药总数的73.8%。用猪、鸡、牛、羊4种不同的脂肪在低、中、高3个添加水平评价了164种农药的方法效率,其中有150种的回收率在70%~120%之间,相对标准偏差(RSDs)在20%以内。本方法适用于不同动物脂肪中150种农药多残留的定量测定和14种农药的定性测定。     

凝胶渗透色谱-高效液相色谱-串联质谱法同时测定烟草中3种抑芽剂残留

建立了用凝胶渗透色谱净化-液相色谱-串联质谱分析烟草中3种抑芽剂残留的方法。卷烟中的待测抑芽剂组分用V(乙酸乙酯)∶V(环己烷)=1∶1超声提取后通过凝胶渗透色谱净化;凝胶色谱柱为Biobeads S-X3玻璃柱(50 g,400 mm×25 mm),流动相为V(乙酸乙酯)∶V(环己烷)=1∶1溶液,流速5 mL/min;收集第10~25 min流出的液体用液相色谱色谱-三重四极杆串联质谱仪测定。在0.5~100 ng/mL的质量浓度范围内,各种抑芽剂标准溶液的线性相关系数均大于0.99。在样品中添加3种抑芽剂(添加水平为5,20,100μg/kg)的混合标准溶液,平均回收率在86.2%~108.4%之间,3种抑芽剂的RSD在1.1%~7.5%之间;方法的检测限在0.01~0.06μg/kg之间。     

凝胶渗透色谱净化-液相色谱-同位素稀释串联质谱法测定肉及肉制品中的甲萘威残留

称取试样约5g(精确至0.01g),加入1.000 mg·L~(-1)甲萘威-D7同位素内标溶液50μL,加入适量水(肉样加水1.5mL,肉制品加水3mL),加40mL丙酮,均质1min,加氯化钠6g,充分摇匀,再加30mL石油醚,振摇30min,静置30min。取有机层上清液,经无水硫酸钠过滤,旋转蒸发浓缩至约1mL,加2mL乙酸乙酯-环己烷(1+1)混合液,再浓缩至约1mL,如此重复3次。用乙酸乙酯-环己烷(1+1)溶液定容至10.0mL,经0.22μm滤膜过滤,进行凝胶色谱(GPC)净化。GPC条件如下:Bio Beads S-X3凝胶色谱净化柱(400mm×30mm),乙酸乙酯-环己烷(1+1)混合液为流动相,馏分收集段10.0～15.0min,在线浓缩加热温度45℃,真空度2.0×10~4Pa。以乙腈为替换溶剂替换两次后将净化液定容至1.0mL,进行液相色谱-串联质谱分析。采用HSS T3色谱柱(100mm×2.1mm,1.7μm)进行分离,以0.1%(体积分数)甲酸溶液-乙腈(6+4)为流动相,质谱分析中采用电喷雾正离子源和多反应监测模式。甲萘威的质量浓度在0.010～0.500mg·L~(-1)内和其峰面积与内标峰面积之比呈线性关系,测定下限(10S/N)为0.005mg·kg~(-1)。加标回收率在81.0%～105%之间,测定值的相对标准偏差(n=6)在3.8%～16%之间。     

菌类食品中多种有机磷农药的气相色谱-离子阱二级质谱联用法测定

研究了气相色谱-二级质谱联用技术测定菌类食品中甲胺磷、速灭磷等44种有机磷农药残留的方法,依据待测物化学性质,对预处理方法和质谱分析条件进行了优化.样品加入水浸泡,氯化钠盐析,采用乙酸乙酯-环己烷(1 ∶ 1,体积比)匀浆提取2次,合并上层有机相,用无水硫酸钠柱脱水,40 ℃水浴旋转蒸发至近干,以乙酸乙酯-环己烷(1 ∶ 1)定容,凝胶渗透色谱和固相萃取方法(石墨化炭黑小柱)两步净化,氮气吹干后,乙酸乙酯定容至0.25 mL,采用HP-5MS柱,无分流进样,气相色谱-离子阱二级质谱方法进行定性和定量分析,外标法定量.44种农药在0.05 ～10.00 mg/L范围内呈线性关系,在0.05 ～0.5 mg/kg加标范围内的回收率为68% ～116%,相对标准偏差为5.4% ～13.4%,44种有机磷农药的检出限为0.01 ～0.1 mg/kg,满足菌类食品中有机磷农药残留限量的检测.     

凝胶渗透色谱-固相萃取净化测定茶叶中16种菊酯残留量

建立了以凝胶渗透色谱(GPC)和固相萃取(SPE)净化,气相色谱-质谱(GC-MS)负化学源(NCI)技术测定茶叶中七氟菊酯、 四氟菊酯、丙烯菊酯、联苯菊酯、胺菊酯、甲氰菊酯、氯氟氰菊酯、氟丙菊酯、苯醚氰菊酯、氟氯氰菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯、 氟胺氰菊酯、溴氰菊酯、氯菊酯等16种菊酯残留量的方法.样品经V(丙酮)∶V(乙酸乙酯)∶V(正己烷)＝1∶2∶1提取,经GPC去除大分子的色素和类脂杂质,弗罗里硅土 SPE柱进一步净化,以毒死蜱同位素D-10作内标,内标法定量.方法的回收率67.2%～108%之间.变异系数小于18%.16种菊酯方法定量限在0.0125～0.025 mg/kg之间.     

凝胶渗透色谱净化-气相色谱-质谱法测定柑橘及其制品中抑霉唑的残留量

提出了气相色谱-质谱法测定柑橘及其制品中抑霉唑保鲜剂残留量的方法。样品用乙酸乙酯-环己烷(1+1)混合溶剂提取,所得提取液须经凝胶色谱净化去除大分子干扰物质。采用气相色谱分离后,选择离子监测模式下质谱法进行测定。方法检出限(3S/N)为0.02mg.kg-1,测定下限(10S/N)为0.05mg.kg-1。在3个标准加入水平下进行了回收试验,所得回收率在79.0%～92.1%之间,相对标准偏差(n=6)小于10%。     

凝胶渗透色谱净化-气相色谱分离同时测定糙米中50种有机磷农药残留

研究了同时检测糙米中50种有机磷农药残留的方法。用乙酸乙酯提取,凝胶渗透色谱净化,环己烷二氯甲烷(50∶50,V/V)作为流动相,气相色谱氮磷检测器检测。方法检出限为0.001～0.089mg/kg;相对标准偏差为1.7%～18.9%;40多种农药平均回收率在70%～120%。     

在线凝胶渗透色谱-二维气相色谱/质谱法测定鲫鱼样品中的14种农药残留

建立了在线凝胶渗透色谱-二维气相色谱/质谱(GPC-MDGC/MS)测定鲫鱼样品中14种农药残留的方法。样品用环己烷/乙酸乙酯(1：1,v/v)提取两次,合并提取液。提取液冷冻、过膜后,经在线凝胶渗透色谱净化后直接进行MDGC/MS分析,通过中心切割的方式将农药组分选择性切割进入二维色谱柱进行进一步分离分析,采用内标法进行定量。实验结果表明：14种农药在0.01~0.9 mg/L范围内具有较好的线性关系,相关系数均大于0.99。14种农药在3个添加水平(0.01、0.05、0.1 mg/kg)的加标回收率为83.0%~112.9%,相对标准偏差为3.2%~12.0%。该方法前处理简单,实现了在线GPC和MDGC的有效结合,准确度好、精密度高,具有很好的推广性。     

凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中的36种农药残留

建立了用凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中36种农药残留的方法。蘑菇中的待测农药组分在30 ℃条件下用乙酸乙酯提取,高速匀浆后通过凝胶渗透色谱净化;选用填料为中性多孔的聚苯乙烯二乙烯基苯微球体的S-X3玻璃柱(22 g,19 cm×2 cm)作为凝胶渗透色谱净化柱,流动相为乙酸乙酯-环己烷(体积比为1∶1)溶液,流速5 mL/min;收集第7~15 min流出的液体用气相色谱-三重四极杆串联质谱仪测定。在0.01~1.0 mg/L的质量浓度范围内,各种农药标准溶液的线性相关系数均大于0.99。在样品中添加36种农药(添加水平为0.01,0.05,0.10 mg/kg)的混合标准溶液,平均回收率为72.6%~117.1%,相对标准偏差为2.0%~10.8%(n=5),最低检出限为 0.1~0.7 μg/kg,最低定量限为 0.2~2 μg/kg。     

凝胶渗透色谱净化-气相色谱-质谱法同时测定金银花中33种农药残留组分

建立了凝胶渗透色谱(GPC)净化、气相色谱-质谱(GC-MS)同时测定金银花中33种有机氯、有机磷和拟除虫菊酯农药残留的方法.样品中的待测农药组分经乙酸乙酯-环己烷混合溶剂(1∶ 1, V/V)提取、GPC净化去除色素等杂质,GC-MS采用全扫描/选择离子监测模式(Scan/SIM)采集数据后进行定性/定量分析.方法的相对标准偏差(RSD)≤16.70 %(6.9～84.6 ng/g,n=5);5种不同加标浓度下,待测农药的标准加入回收率在57.4%(甲胺磷)～109.9%(马拉硫磷)之间;各农药组分的定性检出限(3σ)为0.10～10.5 ng/g,定量检出限(10 σ)为0.33～20.0 ng/g.     

气相色谱-质谱法测定动物源性食品中残留的葚孢菌素

建立了气相色谱-质谱法检测动物源性食品中葚孢菌素残留量的方法.采用环己烷-二氯甲烷(体积比为9:1)振荡提取,中性氧化铝固相萃取柱净化,气相色谱-质谱法进行测定,选择离子监测模式检测.通过方法优化,确定方法检出限为0.01 mg/kg(S/N=10),在0.005～1 mg/kg范围内线性关系良好(R2=0.9999)...     

固相萃取-气相色谱-质谱法测定酱油中3-氯-1,2-丙二醇

建立了酱油中3-氯-1,2-丙二醇(3-MCPD)残留量的同相萃取-气相色谱-质谱(GC/MS)分析方法.利用SampliQ OPT固相萃取柱净化样品,考察了乙醇、丙酮、乙醚、乙醚-正已烷(9:1,V/V)4种洗脱液对3-MCPD回收效果的影响.洗脱液在室温下经氮气吹干后用双(三甲基硅烷基)三氟乙酰胺-三甲基氯硅烷(B...     

气相色谱-质谱法分析乳腺癌患者血清中的代谢物

建立了气相色谱-质谱法分析乳腺癌患者血清中代谢物的分析方法。分别收集乳腺癌患者、一般疾病者和健康对照组血清,样本用甲醇∶乙腈∶丙酮=1∶1∶1(V/V)提取,硅烷化试剂N,O-双甲氧基三氟乙酰胺+1%三甲基氯硅烷(BSTFA+1%TMCS)衍生后,采用气相色谱-质谱法分析其中的氨基酸、脂类和糖类的代谢谱,并用主成分分析(PCA)和随机森林(RF)算法对实验结果进行分析。结果表明,三组实验数据被成功分类,并发现磷酸、N-巴豆酰基甘氨酸、2,4-二羟基丁酸、棕榈酸、N-苯基甘氨酸和N-1-己酰甘氨酸等组分在乳腺癌组和健康对照组中的差异较为显著。     

气相-质谱法测定粮谷中恶草酮的残留量

 应用微量化学法和固相萃取技术 ,建立了粮谷中恶草酮残留量的气相 质谱 (GC MS)测定方法。用苯 正己烷 (体积比为 1∶1)萃取 ,中性氧化铝小柱净化。净化液用GC MS测定 ,采用外标法定量。恶草酮在大米中的回收率为 90 4%～ 115 .7% ,RSD为 2 %～ 6 % ,在玉米中的回收率为 81 3%～ 10 9 7% ,RSD为 4%～ 9% ,最低定量检出限为 0 0 0 5mg/kg。该法快速、灵敏、准确 ,各项技术指标均满足农药残留检测的要求。     

气相色谱-质谱法测定玩具中的4种阻燃剂

建立了玩具中三(2-氯乙基)磷酸酯、磷酸三邻甲苯酯、2,2′,4,4′,5-五溴联苯醚、2,2′,3,3′,4,4′,6,6′-八溴联苯醚等4种阻燃剂的气相色谱-质谱分析方法。玩具样品以V(正己烷):V(二氯甲烷)=1:1混合溶液为提取溶剂,超声提取30min,提取液以DB-5HT石英毛细管色谱柱(15m×0.25mm×0.10μm)分离后进行选择离子监测模式下的定性及定量分析。4种阻燃剂的定量限为0.1mg/kg,在低、中、高3个添加水平范围内,4种阻燃剂的平均回收率为93.5%～97.3%,相对标准偏差在2.4%～4.1%之间。     

A method for measuring specific activities of 14C-labelled compounds by gas chromatography-mass spectrometry-computer system

A method for measuring specific activities of 14C-labelled compounds by gas chromatography-mass spectrometry-computer system (GC-MS-CPU) was developed. This method was proved to provide practically precise and accurate specific activities of various 14C-labelled compounds with such merits as requirement of small amount of samples, being applicable to volatile compounds, and convenience. The C.V. percent obtained for tested compounds was within 3.9 and the reliable sensitivity should be over 37 MBq/mM (1 mCi/mM). This method was also useful for obtaining information on the labelling pattern and the synthetic procedures applied.     

Composition of essential oils in subterranean organs of three species of Valeriana L

Essential oils from the subterranean organs of three species of Valeriana L. from Iran (Valeriana sisymbriifolia Vahl, Valeriana alliariifolia Adams and Valeriana officinalis L.) belonging to Valerianaceae family have been obtained by hydrodistillation and analysed by gas chromatography-mass spectrometry in order to discern the differences and similarities between the volatile chemical compositions of these species. More than 100 components were identified in essential oils of the studied plants (Supplementary Table S1--online only). The principal common constituents of the three species of Valeriana were spathulenol, limonene, γ-terpinene, vulgarone B and p-cymene. The main essential oil ingredients were α-selinene (7.83%) in V. sisymbriifolia, limonene (3.53%) in V. alliariifolia and spathulenol (13.33%), α-campholenal (11.48%), vulgarone B (8.38%) and valerenal (8.32%) in V. officinalis plants. Ageratochromene (precocene II), a chromene substance with antibacterial, antifungal, insecticidal and antijuvenile hormonal activities, was found at high levels (35.59% and 36.58%) in the essential oils of V. sisymbriifolia plants.     

Environmental Monitoring at Terra Nova Bay Station From 1989 to 1991

Abstract

Monitoring was carried on in the Italian Antarctic Station Terra Nova Bay. Airborne particulate matter was sampled at different Base locations during the Italian expeditions; samples were then analyzed at the ENEA laboratories for chemical characterization. The analyses were carried out by INAA (Instrumental Neutron Activation Analysis) for the determination of major, minor and trace elements (Na, K, Cs, Sc, V, Mn, Fe, Co, Zn, La) and by gas chromatography-mass spectrometry for the determination of PAH compounds. Data from the 1989–1990 and 1990–1991 campaigns are reported and discussed. Moreover, isokinetic samplings were carried out at the Base incinerator; the filters were analyzed by INAA; the V, Cr, Cu, Zn, Cd, Sb concentrations are reported.     

固相微萃取/气相色谱-质谱法对乌梅浸膏挥发性成分的分析研究

对乌梅浸膏挥发性物质的固相微萃取条件进行了研究。运用正交实验设计,比较了不同萃取头、平衡温度及采样时间对分析结果的影响,通过气相色谱-质谱(GC-MS)的分析监控,结合信息量最大原则,确定了固相微萃取的最佳条件:萃取纤维头为聚二甲基硅氧烷,平衡温度为70℃,采样时间45 min。通过GC-MS进行定性定量分析,共鉴定出38种成分,主要挥发性成分依次为糠醛(24.88%)、2-甲基-3-羟基苯甲醛(13.57%)和5-甲基糠醛(10.16%)。     

Detection of methandienone (methandrostenolone) and metabolites in horse urine by gas chromatography-mass spectrometry.

The metabolic transformation of methandienone (I) in the horse was investigated. After administration of a commercial drug preparation to a female horse (0.5 mg/kg), urine samples were collected up to 96 h and processed without enzymic hydrolysis. Extraction was performed by a series of solid-liquid and liquid-liquid extractions, thus avoiding laborious purification techniques. For analysis by gas chromatography-mass spectrometry, the extracts were trimethylsilylated. Besides the parent compound I and its C-17 epimer II, three monohydroxylated metabolites were identified: 6 beta-hydroxymethandienone (III), its C-17 epimer (IV) and 16 beta-hydroxymethandienone (V). In addition, three isomers of 6 beta,16-dihydroxymethandienone (VIa-c) were discovered. Apparently, reduction of the delta 4 double bond of 16 beta-hydroxymethandienone (V) in the horse yields 16 beta,17 beta-dihydroxy-17 alpha-methyl-5 beta-androst-1-en-3-one (VII). Reduction of the isomers VIa-c results in the corresponding 6 beta,16,17-trihydroxy-17-methyl-5 beta-androst-1-en-3-ones (VIIIa-c). The data presented here suggest that screening for the isomers of VI and VIII, applying the selected-ion monitoring technique, will be the most successful way of proving methandienone administration to a horse.