气相色谱/双柱双检测器测定塑料制品中10种有机锡

将不同材质塑料样品用四氢呋喃溶解,再用甲醇沉淀杂质大分子后高速离心过滤,各有机锡在乙酸-乙酸钠缓冲溶液中与四乙基硼酸钠反应生成有机锡的乙基化衍生物,经正己烷萃取后进行气相色谱定性、定量分析,并对衍生化条件(如衍生时间、酸度、衍生试剂)进行优化。用双柱-质谱和火焰光度双检测器/气相色谱法测定了PVC,PC,PS,AS及ABS不同塑料样品中的二甲基锡、三甲基锡、二乙基锡、一丁基锡、二丁基锡、四丁基锡、二辛基锡、三环己基锡、二苯基锡和三苯基锡共10种有机锡化合物。采用外标法定量,在0.01~10 mg·L-1浓度范围内,各有机锡化合物均呈良好线性,其相关系数(r)均大于0.999。测得PVC,PS,ABS不同塑料样品中10种有机锡的回收率为75.1%~110.1%,相对标准偏差(n=6)小于10%,检出限为0.005~0.037 mg/kg。该方法重复性好,操作简单,灵敏度高,能广泛应用于各种塑料制品中多种有机锡的检测。     

气相色谱-质谱法测定木材及木制品中的有机锡化合物

建立了木材及木制品中4种有机锡化合物的气相色谱-质谱)测定方法。选取松木和胶合板作为代表性样品,在空白样品中加入模拟防腐剂溶液,制成阳性样品用于实验条件优化。以乙醇为溶剂,超声提取样品中的有机锡化合物,加入乙酸-乙酸钠缓冲溶液(pH 5)调节溶液酸度,经2%四乙基硼化钠(NaBEt4)衍生、正己烷萃取后,GC-MS同时测定一丁基锡(MBT)、二丁基锡(DBT)、三丁基锡(TBT)和三苯基锡(TPhT)。在0.1～20 mg/L范围内,线线性良好,4种有机锡化合物的平均回收率为83.6%～103.2%;RSD小于9.8%。     

气相色谱-质谱法测定纺织助剂中的有机锡

建立了纺织助剂中二丁基锡(dibutyltin, DBT)、三丁基锡(tributyltin, TBT)及三苯基锡(triphenyltin, TPhT)化合物的气相色谱-质谱联用(gas chromatography-mass spectrometry, GC-MS)检测方法。在乙酸-乙酸钠缓冲溶液(pH 4.0)中,用正己烷超声萃取(对疏水性样品)或振荡萃取(对亲水性样品)试样中的有机锡,然后以四乙基硼化钠的四氢呋喃溶液为衍生化试剂进行衍生化,用GC-MS测定,依据保留时间和选择离子定性,外标法定量。实验结果表明,在0.1～8.0 mg/L(对于DBT和TBT)或0.1～4.0 mg/L(对于TPhT)的范围内,有机锡化合物的浓度（以有机锡阳离子计）与其衍生物峰面积呈良好的线性关系,线性相关系数(r2)为0.9994～0.9998,检出限为0.003～0.005 mg/L; 4种聚氨酯类助剂基质中3种有机锡化合物的平均加标回收率为92.6%～108.0%,相对标准偏差为2.5%～10.2%。该方法的技术指标满足纺织助剂中有机锡化合物的测定要求。     

GC-MS/MS法检测并确证纺织品中5种有机锡化合物

建立了气相色谱-串联质谱法(GC-MS/MS)检测和确证纺织品中5种有机锡(一丁基锡、二丁基锡、三丁基锡、二辛基锡、三苯基锡)的快速有效方法。样品经提取、衍生和正己烷液液萃取后,以GC-MS/MS选择反应监测模式(SRM)进行定性定量测定。结果表明,方法在0.02～0.50 mg/L范围内线性关系良好(r>0.999);5种有机锡化合物的定量下限(S/N≥10)为0.03～0.05 mg/kg;加标水平为0.05～0.5 mg/kg时,5种不同材质阴性样品(棉布、真丝、涤纶、羊毛布、棉/尼混纺)的平均回收率为82%～110%,相对标准偏差(RSD,n=5)为2.1%～7.5%。所建立的方法具有选择性强、灵敏度高、定性定量准确等优点,可以弥补气相色谱法(GC)和气相色谱-质谱法(GC-MS)在确证方面的不足,也弥补了液相色谱-串联质谱法(LC-MS/MS)只能检测三取代基有机锡化合物的局限性。     

盐酸甲醇溶液提取-气相色谱-质谱法测定水生动植物样品丁基锡

采用四乙基硼酸钠(NaBEt4)为衍生剂,建立简单、高效的生物样品有机锡气相质谱(GC-MS)分析方法。结果表明,冷冻干燥生物样品粉末0.1 g经15 mL 0.035 mol/L盐酸甲醇振荡提取1 h,定量提取液加入乙酸盐缓冲溶液(pH 4.8)调节溶液酸度,用含内标物正己烷2 mL和0.5 mL 2%(m/V)NaBEt4水溶液衍生萃取30 min后,GC-MS同时测定一丁基锡(MBT)、二丁基锡(DBT)、三丁基锡(TBT)。在0.5~50μg/L范围内,线性良好,3种有机锡加标回收率均在80%以上。此方法能快速简单对复杂生物样品中的有机锡进行分析,其检出限约为0.01μg/L,3个平行样测量值标准偏差都在10%以内。     

气相色谱-质谱法测定电子电气产品塑料部件中有机锡

气相色谱-质谱法(GC-MS)测定电子电气产品塑料部件中一甲基锡(MMT)、二甲基锡(DMT)、一丁基锡(MBT)、二丁基锡(DBT)、三丁基锡(TBT)、一辛基锡(MOT)、二辛基锡(DOT)、三辛基锡(TOT)、三苯基锡(TPhT)。溶解于四氢呋喃的样品经四乙基硼酸钠水溶液衍生、沉淀后,以GC-MS定性定量检测。方法平均回收率为85.9%～107.2%,RSD低于10%。在9个电子电气产品塑料部件样品中,2个样品检出含有0.050%～0.212%的MMT及DMT,GC-MS与ICP-AES方法测得总锡含量分别为0.21%、0.18%,方法间无显著差异。     

微波辅助萃取-衍生气相色谱-电子捕获检测器法测定电子电气产品中的四溴双酚A

以N,O-双(三甲基硅烷基)三氟乙酰胺(BSTFA)作衍生化试剂,采用微波辅助萃取-衍生气相色谱-电子捕获检测器法(GC-ECD)测定电子电气产品中的四溴双酚A。使用V(甲苯)∶V(甲醇)=10∶1微波辅助萃取电子电气样品,用正己烷沉淀萃取液中的高聚物,净化后,将萃取液进行衍生化反应,采用ECD检测器进行定量测定。对衍生化时间、衍生化温度、衍生化试剂用量、沉淀试剂用量等前处理条件进行了优化,并进行了线性、回收率、精密度等试验。结果表明,方法线性范围为0.005~5 mg/L,相关系数为0.9985,方法的检测下限为0.02 mg/kg。采用样品加标的方式进行四溴双酚A的精密度及回收率实验,回收率在81.7%~110%之间,相对标准偏差RSD(n=7)小于7.2%。所建方法能很好的应用于电子电气产品中四溴双酚A的检测。     

阳离子固相萃取-超高效液相色谱-串联质谱法测定皮革制品中的4种三取代有机锡化合物

建立了超高效液相色谱-串联质谱测定皮革制品中三丁基锡、三苯基锡、双-三苯基锡氧化物、三环锡等4种三取代有机锡化合物(TOT)的方法。采用盐酸溶液提取皮革制品中的有机锡化合物,使其呈阳离子态,经阳离子固相萃取净化,有机锡化合物在超高效C18色谱柱中完成分离,在正离子模式下采用多反应监测模式进行串联质谱测定。三丁基锡、三苯基锡、双-三苯基锡氧化物(以三苯基锡计)的定量限为10 μg/kg,三环锡的定量限为20 μg/kg;分别添加4种待测物于空白皮革样品中,加标回收率为54.1%～101.4%,相对标准偏差为4.3%～9.8%。实验结果表明,该方法简单、灵敏、准确,各项技术指标均满足国内外法规的要求,可用于皮革制品中4种三取代有机锡化合物残留的确证检测。     

格氏试剂衍生-气相色谱-串联质谱法同时测定水果和蔬菜中的三环锡、三苯锡和苯丁锡残留

建立了水果和蔬菜中三环锡、三苯锡和苯丁锡同时检测的格氏试剂衍生-气相色谱-串联质谱方法（GC-MS/MS）。样品经盐酸/四氢呋喃（1：10,v/v）消解,正己烷振荡提取,乙基溴化镁衍生和Florisil固相萃取净化,采用GC-MS/MS多反应监测（MRM）模式对3种有机锡化合物进行定性和定量分析。实验结果表明,以苹果为代表性样品基质,三环锡、三苯锡和苯丁锡的检出限（LOD）分别为2.0、1.5和3.4 μg/kg （以Sn计）,在10、20、50、200 μg/kg （以Sn计）共4个添加水平下的平均回收率为72.4%~107.1%,相对标准偏差为0.4%~14.2%。该方法灵敏度高,选择性强,可以实现3种有机锡农药的同时检测,能够满足国内外残留限量的检测要求。     

HPLC-MS-MS对土壤中三有机锡化合物 (三苯基锡和三丁基锡)的定量分析

有机锡类化合物广泛应用于聚合稳定剂、杀虫剂、杀菌剂、农药等,其中三有机锡化合物(三苯基锡TPT和三丁基锡TBT)因其对微小生物具有很强的毒性,而被用作海洋船体防生物附着涂料的毒性添加剂,据报道此类涂料中有机锡化合物的含量最高可达20%,三有机锡化合物经直接与水体接触,进入水环境与海洋底泥中,由于其具有1～2年的活性,而对非目标生物产生很大毒性,尤其是对生物的内分泌系统有干扰作用,并会经食物链关系而影响到人类的健康,因此三有机锡化合物在现代环境科学中亦称为"环境激素".本文通过对土壤样品采用有机溶剂液液萃取的方法提取三有机锡化合物,并用液相色谱-质谱-质谱的方法进行测定,在10 ng/g-2.0 μg/g范围内成线性关系,回收率为40.9%～58.2%;并对部分水产品中三有机锡化合物进行了检测.     

Analysis of organotin compounds by grignard derivatization and gas chromatography-ion trap tandem mass spectrometry

The determination of organotin compounds in water using gas chromatography-tandem mass spectrometry (GC-MS-MS) is described. Several organotin derivatives were synthesized by the reaction of organotin chlorides with Grignard reagents such as methyl-, propyl- and pentylmagnesium halides. After the optimization of the GC-MS-MS conditions, several derivatizations with the Grignard reagents were compared by evaluating the molar responses and volatilities of the derivatives and derivatization yields. As a result, the derivatizing reagent of choice is pentylmagnesium bromide. Calibration curves for the mono-, di- and tributyltins and mono-, di- and triphenyltins with pentylmagnesium bromide were linear in the range of 0.5-100 pg of Sn. The instrumental detection limits of six organotins ranged from 0.20 to 0.35 pg of Sn. The recovery tests from water samples (500 ml) were performed by using sodium diethyldithiocarbamate (DDTC) as a complexing reagent. Except for monophenyltin, the absolute recoveries of organotins from pure water at 200 ng of Sn/l were satisfactory. The recoveries calibrated by surrogate compounds (perdeuterated organotin chlorides) ranged from 71 to 109%. The method detection limits ranged from 0.26 to 0.84 pg of Sn (500-ml sample). This method was applied to the recovery of organotins from river water and seawater. The calibrated recoveries were between 90 and 122%.     

高效液相色谱-柱后衍生法检测养殖水体及沉积物中11种磺胺药物残留

建立了养殖水体及沉积物中11种磺胺化合物的高效液相色谱-柱后衍生分析方法。养殖水体过滤后采用HLB固相萃取柱进行净化、富集;沉积物采用甲醇/EDTA-Mcllvaine缓冲液(1:1, v/v)提取,HLB固相萃取柱净化富集。经高效液相色谱分离,用荧光胺衍生试剂进行柱后衍生,荧光检测器检测。对柱后衍生系统参数进行了优化,确定了荧光胺溶液的浓度、流速和反应温度分别为0.2 g/L、0.15 mL/min和50 ℃,磺胺化合物在0.01~1.0 mg/L范围内线性显著,其相关系数r²值大于0.99995。11种磺胺类药物在养殖水体和沉积物中的加标回收率分别为79.3%~100.7%和74.6%~95.3%,相对标准偏差为2.2%~11.0%和2.6%~10.3%,检出限(LOD, S/N=3)为0.9~5.5 ng/L和0.3~1.3 μg/kg,定量限(LOQ, S/N=10)为3.0~18.1 ng/L和1.0~4.4 μg/kg。该法可应用于养殖环境中磺胺类药物的定性定量检测,具有较好的实用性。     

气相色谱-质谱法测定水体中5种典型有机紫外防晒剂

建立了水体中5种典型有机紫外防晒剂甲氧基肉桂酸乙基己酯（ethylhexyl methoxycinnamate,EHMC）、二苯酮-3（benzophenone-3,BP-3）、4-甲基苄亚基樟脑（4-methylbenzylidene camphor,4-MBC）、奥克立林（octocrylene,OC）和胡莫柳酯（homosalate,HMS）的气相色谱-质谱检测方法。对HMS、BP-3衍生化条件进行了系统的优化。以100 μL双（三甲基硅烷基）三氟乙酰胺（N,O-bis（trimethylsilyl） trifluoroacetamide,BSTFA）为衍生化试剂,在100 ℃下反应100 min。水样固相萃取选用Oasis HLB萃取柱（0.5 g）,洗脱溶剂为乙酸乙酯-二氯甲烷（1：1,v/v）,水样pH 3~5。该方法对5种化合物的检出限范围为0.5~1.2 ng/L,定量限范围为1.4~4.0 ng/L。最佳实验条件下,加标水样回收率为87.85%~102.34%,相对标准偏差（n=3）均小于5%。该方法成功地应用于昆明市第一污水厂进出口水样中目标物质的分析。     

Comparison of sodium tetraethylborate and sodium tetra(n-propyl)borate as derivatization reagent for the speciation of organotin and organolead compounds in water samples

The influence of pH on the propylation with sodium tetra(n-propyl)borate of butyl- and phenyltins as well as for trimethyl- and triethyllead was investigated. Ethylation and propylation with tetraalkylborates were compared with regard to derivatization yields and figures of merit for organotin compounds in real water samples. Similar results for limit of detection (3-12 ng/L as tin), derivatization yield (40-100%) and relative standard deviation of the method (3-10%) were achieved for derivatization with the two tetraalkylborates. Propylation is thus the preferred method for the simultaneous determination of environmentally relevant organotin and organolead compounds. The handling of the hygroscopic and air sensitive reagents NaBEt4 and NaBPr4 was simplified by dissolving them in tetrahydrofurane. The reagent solutions in tetrahydrofurane can be stored for at least one month at 4 degrees C in the dark without observing any decrease in the derivatization efficiency.     

络合萃取-在线衍生土壤酸性除草剂条件选择与优化

以Na4EDTA为络合剂,以五氟苄基溴为衍生试剂,采用快速溶剂萃取仪萃取,同时实现土壤酸性除草剂的络合萃取在线衍生,并以气相色谱-质谱(NCI源)进行检测。对络合条件、衍生条件、萃取条件、离子源选择进行了优化。方法的回收率为75%～95%、相对标准偏差为6.7%～13%、检测限2.8～8.4μg/Kg。     

快速柱前衍生HPLC法检测曲格列汀中(R)-3-氨基哌啶

以邻苯二甲醛(OPA)和3-巯基丙酸为衍生试剂,建立了柱前衍生高效液相色谱(HPLC)测定曲格列汀中(R)-3-氨基哌啶含量的分析方法。(R)-3-氨基哌啶与衍生剂在碱性(p H 10.5)条件下于室温反应30s,进行柱前衍生,并利用高效液相色谱-质谱对衍生产物进行定性分析。采用YMC-Triart C18色谱柱(150 mm×4.6 mm,5μm)分离,流动相采用0.05 mol/L乙酸钠(p H 6.0)-甲醇溶液,梯度洗脱,流速1.0 mL/min,检测波长331 nm,柱温30℃。(R)-3-氨基哌啶质量浓度在0.08~2.0μg/mL范围内线性关系良好(r=0.9993),定量限为1.6 ng,加标回收率在98.0%~10⁶.9%之间,相对标准偏差(RSD)为2.8%。该方法可用于曲格列汀中(R)-3-氨基哌啶含量测定。     

Simultaneous Determination of Organotin Compounds in White Wine by Gas Chromatography-Mass Spectrometry

A simple, reliable, and effective analytical method was developed for the simultaneous determination of five organotin compounds (OTCs) including monobutyltin trichloride dibutyltin dichloride tributyltin chloride tetrabutyltin and triphenyltin chloride in white wines. The OTCs were derivatized with sodium tetraethylborate (NaBEt₄), and their derivatives were extracted by liquid-liquid extraction (LLE) into n-hexane. The experimental variables, such as type and volume of extraction solvents, amount of derivatization reagent NaBEt₄ and extraction time were optimized. The determination of ethylated derivatives of OTCs in the final extracts was carried out by gas chromatography-mass spectrometry (GC-MS). Under optimized conditions, good linearity was observed when analytical concentrations were in the range of 0.01–4.0 µg · mL^?1, the linearity correlation coefficients were between 0.9982 and 0.9987, with the LODs in the range of 0.2–3.0 µg · L^?1, and the LOQs varied from 0.6 to 10.0 µg · L^?1. The obtained recoveries were in the range of 78.0–120.0%, with the relative standard deviations equal to or lower than 8.1%. This method was applied to the determination of OTCs in white wines with satisfactory results.     

Comparison of sodium tetraethylborate and sodium tetra(n-propyl)borate as derivatization reagent for the speciation of organotin and organolead compounds in water samples

The influence of pH on the propylation with sodium tetra(n-propyl)borate of butyl- and phenyltins as well as for trimethyl- and triethyllead was investigated. Ethylation and propylation with tetraalkylborates were compared with regard to derivatization yields and figures of merit for organotin compounds in real water samples. Similar results for limit of detection (3–12 ng/L as tin), derivatization yield (40–100%) and relative standard deviation of the method (3–10%) were achieved for derivatization with the two tetraalkylborates. Propylation is thus the preferred method for the simultaneous determination of environmentally relevant organotin and organolead compounds. The handling of the hygroscopic and air sensitive reagents NaBEt₄ and NaBPr₄ was simplified by dissolving them in tetrahydrofurane. The reagent solutions in tetrahydrofurane can be stored for at least one month at ¶4?°C in the dark without observing any decrease in the derivatization efficiency.