为了研究滤嘴添加剂对降低卷烟烟气中部分有害物质的影响,本文采用溶胶-凝胶法制备了两种二氧化硅气凝胶材料,对材料微结构进行了初步表征,研究了两种气凝胶材料不同添加量对卷烟烟气中部分有害成分的吸附效果.结果表明:(1)亲水性二氧化硅气凝胶对卷烟烟气中总粒相物的截留率为24.8％,对卷烟烟气在的一氧化碳(CO)、氰化氢(HCN)、氨(NH3)、4-甲亚硝胺基-(3-吡啶基)-1-丁酮(NNK)、苯并吡、苯酚、巴豆醛的截留率依次为2.73％、7.95％、5.96％、6.49％、13.21％、35.64％、23.88％.烟气危害性指数降低0.38;(2)疏水性二氧化硅气凝胶对卷烟烟气中总粒相物的截留率为13.1％,对卷烟烟气CO、HCN、NH3、苯并吡、苯酚、巴豆醛的截留率依次3.46％、5.95％、16.88％、21.70％、50.91％、14.93％.烟气危害性指数降低0.75.

In order to accurately determine the major phenolic compounds (hydroquinol, resorcinol, catechol, phenol, p-cresol, m-cresol, o-cresol) retained by cigarette filters, a rapid and accurate high performance liquid chromatography (HPLC) method was developed by investigating sample pretreatment conditions, such as filter-slitting means, extraction solvent, extraction method, and extraction time. A comparative experiment on seven filter cigarette samples was performed with the developed method among six laboratories. The results showed that: 1) By slitting the filter longitudinally from the tobacco end to the mouth end, then subjecting it to ultrasonic extraction with 50 mL solution (1% acetic acid, 79% methanol and 20% water, V/V) for 30 minutes at room temperature, the said phenolic compounds retained in the filter could be completely extracted. 2) Within the concentration of 0.04-4.00 μg/mL, the said phenolic compounds exhibited good linear relations with R2 > 0.999, the recoveries ranged from 93.35% to 104.50% with relative standard deviations (RSDs) < 7.3%. 3) The RSD of the six laboratories in resorcinol and phenol determination was less than 15%, in the other five phenolic compounds determination was less than 10%. This method is suitable for determining the said phenolic compounds in mainstream cigarette smoke retained by cigarette filter.

建立了可释放特定芳香胺的偶氮染料的测定方法.相对现有方法,在前处理过程中增加了酸碱处理步骤,显著提高了部分芳香胺的回收率.采用中等极性色谱柱,避免了假阳性情况出现.采用该方法,2,4-二氨基苯甲醚平均回收率为36％,邻甲苯胺和2,4-二氨基甲苯平均回收率分别为74％和63％,其他芳香胺平均回收率在85％～108％.

以连续流动分析仪分析滤嘴中截留主流烟气中的氰化氢含量,滤嘴萃取液过滤膜后直接进样.考察了萃取液体积、萃取方式和萃取时间等前处理对氰化氢分析的影响.结果表明,4支抽吸后的滤嘴用0.1 mol/L的NaOH取液,室温下振荡萃取30 min,过水系滤膜后直接进样分析,方程线性关系良好、回收率高、稳定性和精密度良好,可作为滤嘴截留氰化氢含量的检测方法.

建立了用凝胶渗透色谱-高效液相色谱-串联质谱分析烟草中50种农药残留的方法.卷烟中的待测农药组分用乙酸乙酯-环己烷(体积比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 ),流动相为乙酸乙酯-环己烷(体积比为1∶1)溶液,流速5 mL/min),收集第12～35 min流出的液体,用液相色谱-三重四极杆串联质谱仪测定.在0.2～50 ng/mL,农药标准溶液的线性相关系数均大于0.99.在样品中添加50种农药(添加水平为2,50,100 μg/kg)的混合标准溶液,平均回收率为61.35%～122.22%.50种农药的RSD为1.00%～10.80%;方法的检测限为0.01～10.00 μg/kg.

A method for separation and determination of formaldehyde, acetaldehyde, acetone, acrolein, crotonaldehyde, methyl ethyl ketone and butyraldehyde in cigarette filter was developed by SPE-GC. The carbonyl compounds in filter were derivated and extracted by 2,4-dinitrophenyhydrazine acid solution, purified by solid phase extraction, and analyzed without further sample cleanup. Good linear relationships were observed; the detection limits were 0.02, 0.07, 0.04, 0.03, 0.03, 0.02, 0.03 μg/mL for 7 carbonyl compounds respectively; the recoveries ranged from 92.0% to 99.5%; the relative standard deviations were all below 5%. Filter samples of 5 brand Virginia cigarettes from local were analyzed and satisfactory results were obtained.

Cigarettes of the same blend assembled with cellulose acetate(CA) filter and modified polypropylene(MPF) filter separately were used for studying their filtration effects for the harmful components in cigarette smoke,including tobacco-specific nitrosamines,aromatic amines,phenols,polycyclic aromatic hydrocarbons,ammonia and volatile carbonyl compounds.The results indicated that:for polycyclic aromatic hydrocarbons,the filtration efficiency of CA filter was higher than that of MPF filter,while it was on the contrary for ammonia;as for aromatic amines,tobacco-specific nitrosamines,volatile carbonyl compounds and phenols,the filtration efficiency of CA filter was slightly higher.

对近年来应用液相色谱与质谱联用(LC/MS)技术分析检测烟草农药残留进行了综述,为我国烟草行业在农药残留方面的监测工作提供参考.

An improved method was developed for the determination of the four major tobacco-specific nitrosamines(TSNAs) in mainstream cigarette smoke. The new method offers decreased sample preparation and analysis time as compared to traditional methods. This method uses isotope dilution liquid chromatography coupled with a tandem mass spectrometer with electrospray ionization and is significantly more sensitive than traditional methods. It also shows no evidence of artifactual formation of TSNAs. Sample concentrations were determined for four TSNAs in mainstream smoke using two isotopically labeled TSNAs analogues as internal standards. Mainstream smoke was collected on an industry standard 44-mm Cambridge filter pad, extracted with 0.1 mol/L ammonium acetate, purified by solid-phase extraction, and analyzed without further sample cleanup. The analytical column is a 3.9 mm × 150 mm Waters Symmertry Shield RP18 column and volume fraction of the mobile phase is 50% methanol, 50% water containing 0.1% acetic acid. The results show that the linear range is 0.5–100.0 mg/L except for N-nitrosoanabasine (NAB) from 0.25 to 50.0 mg/L. The limits of detection are 0.1 mg/L for N-nitrosonornicotine (NNN), 0.08 mg/L for 4-(methylnitrosamino)-1-(3-py-ridyl)-1-butanone (NNK), 0.05 mg/L for N-nitrosoanatabine (NAT) and 0.06 mg/L for NAB. The recoveries of the four TSNAs are from 90.2% to 105.7%.

In order to investigate the removal efficiency of filter to tobacco-specific nitrosamines (TSNAs),the TSNAs in cigarette smoke,NNN,NAT,NNK and NAB,captured by the filters of 30 cigarette samples were determined by liquid chromatography and tandem mass spectrometry (LC-MS/MS). The filters were cut off the butts after smoking and extracted with 0.1 mol/L ammonium acetate aqueous solution. The resultant extraction passed through an OASIS MCX column,eluted with 50% (v/v) methanol,and analyzed by LC-MS/MS directly. The analytical conditions were:chromatographic column,Waters Symmetry Shield TM RP18,column temperature 65 ℃,mobile phase,50% of methanol-water (containing 0.1% acetic acid) solution at the flow rate of 0.25 mL/min and isogradient elution mode. The results showed that:1) the recoveries of NNN,NAT,NNK and NAB were from 96.0% to 103.5% with the relative standard deviations (RSD) of less than 8% and the limits of detection of 0.7,0.3,0.6 and 0.4 ng/cig.,respectively; 2) the removal efficiencies of filters to NNN,NNK,NAT and NAB were 16.67% to 43.05%,30.51% to 55.97%,16.19% to 45.00%,and 41.68% to 49.08%,respectively; 3) the NNN and NAT removal efficiencies of the filters attached to blended type cigarettes were higher than those of the filters attached to Virginia type cigarettes,while the NNK,NAB and total TSNAs removal efficiencies of the filters of the two cigarette types were similar; 4) the NNN and NAT removal efficiencies of cellulose acetate filter were higher than those of polypropylene filter,while NNK and NAB removal efficiencies of the two filters were similar.

4 tobacco-specific nitrosamines(TSNAs) in mainstream smoke of 12 cigarette samples were extracted with 0.1 mol/L ammonium acetate solution,purified by solid-phase extraction,and analyzed with HPLC-MS-MS.The limits of detection for NNN,NAT,NNK and NAB were 0.07,0.05,0.05 and 0.04 ng/mL,respectively.Their recoveries were in the range of 94.0% to 103.5% with relative standard deviations of 3.02%,4.19%,6.10% and 6.62%.The total TSNAs in mainstream smoke of two imported blended type cigarette brands were far higher than those in ten domestic Virginia type cigarette brands.The method is suitable to quantitative analysis of TSNAs in mainstream cigarette smoke of batches of samples.