研究在建立气相色谱方法时,用保留指数(RI)值推导保留时间(RT)并进行改进和验证.用Agilent 6890-5975气相色谱质谱联用仪,35℃柱温,保持5 min,5℃/min升温至100℃,25℃/min升温至200℃,保持6 min,进样口恒压模式保持6.78 PSI,乙苯保留时间锁定至8.170 min,20∶1分流比,进样1μl.测定了53种挥发性有机物(VOCs)的RT,根据实测RT与RI值的拟合方程,推算未知VOCs的RT,并进行改进和验证.结果显示,利用RI值推导出的R与实测RT符合得很好.提示,无标建立VOCs定性方法不仅省时,方便,且具有良好的准确性,在多成分定性检测时可以发挥重要作用.

目的 评估硝酸消解法、洗脱法2种前处理方法 以及电感耦合等离子体-质谱法(ICP-MS)的无气体(No Gas)模式和氦碰撞(He)模式2种测定模式用于测定工作场所空气中锂及其化合物的适用性.方法 采用微孔滤膜采集工作场所空气中锂及其化合物,分别采用硝酸消解法、洗脱法2种前处理方法 处理后,采用ICP-MS法No Gas模式或He模式测定.结果 ICP-MS法No Gas模式和He模式下,锂在质量浓度为0.00～500.00μg/L时线性关系良好,相关系数均为0.999;锂的检出限、定量下限在No Gas模式下分别为0.04和0.13μg/L,在He模式下分别为0.12和0.39μg/L.采用酸消解法进行前处理,锂的加标回收率为96.9％ ～104.9％,批内相对标准偏差(RSD)为3.3％ ～5.0％,批间RSD为2.9％ ～5.3％;采用洗脱法进行前处理,锂的加标回收率为97.6％～102.1％,批内RSD为3.3％～4.6％,批间RSD为3.4％～4.8％.样品在常温下可至少保存14 d.结论 ICP-MS法可作为工作场所空气中锂及其化合物的检测新技术,在仅测定锂及其化合物时建议首选洗脱法和No Gas模式.

目的 室内空气污染与每个人的健康密切相关,室内也是人类活动的主要场所.因此,调查研究室内空气污染物的污染状况很有必要.方法 对深圳市某区35户家庭室内空气污染物进行调查分析,调查的污染物包括甲醛、二氧化氮和苯系物(苯、甲苯、二甲苯),参考室内空气质量标准(GB/T 18883-2002)中的标准值进行判断.结果 通过研究发现,这5种室内污染物的浓度均未超过国家室内空气质量标准,表明深圳市宝安区家庭室内空气质量良好,不会对居民健康产生威胁和危害.结论 深圳市某区室内二氧化氮、甲醛、苯、甲苯、二甲苯的整体污染情况较轻,对居民的居室环境影响较小.

Objective To explore an improved method for determination of cyclohexane and methylcyclohexane in workplace air by solvent desorption-gas chromatography.Methods Cyclohexane and methylcyclohexane in workplace air were collected by activated carbon tubes, desorbed with carbon disulfide, separated by DB-1 capillary chromatography column, detected by flame ionization detector and quantified using the standard calibration curves.Results The linear range of the concentration of cyclohexane and methylcyclohexane were 1.0-1 402.2 and 0.8-1 999.4 mg/L respectively. Both the correlation coefficients were 0.999 9.Both the detection limits were 0.3 mg/L.The limits of quantification were 1.0 and 0.8 mg/L respectively.Both the minimum detectable concentrations were 0.2 mg/m3 .The minimum quantitative mass concentrations of cyclohexane and methylcyclohexane were 0.7 and 0.6 mg/m3 respectively ( sample volume was 1.5 L) .The average desorption efficiencies were 98.5%-99.3% and 97.6%-99.0% respectively.The relative standard deviations ( RSD) of within-run precision were 0.36%-0.59%and 0.34%-0.50%respectively.The RSD of between-run precision were 0.89%-2.04% and 0.87%-2.22% respectively.The samples could be stored for up to 7 days at room temperature.Conclusion This method has features of simple operation, high sensitivity and good precision, which is suitable for simultaneous determination of cyclohexane and methylcyclohexane in workplace air.

Objective To improve the determination method for isopropyl alcohol in the air of workplace by solvent desorption-gas chromatography.Methods Isopropyl alcohol in the air of workplace was collected by activated carbon tubes, desorbed by different kinds of eluents which were chosen for optimization, separated by gas chromatography with HP-5 capillary column and flame ionization detector.Results When isopropyl alcohol was desorbed with 5% ( V/V ) isobutyl alcohol in carbon disulfide ( CS2 ), the average desorption efficiency was 101.50%-104.60% and the relative standard deviation within the group was 0.28%-0.71%.The linear range of isopropyl alcohol was 1.35-2 200.80 mg/L, and the related coefficient was 0.999 9.The limited detectable mass concentration was 0.40 mg/L, and the limited quantitative mass concentration was 1.35 mg/L.The minimum detectable and quantitative mass concentration were 0.30 and 0.90 mg/m3 respectively (sample volume was 1.5 L).With HP-5 capillary column, isopropyl alcohol could be separated effectively from ethanol as an interference in the sample.Conclusion The desorption efficiency of isopropyl alcohol was obviously enhanced with the use of 5% ( V/V) isobutyl alcohol-CS2 solution as the eluent.The method can provide high sensitivity and good precision, and may be applicable for determination of isopropyl alcohol in the workplace air.

作者通过对目前采用的气质联用技术测定工作场所所使用的原材料中挥发性有机物的测定方法进行分析,发现在方法中存在的技术问题和不足,同时提出多种风险的控制措施,以减少技术人员在应用该方法时面临的风险,旨在将该方法更好地应用于职业病危害因素的识别工作中.

目的 建立空气中二丙二醇甲醚的采样和气相色谱测定方法.方法 用活性炭管采集,二氯甲烷-甲醇(85∶15,V/V)解吸,经HP FFAP毛细管柱分离后,用火焰离子化检测器(FID)测定,以外标法定量.结果 标准曲线在20 μg/ml ～ 500 μg/ml线性关系良好,回归方程为y=56.70x-0.166,相关系数r=0.9992.最低检出限为0.75μg/ml,定量下限为2.5 μg/ml,以采集1.5L标准状态下的空气计算,最低检出浓度为0.5 mg/m3,定量下限为1.7 mg/m3.一缩二乙二醇、一缩二丙二醇、二乙二醇甲醚、二乙二醇二甲醚、二乙二醇二乙醚等共存时,不干扰测定.日内精密度为0.4％ ～2.5％,日间精密度为2.5％～4.5％.100 mg活性炭的穿透容量＞14.0 mg,采样效率为100％.解吸效率为86.4％ ～ 95.5％,RSD为2.3％ ～3.0％.结论 本法满足GBZ/T 210-2008的要求,可用于空气中二丙二醇甲醚的测定.

目的 建立工作场所空气中二丙二醇甲醚的采样和气相色谱测定方法.方法 用活性炭管采集,85+15二氯甲烷-甲醇(v/v)解吸,经HP FFAP毛细管柱分离,火焰离子化检测器(FID)测定,外标法定量.结果 在20～500μg/ml范围内线性好,回归方程A=56.70C-0.166,相关系数r=0.999 2.一缩二乙二醇,一缩二丙二醇,二乙二醇甲醚,二乙二醇二甲醚,二乙二醇二乙醚等共存时不干扰测定.结论 本法满足《工作场所空气中毒物检测方法的研制规范》的要求,可用于工作场所空气中二丙二醇甲醚的测定.

目的 建立利用气相色谱同时测定工作场所中叔丁醇、正丙醇、异丁醇和正丁醇的方法.方法 用活性炭管采样,二硫化碳解吸,DB-WAX(30 m×0.25 mm,0.25 μm)毛细管柱分离,氢火焰离子化检测器检测,标准曲线法定量.结果 4种醇在5.0 μg/ml ～5 300 μg/ml范围内呈良好的线性关系,相关性系数均在0.9999以上,检出限为1.5μg/ml～1.6μg/ml.以1.5L采样量计算对应于空气中的最低检出浓度为1.0 mg/m3～1.1 mg/m3,定量检出浓度为3.4mg/m3～3.5 mg/m3,解吸效率为77.8％～89.4％,相对标准偏差(RSD)均＜3.0％.高、中、低浓度的重复测定的相对标准偏差(RSD)均＜1.0％.结论 建立的方法准确、灵敏、可靠,可应用于工作场所空气中4种醇的同时测定.

研究用气相色谱质谱联用仪(GC-MS)测定挥发性有机物(VOCs)灵敏度的规律.用Agilent 6890-5975气相色谱质谱联用仪,低质量数自动调谐方式调谐,柱温为45℃,10℃/min升温至200℃,流量为1 ml/min,分流比为20∶1,进样1μl,测定烷烃、芳香烃、醇类、醛酮类、羧酸酯类、氯代烃类及其他共68种VOCs的灵敏度,对各类型有机物的灵敏度数据进行归纳总结.结果显示,不同类型VOCs的灵敏度随相对分子质量的增大而增高,具有一定的线性关系,灵敏度还与支链、共轭结构和取代基有关,还可根据现有数据推测其他VOCs的灵敏度水平.提示,GC-MS可用于定性发现及半定量测定各种环境下的VOCs,为有机物料分析和工作场所现场监测提供重要的技术手段.

Objective:To explore a method for qualitative and semi-quantitative determination of organic vapor by GC-MS.Methods: The optimized conditions were identified based on some influence factors of sensitivity including the storage of sample,the temperature of sample,sampling point height,the column flow rate,column temperature,heating rate,split ratio and other factors.In this condition,the linear range and detection limit of the common organic vapor had been studied and 68 kinds of organic vapor had been measured the sensitivity.The qualitative analysis methods with GC-MS had been discussed on incidental problems and solution.Results: The method for qualitative and quantitative analysis of organic vapor with GC-MS had been obtained.Headspace samples of actual organic solvent had been measured by National standard method and the semi-quantitative de termination method,the results were very close by comparison.Conclusion: With this method,reliable qualitative analysis results and relatively accurate quantitative analysis results can be obtained in the case of know nothing of the composition and concentration of the vapor,so it is an important means of detecting and determining rough concentration of VOCs in a variety of circumstances.

目的探讨适合工作场所空气中异佛尔酮的溶剂解吸气相色谱测定法中的解吸液,提高解吸效率。方法用活性炭管采样,硝基对苯二酸改性的聚乙二醇石英弹性毛细管柱(30.00 m×0.32 mm×0.25μm)分离,火焰离子化检测器检测,标准曲线法定量。采用不同的解吸液对异佛尔酮进行解吸,测定解吸效率。结果采用甲基异丁基甲酮(MIBK)解吸,平均解吸效率为83.8%,相对标准偏差(RSD)为3.2%;二硫化碳(CS2)解吸效率低于71%;MIBK解吸效率较CS2提高10%以上。以MIBK为溶剂的高、中、低水平异佛尔酮标准溶液重复测定RSD均小于1.0%;异佛尔酮在0.18～369.20 mg/L呈线性关系,回归方程y=0.920 00 x-0.802 22,相关系数=0.999 93;方法检出限为0.18 mg/L,以3L采样量计算对应于空气中的质量浓度为0.06 mg/m3,溶液和空气中的定量下限分别为0.61 mg/L和0.20 mg/m3。结论采用MIBK为解吸液,方法灵敏度、准确度高,解吸效率满足标准要求,可以应用于工作场所空气中异佛尔酮的测定。

[Objective]To develop a method for determining carbon disulfide in air by gas chromatography.[Methods]Solution was separated with gas chromatography and determined with FPD detection,the desorption efficiency of toluene to carbon disulfide from activated carbon was observed.[Results] Quadratic equation was a better calibration method of standard curve,y = 0.001,x2 + 0.081 x + 0.118 7,r = 1.The errors were below 6%.The repeated RSD was below 2%.The lower limit of quantization was 0.21 μg/ml.Determination of the concentration of carbon disulfide solution could satisfy the work requirements.Toluene as a desorption solution,the desorption efficiencies were between 20%-27%,the results were much lower.[Conclusion]The established GC-FPD separation and detection,quadratic fitted standard curve method can be used for quantitative determination of carbon disulfide solution.The techniques of desorption on activated carbon disulfide with toluene as desorption solution even other desorption solution need to be further studied.

目的:研究2010~2011年年深圳市光明新区蔬菜中拟除虫菊酯农药残留状况.方法:2010~2011年每年的3月、6月、9月和12月,分别从深圳市光明新区所管辖的公明和光明2个街道内9个蔬菜销售市场采集了市售各种蔬菜,经过提取、净化和浓缩后,采用气相色谱法检测拟除虫菊酯类农药的残留量,按照 GB 18406.1-2001对残留量进行评价.结果:2010~2011年共抽样检测样品240份,其中有58份样品检出拟除虫菊酯类农药(24.1%),4份超标(1.7%).叶菜类、果实类和其他类别的检出率差异无统计学意义(χ2=0.178,P=0.915),氯氰菊酯检出最高(15.8%),农贸市场和大型超市之间的检出率差异没有统计学意义(χ2=1.055,P=0.304).计算得到氯氰菊酯的标准人日每公斤体重摄入量为0.00111 mg/kg bw.结论:深圳市光明新区蔬菜中拟除虫菊酯类农药的残留量处于安全水平.

目的改进工作场所空气中乙醚的气相色谱法测定方法。方法采样后的活性炭管用二硫化碳(CS2)解吸,经DB-1毛细管色谱柱分离,火焰离子化检测器测定。结果乙醚在0～3 000 mg/L线性关系良好,回归方程:y=0.336 9x+1.130 3,相关系数(r)=0.999 3。最低检出限0.81 mg/L,空气中最低检出质量浓度0.3 mg/m3(以采气3.0 L计)。溶剂解吸法和热解吸法平均解吸效率分别为91.5%和66.6%,相对标准偏差(RSD)分别为2.6%和8.3%。结论该方法灵敏度、准确度、精密度都满足职业卫生检测方法的要求,便于日常的监测工作。

目的 采用柱层析法和乙醇提取法两种前处理方法,对食品中的丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)叔丁基对苯二酚(TBHQ)进行取纯.方法 气相色谱分析.色谱条件:色谱柱,HP-5 25m×0.32mm×0.17um柱温160℃,进样口、检测器温度250℃,柱流量:2.0mL/min.结果 两种方法的相对标准差小于2.5%,回收率在88-104%之间,检出限在0.04-1.35μg/mL之间,且有较高的相关性(P>0.05).结论 说明两种方法可以相互代替.

[Objective]To make an affordable and practical quality control materials for daily air detection.[Methods]The quality control materials of benzene,toluene,trichloroethylene and n-hexane were prepared by Bao'an Center for Disease Control and Prevention of Shenzhen City,and were fixed value by three detection institutions.The application status of seven detection institutions were summarized and analyzed.[Results]The quality control materials were can be kept stable at least 15 months.The results of three fixed value institutions showed that the four kinds of quality control materials had good consistency,and the differences between results between mean values were less than 3%.The results of seven application institutions were controlled within the range of ±10% of definition value.[Conclusion]The quality control materials are well-directed,affordable and practical,and have long stability time,which can be obtained and controlled by the application institutions.And it can be applied to the quality control of occupational health detection in Bao'an district.

Objective To establish method for the determination of 7 free fatty acids in human serum.Methods By adding n-Heptadecanoic acid as internal standard,Stearic Acid,oleic acid,linoleic acid,Linolenic acid, arachidonic acid,eicosapentaenoic acid and Docosahexaenoic Acid in human serum were methylesterified by H_2SO_4/methanol,extracted and concentrated by n-hexane,detected by gas chromatography.Results 7 kinds of fatty methyl ester could be separated completely after methylesterified,The linearity were ranged from 5.0～500μg/mL(r0.999),Minimum Limited Determination≤1.1μg/mL,The average recovery rate of 3 levels (20μg/mL,100μg/mL,300μg/mL) was91.7%～98.1%,RSD 1.9%～4.1%.Conclusion The method could be used to the determination of free fatty acids in human serum.

Objective: To establish a method for determination of 8 kinds of organ-phosphorus pesticide residues in Chinese herbs.Method: The sample was extracted with acetonitrile and the acetonitrile extraction was concentrated.HP-17 /HP-1 double columns gas chromatograph was used for qualitative and quantitative analysis of the samples,which was verified by gas chromatograph-mass spectrometer.Result: Eight kinds of organ-phosphorus in the extract were well separated by this method.Linearities of the 8 kinds of organ-phosphorus pesticides were good(r=0.997 0-0.999 9) in ranges of 0.5-2.0 μg.The minimum determination limited range is 0.007-0.126 mg·kg-1.In the recovery test,the average recoveries ranged from 81.1% to 113.7%(RSD 2.4%-14.1%,n = 5) and from 86.8% to 116.0%(RSD 4.5%-11.7%,n = 5) in the levels of 0.5 mg.kg-1 and 5.0 mg·kg-1 of organ-phosphorus reference substances,respectively.Conclusion: This method was sensitive,accurate and precise and can be used as a reference for the national standard.

目的改进尿中的三氯乙酸顶空气相色谱法。方法取一定体积的尿样,加入正丁醇作为内标,密封,90℃水浴30min后置于顶空进样器中进样,毛细管柱气相色谱法分离测定,内标法定量。结果HP-5和FFAP毛细管柱分析尿中三氯乙酸分离效能好,90℃水浴60min为最佳脱羧条件,10.0～400.0mg/L范围内回归方程y=1.1427x+0.16479,相关系数(r)=0.9999,检出限0.05mg/L,尿液中加标质量浓度分别为10、50、100mg/L时,平均回收率分别是98.6%、99.3%、97.5%,相对标准偏差(RSD)%=1.2%～2.2%。结论本法快速准确,灵敏度高,适用于三氯乙烯接触者尿中的三氯乙酸水平测定。