自动顶空固相微萃取气相色谱法同步分析水中17种有机物

采用自动顶空固相微萃取(HS-SPME)技术与气相色谱联用同步分析水中1,4-二氯苯、1,2-二氯苯、1,3,5-三氯苯、1,2,4-三氯苯、1,2,3-三氯苯、六氯苯、硝基苯、对硝基甲苯、α-666、β-666、γ-666、δ-666、七氯、ρ,ρ′-DDE、ρ,ρ′-DDD、o,ρ′-DDT、ρ,ρ′-DDT17种有机物。方法的最低检出浓度为0.001~0.044μg/L,线性相关系数均大于0.999,相对标准偏差为1.4%~8.7%,加标回收率在81.3%~122.9%之间。     

固相萃取–气相色谱–质谱法测定地表水中的三氯苯

建立固相萃取–气相色谱–质谱联用法测定地表水中三氯苯的方法,对固相萃取柱、洗脱剂、甲醇用量进行优化试验。在200 m L水样中加入20 m L甲醇,采用C18固相萃取柱,以正己烷为洗脱溶剂萃取水中的三氯苯,用气相色谱–质谱法测定。结果表明,三氯苯的三种同分异构体分离良好,1,2,3-三氯苯、1,2,4-三氯苯、1,3,5-三氯苯的质量浓度在2.0~100μg/L范围内与其色谱峰面积均呈良好的线性,线性相关系数分别为0.999 1,0.999 4,0.999 2,检出限分别为0.004,0.005,0.005μg/L,加标回收率为90.3%~96.5%,测定结果的相对标准偏差均小于2%(n=7)。该方法操作简便、快速,定性定量准确,有机试剂用量少,适用于地表水中三氯苯的检测。     

吹扫捕集-气相色谱-质谱法测定水中10种半挥发性有机物

提出了吹扫捕集-气相色谱-质谱法测定水中硝基苯、三氯苯、硝基氯苯、四氯苯、六氯苯等10种半挥发性有机物含量的方法。选择吹扫温度和吹扫时间分别为60℃和8min。在气相色谱分离中用DB-5MS毛细管色谱柱为固定相,在质谱分析中采用全扫描监测模式,内标法定量。10种半挥发性有机物的线性范围均为0.5~20μg·L-1,检出限(3S/N)在0.005 9~0.073μg·L-1之间。以地表水、生活污水和工业废水为基体做加标回收试验,测得10种半挥发性有机物的回收率在80.4%~105%之间,测定值的相对标准偏差(n=6)在2.4%~16%之间。     

气相色谱-微池电子捕获检测法同时检测饮用水中多种有机污染物

本文建立了气相色谱-微池电子捕获检测法(GC-μECD),同时测定生活饮用水中百菌清、七氯、滴滴涕、六六六、林丹、六氯丁二烯、溴氰菊酯、1,1-二-氯苯、1,2-二氯苯、三氯苯、六氯苯11种有机氯,马拉硫磷、对硫磷、甲基对硫磷、毒死蜱、乐果、敌敌畏6种有机磷,以及硝基苯、2,4,6-三硝基甲苯、1,3-二硝基苯、邻,间,对硝基氯苯、2,4-二硝基氯苯,2,4-二硝基甲苯6种硝基苯类有机物的分析方法.样品经萃取后,采用OV-1701色谱柱(30 m×0.25 mm×0.25μtm)程序升温进行分离,用微池电子捕获检测器(μECD)进行检测,通过保留时间定性,外标法定量.结果表明该方法分离效果好,灵敏度高,选择性强,简便、快速、准确,能够满足同时测定生活饮用水中上述23种有机化合物的需要.     

吹扫捕集-气相色谱-质谱法同时分析饮用水源水中9种氯苯系化合物

建立了饮用水源水中氯苯、二氯苯、三氯苯和四氯苯等共9种氯苯系化合物同时测定的吹扫捕集-气相色谱-质谱法(P&T-GC- MS).优化了吹扫捕集时间及解析时间,采用质谱的选择离子监测模式和内标定量法进行定量分析.在优化的吹扫捕集条件下,线性回归方程的相关系数均大于0.999 8;氯苯、二氯苯、三氯苯和四氯苯的方法检出限(...     

顶空固相微萃取-气相色谱-质谱法测定饮用水源水中1,3,5-三氯苯

采用顶空固相微萃取-气相色谱-质谱法对饮用水源水中1,3,5-三氯苯进行了测定。以1,2-二氯苯-d4为内标,用PDMS萃取头顶空萃取20min,萃取头于气相色谱进样口解析5min。采用DB-624色谱柱在程序升温条件下进行分离,质谱分析中采用电子轰击离子源(230℃,70eV)及选择离子监测模式测定。结果表明:1,3,5-三氯苯在0.100～2.50μg.L-1范围内呈线性,检出限(3S/N)为0.019μg.L-1。方法用于河流及水库水中的1,3,5-三氯苯的测定,加标回收率在91.5%～126.0%之间。     

静态顶空-气相色谱法测定养殖用水中11种氯苯类化合物

提出了静态顶空-气相色谱法测定养殖用水中11种氯苯类化合物的方法。取10mL含200g·L-1氯化钠的水样在20mL顶空瓶中于70℃振摇30min进行顶空进样的条件优化。选用DB-35MS毛细管气相色谱柱(30m×0.25mm,0.25μm)分离,电子捕获检测器检测,外标法或标准加入法定量。在优化条件下,二氯苯、三氯苯、四氯苯的线性范围分别为0.16~8μg·L-1,0.017 6~0.88μg·L-1,0.004~0.2μg·L-1,五氯苯和六氯苯的线性范围均为0.001~0.05μg·L-1。11种氯苯类化合物检出限(3S/N)为0.0002~0.04μg·L-1,应用此方法对养殖用水进行测定,回收率在86.0%~106%之间,测定值的相对标准偏差(n=5)在2.1%~5.8%之间。     

气相色谱-质谱法测定修正产品中11种苯系物

建立了气相色谱-质谱法同时测定修正产品中11种苯系物(苯,甲苯,乙苯,对-二甲苯,间-二甲苯,邻-二甲苯,苯乙烯,氯苯,1,3-二氯苯,1,4-二氯苯,1,2-二氯苯)含量的检测技术。试样中苯系物经二甲亚砜萃取,经DBWAX型毛细管色谱柱分离,质谱定量。结果表明:11种苯系物在1.0~20.0 mg/kg范围内呈良好的线性关系,相关系数R20.9996;方法检出限在0.04~0.07 mg/kg之间;回收率为89.1%~101.1%,相对标准偏差(RSD)1.5%~4.4%。方法能够满足对修正产品中11种苯系物的分析要求。     

QuEChERS/气相色谱-质谱法同时测定污染土壤中六种芳香化合物

建立了样品采用QuEChERS前处理,结合气相色谱-质谱(GC-MS)法同时测定污染土壤中苯酚、2,4-二氯苯酚、2,4,6-三氯苯酚、邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、苯并[a]芘6种化合物的分析方法,选择离子模式(SIM)检测,外标法定量。测定得到平均回收率为64.0%~105.5%,相对标准偏差在0.43%~3.25%范围。结果表明,该方法快速、简便、灵敏、准确,适用于污染土壤中上述6种物质含量的测定。     

CTMAB对反相高效液相色谱-电化学检测法测定水中痕量酚类化合物的增敏、增稳作用

研究了阳离子表面活性剂CTMAB对高效液相色谱 -电化学检测法测定水中痕量酚类化合物的增敏、增稳作用。流动相中CTMAB的最佳浓度为 0 .80mmol/L。使用NucleosilC8色谱柱 (2 0 0mm× 4 .6mmi.d .) ,流动相为甲醇 - 0 .0 2 5mol/L邻苯二甲酸氢钾缓冲液 (体积比为 6 0∶4 0 ,pH =5 .0 ,含 0 .0 6mmol/LEDTA、0 .80mmol/LCTMAB)。该方法测定苯酚、4 氯苯酚、2 ,4 二氯苯酚、2 ,4 ,5 三氯苯酚的线性范围分别为 0 .10～ 15 .0 0、0 .15～ 12 .5 0、0 .15～ 2 2 .5 0、0 .30～ 5 0 .0 0 μg/mL ,检出限分别为 0 .0 0 8、0 .0 10、0 .0 16、0 .0 34μg/mL ,测定结果的相对标准偏差分别为 7.0 %、7.2 %、6 .0 %、7.0 % ,回收率分别为 4 8.0 %、80 .0 %、76 .0 %、85 .0 %。     

Accurate analysis of trace earthy-musty odorants in water by headspace solid phase microextraction gas chromatography-mass spectrometry

A simple and sensitive method was developed for the simultaneous separation and determination of trace earthy-musty compounds including geosmin, 2-methylisoborneol, 2-isobutyl-3-methoxypyrazine, 2-isopropyl-3-methoxypyrazine, 2,3,4-trichloroanisole, 2,4,6-trichloroanisole, and 2,3,6-trichloroanisole in water samples. This method combined headspace solid-phase microextraction (HS-SPME) with gas chromatography-mass spectrometry and used naphthalene-d(8) as internal standard. A divinylbenzene/carboxen/polydimethylsiloxane fiber exposing at 90°C for 30 min provided effective sample enrichment in HS-SPME. These compounds were separated by a DB-1701MS capillary column and detected in selected ion monitoring mode within 12 min. The method showed a good linearity from 1 to 100 ng L(-1) and detection limits within (0.25-0.61 ng L(-1)) for all compounds. Using naphthalene-d(8) as the internal standard, the intra-day relative standard deviation (RSD) was within (2.6-3.4%), while the inter-day RSD was (3.5-4.9%). Good recoveries were obtained for tap water (80.5-90.6%), river water (81.5-92.4%), and lake water (83.5-95.2%) spiked at 10 ng L(-1). Compared with other methods using HS-SPME for determination of odor compounds in water samples, this present method had more analytes, better precision, and recovery. This method was successfully applied for analysis of earthy-musty odors in water samples from different sources.     

顶空固相微萃取–气相色谱–质谱法测定饮用水中9种嗅味物质

建立顶空固相微萃取–气相色谱–质谱法同时测定水中的2-甲基异莰醇、土臭素、2-异丙基-3甲氧基吡嗪、2-异丁基-3-甲氧基吡嗪、三氯苯甲醚、β-环柠檬醛、β-紫罗兰酮等9种嗅味物质。以内标法定量,嗅味物质在1~200 ng/L范围内线性良好,线性相关系数r~2为0.993 7~0.999 9,方法检出限为0.38~0.55 ng/L。水样的加标回收率为72.1%~130.0%,测定结果的相对标准偏差小于10%(n=5)。同时对样品的保存期限、保存剂、余氯的影响进行了研究。该法适用于饮用水中嗅味物质的测定。     

Determination of semivolatile organic compounds in environmental samples by gas chromatography/mass spectrometry after extraction by cyclic steam distillation

A method was developed for the multiple determination of semivolatile organic compounds found in groundwater, river water, seawater, sediment, and soil. Forty standard compounds were determined: n-alkenes, cycloalkanes, aromatic hydrocarbons, and polycyclic aromatic hydrocarbons. The compounds were isolated from water and soil samples by using an essential oil distillator (cyclic steam distillator) with hexane as a solvent. The extract was cleaned by using a silica gel cartridge with an acetone-hexane solution. The compounds were determined by using a gas chromatograph/mass spectrometer with 12 stable isotope-labeled compounds (surrogate compounds). The efficiencies of recoveries from water samples were 80.0-106% for groundwater, 80.1-106% for river water, and 81.2-103% for seawater. The relative standard deviation (RSD) values were 2.05-16.0% for groundwater, 3.22-16.6% for river water, and 4.45-16.0% for seawater. The efficiencies of recoveries from sediment and soil were 71.5-96.4% and 70.1-99.8%, respectively. RSD values ranged from 2.27 to 16.0% for sediment and from 2.12 to 15.1% for soil. Adjustment of recovery efficiencies of standard compounds by using surrogate compounds gave more accurate values. The present study proved that an essential oil distillator provides satisfactory results for multiple determinations of the semivolatile compounds in environmental waters, sediment, and soil.     

Simultaneous determination of benzotriazoles and ultraviolet filters in ground water, effluent and biosolid samples using gas chromatography-tandem mass spectrometry

A new method using gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the determination of four benzotriazoles, i.e. benzotriazole (BT), 5-methylbenzotriazole (5-TTri), 5-chlorobenzotriazole (CBT), 5,6-dimethylbenzotriazole (XTri), and six UV filters, i.e. benzophenone-3 (BP-3), 3-(4-methylbenzylidene)camphor (4-MBC), octyl 4-methoxycinnamate (OMC), 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro benzotriazole (UV-326), 2-(2'-hydroxy-5'-octylphenyl)-benzotriazole (UV-329), and octocrylene (OC) in ground water, effluent and biosolid samples. Solid phase extraction (SPE) and pressurized liquid extraction (PLE) were applied as the preconcentration method for water samples (ground water and effluent) and biosolid samples, respectively. The optimized method allowed us to quantify all target compounds with the method detection limits ranging from 0.29 to 11.02 ng/L, 0.5 to 14.1 ng/L and 0.33 to 8.23 ng/g in tap water, effluent and biosolid samples, respectively. The recoveries of the target analytes in tap water, effluent and biosolid samples were 70-150%, 82-127% and 81-133%, respectively. The developed analytical method was applied in the determination of these target compounds in ground water, effluent and biosolid samples collected from Bolivar sewage treatment plants in South Australia. In effluent samples, the target compounds BT, 5-TTri, CBT, XTri and BP-3 tested were detected with the maximum concentration up to 2.2 μg/L for BT. In biosolid samples, eight out of ten compounds tested were found to be present at the concentrations ranging between 18.7 ng/g (5-TTri) and 250 ng/g (4-MBC).     

直接进样-液相色谱-串联质谱法同时测定水中的5种苯胺类化合物

建立了直接进样测定生活饮用水及其水源水中5种苯胺类化合物(苯胺、3-硝基苯胺、4-硝基苯胺、2,6-二氯-4-硝基苯胺和六硝基二苯胺)的液相色谱-串联质谱法。水样经0.22μm 聚醚砜滤膜过滤后直接进样,目标化合物在 HSS T3色谱柱上经梯度洗脱,于4 min 完成分离,多反应监测模式检测。5种苯胺类化合物在各自线性范围内线性良好,相关系数 R≥0.995。方法的检出限为0.773~1.88μg/ L(S/ N =3),定量限为2.58~6.27μg/ L(S/ N=10);峰面积的日内和日间相对标准偏差(RSD)分别为0.8%~1.9%和3.3%~4.9%;样品加标回收率为84.1%~105.0%,加标样品的 RSD 为1.0%~3.1%。应用本方法对35份水样进行了分析。结果表明,本方法准确、灵敏、快速,适用于生活饮用水及其水源水的常规分析,可为苯胺类化合物的污染评价提供技术支持。     

气相色谱-负化学源-质谱法检测水中10种全氟羧酸化合物

建立了气相色谱-负化学源-质谱（GC-NCI-MS）检测水中10种全氟羧酸化合物的分析方法。使用硅烷衍生化试剂N-甲基-N-三甲基硅基三氟乙酰胺（MSTFA）对全氟羧酸化合物进行衍生化，水样经弱阴离子交换固相萃取柱净化富集后进样。实验优化了样品前处理、衍生化和仪器条件。结果表明，10种全氟羧酸化合物在0.1~10 mg/L范围内线性关系良好，相关系数为0.9956~0.9993；方法的检测限（LOD）和定量限（LOQ）分别为0.5~1.5 μg/L和1.5~4.5 μg/L。在空白水样中进行了3个添加水平的加标回收试验，10种全氟羧酸化合物的平均回收率为70.2%~112.6%，相对标准偏差（RSD）为2.1%~14.5%（n=6）。该法原理简单，灵敏度高，准确、精密，可实现水体中10种全氟羧酸化合物同时检测的要求。     

直接进样–超高效液相色谱串联质谱法同时测定水源水中9种农药

建立直接进样–超高效液相色谱三重四级杆质谱联用(UPLC–MS–MS)快速测定水源水中9种痕量农药残留的方法。水样无需富集,经超高效液相色谱分离,串联三重四级杆质谱检测,在7.5 min内完成9种目标化合物的分析。9种农药的检出限(S/N≥3)在0.01~1.4μg/L之间,在各自的考察浓度范围内线性关系良好(r≥0.995)。在1.0~80μg/L添加水平内,实际样品的平均加标回收率为66.2%~114.0%,测定结果的相对标准偏差为2.3%~20.4%(n=6)。该法操作简便,重现性好,可用于饮用水源水中农药残留的快速测定。     

固相萃取-大体积程序升温进样气相色谱-三重四极杆串联质谱测定饮用水中3种挥发性N-亚硝胺

建立了固相萃取大体积程序升温进样气相色谱-三重四极杆质谱联用（GC-QqQ-MS/MS）同时测定饮用水中N-亚硝基二甲胺、N-亚硝基甲基乙基胺及N-亚硝基二乙基胺的分析方法。用椰壳活性炭固相萃取小柱萃取水样中待测物组分，少量二氯甲烷洗脱、无水硫酸钠脱水，大体积程序升温进样，气相色谱-三重四极杆质谱联用仪进行多反应监测（MRM）模式检测，外标法定量。3种N-亚硝胺在1~50 ng/L范围内线性关系良好，相关系数（r²）均大于0.999，在饮用水中进行10、20和50 ng/L水平的添加，3种待测物平均加标回收率为94.8%~109%，相对标准偏差（RSD）为4.44%~8.10%（n=5），定量限（LOQ）为0.08~0.7 ng/L。该法灵敏、准确、简单、可靠，适用于饮用水中3种N-亚硝胺组分的痕量检测。     

Liquid chromatography and tandem mass spectrometry: a powerful approach for the sensitive and rapid multiclass determination of pesticides and transformation products in water

In this paper we will show the results of our research on the direct simultaneous determination of multi-class pesticides and transformation products with different polarities and acid-base properties by applying an on-line trace enrichment coupled to the chromatographic system supplied with electrospray interface (SPE-LC-MS/MS method). The specific chromatographic separation allows the correct determination of almost fifty compounds (37 pesticides and 10 transformation products) using very low sample volume and very little sample handling. Recoveries between 70-120% were obtained for all compounds in drinking and groundwater, meanwhile in surface water 44 compounds were correctly quantified. Relative standard deviations lower than 15% were obtained for all compounds. Even at the lowest concentration level tested (25 ng L(-1)) 40 compounds presented satisfactory recoveries and repeatability. The use of methanol as organic modifier and the increase of injection volume are also studied. The applicability of the developed method to a monitoring programme is demonstrated by applying it to the analysis of hundreds of samples.     

Gas chromatographic-mass spectrometric determination of hydrophilic compounds in environmental water by solid-phase extraction with activated carbon fiber felt

Simple gas chromatographic-mass spectrometric determination of hydrophilic organic compounds in environmental water was developed. A cartridge containing activated carbon fiber felt was made by way of trial and was evaluated for solid-phase extraction of the compounds in water. The hydrophilic compounds investigated were acrylamide, N,N-dimethylacetamide, N,N-dimethylformamide, 1,4-dioxane, furfural, furfuryl alcohol, N-nitrosodiethylamine and N-nitrosodimethylamine. Overall recoveries were good (80-100%) from groundwater and river water. The relative standard deviations ranged from 4.5 to 16% for the target compounds. The minimum detectable concentrations were 0.02 to 0.03 microg/l. This method was successfully applied to several river water samples.