加速溶剂萃取-色谱质谱联用法测定土壤中的多环芳烃

采用加速溶剂萃取-色谱质谱联用法测定土壤中的多环芳烃.土壤样品与无水硫酸钠(质量比为1:2) 混合后,再加适量中性氧化铝,用丙酮-二氯甲烷(体积比为1:1)在加速溶剂萃取仪上以10.3 Mpa、80℃提取10 min,用色谱进行分离,质谱检测器进行分析,土壤中16种多环芳烃的回收率为76.9%～101.4%,测定结果的相对标准偏差为1.6%～15.8%(n=7).     

快速溶剂萃取-气相色谱-串联质谱法分析海洋沉积物中16种多环芳烃

建立了快速溶剂萃取（ASE）-气相色谱-串联质谱（GC-MS/MS）分析海洋沉积物中16种多环芳烃（PAHs）的分析方法。样品由正己烷-丙酮（1∶1,v/v）溶液萃取,经无水硫酸钠脱水、氮吹浓缩后,采用硅胶固相萃取小柱进行净化,然后经HP-5MS色谱柱（30 m×0.25 mm×0.25 μm）分离,在电子轰击电离源下以多反应监测（MRM）模式进行检测,内标法定量。分析结果表明,16种PAHs在0.01~1.00 mg/L范围内线性关系良好,相关系数（R）大于0.997;目标物的加标回收率为75.8%~97.8%;日内与日间精密度（RSD）均小于10%。当取样量为20.0 g时,16种PAHs的方法检出限为0.048~0.234 μg/kg。该法快速、准确、稳定,能够满足海洋沉积物中痕量PAHs的测定。     

加速溶剂萃取-气相色谱法测定土壤中16种多环芳烃

利用加速溶剂萃取-气相色谱法测定土壤中16种多环芳烃的分析。研究了萃取时间、温度、压力、样品的粒度对萃取效率的影响及不同淋洗液在硅胶柱净化过程中对方法回收率的影响。实验结果表明,加速溶剂萃取方法对16种多环芳烃的萃取溶剂量小,萃取时间短萃取回收率分别在74%~95%之间;对标准样品的检出限为0.00004~0.02 mg/kg;方法RSD为4%~15%。用此方法测定了株洲土壤中的多环芳烃含量。     

多次溶剂萃取-气相色谱/串联质谱法测定热熔胶中的多环芳烃

建立了热熔胶中16种多环芳烃( PAHs)的多次溶剂萃取-气相色谱/串联质谱测定方法。详细研究了样品的萃取条件、净化条件和气相色谱/串联质谱测定条件,并与气相色谱-质谱法进行了对比。样品以10 mL正己烷为萃取溶剂,于60℃超声萃取20 min,萃取液依次经冷冻后离心、二甲基亚砜萃取2次、正己烷反萃取2次进行净化,得到的净化液以气相色谱/串联质谱法多反应监测( MRM)模式进行检测。本方法的线性相关系数( R2)均大于0.9969,检出限为1.0~10μg/kg,精密度小于6.3%,16种PAHs的加标回收率为80.4%~117.6%。考察了串联质谱检测的基质效应,发现基质效应不明显。本方法检出限优于气相色谱-质谱法(23~94μg/kg),并能增加定性和定量分析的准确性。本方法灵敏、准确可靠,满足热熔胶中PAHs测试要求。     

加速溶剂萃取-固相萃取净化-气相色谱/质谱法测定沉积物中多氯联苯和多环芳烃

建立了加速溶剂萃取-固相萃取净化-气相色谱/三重四极杆串联质谱联用(ASE-SPE-GC-QqQ-MS/MS)法同时测定沉积物中28种多氯联苯(PCBs)和16种多环芳烃(PAHs)。对萃取、净化及仪器分析条件进行了优化。优化条件为:ASE萃取温度90℃,萃取时间6 min;净化小柱为硅胶-Florisil固相复合柱(填料自下而上为弗罗里硅土、0.7 g活化硅胶、1 g无水硫酸钠);洗脱溶液为丙酮-正己烷(1∶19,V/V)混合溶液,洗脱速率为0.6 mL/min。PCBs和PAHs在2～500μg/L和5～1000μg/L浓度范围内的线性相关系数(R2)分别为0.9987～0.9999和0.9939～0.9999;PCBs和PAHs方法检出限分别为0.001～0.08 ng/g和0.07～0.45 ng/g;定量限为0.003～0.25 ng/g和0.24～1.67 ng/g;实际样品平均加标回收率为95.6%～125.7%和70.4%～124.7%;方法相对标准偏差(n=6)为0.7%～6.4%和1.1%～12.8%。运用本方法对滇池入湖河口表层沉积物样品进行测定,该区域PCBs单体浓度为n.d.(未检出)～0.13 ng/g,PAHs单体浓度为0.79～131.12 ng/g。     

加速溶剂提取凝胶渗透色谱净化气相色谱质谱快速测定玉米中多环芳烃

研究了玉米中16种多环芳烃的快速分析方法.采用加速溶剂萃取法(ASE)对玉米样品进行提取,提取溶剂为二氯甲烷,萃取池中依次加入3 g中性氧化铝吸附剂和10 g待测样品,提取的同时能够在线净化除去小分子杂质.收集的提取液进一步用凝胶渗透色谱(GPC)除去样品中大分子油脂和色素,流动相为二氯甲烷,流速为3 mL/min,收集9～13 min的流出液,提取液浓缩定容至1 mL后用GC-SIM-MS进行分析.16种 PAHs以及4种替代物在2个浓度水平添加时的平均添加回收率在55.7%～145.3%之间; RSD为1 4%～16.8%;方法检出限为0.005～0.120 ng/g.本方法简便、快速、准确,净化效果较好,满足残留分析的要求,且能应用于其它谷物样品的日常分析.     

加速溶剂萃取-液相色谱法测定运动地坪材料中 16种多环芳烃

提出了加速溶剂萃取-液相色谱法测定运动地坪材料中16种多环芳烃含量的方法。优化的加速溶剂萃取条件如下:①萃取溶剂为丙酮-正己烷(1+1)混合液;②萃取温度为100℃;③静态萃取时间5min;④循环萃取2次。以Hypersil Green PAH色谱柱为分离柱,用水和乙腈以不同比例混合的溶液为流动相进行梯度洗脱,用紫外检测器和荧光检测器测定。16种多环芳烃的质量浓度均在5.0～500.0μg·L~(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)为0.04～1.67μg·kg~(-1)。以空白样品为基体进行加标回收试验,所得回收率为70.9%～117%,测定值的相对标准偏差(n=6)为1.5%～6.7%。     

加速溶剂萃取-固相萃取净化-气相色谱/质谱法测定土壤中的多环芳烃

建立了加速溶剂萃取-固相萃取净化-气相色谱/质谱法同时测定土壤中16种多环芳烃的方法。土壤样品经正己烷-丙酮提取,经无水Na₂SO₄脱水、氮吹浓缩后,弗罗里土小柱净化,采用气相色谱/质谱检测,内标法定量。结果表明:该方法在质量浓度0.4～10μg/mL范围内线性良好,相关系数(r²)大于0.9962,检出限为4.8～25μg/kg,定量限为19.2～100μg/kg;在0.05,0.15,0.40 mg/kg 3个加标水平下的平均回收率为55.4%～129.0%,相对标准偏差为1.5%～11%。采用该方法检测土壤样品,除苊烯、苊、芴3种多环芳烃未检出外,其他13种多环芳烃均有检出,其含量范围在6.6～86μg/kg。     

加速溶剂萃取/气相色谱-三重四极杆串联质谱法测定纺织品中24种多环芳烃

建立了加速溶剂萃取/气相色谱-三重四极杆串联质谱(ASE/GC-MS/MS)同时测定纺织品中24种多环芳烃(PAHs)的方法。样品经丙酮加速溶剂萃取,旋蒸浓缩后采用DB-35色谱柱程序升温分离,选择多反应监测模式(MRM)采集,外标法定量。结果表明,在一定浓度范围内多环芳烃的峰面积与质量浓度呈良好的线性关系,相关系数(r~2)均大于0.994,方法检出限为0.000 3~0.03 mg/kg,方法定量下限为0.001~0.10 mg/kg,加标回收率为80.3%~103%,相对标准偏差(RSD)为1.3%~9.2%。该方法灵敏、准确可靠,能满足纺织品中24种多环芳烃的测试要求。     

固相微萃取-气相色谱-质谱联用测定海水和沉积物间隙水中的痕量多环芳烃

建立了固相微萃取(SPME)与气相色谱-质谱(GC-MS)联用同时测定海水中16种多环芳烃的分析方法, 研究了萃取时间、盐度条件的影响. 同时用SPME的方法研究了海水中的溶解有机物(DOM)对多环芳烃萃取的影响. 计算出不同DOM浓度下多环芳烃K_DOM与K_OW的关系: C_DOM=5 mg/L时, logK_DOM = 0.7944K_OW + 0.773 (R² = 0.91). C_DOM=10 mg/L时, logK_DOM = 0.7905K_OW + 0.668 (R² = 0.97); C_DOM=30 mg/L时, logK_DOM = 0.714K_OW + 1.0407(R² = 0.91). 该法对16种多环芳烃的检出限为0.1~3.5 ng/L, 相对标准偏差(RSD, n=5)为 4%~23%. 用该法分析海洋环境中的痕量多环芳烃, 16种多环芳烃的平均回收率为88.2±20.4%, 方法快速、灵敏、简单, 适用于快速分析海水和沉积物间隙水样中的痕量多环芳烃.     

The Extraction of Polycyclic Aromatic Hydrocarbons from Atmospheric Particulate Matter Samples by Accelerated Solvent Extraction (ASE)

Abstract

The Accelerated solvent extraction (ASE) of PAHs (23 2- to 6-ring species) spiked onto glass fibre filters (GFFs) was studied as a function of variable extraction solvents, pressure, temperature and extraction times. Acceptable recoveries (85% ± 15%) were obtained for certain combinations of conditions and a tentative method (1500 psi, 150°C, 70:30 hexane:acetone mixture, 7 min heat-up time, 5 min static extraction time, 60% flush volume, 2 static cycles was selected for further testing. However, this method did not prove as effective as the traditional Soxhlet method of extraction when these parameters were used to extract native PAHs from ambient atmospheric particulate matter collected on a GFF by Integrated Atmospheric Deposition Network (IADN) sampling protocols. The extraction recovery study for spiked GFFs was repeated using slightly different extraction conditions: 2000 psi, 100°C, 70:30 hexane:acetone, 5 min heat-up time, 5 min static extraction time, 150% flush volume, 3 static cycles. When this method was applied to the extraction of native PAHs from ambient atmospheric particulate matter collected on GFFs, the results showed equivalent or better recoveries to that of the Soxhlet method. The total time of extraction was 25 min requiring only 30 mL of solvent. This ASE method is presently used to quantitatively determine PAHs in IADN particle-phase samples.     

液液萃取-气相色谱-质谱法测定墨水中的16种多环芳烃

采用液液萃取-气相色谱-质谱法测定墨水中的16种多环芳烃。样品经二氯甲烷液液萃取后,使用固相萃取技术进行纯化。在气相色谱分离中用DB-5MS色谱柱为固定相,在质谱分析中采用选择离子监测模式。16种多环芳烃在一定的质量浓度范围内与其峰面积呈线性关系,方法的检出限(3S/N)在5.0~30μg·kg-1之间。以空白样品为基体进行加标回收试验,所得回收率在60.6%~116%之间,测定值的相对标准偏差(n=6)在1.5%~5.3%之间。     

超声萃取-高效液相色谱法测定沉积物中多环芳烃

提出了高效液相色谱法测定沉积物中多环芳烃(PAH′s)含量的方法。样品中多环芳烃用正己烷-丙酮(1+1)混合溶液超声提取,离心分离后,所得萃取液经蒸发浓缩,然后过装有1g无水硫酸钠和2g硅胶的层析柱净化。以Varian PAHs色谱柱为分离柱,不同比例配成的甲醇和水为流动相梯度洗脱,用荧光检测器检测。方法的检出限(3S/N)在0.34～1.52ng.g-1之间。方法用于沉积物中多环芳烃的测定,测定结果的相对标准偏差(n=5)在3.2%～10.6%之间。用标准加入法测定方法的回收率,结果在57.1%～103.4%之间     

Determination of Atmospheric Polycyclic Aromatic Hydrocarbons Using Accelerated Solvent Extraction

Abstract

An accelerated solvent extraction (ASE) method has been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) present in both atmospheric particulate and gaseous phases in this study. Extraction parameters such as the combination of solvents, extraction temperature, and static extraction time were investigated and optimized. Effective extraction was achieved using a 3:1 mixture of n-hexane and acetone as extraction solvents at 100°C in 30 min for all the compounds studied. The optimized extraction method was compared with conventional extraction methods and validated using National Institute of Standards and Technology (NIST)–certified standard reference material (SRM) 1649a. The recoveries obtained for certified 12 PAHs were in the range of 82–126% with relative standard deviation (RSD) between 6 and 28%. The validated ASE technique was used followed by gas chromatography–mass spectrometry (GC-MS) for the determination of PAHs distributed between gaseous and particulate phases in the atmosphere of Singapore. Total average concentrations of PAHs in air samples were 33.54 ± 19.32 ng m^?3, with 4.72 ± 2.80 ng m^?3 in particulate phase and 28.82 ± 16.92 ng m^?3 in gaseous phase, respectively. The results obtained from this study are compared to those reported from other areas of the world.     

加速溶剂萃取和凝胶渗透色谱净化GC–MS法测定烟熏腊肉中16种多环芳烃

采用ASE萃取、GPC净化和浓缩,建立GC–MS法快速检测烟熏腊肉中16种多环芳烃(PAHs)的分析方法。将烟熏腊肉与硅藻土充分混合后,放到萃取池中加速溶剂萃取,在优化仪器条件下测定,16种PAHs的线性范围为0.1~4 ng/m L,线性相关系数r为0.985 3~0.999 9。方法检出限在0.172~0.233μg/kg之间,加标回收率为60.3%~93.2%,测定结果的相对标准偏差为4.06%~11.60%(n=6)。该方法检测快速,准确度高,重现性好,适合于烟熏腊肉中16种PAHs的同时测定。     

A Simple Extraction Method for Determination of High Molecular Weight Polycyclic Aromatic Hydrocarbons in Sediments by Gas Chromatography–Mass Spectrometry

A simplified extraction method was developed for extracting high molecular weight polycyclic aromatic hydrocarbons (PAHs) from river sediments. The samples were extracted 3 times with 5 mL of solvent (toluene:methanol, 9 : 1, v/v) at 100 °C, 10 minutes for each extraction. After clean‐up and concentration, extracts were analyzed by gas chromatography coupled with mass spectrometer (GC‐MS). The extraction efficiency and accuracy was evaluated by the standard reference material (SRM‐1941b). Comparing to certified values, the average recoveries of high molecular weight PAHs with 3, 4, 5 and 6 fused benzene rings were 72.9∼113.2 % (R.S.D. 2.3∼6.3 %) except those of dibenz[a,h]anthracene (206.2±4.6 %). The average recoveries for PAHs spiked sediment samples were comparable with accelerated solvent extraction (ASE) and Soxhlet methods. The simple extraction method consumes less solvent, fewer amount of sample than those of conventional methods. The lowest quantitation limit of PAHs is 1.1 μg/kg.     

快速溶剂提取-高效液相色谱法测定PM2.5中16种多环芳烃

建立大气细颗粒物(PM2.5)中16种多环芳烃(PAHs)的快速溶剂提取-直接进样-高效液相色谱测定方法.PM2.5经玻璃纤维滤膜收集,采样后的滤膜直接用乙腈经快速溶剂萃取仪提取,以乙腈和水作为流动相,提取液通过ZORBAX Eclipse PAH液相色谱柱分离,紫外串联荧光检测器检测.16种PAHs分离效果良好,在0.025~5.000μg/mL范围内线性相关系数r≥0.9998,方法加标回收率为78.3%~113.2%,相对标准偏差为0.5%~9.5%,检出限为0.007~0.062 ng/m3.本方法操作简便、快速、准确、灵敏,适于PM2.5中16种PAHs的同时测定.     

气相色谱-质谱法测定三七提取物中16种多环芳烃

提出了气相色谱-质谱法测定三七提取物中16种多环芳烃。样品用环己烷萃取,经凝胶渗透色谱净化处理后,采用HP-5MS色谱柱分离,电子轰击离子源-选择离子检测模式检测,外标法定量。16种多环芳烃的质量浓度在0.01~1.0mg·L-1范围内与其峰面积呈线性关系,方法的测定下限(10S/N)在0.3~9.5μg·kg-1之间。在0.01,0.05,0.1mg·kg-1添加水平下,16种多环芳烃的加标回收率在70.1%~111%之间,相对标准偏差(n=6)在3.0%~9.4%之间。     

超速匀质超声波辅助萃取—气相色谱/质谱法测定沉积物中16种多环芳烃

建立了用于检测沉积物中多环芳烃PAHs的超速匀质超声波辅助萃取—气相色谱/质谱法。以乙腈为提取剂对水体沉积物中16种PAHs进行提取,铜粉净化,所得净化液浓缩丙酮定容用Agilent HP-5MS毛细管柱进行分离,质谱全扫描检测。采用质谱检测器根据NIST 05谱图库比对进行定性分析;外标法进行定量分析。结果表明：16种PAHs的检出限在0.004~0.028 μg?kg-1之间。用标准加入法测得回收率在71.3%~117.2%,相对标准偏差（n＝7）在1.2%~9.8%之间。通过实际样品中PAHs的分析表明,该法快速、溶剂用量小,满足痕量分析的要求。     

气相色谱-质谱法测定塑料玩具中多环芳烃

提出了气相色谱-质谱法测定塑料玩具中16种多环芳烃(PAH′s)含量的方法。样品经正己烷超声提取30min后,40℃水浴氮气吹干。用水、甲醇和正己烷-二氯甲烷(3+2)混合溶剂各5mL溶解残渣,过C18固相萃取柱净化,用正己烷-二氯甲烷(3+2)混合溶液洗脱,所得洗脱液过HP-5MS色谱柱分离,电子轰击离子源检测。16种多环芳烃的质量浓度在0.2～4.0mg·L-1范围内与其峰面积呈线性关系,方法的检出限(3S/N)在0.002～0.021mg·kg-1之间。以聚丙乙烯、聚乙烯、聚氯乙烯或丙烯腈-丁二烯-苯乙烯共聚物等4种材质的塑料玩具为基体,进行加标回收试验,回收率在79.6%～95.2%之间。