食品中多环芳烃的提取、纯化、以及检测方法的研究进展

对食品中多环芳烃(PAHs)的提取、纯化机理和检测方法进行了概述,侧重介绍了样品提取、纯化和分离过程中影响PAHs回收率的各种因素。     

纺织品中16种多环芳烃化合物测定的研究

本文选用索氏抽提、超声提取和微波萃取等3种不同前处理方法对纺织品中的16种多环芳烃化合物(PAHs)进行提取。通过提取方法优化、干扰物纯化、总离子流图、定性和定量离子等分析,建立了气相色谱-质谱法测定纺织品中PAHs含量的试验方法。结果表明:16种PAHs线性关系良好,相关系数均大于0.995%,检出限在0.002mg/L～0.010mg/L之间,相对标准偏差(RSD)<3%,加标最低回收率在85%～98%之间。方法可满足纺织品中16种PAHs的符合性检测要求。     

气质联用法测定纺织品中多环芳烃(PAHs)

建立了超声提取气相色谱/质谱联用(GC/MS)测定纺织品中多环芳烃(PAHs)含量的分析方法,研究了提取溶剂、提取时间和温度对提取效率的影响,确定最佳提取条件。该方法应用于纺织品中PAHs的检测,16种PAHs的线性范围为0.05～4.0mg/L,方法检出限在0.012～0.094mg/kg内,加标回收率为68.7%～107.3%,相对标准偏差为0.58%～11.9%。方法简便可靠,能够达到纺织品中16种多环芳烃的检测要求。     

以离子液作为介质萃取水中的多环芳烃

多环芳烃(PAHs)是一类具有难降解性、致癌性、环境累积性及非挥发性的有害化学物质。以16种EPA PAHs中的菲、荧蒽、芘这3种物质为研究对象,从检测器、提取试剂、提取方法等方面入手,对分析过程进行优化。在保证分析结果有较高精度的前提下,尽量地使分析过程简洁、高效。在样品的前处理阶段,选用超声提取法进行样品的前处理比较快捷。通过对3种多环芳烃(PAHs)标准样品的高效液相色谱法的定性、定量分析,结果表明,该方法可有效分离PAHs,回收率较高。最后,通过对实际水样中多环芳烃(PAHs)的测定验证该方法是令人满意的。     

采用GC-MS测定涂层面料中16种多环芳烃的方法

针对纺织品中多环芳烃(PAHs)检测要求,建立了涂层面料经超声提取后液液萃取、固相萃取净化方法,采用气相色谱质谱(GC-MS)测定面料中PAHs含量,并详细考察了该方法的回收率和检出限。结果表明,该方法测定纺织品中PAHs最低检出限(LOD)为0.4～3.8μg/L,最低定量限(LOQ)为1.3～12.2μg/L,加标回收率74.0%～99.0%,相对标准偏差为0.89%～4.94%。检测结果表明,该方法准确,快速,简便可靠,能够满足纺织品及装饰材料中对16种PAHs的检测要求。     

不同工艺即食烤鱼多环芳烃检测方法及变化研究

目的:建立即食烤鱼16种多环芳烃（Polycyclic aromatic hydrocarbons, PAHs）检测方法,分析不同工艺对烤鱼PAHs种类及含量的影响。方法:样品经正己烷提取,采用固相萃取柱净化,二氯甲烷洗脱,高效液相色谱法测定。结果:16种PAH_S相关系数为0.9993~0.9998,检出限为0.20~2.50 μg/kg;加标回收率为64.25%~122.8%,相对标准偏差为1.38%~7.13%。在碳烤、油炸、电烤三种不同熟化方式下,烤鱼中调味料的添加可减少PAHs的生成量;烤鱼中PAHs的种类和含量为碳烤>油炸>电烤,样品中萘、苊烯、菲和芘检出含量较高,碳烤样品PAHs总量高达58.74 μg/kg,明显高于油炸和电烤样品组;熟化时间和温度对烤鱼PAHs种类及含量均有影响,随油炸时间延长、油炸温度增高,样品PAHs检出种类和含量增加明显,其中,萘、苊烯、菲、荧蒽和芘含量增高达3~5倍;随电烤时间和温度的增加,样品中PAHs种类增多,PAHs总量亦提高;通过风险评估,烤鱼加热时间控制在6 min,温度200 ℃以内,摄入频率小于每月2次,食用风险低。结论:建立了烤鱼中16种PAHs的检测方法;进行了不同工艺烤鱼样品中PAHs的种类、含量变化分析及风险评估,为即食烤鱼熟化工艺选择提供依据。     

食品中多环芳烃残留分析前处理方法的研究

文中设计并比较了水解-液液萃取法、水解-微波辅助萃取法、微波辅助萃取-水解法和水解一超声波萃取法4种食品中多环芳烃(PAHs)残留分析的提取方法;同时进行了净化实验。结果表明,水解-液液萃取法和水解-微波辅助萃取法的提取效果理想;采用中性氧化铝固相萃取回收率高,除杂效果明显。将水解-微波辅助萃取-中性氧化铝固相萃取净化法应用于多种食品进行分析,结果表明该方法适用于食品中PAHs残留分析。     

卵磷脂提取、分离纯化的研究进展

该文综述了卵磷脂的提取和分离纯化方法,阐述了卵磷脂有机溶剂提取法、酶解法、超临界流体萃取法、超声微波协同萃取等提取方法的优缺点,并对卵磷脂的无机盐复合沉淀法、乙酰化沉淀法、柱层析法、膜分离法等分离纯化方法进行了比较,提出了当前卵磷脂提取和分离纯化存在的问题,总结了卵磷脂的提取及分离纯化方法的研究发展趋势和前景。     

油脂脱臭馏出物中多环芳烃含量及检测方法研究

植物油精炼的副产物——脱臭馏出物是提取和生产天然维生素E和植物甾醇的原料,针对油脂脱臭馏出物特殊的黏稠性状和复杂组分,对其中多环芳烃(PAHs)含量检测方法和样品前处理条件进行优化研究,建立了液液分配萃取-硅胶SPE柱净化-同位素稀释法-气相色谱串联质谱法(GC-MS)定量检测油脂脱臭馏出物中16种PAHs的方法。结果表明:油脂脱臭馏出物中16种PAHs的检出限和定量限分别为0. 10～0. 28μg/kg和0. 33～0. 92μg/kg,回收率为83. 92%～112. 34%,方法检测灵敏度高、稳定性好、定性及定量准确,能很好地满足对脱臭馏出物中PAHs的检测。利用优化的检测方法分别对6个不同的脱臭馏出物样品中PAHs含量进行检测分析,结果发现脱臭馏出物中BaP、PAH4、PAH16的平均含量分别为11. 89、217. 19、2 268. 85μg/kg,其中LPAHs是主要的PAHs污染物,占PAH16总量的90. 34%～95. 61%。结果提示在利用油脂脱臭馏出物作为维生素E和植物甾醇的提取原料时应充分注意其多环芳烃的安全风险。     

紫苏油中的多环芳烃残留量的测定方法研究

对不同方法提取的紫苏油,经超声波辅助正己烷-丙酮提取、硅胶-氧化铝复合柱净化后,采用气相色谱-质谱-选择离子检测法对其中多环芳烃的残留量进行定性和定量检测,结果表明:在10~1000μg/L浓度范围内,16种PAHs有良好的线性关系,相关系数为0.994~0.999,加标回收率在77.4%~91.7%,日内(n=10)相对标准偏差为3.20%~6.92%,检测限为0.08~0.45μg/kg。该方法快速准确、分析灵敏度高、重复性好,可适合于食用油中PAHs的快速分离与检测。3种方法提取的紫苏油中PAHs残留量均在国家规定的食用油中多环芳烃含量标准范围内。     

Supercritical fluid extraction of mononitrated polycyclic aromatic hydrocarbons from tea – correlation with the PAH concentration

The ability of supercritical fluid extraction (SFE) to extract nitropolycyclic aromatic hydrocarbons (nitro-PAHs) from tea matrices is described and discussed. An experimental approach was set up to determine the influences of various extraction parameters, i.?e. pressure, temperature, extraction time and addition of modifier. The evaluation of the method was carried out by analysing samples of fortified tea and then comparing the results with those obtained from conventional extraction procedures, such as Soxhlet extraction and ultrasonication. SFE proved to be far better than the conventional methods at monitoring levels of nitro-PAHs in tea. However, due to the wide range of polarity of the analytes investigated, selective extraction with supercritical carbon dioxide was not possible; hence, subsequent purification steps were necessary, prior to the final GC/MSD analyses. The nitro-PAHs and PAHs concentrations in several tea samples were determined, any correlation between nitro-PAHs and PAHs was studied and the results are presented in this article.     

Supercritical fluid extraction of mononitrated polycyclic aromatic hydrocarbons from tea – correlation with the PAH concentration

 The ability of supercritical fluid extraction (SFE) to extract nitropolycyclic aromatic hydrocarbons (nitro-PAHs) from tea matrices is described and discussed. An experimental approach was set up to determine the influences of various extraction parameters, i. e. pressure, temperature, extraction time and addition of modifier. The evaluation of the method was carried out by analysing samples of fortified tea and then comparing the results with those obtained from conventional extraction procedures, such as Soxhlet extraction and ultrasonication. SFE proved to be far better than the conventional methods at monitoring levels of nitro-PAHs in tea. However, due to the wide range of polarity of the analytes investigated, selective extraction with supercritical carbon dioxide was not possible; hence, subsequent purification steps were necessary, prior to the final GC/MSD analyses. The nitro-PAHs and PAHs concentrations in several tea samples were determined, any correlation between nitro-PAHs and PAHs was studied and the results are presented in this article. Received: 13 January 1997 / Revised version: 21 February 1997     

超声提取-气相色谱-串联质谱法测定煎烤鱿鱼中16种多环芳烃

本实验建立了超声提取-气相色谱-串联质谱法（polycyclic aromatic hydrocarbons, PAHs）测定煎烤鱿鱼中16种多环芳烃的分析方法。考察了提取试剂配比、提取试剂用量、提取温度等对回收率的影响,确定了最佳的提取和检测方法:5.00 g样品冷冻干燥后经25 mL正己烷30 ℃超声提取20 min,复提一次,经碱性氧化铝-中性硅胶复合固相萃取柱净化后,采用气相色谱-串联质谱法测定,多环芳烃氘代内标法定量。在此实验条件下,16种目标物在1~100 ng/mL范围内呈良好线性关系,线性相关系数（r）不低于0.9994,检出限为0.09~0.52 μg/kg,定量限为0.21~1.21 μg/kg。在1、2、20 μg/kg 3个加标水平下回收率分别为73.98%~128.17%、73.21%~133.24%、76.35%~133.68%,相对标准偏差（RSD,n=6）分别为1.32%~2.98%、0.93%~2.47%、1.08%~2.87%。在实际样品检测应用中,6个样品均有不同程度的多环芳烃检出,单一组分检出范围从0~48.65 μg/kg不等。结果表明,该方法选择性好,可用于煎烤鱿鱼中多环芳烃的检测,也可应用于其他类似的加工水产品中多环芳烃的提取与检测。     

Radiocarbon as a tool to apportion the sources of polycyclic aromatic hydrocarbons and black carbon in environmental samples

To determine the relative inputs of polycyclic aromatic hydrocarbons (PAHs) and black carbon (BC) in environmental samples from the combustion of fossil fuels and biomass, we have developed two independent analytical methods for determining the 14C abundance of PAHs and BC. The 5730 yr half-life of 14C makes it an ideal tracer for identifying combustion products derived from fossil fuels (14C-free) versus those stemming from modern biomass (contemporary 14C). The 14C abundance of PAHs in several environmental Standard Reference Materials was measured by accelerator mass spectrometry after extraction and then purification by high-performance liquid chromatography and preparative capillary gas chromatography. This method yields pure compounds that allow for a high degree of confidence in the 14C results. The PAHs data were then used to compare and evaluate results from an operationally defined thermal oxidation method used to isolate a BC fraction. The 14C compositions of PAHs and BC were very similar and suggest that the thermal oxidation method employed for isolating BC is robust and free from interferences by non-BC components. In addition, these data indicate that both the PAHs and the BC species derive mostly from fossil fuels and/or their combustion products.     

HPLC determination of polycyclic aromatic hydrocarbons in olive oils

 In this paper, HPLC with spectrofluorimetric detection was applied to the determination of polycyclic aromatic hydrocarbons (PAHs) in olive oils. These compounds may sometimes contaminate vegetable oils because of their specific lipophilic characteristics, which are a significant problem for their extraction and purification from lipid matrices. Some improvements to previously published methods are introduced and satisfactory results for repeatability and recovery were obtained. Data on 51 authentic olive oil samples are reported and it was found that there is usually a limited presence of PAHs in extra virgin olive oils; furthermore, the analysis of some blends of refined and virgin oils shows that the distributions of light and heavy PAHs are different with the content of the former being lower in refined samples. As an example of this fact, two samples of lampante oil were followed throughout the refining step. Received: 23 September 1996 / Revised version: 17 December 1996     

Determination of polycyclic aromatic hydrocarbons in edible oils and barbecued food by HPLC/UV–Vis detection

Determination of nine polycyclic aromatic hydrocarbons in corn, sunflower, olive oils and barbecued meat and fish by HPLC/UV–Vis method is described. The extraction procedure included a saponification, liquid–liquid extraction and finally purification of PAHs through a house-made silica–alumina column. Chromatographic determination was based on separation of PAHs on ODS column and measurement at 254 nm. All polycyclic aromatic hydrocarbons were separated and analyzed in 12 min on reversed phase ODS column with acetonitrile/water mobile phase at 1.5 mL min⁻¹ flow rate. The detection limits of nine polycyclic aromatic hydrocarbons ranged from 0.26 to 1.15 μg L⁻¹ at a signal/noise ratio of 3. The linearity of the method was between 0.9951 and 0.9996. Oil samples contain different PAHs ranging from 0.44 to 98.92 μg L⁻¹. Barbecuing process increased the concentration (in the range of 2- to 8-fold) and caused the formation of PAHs in food samples.     

气相色谱-同位素稀释质谱法测定肉中多环芳烃含量

采用分子印迹固相萃取技术,建立肉中多环芳烃残留的气相色谱-同位素稀释质谱检测方法。以萘-D8为内标、正己烷-二氯甲烷（7∶3,V/V）混合溶液为提取试剂,经过匀浆、超声提取、离心、分子印迹固相萃取等步骤,在优化仪器条件下进行定性、定量分析。在5～100 ng/mL范围内,16 种多环芳烃峰面积与内标物峰面积的比值均与质量浓度的比值呈良好的线性关系,线性相关系数不小于0.999 9,肉及肉制品中检出限为0.125～0.625 μg/kg。3 个加标水平下的样品回收率在85.7%～109%之间,相对标准偏差（n=6）在0.75%～4.90%之间。该方法前处理效率高,定量法灵敏、准确,适合于监控肉类中多环芳烃的含量。     

多环芳烃脱除方法及其在维生素E油中的应用

介绍了多环芳烃（PAHs）的性质、来源和危害，详述了油、污水、土壤中多环芳烃的脱除方法：物理法（包括萃取法、吸附法、层析法及人造纤维富集法等）、化学反应法、生物反应法、化学-生物降解法等，比较了各种脱除方法的优缺点。分析了维生素E油中的PAHs的来源。实验结果显示，硅胶柱层析法、微波萃取法、人造纤维bluerayon吸附等方法对维生素E油中PAHs的脱除有较好的效果。     

Sources of contamination by polycyclic aromatic hydrocarbons in Spanish virgin olive oils

The presence of polycyclic aromatic hydrocarbons (PAHs) in virgin olive oils results from contamination on olive skins and the oil itself during processing. Determination of nine PAHs was carried out by isolation of the hydrocarbon fraction and subsequent clean-up by solid phase extraction, followed by RP-HPLC analysis using a programmable fluorescence detector. Contamination of olive skins depends directly on environmental pollution levels and inversely on fruit size. In the oil mill, PAHs levels were increased by contamination from combustion fumes during the extraction process. Other procedures, such as washing or talc addition during extraction, did not affect PAHs levels. High concentrations of PAHs were only found as a consequence of accidental exposure to contamination, such as direct contact of olives with diesel exhaust and oil extraction in a polluted environment.