【作者】 吴凌；

【导师】 孙成均；

【作者基本信息】 四川大学 ， 卫生检验与检疫， 2021， 硕士

【摘要】 多环芳烃（PAHs）是一类由两个或两个以上苯环相嵌组成的持久性有机污染物（POPs）,在环境中普遍存在,有天然和人为两种来源方式。自然来源包括:火山爆发、森林植被和灌木丛燃烧以及细菌对动物、植物的生化作用等,但环境中PAHs主要来源于化石燃料和生物质料以及其他含碳氢化合物的不完全燃烧或在还原条件下热解所形成。因其具有致癌、致畸、致突变的“三致”效应,能对人体造成多种危害,引起了全世界科学家的广泛关注。到目前为止,已在环境中检测和鉴定了200多种多环芳烃,多数是致癌物质,其中毒性和危害最大的是苯并[a]芘（Ba P）属于一类致癌物质。美国环保署（US-EPA）将PAHs中毒性大、分布广且对人体危害大的16种PAHs列为优先控制污染物,我国也制定了相关的卫生标准,如饮用水及水源水中Ba P浓度不得超过0.01μg/L,多环芳烃总量不得超过2μg/L。因此,对环境基质中多种多环芳烃进行同时检测的方法研究具有重要意义。目的:建立底泥中16种多环芳烃的超声辅助萃取-Qu ECh ERS净化-高效液相色谱测定方法;建立土壤中16种多环芳烃的超声辅助萃取-高效液相色谱测定方法和水中16种多环芳烃的多壁碳纳米管（MWCNTs）固相萃取-高效液相色谱测定方法,并应用于成都市府南河底泥、城区土壤以及成都市自来水中多环芳烃污染水平的研究。方法:1.底泥中16种多环芳烃的超声辅助萃取-Qu ECh ERS净化-高效液相色谱测定法底泥样品经室温风干研磨过100目筛后,采用丙酮超声提取,然后用改进的Qu ECh ERS方法纯化上清液。离心后取上清液经0.22μm有机滤膜过滤,最后用高效液相色谱-紫外串联荧光检测法分析测定。分离柱为ZORBAX Eclipse PAH色谱柱（150×4.6 mm,3.5μm）,柱温为30℃,流动相为乙腈-水,梯度洗脱,流速为0.90 m L/min。以保留时间定性,外标标准曲线法定量。2.土壤中16种多环芳烃的超声辅助萃取-高效液相色谱测定法土壤样品经室温下风干研磨过100目筛后,采用正己烷-丙酮（3:7,v/v）超声提取,离心后取上清液经0.22μm有机滤膜过滤后用高效液相色谱-紫外串联荧光检测法分析测定。分离柱为ZORBAX Eclipse PAH色谱柱（150×4.6 mm,3.5μm）,柱温为30℃,流动相为乙腈-水,梯度洗脱,流速为0.90 m L/min。以保留时间定性,外标标准曲线法定量。3.水中16种多环芳烃的多壁碳纳米管（MWCNTs）固相萃取-高效液相色谱测定法水样经多壁碳纳米管固相萃取小柱吸附后,用二氯甲烷和乙酸乙酯先后洗脱,洗脱液经氮吹浓缩至干,乙腈复溶后用高效液相色谱-紫外串联荧光检测法检测分析。分离柱为ZORBAX Eclipse PAH色谱柱（150×4.6 mm,3.5μm）,柱温为30℃,流动相为乙腈-水,梯度洗脱,流速为0.90 m L/min。以保留时间定性,外标标准曲线法定量。结果:1.对于底泥中的PAHs测定,16种PAHs在10-200μg/L范围内线性良好,相关系数均大于0.9993,方法的检出限和定量限分别为0.108-31.4×10^-2和0.360-104×10^-2μg/kg·dw,平均回收率为78.4%-117%,日内和日间相对标准偏差分别为0.592%-10.7%和1.01%-13.0%。所建立的方法已成功地用于成都市府南河23个底泥样品中的PAHs的测定。结果表明,所有样品均检出全部16种PAHs,总含量为431-2.14×10³（1.22×10³±463）μg/kg·dw。在大多数样品中,PAH中的萘（Nap）含量最高,为23.1-898μg/kg·dw。苯并[a]芘（Ba P）含量范围为15.2-126μg/kg·dw,苯并[g,h,i]芘（Bghi P）的含量范围为18.9-124μg/kg·dw,Ba P/Bghi P之比为0.58-1.38,因其比值大多数>0.6,说明PAHs主要来源于交通排放。2.对于土壤中的PAHs测定,16种PAHs在0.500-100μg/L的浓度范围内线性良好,相关系数大于0.9976,方法检出限为0.31-15.31μg/kg·dw,定量限为1.03-51.03μg/kg·dw,平均回收率为84.1%-109%,日内和日间相对标准差分别为1.14%-5.38%和1.21%-6.87%。所建立的方法已成功地用于测定从成都市采集的12个土壤样品中的PAHs。结果表明,所有样品均检测出16种PAHs,总含量为345.2-544.2μg/kg·dw。其中某交通主干道旁土壤中含量最高,推测与机动车尾气排放有关。3.对于水中PAHs测定,16种PAHs在0.0500-1.00μg/L范围内线性良好,相关系数达0.9996-0.9999,方法检出限为0.00126-0.181μg/L,定量限为0.00420-0.604μg/L,平均回收率为74.6%-96.7%,日内和日间相对标准差分别为1.07%-6.68%和2.47%-9.25%。所建立的方法已成功地用于成都市采集的20份自来水样品中16种PAHs的测定,但均未检出。结论:本文建立的底泥、土壤和河水样中16种多环芳烃的同时分析方法,其线性范围、准确度、精密度和灵敏度均达到分析要求,具有简便、快速、低成本和环境友好等特点。所建立的方法已成功应用于实际样品中16种多环芳烃的分析,并与文献报道的环境中PAHs的污染水平进行比较,分析了环境样品中PAHs的污染来源,为环境治理提供了技术支撑和参考依据。更多还原

【Abstract】 Polycyclic aromatic hydrocarbons（PAHs）,a large category of persistent organic pollutants（POPs）composed of two or more fused benzene rings,are ubiquitous in the environment and come from both natural and man-made sources.Natural sources include volcanic eruption,burning of forest vegetation and bushes,and biochemical effects of bacteria on animals and plants,etc.However,PAHs in the environment mainly come from incomplete combustion of fossil fuels,biomass and other hydrocarbons or pyrolysis under reduction conditions.They have attracted wide attention all over the world because of their carcinogenic,teratogenic and mutagenic effects,environmental persistence and bioaccumulation.Up to now,more than 200 kinds of PAHs have been detected and identified in the environment,most of which are carcinogens,among which benzo[a]pyrene（Ba P）is a kind of carcinogen with the greatest toxicity and harm.The U.S.Environmental Protection Agency（US-EPA）has listed 16 kinds of PAHs with high toxicity,wide distribution and great harm to human health as priority control pollutants.China has also formulated relevant health standards,such as the concentration of Ba P in drinking water and source water should not exceed 0.01μg/L,and the total amount of PAHs should not exceed 2μg/L.Therefore,it is of great significance to study the analytical methods for multiple PAHs in environmental matrices.Objectives:To establish the Qu ECh ERS with ultrasound-assisted extraction combined with high-performance liquid chromatography for the determination of 16polycyclic aromatic hydrocarbons in sediment,the analytical method for 16 PAHs in soil using ultrasound-assisted extraction coupled with HPLC and the determination method for 16 PAHs in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with HPLC,and apply the established methods to the study of the contamination status of 16PAHs in the sediment of Funan River,urban soil and drinking water in Chengdu city.Methods:1.Qu ECh ERS with ultrasound-assisted extraction combined with high-performance liquid chromatography for the determination of 16 polycyclic aromatic hydrocarbons in sedimentThe samples were ultrasonically extracted with acetone and then the supernatant was purified with a modified Qu ECh ERS method.After centrifugation,the supernatant was filtered with a 0.22μm organic membrane and injected into the HPLC system for analysis.The separation was accomplished on a ZORBAX Eclipse PAH column（150×4.6 mm,3.5μm）and the column temperature was set at30℃.The flow rate of the mobile phase consisting of water and acetonitrile in gradient elution mode was set at 0.9 m L/min.Detection was conducted on an ultraviolet detector and a fluorescence detector simultaneously.The qualitative analysis was based on retention times and the quantification was based on standard curves.2.Determination of 16 polycyclic aromatic hydrocarbons in soil by ultrasound-assisted extraction combined with high-performance liquid chromatographyThe sample was extracted ultrasonically with n-hexane-acetone（3:7,v/v）and then the extract was filtered with a 0.22μm organic membrane.The separation was accomplished on a ZORBAX Eclipse PAH column（150×4.6 mm,3.5μm）and the column temperature was set at 30℃.The flow rate of the mobile phase consisting of water and acetonitrile in gradient elution mode was set at 0.9 m L/min.Detection was conducted on an ultraviolet detector and a fluorescence detector simultaneously.The qualitative analysis was based on retention times and the quantification was based on standard curves.3.Determination of 16 polycyclic aromatic hydrocarbons in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with high-performance liquid chromatographyThe water sample was extracted with solid phase extraction cartridge using multi-wall carbon nanotubes as sorbent,and the PAHs adsorbed on the nanotubes were eluted with dichloromethane and ethyl acetate successively.The eluent was concentrated under nitrogen blowing,and then reconstituted with acetonitrile for HPLC analysis.The separation was accomplished on a ZORBAX Eclipse PAH column（150×4.6 mm,3.5μm）and the column temperature was set at 30℃.The flow rate of the mobile phase consisting of water and acetonitrile in gradient elution mode was fixed at 0.9 m L/min.Detection was conducted on an ultraviolet detector and a fluorescence detector simultaneously.The qualitative analysis was based on retention times and the quantification was based on standard curves.Results:1.For PAHs analysis in sediment,the linearities of the method were in the range from 10 to 200μg/L for all the PAHs with satisfactory correlation coefficients（between 0.9993 and 1,000）.The limits of detection（LODs）and limits of quantification（LOQs）of the method were 0.108–31.4×10^–2and 0.360–104×10^–2μg/kg·dry weight（dw）,respectively.The mean recoveries ranged from 78.4 to117%with the intra-day and inter-day RSDs of 0.592–10.7 and 1.01–13.0%,respectively.The established method has been successfully applied for the determination of 16 PAHs in 23 sediment samples collected from the Funan River in Chengdu,China.The results showed that 16 PAHs were all detected in the samples with the total contents of 431–2.14×10³（1.22×103±463）μg/kg·dw.Nap had the highest contents of 23.1–898μg/kg·dw among the PAHs in most samples.Ba P,the powerful carcinogen,had the content range of 15.2 to 126μg/kg·dw and the ratio of Ba P/Bghi P in the range of 0.58–1.38.The ratio of Ba P/Bghi P>0.6indicates traffic emissions,and the ratio<0.6 indicates non-traffic emissions.2.For the PAHs analysis in soil samples,the linearities of the method were investigated in the range from 0.500 to 100μg/L for all the PAHs with satisfactory correlation coefficients greater than 0.9976.The LODs and LOQs of the method were 0.31-15.31 and 1.03-51.03μg/kg·dw,respectively.The mean recoveries ranged from 84.1 to 109%with the intra-day and inter-day RSDs of 1.14-5.38 and1.21-6.87%,respectively.The established method has been successfully applied for the determination of 16 PAHs in 12 soil samples collected from Chengdu city.The results show that 16 PAHs were all detected in the samples with the total contents of 345.2-544.2μg/kg·dw.Among them,the soil sample collected from the traffic trunk road had the highest content,which might be related to motor vehicle exhaust emissions.3.For the PAHs analysis in water samples,the linearities of the method were investigated in the range from 0.0500 to 1.00μg/L for all the PAHs with satisfactory correlation coefficients（between 0.9996 and 0.9999）.The LODs and LOQs of the method were 0.00126-0.181 and 0.00420-0.604μg/L,respectively.The mean recoveries ranged from 74.6 to 96.7%with the intra-day and inter-day RSDs of 1.07-6.68 and 2.47-9.25%,respectively.The established method had been successfully used for the determination of 20 tap water samples collected from Chengdu city,but no PAH was detected in all samples.Conclusions:In this study,the simple,rapid,environment-friendly and cost-effective methods were established for simultaneous determination of 16 US EPA priority PAHs in sediment,soil and water samples.Under optimal conditions,those methods have satisfactory linearities,recoveries,sensitivity,and precisions which can meet various analytical requirements.The established methods have been successfully applied to the detection of 16 PAHs in the real samples,and the results have been compared with the detection results of other countries and regions in the literature and the pollution sources were analyzed too.They can provide scientific and technical reference for for environmental pollution control.更多还原