固相萃取-高效液相色谱法测定环境水样中多环芳烃

1　引　　言多环芳烃是一类重要的致癌物质 ,故对环境样品中痕量的多环芳烃分析具有重要意义。高效液相色谱 荧光检测器检测是测定多环芳烃最常用的方法。由于传统方法样品处理需用溶剂萃取 ,操作麻烦 ,污染大 ,引入误差因素多 ,故我们研究了用固相萃取预分离和富集 ,高效液相色谱程序波长荧光检测器检测的方法 ,并用二极管矩阵检测器 (ＰＤＡ)辅助作峰识别和纯度分辨。该方法采用固相萃取小柱富集 ,具有富集倍数高 ,节省时间 ,环境污染小 ,不易乳化的优点 ,采用程序波长荧光检测器检测的同时又用ＰＤＡ检测器作了辅助峰识别和纯度分辨 ,利…     

高效液相色谱-荧光检测法测定橄榄油中4种多环芳烃

建立了高效液相色谱-荧光检测(HPLC-FLD)测定橄榄油中苯并[a]蒽、屈艹、苯并[b]荧蒽、苯并[a]芘4种多环芳烃(PAHs)的分析方法。橄榄油样品经异丙醇稀释,采用具有π-π特异性作用的固相萃取柱净化,Agilent ZORBAX Eclipse PAH色谱柱(100 m m×2.1 m m,1.8μm)分离,以水-乙腈为流动相,梯度洗脱,实现了4种化合物的基线分离,并用基质匹配校准溶液进行外标法定量。4种多环芳烃的线性范围为2.4~40μg/L,相关系数(r)为0.999 0~0.999 9,方法的定量限为0.147~0.413μg/L,加标回收率为95.5%~103.2%,日内和日间精密度(RSD)分别为0.10%~1.69%和2.48%~2.93%(n=5)。该法具有灵敏度高、检出限低、重复性好等特点,适用于橄榄油中4种PAHs快速、准确的定量检测。     

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。     

竹炭固相萃取-高效液相色谱法测定河水中多环芳烃

建立了竹炭固相萃取-反相高效液相色谱法检测水中16种多环芳烃的方法。通过实验综合分析,选定正己烷为洗脱溶剂,洗脱溶剂体积为15mL,上样速率为5mL/min,上样体积为750mL。此萃取条件下的萃取回收率在50.3%～143.2%之间。经萃取后,方法的最低检出限范围为0.011～0.069μg/L,精密度在3.3%～11%之间。用该法测定河水中多环芳烃的含量,水样的加标回收率在50.3%～138.4%范围内。     

固相萃取-高效液相色谱法测定卷烟主流烟气中的多环芳烃

通过超声提取、固相萃取(SPE）纯化、反相高效液相色谱分离及荧光检测,建立了测定卷烟主流烟气中荧葸、苯并(k)荧蒽、苯并(a)芘、茚并[1,2、3-cd]芘和苯并[g,h,i]菲等5种多环芳烃的方法。方法的相对标准偏差为2．1％～4,1％,平均回收率为77．2％～90．1％。     

在线固相萃取-高效液相色谱法测定水体中的多环芳烃

建立了在线固相萃取-液相色谱测定水体残留的多环芳烃的方法,用于测定自来水中的20种多环芳烃( PAHs)。直接进样1 mL经过过滤的水体样品,其中的被测组分富集在SPE柱( Acclaim PA II,50 mm×4.6 mm,3μm)上,在线完成净化和萃取富集;再通过阀切换将它们转移至分析流路,在Hypersil Green PAH色谱柱(150 mm ×3 mm,3μm)上分离检测。在线固相萃取流路以水和乙腈为流动相,0.4和0.6 mL/min流速梯度富集/萃取和洗脱;分析流路亦以水和乙腈为流动相,0.8 mL/min流速梯度洗脱,采用紫外254 nm检测无荧光效应的苊烯和弱荧光效应的萘,其它的多环芳烃化合物则于不同的荧光检测通道里,在其对应的最大激发/发射波长下灵敏测定。整个分析流程32 min即可完成。20种PAHs的保留时间的相对标准偏差均小于0.2％,色谱峰面积的相对标准偏差均小于1.3％(n=7);在3个浓度数量级范围内峰面积与进样质量浓度的线性相关系数均大于0.9910,0.05μg/L的自来水加标样品的回收率为57％~140％,5μg/L的自来水加标样品的回收率为85％~116％;多数有荧光响应的PAHs的方法检出限均小于0.02μg/L (S/N=3)。     

固相萃取-气相色谱-质谱法测定3种中药材中18种多环芳烃

建立了固相萃取-气相色谱-质谱法测定3种中药材中18种多环芳烃(PAHs)的检测方法.选取丹参、平贝母、厚朴为样品基质,以正己烷提取,经Fiorisil、ProElut PAH专用固相萃取柱联合净化.采用DM-PAH柱分离,选择离子监测(SIM)模式检测,基质匹配外标法定量.结果表明:实际样品中,18种PAHs在5～2...     

毛细管固相微萃取-液相色谱法测定水中的多环芳烃

建立了一种新的水环境样品项处理方法。将水相中目标污染物萃取至毛细管固定相中，经微量有机溶剂解吸，直接在高效液相色谱上进样分析。该方法对蒽、荧蒽和1，2—苯并蒽3种多环芳烃的检测限分别为0．9μg/L，0．7μg/L和0．1μg/L。相对标准偏差5．1％-6．3％(n＝7)。     

分散固相萃取-气相色谱-串联质谱法测定蔬菜中多环芳烃及卤代多环芳烃

建立了同时检测蔬菜中16种多环芳烃(PAHs)和11种卤代多环芳烃(X-PAHs)污染水平的分散固相萃取-气相色谱-串联质谱(GC-MS/MS)分析方法。样品中的多环芳烃和卤代多环芳烃经正己烷提取,N-丙基乙二胺吸附剂(PSA)和十八烷基键合硅胶吸附剂(C18)分散固相萃取净化剂净化,气相色谱-串联质谱方法测定,外标法定量。16种PAHs和11种X-PAHs在50,100和200μg/kg添加浓度下的回收率为74.7%～115.1%,相对标准偏差为1.6%～15.3%,方法检出限为0.03～7.4μg/kg。     

石墨烯固相萃取测定水中稠环芳烃

建立了石墨烯固相萃取柱萃取和高效液相色谱法检测8种稠环芳烃的方法。采用紫外检测器进行定性和定量分析。对包括吸附剂的种类、洗脱剂的种类和用量、样品溶液的pH和样品体积等实验参数进行了详细优化。在优化条件下,8种稠环芳烃在0.0200～150μg/L浓度范围内与峰面积呈良好的线性关系,相关系数为0.990～0.996。信噪比为3时,稠环芳烃的检出限为0.0020～0.080μg/L。方法的精密度为1.30%～4.65%。将该方法用于环境水样分析,回收率为82.50%～106.5%。     

Rapid SPE-HPLC determination of the 16 European priority polycyclic aromatic hydrocarbons in olive oils

Polycyclic aromatic hydrocarbons (PAHs) are a large class of organic compounds. It has been established that the main source of exposure to these compounds for human beings is through food, particularly fats and oils, due to the lipophilic nature of these polycyclic compounds. The aim of this work was to optimise and validate a method involving SPE and HPLC for rapid determination of the 16 European Union (EU) priority PAHs (required by the Recommendation 2005/108/EC) in vegetable oils. Two spectrofluorometric detectors and a UV-Visible detector in series were used to identify and quantify the target compounds. Linearity, recoveries, LOD, and LOQ were found to be in agreement with the performance criteria for benzo[a]pyrene (BaP) analysis as required by the Commission Directive 2005/10/EC, and satisfactory for all the compounds of interest, except for cyclopenta[c,d]pyrene, which presented a very low signal in the UV. Optimised chromatographic conditions for the separation of 25 PAHs, comprising both EPA and EU priority PAHs plus benzo[e]pyrene and benzo[b]chrysene, have been also proposed.     

多环芳烃水中溶解度的理论计算

建立了计算多环芳烃水中溶解度的数学表达式，用量子化学方法计算了7个多环芳烃的水中溶解度，计算结果与实验测定结果相符合．多环芳烃处于水体内体系状态能量愈高，其溶解度愈小，多环芳烃中的碳氢基团越多，溶解度越小．此时体系中的溶质呈单分子态，而不是聚集态．     

Fluorescent detection of polycyclic aromatic hydrocarbons in ternary cyclodextrin complexes

Reported herein is a new method for the detection of polycyclic aromatic hydrocarbons (PAHs) which relies on energy transfer from the PAH to a near-infrared emitting squaraine fluorophore. This energy transfer occurs inside the γ-cyclodextrin cavity, with up to 35% emission observed from energy transfer compared with exciting the squaraine directly.     

Trace level determination of polycyclic aromatic hydrocarbons in river water with automated pretreatment HPLC

A novel on‐line pretreatment pump‐injection HPLC system for polycyclic aromatic hydrocarbons is proposed. We report novel pump‐injection HPLC‐based on‐line SPE with a specially designed pretreatment column for the determination of trace amounts of chemical substances in surface water. Polycyclic aromatic hydrocarbons are well known for strong carcinogenicity and thus a severe concentration control is required for drinking water and/or river water, which is the main resource of tap water. We found it possible to detect ng/L levels of polycyclic aromatic hydrocarbons by using pump‐injection column switching HPLC with fluorescence detection. To avoid the phenomenon, in which polycyclic aromatic hydrocarbons can be often adsorbed on the surface of flow lines of HPLC by their highly hydrophobicity especially resin‐made parts in sample delivery pump, we employed “autodilution” device that provides reliable recovery and repeatability. Additionally, real water samples were collected and then the spiked polycyclic aromatic hydrocarbons were determined at ng/L levels.     

A review of techniques for the determination of polycyclic aromatic hydrocarbons in air

We provide an extensive review of the common methodologies employed in the analysis of airborne polycyclic aromatic hydrocarbons (PAHs). The review focuses on gas-chromatography-based approaches, in the light of their universal application with excellent separation, resolution, and sensitivity.We first describe collection methods for airborne PAHs in the gas and particle phases. We then evaluate the efficiency of extraction techniques employed for separating target PAHs from sampling media, using conventional solvent-based and emerging thermal-desorption approaches.We also describe commonly employed analytical methods with respect to their applicability to PAHs in gas and particle phases, collected from diverse environmental settings. As an essential part of basic quality assurance, we examine each method with special emphasis on key parameters (e.g., limit of detection and reproducibility).Finally, we address the likely directions of methodological developments, their limitations, and the future prospects for PAH analysis.     

Sensitive determination of polycyclic aromatic hydrocarbons in water samples by HPLC coupled with SPE based on graphene functionalized with triethoxysilane

The graphene functionalized with (3‐aminopropyl) triethoxysilane was synthesized by a simple hydrothermal reaction and applied as SPE sorbents to extract trace polycyclic aromatic hydrocarbons (PAHs) from environmental water samples. These sorbents possess high adsorption capacity and extraction efficiency due to strong adsorption ability of carbon materials and large specific surface area of nanoparticles, and only 10 mg of sorbents are required to extract PAHs from 100 mL water samples. Several condition parameters, such as eluent and its volume, adsorbent amount, sample volume, sample pH, and sample flow rate, were optimized to achieve good sensitivity and precision. Under the optimized extraction conditions, the method showed good linearity in the range of 1–100 μg/L, repeatability of the extraction (the RSDs were between 1.8 and 2.9%, n = 6), and satisfactory detection limits of 0.029–0.1 μg/L. The recoveries of PAHs spiked in environmental water samples ranged from 84.6 to 109.5%. All these results demonstrated that this new SPE technique was a viable alternative to conventional enrichment techniques for the extraction and analysis of PAHs in complex samples.     

In-tube silylation in combination with thermal desorption gas chromatography-mass spectrometry for the determination of hydroxy polycyclic aromatic hydrocarbons in water

For the determination of hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), a simple and sensitive method based on the silylation of OH-PAHs using N,O-bis(trimethylsilyl)trifluoro acetamide (BSTFA) in combination with thermal desorption gas chromatography-mass spectrometry (TD-GC-MS) is described. This method was performed by way of direct silylation in a TD unit (in-tube silylation) coupled to a GC inlet. Both a good detection limit (4.1-1200 pg L⁻¹, S/N = 3) and higher precision (relative standard deviation < 4% on average) were achieved for 21 OH-PAHs studied using the full scan mode (m/z = 40-550). These good results were due to the highly efficient derivatization of the OH-PAHs, which was attributed to not only the moisture-free environment and programmable heating in the TD tube for the in-tube silylation, but also to the constant vapor generation of BSTFA using a capillary introduction method. Although recoveries of 21 OH-PAHs from the spiked 3% NaCl solution ranged between 9 and 304%, those of 11 OH-PAHs fell between 70 and 130% (R.S.D. < 11%). Thus, the present method was applied to a seawater sample collected from an industrial port, and nine OH-PAHs including 1- and 2-OH-fluorenone and 1,8- and 2,6-OH-anthraquinone were determined at concentrations of 0.49-5.8 ng L⁻¹. Along with these OH-PAHs, significant amounts of several long chain fatty acids (C₁₂, C₁₆, C₁₈, C₂₀ and C₂₂) and bisphenol A were also identified in the seawater sample using reference data in a library of mass spectra (match factor: >80%).     

超分子溶剂直提测定水中的多环芳烃

超分子溶剂是两亲化合物通过分子间有序的自组装过程形成的具有纳米结构的胶束聚集体,是一种高效提取溶剂。该文以高效液相色谱-荧光检测法为测试手段,系统地对超分子溶剂组成及用量进行了优化,发展了一种直接提取、快速测定水中多环芳烃的方法,并进行了方法学验证及实际样品检测。结果表明,采用四氢呋喃和1-辛醇制备的超分子溶剂对4种多环芳烃的回收率为89.08%~102.47%,相对标准偏差(RSD,n=5)为1.38%~3.92%。4种多环芳烃在一定范围内线性关系良好(相关系数R~20.999),检出限为1.26~9.23 ng/L。该方法前处理过程简单,有利于实现快速分析;溶剂使用量少,符合绿色化学的发展趋势,具有一定的推广价值。     

Admicelle-enhanced synchronous fluorescence spectrometry for the selective determination of polycyclic aromatic hydrocarbons in water

A simple and rapid method for the highly sensitive determination of polycyclic aromatic hydrocarbons (PAHs) in water was developed. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene in water were concentrated into sodium dodecyl sulfate (SDS)-alumina admicelles. The collection was performed by adding SDS and alumina particles into the sample solution at pH 2. After gentle mixing, the resulting suspension was passed through a membrane filter to collect the SDS admicelles containing highly concentrated PAHs. The filter was placed on a slide glass and then covered admicellar layer with a fused silica glass plate before setting in a fluorescence spectrometer. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene were selectively determined by the synchronous fluorescence scan (SFS) analysis with keeping wavelength intervals between excitation and emission to 98, 35, 29, and 45 nm, respectively. Because of the minimum spectral overlapping, 1-40 ng l⁻¹ of benzo[a]pyrene, benzo[k]fluoranthene, and perylene as well as 10-150 ng l⁻¹ of pyrene were selectively determined with eliminating the interferences of other 12 PAHs. The detection limits were 0.3 ng l⁻¹ for benzo[a]pyrene, benzo[k]fluoranthene, and perylene, and 1 ng l⁻¹ for pyrene. They were 2-3 orders of magnitude lower than the detection limits in normal aqueous micellar solutions. The application to water analysis was studied.     

在线固相萃取-液相色谱法直接测定水中超痕量多环芳烃

建立了在线固相萃取-液相色谱直接测定水体中16种超痕量多环芳烃（PAHs）的方法。水样经高速离心后，加入适量甲醇，配制成40%（体积分数）甲醇水溶液，直接进样2 mL至在线固相萃取流路，进行萃取富集，再通过阀切换将洗脱的PAHs转移至分析流路进行分离检测。16种PAHs在各自范围内线性关系良好，相关系数均大于0.996；方法的检出限为0.14~12.50 ng/L，其中苯并[a]芘（B（a）P）的检出限为0.38 ng/L。实际水样在10、40和200 ng/L加标水平下的加标回收率为76.1%~134.9%，RSD为0.3%~16.6%。B（a）P在1 ng/L加标水平下的回收率为71.8%~92.7%，RSD为3.9%。结果表明，该方法操作简单，灵敏度高，溶剂消耗量少，可满足水样中PAHs，尤其是B（a）P的超痕量分析要求。