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。     

高效液相色谱法测定黄浦江表层沉积物中的痕量多环芳烃

建立了高效液相色谱-二极管阵列检测器(PDA)测定上海市黄浦江表层沉积物中16种多环芳烃(PAHs)的方法。在保留时间定性分析的基础上,利用PDA获取的紫外扫描光谱图对目标组分进行了准确的定性,并通过异构体紫外光谱图中特征峰的差异有效地识别了样品中的4种异构体,即苯并［b］荧蒽、 苯并［k］荧蒽、 苯并［a］芘和苯并［e］芘。通过检测波长的优化,减少了干扰物的影响,提高了检测灵敏度;针对分离度较差的两种目标组分(苯并［b］荧蒽和苯并［k］荧蒽)的定量进行了分析讨论。该方法对16种PAHs的检出限(以干基计)介于1.1～18.3 ng/g之间,具有较高的方法灵敏度。黄浦江表层沉积物测定结果表明,除二氢苊外的15种PAHs都被检出,含量为10.1～253.0 ng/g。     

Production of three certified reference materials for water content based on mixed solutions of butanol, xylene and propylene carbonate

Certified reference materials (CRMs) for water content with good accuracy and homogeneity are required for calibration or validation of the Karl Fischer titration and for establishing the traceability of water content results. Three such CRMs were produced and certified: GBW 13512, 13513 and 13514 are based on solvent mixtures consisting of butanol, xylene and propylene carbonate with water contents of 10.01, 1.067 and 0.139?mg/g, respectively, certified by the Karl Fischer coulometric and volumetric methods. These CRMs were prepared, dispensed and sealed under a humidity equal to the equilibrated humidity of their headspace. In this way, the between-bottle homogeneity uncertainty (u _H,rel) could be kept as low as u _H,rel?=?0.12?% for GBW 13512. The certification methods, that is, Karl Fischer coulometric and volumetric methods, were calibrated using in-house water standards prepared by gravimetry. The results were traceable to the SI unit of mass. The relative deviation of the water contents between the two methods for GBW 13512 was only 0.05?%. The expanded uncertainty (U, k?=?2) of three CRMs was 0.12, 0.024 and 0.012?mg/g, respectively. These CRMs for water content with good accuracy can be applied in the calibration or validation of measurement procedures to ensure accurate and comparable results.     

Certified reference material for quantification of polycyclic aromatic hydrocarbons in sediment from the National Metrology Institute of Japan

The National Metrology Institute of Japan has issued a certified reference material (CRM) of freshwater lake sediment for polycyclic aromatic hydrocarbon (PAHs) analyses. The certification used three extraction techniques: pressurized liquid extraction (PLE) with toluene, PLE with dichloromethane/ethyl acetate (1:1 by volume), and alkaline extraction (1 M KOH in methanol) in combination with microwave-assisted extraction. Both gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/dopant-assisted atmospheric pressure photoionization/MS (LC/DA-APPI/MS) analyses were used. Certified values are provided for 18 PAHs at 1–25 μg kg⁻¹ except for perylene (2.08 × 10³ μg kg⁻¹), and information values are provided for two. Since the values of PAHs in the CRM are much lower than those in other CRMs and are comparable to those found at sites with little human influence, the CRM is suitable for PAH monitoring in sediment and soil samples.     

Use of multivariate statistical analysis to evaluate experimental results for certification of two pharmaceutical reference materials

This paper demonstrates the use of the multivariate analysis for the quick and easy evaluation of the experimental results from the homogeneity test of two new certified reference materials (CRM) of active pharmaceutical ingredients (API): metronidazole and captopril. The principal component analysis (PCA) and the hierarchical cluster analysis (HCA) indicated that some results from the homogeneity test were statistically different when the concentrations of all API impurities were considered simultaneously. Through the use of these statistical tools, it was possible to reduce the standard uncertainty due to between-bottle (in)homogeneity (u _bb) and consequently the combined standard uncertainty of the certified reference materials (u _CRM) with 95% confidence level.     

Multifactorial optimization approach for the determination of polycyclic aromatic hydrocarbons in river sediments by gas chromatography-quadrupole ion trap selected ion storage mass spectrometry

A procedure for the determination of very low polycyclic aromatic hydrocarbons (PAHs) concentrations in sediment samples has been developed by gas chromatography-quadrupole ion trap mass spectrometry (GC-QIT MS) after extraction with dichloromethane and purification by using silica gel cleanup. Identification and quantification of analytes were based on the selected ion storage (SIS) strategy using deuterated PAHs as internal standards. In order to search out the main factors affecting the SIS mass spectrometry efficiency, four MS parameters, including target total ion count (TTIC), waveform amplitude (WA), transfer line (XLT) and ion trap temperatures (ITT) were subjected to a complete multifactorial design. The most relevant parameters obtained (TTIC and WA) were optimized by a rotatable and orthogonal composite design. Optimum values for these parameters were selected for the development of the method involving PAH determination in sediment samples. The optimized method exhibited a range of 111-760% higher signal-to-noise (S/N) ratios for PAHs in comparison with the method operated by the default conditions, demonstrating that the multifactorial optimization contributed to substantially improve the sensitivity of the GC-QIT MS determination. The accuracy of the method was verified by analyzing NWRI EC-3 certified reference material (Lake Ontario sediment). The selectivity, sensitivity (limits of quantification were in the range of 0.02-11.0 ng g(-1)), accuracy (recoveries >or=77%) and precision (RSD相似文献   

超声提取-气相色谱-质谱法测定本草香中16种颗粒态多环芳烃含量及其排放特征分析

本草香颗粒态多环芳烃(PAHs)的分析对探究人体健康和环境安全的影响具有重要意义,但目前相关研究主要针对竹签香,对于配方更为复杂、日常使用更为频繁的本草香颗粒态PAHs定量分析研究十分有限且缺少针对性。为了研究本草香颗粒态PAHs的排放因子和排放特征,在自制的试验舱内采集5种本草香燃烧后的颗粒物,通过优化萃取溶剂、超声时间和仪器分析条件,建立了超声提取-气相色谱-质谱(GC-MS)测定本草香燃烧后颗粒物上所吸附的16种PAHs的方法。通过采集0.8 g样品,切取整片滤膜样品,使用正己烷-二氯甲烷(1∶1, v/v)进行超声萃取,经浓缩定容过滤后使用气相色谱-质谱分析,内标法定量。结果表明,16种PAHs在0.1~5.0 μg/mL范围内线性良好(相关系数r²>0.998),方法检出限(MDL)为0.4~3.8 ng/g;低、高2个水平的加标回收率分别为77.4%~99.5%和82.0%~101.3%;相对标准偏差(RSD)为0.7%~7.2%。5种本草香颗粒态PAHs的排放因子为4.60~11.89 μg/g。本草香的16种颗粒态PAHs中菲(Phe)的含量均为最高,所占比例为24.85%~42.59%,其次为荧蒽(Flu)、芘(Pyr)、 \stackrel{艹}{屈} (Chr)、蒽(Ant)。本草香颗粒态PAHs中Phe的含量稳定且占比明显高于其他室内燃烧源,可将Phe作为本草香的颗粒态特征PAHs。颗粒态PAHs主要分布在3环和4环上,3环和4环PAHs占比之和为83.84%~96.31%。颗粒态的Phe/Flu比值可作为辨别不同室内燃烧源中燃香释放源的特征比值。该方法所需样品量少,灵敏度高,前处理操作简便,适用于燃香类产品中PAHs的快速检测,同时为了解本草香颗粒态PAHs分布规律和健康危害提供科学数据。     

Determination of Polycyclic Aromatic Hydrocarbons in Mangrove Sediments: Comparison of Two Internal Standard Surrogate Methods and Quality-Control Procedures

Two internal standard surrogate (ISS) methods, ISS-I (with m-terphenyl as a single ISS) and ISS-2 (using five deuterated PAHs as a multi-ISS), for the determination of polycyclic aromatic hydrocarbons (PAHs) in mangrove sediments were compared. The recovery percentages of 16 PAHs except naphthalene in HS-6 (a certified reference material) were high, ranging from 69.3 to 111.8% for ISS-1 and from 71.8 to 120.3% for the ISS-2 method. Similarly, the PAH recovery percentages in spiked mangrove sediments and clean sand were lower for ISS-I than for ISS-2, but both methods met the accurate acceptance criteria for PAH recoveries. The reproducibility (i.e. the method precision) between the two ISS methods was also comparable and satisfactory, with relative standard deviation values in most cases within 20% of the data variability. These results indicate that both ISS methods were acceptable for the determination of PAHs in mangrove sediments, despite the fact that the matrix of mangrove sediments may interfere with the PAH recovery efficiency.     

A greener microwave-assisted extraction method for rapid spectroscopic determination of selected metals in river and freshwater sediment certified reference materials

The current study describes development of novel, cost-effective, rapid and greener microwave-assisted extraction (MW-AE) method using diluted hydrogen peroxide (H₂O₂) and 400 µL of concentrated aqua-regia for the extraction of 10 selected metals (Ba, Cr, Cu, Co Fe, Mn, Ni, Pb, V and Zn) in sediment certified reference materials (CRMs), prior to inductively coupled plasma-optical emission spectroscopic analysis. The optimum extraction conditions were achieved when 0.2 g of sediment was extracted with 1 mol L^?1 of H₂O₂ (12.00 mL) and 400 µL of concentrated aqua-regia, at 180°C microwave extraction temperature for 30 min. Accuracy of the proposed MW-AE method was evaluated by using river (LGC6187) and freshwater (CRM015-050) sediment CRMs. Quantitative extraction recoveries of 80–120% in LGC6187 and 74–124% in CRM0150-050 were obtained with acceptable precision (0.4–1.0%). The proposed extraction method has a clear advantage over classical approaches as 1 mol L^?1 H₂O₂ was used instead of notorious acidic mixture (Hydrochloric acid/ nitric acid/ hydrofluoric). The method detection limits (MDLs) of 0.03–0.9 μg g^?1 were obtained for all the investigated metals and were fairly comparable with the MDLs of the published literature reports. Therefore, the proposed MW-AE method can be routinely used for monitoring of metal ions in various river and fresh water sediments.     

Standard reference materials (SRMs) for determination of organic contaminants in environmental samples

For the past 25 years the National Institute of Standards and Technology (NIST) has developed certified reference materials (CRMs), known as standard reference materials (SRMs), for determination of organic contaminants in environmental matrices. Assignment of certified concentrations has usually been based on combining results from two or more independent analytical methods. The first-generation environmental-matrix SRMs were issued with certified concentrations for a limited number (5 to 10) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Improvements in the analytical certification approach significantly expanded the number and classes of contaminants determined. Environmental-matrix SRMs currently available include air and diesel particulate matter, coal tar, marine and river sediment, mussel tissue, fish oil and tissue, and human serum, with concentrations typically assigned for 50 to 90 organic contaminants, for example PAHs, nitro-substituted PAHs, PCBs, chlorinated pesticides, and polybrominated diphenyl ethers (PBDEs). Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Determination of semi-volatile priority pollutants in landfill leachates and sediments using microwave-assisted headspace solid-phase microextraction

The present work was focused on the development of a simple method aimed at the determination of 12 polycyclic aromatic hydrocarbons (PAHs) and 15 polychlorinated biphenyls (PCBs) in landfill leachates and sediments by adapting a domestic microwave oven to perform microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) followed by gas chromatographic separation and tandem mass spectrometric detection. Good linearity was observed within the concentration range studied; detection limits ranged from 0.1 ng/l to 7 ng/l for PCBs and from 5 ng/l to 926 ng/l for PAHs. Concerning precision, the relative standard deviations obtained were, on average for the leachate and sediment samples analysed, 18% for PCBs and 20% for PAHs. Average recovery values were 37% and 76% for PCBs, and 58% and 48% for PAHs, respectively, for the leachate and reference sediment studied. The method allows the determination of PAHs and PCBs in landfill leachates and sediments, avoiding clean-up steps and the consumption of organic solvents.     

Analysis of alkyl and 2-6-ringed polycyclic aromatic hydrocarbons by isotope dilution gas chromatography/mass spectrometry. Quality assurance and determination in Spanish river sediments

An accurate, precise and sensitive method is described for the analysis of 29 polycyclic aromatic hydrocarbons (PAHs), including 19 2-6-ringed PAHs and 10 alkyl-PAHs. The method is based on an isotope dilution technique using gas chromatography/mass spectrometry (GC/MS) and available labeled PAHs as internal standards. Quality parameters were calculated with satisfactory results and 36 Spanish river sediments were analysed. Results were evaluated regarding to the sediment quality guidelines (SQGs) based on the effects range-low (ERL) and the effects range-median (ERM) values. Most analysed sediments showed a good quality, since only 7 of them exceeded ERL values, including one sample surpassing ERM values. PAH profiles were studied in order to identify PAH sources as mainly petrogenic or pyrogenic. Most samples showed petrogenic-type fingerprints, although 6 of the 11 sediments with the highest PAH concentrations (> 1000 ng/g) were classified as pyrogenic, including 4 of the 7 samples exceeding ERL values. Quality assurance was carried out by the triplicate analysis of one preanalysed river sediment without PAHs subsequently spiked at a medium (500 ng/g) and a low concentration level (10 ng/g) of each analyte. Main quality requirements for methods based on isotope dilution were accomplished. Method accuracy was 80-120% for most PAHs, method precision was <15% for all the analysed compounds and method detection limits (MDLs) were 1-3 ng/g.     

Determination of Polycyclic Aromatic Hydrocarbons in Tobacco Smoke by Ionic Liquid Enrichment and Gas Chromatography – Mass Spectrometry

A rapid, efficient and environmentally friendly method based on the ionic liquid (IL) 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆MIM][PF₆]) was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in mainstream tobacco smoke. This technique combined ionic liquid (IL) enrichment with solvent reverse extraction for the replacement of solid phase extraction and rotary evaporation in the traditional method and enriched PAHs in the organic solvent. Several parameters, including the type of ionic liquid, volume of ionic liquid and water, extraction time, vortex time and reverse extraction time, were optimized. After pretreatment, the analytes were analyzed by gas chromatography-mass spectrometry (GC-MS) using selective ion monitoring (SIM). Satisfactory results were achieved when this method was applied to determine PAHs in mainstream tobacco smoke. The calibration curves were linear with correlation coefficients ranging from 0.9955 to 0.9999 at concentration levels of 10–800?µg?L^?1, and the relative standard deviations of the optimized method were between 0.7% and 5.3%. The limits of detection were 0.01–0.6?ng cig^?1, and the recoveries of the compounds were 80.2–118%. A comparison of this protocol with literature methods demonstrated that the proposed procedure provides accurate and reliable sample-treatment for the determination of PAHs in tobacco samples.     

Preliminary evidence for in vitro methylation of tributyltin in a marine sediment

Recent reports from our laboratory on the occurrence of methylbutyltins in marine sediments and seawater suggest that these compounds are formed in the environment by the methylation of both tributyltin (TBT) and that­of its degradation products, i.e. dibutyltin and monobutyltin, to give Me_nBu_(4?n)Sn for which n = 1, 2 and 3 respectively. We investigated the possibility of inducing methylation of TBT in seawater–sediment mixtures in experiments carried out in vitro using environmental materials collected from a yacht marina in Msida, Malta. Three water–sediment mixtures, which were shown to contain TBT, dibutyltin and monobutyltin but no other organotins, were spiked with tributyltin chloride (90 mg in 100 ml sea‐water/100 ml sediment); to one mixture was added sodium acetate and to another methanol, to act as possible additional carbon sources, and all mixtures were allowed to stand at 25 °C in stoppered clear‐glass bottles in diffused light for a maximum of 315 days. Speciation and quantification of organotins was performed using aqueous phase boroethylation with simultaneous solvent extraction followed by gas chromatography with flame photometric detection. The atmosphere inside the bottles quickly became reducing with abundant presence of H₂S, and after an induction period of about 112 days, and only in the reaction mixture containing methanol, methyltributyltin (MeBu₃Sn) was observed in both sediment (maximum concentration 0.87 µg_Sn g^?1) and overlying water (maximum concentration 6.0 µg_Sn l^?1). The minimum conversion yield of TBT into MeBu₃Sn was estimated to be 0.3%. MeBu₃Sn has a significantly lower affinity for sediment than TBT and, therefore, is more mobile in the marine environment, possibly also migrating into the atmosphere to generate a hitherto unsuspected flux of organotin into that phase. Copyright © 2001 John Wiley & Sons, Ltd.     

Microheterogeneity evaluation of polycyclic aromatic hydrocarbons in particulate standard reference materials

With the emergence of highly sensitive analytical techniques, the microanalysis of natural-matrix materials employing smaller sample sizes is increasingly more common, which subsequently warrants a homogeneity assessment for the individual components at the appropriate sampling level. Pressurized liquid extraction (PLE) in combination with gas chromatography/mass spectrometry (GC/MS) has been used to determine the sampling constants and evaluate the relative homogeneity of trace levels of polycyclic aromatic hydrocarbons (PAHs) for two previously certified particulate standard reference materials, SRM 1649a Urban Dust and SRM 1650b Diesel Particulate Matter, in the milligram sampling range. Fluoranthene, pyrene, benz[a]anthracene and benzo[e]pyrene within SRM 1650b Diesel Particulate Matter were deemed to be homogeneous, based on relatively small sampling constants (K _S<100 mg), whereas the larger sampling constants (K _S>100 mg) obtained for all PAHs in SRM 1649a Urban Dust suggest more material heterogeneity. The material heterogeneity of ten individual PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene) was also described via nonlinear relationships (i.e., power law) between subsampling error S _s (%) and sample mass, which are used to predict analyte-specific minimum sample masses that result in a specific level of analytical uncertainty. Electronic supplementary material Supplementary material is available for this article at and is accessible for authorized users.     

Preparation and homogeneity study of a mussel candidate reference material for certification of organotin compounds

Organotin compounds are currently determined in various environmental matrices (in particular water, sediment and shellfish) to form the basis of control measures for the levels of contamination, as required in some EC Directives. Accurate measurements are a prerequisite for the enforcement of this legislation, which implies that good quality control of determinations should be ensured. One of the tools for achieving accuracy is to use certified reference materials (CRMs). With regard to tin species, however, CRMs are rather scarce and mainly concern sediment and fish matrices certified for their butyltin content. The present study deals with the preparation of a mussel candidate reference material and the verification of its homogeneity prior to the certification of the contents of butyl- and phenyl-tin compounds. 100kg of mussels (Mytilus edulis) were collected, carefully washed with fresh water in order to eliminate matrix salts and immediately frozen by immersion in liquid nitrogen. The mussels were shelled (in the frozen state) and the edible part was stored in thermally sealed polyethylene bags which were stored at –25 °C. The frozen material was ground in a Teflon-coated grinding mill, spread on sterilized flat trays and freeze-dried. The freeze-dried material was then ground for 15 days in a zirconia ball mill and sieved on a titanium sieve to separate the fibrous part. Successively, the material was mixed for 15 days under argon atmosphere in a special polyethylene-lined mixing drum and bottled in brown Pyrex-glass bottles. 21 bottles were selected during the course of the bottling procedure to verify the within- and between-bottle homogeneity of the overall batch. The within-bottle homogeneity was verified by determining the organotin (butyl- and phenyltins) content for subsamples of 500 mg in ten replicates from one bottle, whereas the between-bottle homogeneity was controlled by one organotin measurement from each of 20 bottles. The analyses were performed by GC-MS. The results showed that the homogeneity of the material makes it suitable as a candidate reference material.     

Determination of polycyclic aromatic hydrocarbons in coastal sediments from the Porto region (Portugal) by microwave-assisted extraction, followed by SPME and GC-MS

A simple low-cost, analytical method based on microwave-assisted extraction of sediments, followed by solid phase micro-extraction and gas chromatography mass spectrometry, was developed and validated for the quantification of sixteen polycyclic aromatic hydrocarbons (PAHs) in marine and estuarine sediment samples. The PAHs were those included in the United States Environmental Protection Agency (US EPA) priority list. Method detection limits were between 0.07 and 0.76 μg/kg dry weight (dw), which makes the current method suitable for environmental analysis. Sediments screened for PAHs from the Douro River estuary and the Porto seacoast exhibit total concentrations that ranged from 58.98 to 156.45 μg/kg dw, and from 51.98 to 54.79 μg/kg dw, respectively. The presence of almost all human carcinogenic PAHs in the analyzed areas indicate that these sediments can be considered polluted, suggesting that future monitoring programs together with an effective coastal management program must be implemented to guarantee the safe usage of the current areas for fishing and bathing.     

Two new marine sediment standard reference materials (SRMs) for the determination of organic contaminants

Two new marine sediment standard reference materials (SRMs), SRM 1941b Organics in Marine Sediment and SRM 1944 New York/New Jersey Waterway Sediment, have been recently issued by the National Institute of Standards and Technology (NIST) for the determination of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pesticides. Both sediment SRMs were analyzed using multiple analytical methods including gas chromatography/mass spectrometry (GC/MS) on columns with different selectivity, reversed-phase liquid chromatography with fluorescence detection (for PAHs only), and GC with electron capture detection (for PCBs and pesticides only). SRM 1941b has certified concentrations for 24 PAHs, 29 PCB congeners, and 7 pesticides, and SRM 1944 has certified concentrations for 24 PAHs, 29 PCB congeners, and 4 pesticides. Reference concentrations are also provided for an additional 58 (SRM 1941b) and 39 (SRM 1944) PAHs, PCB congeners, and pesticides. SRM 1944, which was collected from multiple sites within New York/New Jersey coastal waterways, has contaminant concentrations that are generally a factor of 10–20 greater than SRM 1941b, which was collected in the Baltimore (Maryland) harbor. These two SRMs represent the most extensively characterized marine sediment certified reference materials available for the determination of organic contaminants.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Closed-vessel miniaturised microwave-assisted EDTA extraction to determine trace metals in plant materials

The demonstration of an innovative miniaturised closed-vessel microwave-assisted extraction (µMAE) method under the use of EDTA (µMAE-EDTA) for determination of trace metal contents in grassland (Lolio-Cynosuretum) was examined by ICP-OES. The evaluation of the method was done by comparison of the results with another miniaturised closed-vessel microwave HNO₃ method (µMAE-H) and with a macro-scale microwave procedure (MAE-H). Concerning their homogeneity certified plant reference materials (CRMs) were used for validation of the applicability of µMAE-EDTA procedure. For CRMs and 72 real plant samples, no significant differences were found between µMAE-EDTA and MAE-H in the determination of Cd, Co, Cu, Mn, Ni, Pb, and Zn contents. Recovery rates achieved from µMAE-EDTA for CRMs ranged between 100.0–102.6% for the investigated elements. The key characteristics of µMAE-EDTA for determination of trace metal contents in plant samples are: (i) suitability as a high-throughput procedure; (ii) consumption of minimum volume of extracting agent and minimum amount of sample; and (iii) combination of fast, safe and environmentally friendly extraction procedure.     

溶胶-凝胶杂化整体柱修饰及在多环芳烃检测中的应用

利用点击反应对含叠氮基的溶胶-凝胶整体柱进行了表面修饰,制备了C₆-硅胶杂化整体萃取柱。实验以多环芳烃为分析对象,考察了制备和修饰条件对萃取效率的影响,在优化的条件下,新制备的整体柱对萘、菲、芘和苯并[a]芘的萃取富集倍数分别达到95.9、114.2、103.2和57.8。萃取实验的日内和日间精密度(RSD)分别小于5.5%(n=8)和7.3%(n=10)。建立的管内固相微萃取-高效液相色谱检测16种常见多环芳烃方法的检出限(S/N=3)达到0.08~3.72 μg/L,定量限(S/N=10)达到0.26~12.40 μg/L。土壤中多环芳烃分析的加标回收率为82.4%~110.6%, RSD为2.6%~7.9%(n=3)。与美国国家环境保护局检测土壤中多环芳烃的方法比较,结果一致,准确性高。实验表明,该方法萃取效率高,灵敏可靠,操作简便,重现性好,可满足土壤等样品中痕量多环芳烃检测的要求。