Solid-phase microextraction and gas chromatography-mass spectrometry for the determination of polycyclic aromatic hydrocarbons in environmental solid matrices

A solid-phase microextraction (SPME) and gas chromatography-mass spectrometry method for determining polycyclic aromatic hydrocarbons (PAHs) in environmental solid matrices is developed. Investigated matrices include seaweed (Undaria pinnatifida and Himanthalia elongata), humic substances (isolated from a wetland out-flow and purchased from Aldrich), and soil. Optimal conditions for a good SPME efficiency of 16 hydrocarbon compounds are obtained using a 100- micro m polydimethylsiloxane fiber directly immersed in aqueous carrier medium. The method is remarkable for presenting short extraction times and considerably high sensitivities. The SPME results obtained by using internal calibration give the total analyte concentration based on the identical partitioning behavior of native and spiked pollutants. The detection limits range from 0.001 to 0.1 mg of PAH per kilogram of dry matrix. SPME external calibration provides information regarding freely dissolved analytes. The detection limits range from 0.001 to 0.05 micro g of PAH per liter of carrier medium. The SPME with external calibration procedure can be applied to measure free concentrations of a target compound spiked into a carrier medium and onto a matrix. Based on a comparison of results obtained for the two samples, the partitioning of the target analyte between the matrix and the carrier medium is calculated.     

In-tube solid-phase microextraction-capillary liquid chromatography as a solution for the screening analysis of organophosphorus pesticides in untreated environmental water samples

This paper describes a method for the selective screening of organophosphorus pesticides in water. In-tube solid-phase microextraction (SPME) in an open capillary column coupled to capillary liquid chromatography (LC) with UV detection has been used to effect preconcentration, separation and detection of the analytes in the same assembly. For in-tube SPME two capillary columns of the same length and different internal diameters and coating thicknesses have been tested and compared, a 30 cm x 0.25 mm I.D., 0.25 micro m thickness coating column, and a 30 cm x 0.1 mm I.D., 0.1 micro m of coating thickness column. In both columns the coating was 95% dimethylpolysiloxane (PDMS)-5% diphenylpolysiloxane. The proposed methodology provided limits of detections (LODs) for the tested organophosphorus pesticides in the 0.1-10 micro g/L range, whereas the direct injection of the samples onto the capillary LC system provided LODs in the 50-1000 micro g/L range. The sensitivity of the proposed in-tube SPME-capillary LC method is adequate to monitorize the analyte levels in drinking water. Several triazines, polycyclic aromatic hydrocarbons (PAHs), nonylphenol, organochloride pesticides or polybrominated diphenyl ethers (PBDEs) have been evaluated as possible interferents. The reliability of the described method is demonstrated by analysing different real water samples.     

Optimization of solid‐phase microextraction using Taguchi design to quantify trace level polycyclic aromatic hydrocarbons in water

This article introduces a simple, rapid, and reliable solid‐phase microextraction (SPME) method coupled with GC‐MS for the quantitative determination of 16 polycyclic aromatic hydrocarbons in water. In this study, the Taguchi experimental design was used to optimize extraction conditions of polycyclic aromatic hydrocarbons using SPME method to obtain highly enriched analytes. Consequently, quantitative determination of polycyclic aromatic hydrocarbons in water was achieved by GC‐MS technique. The selected parameters affecting enrichment of polycyclic aromatic hydrocarbons were sample extraction time, stirring speed, temperature, ionic strength, and pH. The study revealed that optimal operating conditions were found to be 90‐min extraction time, 1400 rpm stirring speed, and 60°C sample temperature. The effect of ionic strength and pH were shown to be insignificant. Optimized conditions were also reevaluated by placing the 16 polycyclic aromatic hydrocarbons into several subgroups based on their molecular weight. The extraction efficiency of polycyclic aromatic hydrocarbons with low molecular weight was shown to be a function of only the extracting temperature. Satisfactory results were obtained for linearity (0.983–0.999), detection limits (2.67–18.02 ng/L), accuracy (71.2–99.3%), and precision (4.3–13.5%). The optimum conditions reported by other design approaches were evaluated and generalized optimum conditions were suggested.     

Polythiophene/hexagonally ordered silica nanocomposite coating as a solid‐phase microextraction fiber for the determination of polycyclic aromatic hydrocarbons in water

A highly porous fiber coated with polythiophene/hexagonally ordered silica nanocomposite was prepared for solid‐phase microextraction (SPME). The prepared nanomaterial was immobilized onto a stainless‐steel wire for the fabrication of the SPME fiber. Polythiophene/hexagonally ordered silica nanocomposite fibers were used for the extraction of some polycyclic aromatic hydrocarbons from water samples. The extracted analytes were transferred to the injection port of a gas chromatograph using a laboratory‐designed SPME device. The results obtained prove the ability of the polythiophene/hexagonally ordered silica material as a new fiber for the sampling of organic compounds from water samples. This behavior is due most probably to the increased surface area of the polythiophene/hexagonally ordered silica nanocomposite. A one‐at‐a‐time optimization strategy was applied for optimizing the important extraction parameters such as extraction temperature, extraction time, ionic strength, stirring rate, and desorption temperature and time. Under the optimum conditions, the LOD of the proposed method is 0.1–3 pg/mL for analysis of polycyclic aromatic hydrocarbons from aqueous samples, and the calibration graphs were linear in a concentration range of 0.001–20 ng/mL (R² > 0.990) for most of the polycyclic aromatic hydrocarbons. The single fiber repeatability and fiber‐to‐fiber reproducibility were less than 8.6 and 19.1% (n = 5), respectively.     

Determination of trace PAHs in seawater and sediment pore-water by solid-phase microextraction (SPME) coupled with GC/MS

A fast and reliable method for the determination of trace PAHs (polynuclear aromatic hydrocarbons) in seawater by solid-phase microextraction (SPME) followed by gas chromatographic (GC) analysis has been developed. The SPME operational parameters have been optimized, and the effects of salinity and dissolved organic matter (DOM) on PAHs recoveries have been investigated. SPME measures only the portion of PAHs which are water soluble, and can be used to quantify PAH partition coefficient between water and DOM phases. The detection limits of the overall method for the measurement of sixteen PAHs range from 0.1 to 3.5 ng/g, and the precisions of individual PAH measurements range from 4% to 23% RSD. The average recovery for PAHs is 88.2±20.4%. The method has been applied to the determination of PAHs in seawater and sediment porewater samples collected in Jiaozhou Bay and Laizhou Bay in Shandong Peninsula, China. The overall levels of PAHs in these samples reflect moderate pollution compared to seawater samples reported elsewhere. The PAH distribution pattern shows that the soluble PAHs in seawater and porewater samples are dominated by naphthalenes and 3 ring PAHs. This is in direct contrast to those of the sediment samples reported earlier, in which both light and heavy PAHs are present at comparable concentrations. The absence of heavy PAHs in soluble forms (<0.1-3.5 ng/L) is indicative of the strong binding of these PAHs to the dissolved or solid matters and their low seawater solubility.     

New micromethod combining miniaturized matrix solid-phase dispersion and in-tube in-valve solid-phase microextraction for estimating polycyclic aromatic hydrocarbons in bivalves

Miniaturized matrix solid-phase dispersion (MSPD) was developed for the extraction of common polycyclic aromatic hydrocarbons (PAHs) from bivalve samples (100mg, dry weight). Additional clean-up and analyte enrichment was accomplished by in-tube solid-phase microextraction (SPME). For this purpose the extracts collected after MSPD were diluted with water and injected into a capillary column coated with the extractive phase. This capillary column was connected to the analytical column by means of a switching valve. Separation and quantification of the PAHs were carried out using a monolithic LC column and fluorescence detection. Since the in-tube SPME device allowed the processing of large volumes of the extracts (2.0 mL) excellent sensitivity was achieved, thus making solvent evaporation operations unnecessary. The overall recoveries ranged from 10% to 28% for the studied compounds. The relative standard deviation (RSD) ranged from 2% to 10% for intra-day variation (n=3), and the limits of detection (LODs) were < or =0.6 ng/g (dry weight). The proposed procedure was very simple and rapid (total analysis time was approximately 20 min), and the consumption of organic solvents and extractive phases was drastically reduced. The reliability of the proposed MSPD/in-tube SPME method was tested by analysing several bivalves (mussels and tellins) as well as a standard reference material (SRM).     

Application of solid phase microextraction for the determination of soil fumigants in water and soil samples

The potential of solid phase microextraction (SPME) for the determination of the soil fumigants 1,3-dichloropropene (1,3-DCP) and methyl isothiocyanate (MITC) in environmental samples such as soil and water samples has been investigated. Direct immersion SPME followed by GC/ECD/NPD analysis allowed the rapid determination of the two fumigants in water samples, with very little sample manipulation, giving an LOD of 0.5 microg L(-1). Precision, calculated as relative standard deviation (RSD) for six replicates at three concentration levels, was found to be lower than 20% at the concentration levels tested. For the analysis of soil samples, headspace (HS)-SPME combined with GC/ECD/NPD analysis has been applied. Quantification using matrix-matched calibration curves allowed determination of both analytes (MITC and 1-3-DCP) with a LOD of 0.1 microg kg(-1) (RSD < 10%) for the two concentration levels assayed (0.02 and 0.2 mg kg(-1)). The HS-SPME procedure developed in this paper was applied to soil samples from experimental green house plots treated with metham-Na, a soil disinfestation agent that decomposes in soil to MITC. The absence of sample manipulation as well as the low solvent consumption in SPME methodology are among the main advantages of this analytical approach.     

Determination of polycyclic aromatic hydrocarbons in sediment using solid-phase microextraction with gas chromatography-mass spectrometry

Manual solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) is applied for the determination of polycyclic aromatic hydrocarbons (PAHs) from natural matrix through a distilled water medium. Seven of the 16 PAH standards (naphthalene, acenaphthene, fluorene, anthracene, fluoranthene, pyrene, benzo[a]anthracene) are spiked on a marine muddy sediment. The samples, containing PAHs in the range of 10-20 ppm, are then aged at room temperature more than 10 days before analysis. The influence of the matrix, SPME adsorption time, pH, salt content, and SPME adsorption temperature are investigated. The reproducibility of the technique is less than 13% (RDS) for the first 6 considered PAHs and 28% (RDS) for benzo(a)anthracene with a fiber containing a 100-micron poly dimethylsiloxane coating. Linearity extended in the range of 5-50 picograms for PAHs direct injection, 5-70 picograms for PAHs in water, and 1-170 picograms for PAHs in sediment. The detection limit is estimated less than 1 microgram/kg of dry sample for the first 6 considered PAHs in sediment and 1.5 micrograms/kg of dry sample for benzo(a)anthracene using the selected ion monitoring mode in GC-MS. The recoveries of the considered PAHs are evaluated.     

基于低共熔溶剂的整体式萃取头的制备及其对湖水中3种多环芳烃的固相微萃取（英文）

采用氯化胆碱-乙二醇低共熔溶剂(DES)作致孔剂,制备了聚(甲基丙烯酸丁酯-乙二醇二甲基丙烯酸酯)[poly(BMA-EDMA)]固相微萃取头,并与超高效液相色谱法(UPLC)结合测定了湖水中的3种多环芳烃(PAHs)。实验与不使用DES致孔剂的固相微萃取头和商品化聚二甲硅氧烷(PDMS)萃取头进行比较,含DES的poly(BMA-EDMA)固相微萃取头的富集效果最好。系统考察了萃取条件(萃取时间、萃取溶剂、解吸时间、解吸溶剂及离子强度)对水样中多环芳烃萃取效率的影响。在最优的实验条件下,3种多环芳烃类化合物(萘、联苯、菲)的线性范围为0.1~6.0 mg/L(r≥0.990 3),检出限为2.1~4.9μg/L,回收率为86.4%~111.3%,相对标准偏差(RSD,n=6)为11.2%~15.1%。该法操作简便,稳定性好,成本低,适用于实际环境水样中多环芳烃类化合物的测定。     

Determination of polycyclic aromatic hydrocarbons in aqueous samples by microwave assisted headspace solid-phase microextraction and gas chromatography/flame ionization detection

The novel pretreatment technique, microwave-assisted heating coupled to headspace solid-phase microextraction (MA-HS-SPME) has been studied for one-step in situ sample preparation for polycyclic aromatic hydrocarbons (PAHs) in aqueous samples before gas chromatography/flame ionization detection (GC/FID). The PAHs evaporated into headspace with the water by microwave irradiation, and absorbed directly on a SPME fiber in the headspace. After being desorbed from the SPME fiber in the GC injection port, PAHs were analyzed by GC/FID. Parameters affecting extraction efficiency, such as SPME fiber coating, adsorption temperature, microwave power and irradiation time, and desorption conditions were investigated.Experimental results indicated that extraction of 20 mL aqueous sample containing PAHs at optional pH, by microwave irradiation with effective power 145 W for 30 min (the same as the extraction time), and collection with a 65 μm PDMS/DVB fiber at 20 °C circular cooling water to control sampling temperature, resulted in the best extraction efficiency. Optimum desorption of PAHs from the SPME fiber in the GC hot injection port was achieved at 290 °C for 5 min. The method was developed using spiked water sample such as field water with a range of 0.1-200 μg/L PAHs. Detection limits varied from 0.03 to 1.0 μg/L for different PAHs based on S/N = 3 and the relative standard deviations for repeatability were <13%. A real sample was collected from the scrubber water of an incineration system. PAHs of two to three rings were measured with concentrations varied from 0.35 to 7.53 μg/L. Recovery was more than 88% and R.S.D. was less than 17%. The proposed method is a simple, rapid, and organic solvent-free procedure for determination of PAHs in wastewater.     

苯基修饰二氧化硅纳米片纤维的制备及其对多环芳烃的固相微萃取

采用水热处理和溶胶-凝胶法在镍钛合金（NiTi）纤维表面组装了二氧化硅纳米片（SiO₂NFs）,成功制备了新型SiO₂纤维涂层,并用苯基三氯硅烷进行了自组装表面修饰,得到了可用于固相微萃取（SPME）的NiO/TiO₂@SiO₂NFs-Ph纤维。将制备的SPME纤维与高效液相色谱联用,通过对典型芳香化合物的分析评价了所制备纤维的萃取性能。该纤维对多环芳烃（PAHs）具有较高的萃取率和良好的萃取选择性。实验优化了pH值、搅拌速率、萃取温度、萃取时间和离子强度对PAHs萃取率的影响。在优化条件下,5种PAHs在各自的范围内呈良好的线性关系,相关系数（r）大于0.999,检出限为0.013~0.108 μg/L。使用单根纤维对含有50 μg/L PAHs的加标水样进行萃取,其含量的日内及日间RSD分别为4.1%~5.9%和4.8%~6.8%。实际环境水样中5种PAHs在10 μg/L和30 μg/L加标水平下的加标回收率分别为90.8%~105.7%和93.6%~103.1%。该法制备的NiO/TiO₂@SiO₂NFs-Ph纤维稳定性高、制备重现性好,适用于环境水样中目标PAHs的富集和测定。     

Laser-based detection of PAHs and BTXE-aromatics in oil polluted soil samples

Time-resolved laser-induced fluorescence spectroscopy and fiber optics are applied for the detection of aromatic hydrocarbons in oil contaminated water and soil samples. Time-integrated data accumulation of fluorescence intensities in an "early" and in a "late" time window with respect to the exciting laser pulse simplifies the method in such a way that it becomes very attractive for practical applications. For ultraviolet laser excitation at 337 nm and recording fluorescence signals at 400 nm, typical detection limits of the present set-up are 0.5 mg engine oil/L in water and 5 mg engine oil/kg in soil. A discrimination between BTXE-aromatics and PAHs in oil polluted soil or water samples is possible, when more than one laser wavelength in the ultraviolet is used for the excitation. The possibilities for a thermal discrimination between different aromatics are also discussed.     

Hydroxyundecanethiol-Modified Steel Fibers for the Selective Solid-Phase Microextraction of Polycyclic Aromatic Hydrocarbons from River and Wastewater

A novel organic–inorganic composite-coated fiber was developed for selective solid-phase microextraction (SPME) by direct electrodeposition of zinc oxide microparticles on a pretreated stainless steel wire followed by self-assembly of hydroxyundecanethiol with zinc–sulfur bonds. The performance of the hydroxyundecyl-modified zinc oxide-coated steel fiber was then assessed for SPME of polar aromatic compounds coupled to high-performance liquid chromatography with ultraviolet detection. Excellent extraction and selectivity were obtained for polycyclic aromatic hydrocarbons. The extraction and desorption times, temperature, stirring rate, and ionic strength were optimized. The limits of detection were from 0.034 to 0.132?µg?L^?1. The relative standard deviations were from 3.4 to 4.9% for a single fiber and from 5.1 to 6.4% for multiple fibers. The recovery of polycyclic aromatic hydrocarbons in environmental water fortified at 5.0 and 50?µg?L^?1 was from 83.1 to 103% with relative standard deviations below 8.4%. This fiber was shown to withstand at least 200 extraction and desorption cycles. The method was used for the preconcentration and determination of polycyclic aromatic hydrocarbons in environmental water.     

应用二极管阵列串联荧光检测-高效液相色谱技术快速测定玩具材料中蒽油的4种成分

采用二极管阵列串联荧光检测-高效液相色谱法对玩具材料中蒽油的4种主要成分蒽、菲、芘、荧蒽进行了检测。样品用正己烷-丙酮溶液超声提取,硅胶小柱净化。方法的荧光检测线性范围为0.5～1000 μg/L,二极管阵列检测线性范围为0.5～1000 mg/L。加标回收、精密度试验表明4种成分的回收率为70.0%～120%,精密度为0.7%～8.8%。蒽、菲、芘、荧蒽的检出限分别为0.1、0.1、0.2、0.3 μg/L,定量限分别为0.4、0.2、0.5、0.8 μg/L。方法具有灵敏度高、检出限低的特点,适用于玩具材料中蒽油4种成分的快速定性、定量检测。     

Application of solid-phase microextraction for the determination of pyrethroid residues in vegetable samples by GC-MS

A solid-phase microextraction (SPME) method has been developed for the determination of 7 pyrethroid insecticides (bifenthrin, lambda-cyhalothrin, permethrin, cyfluthrin, cypermethrin, fenvalerate, and tau-fluvalinate) in water, vegetable (tomato), and fruit (strawberry) samples, based on direct immersion mode and subsequent desorption into the injection port of a GC/MS. The SPME procedure showed linear behavior in the range tested (0.5-50 microg L(-1) in water and 0.01-0.1 mg kg(-1) in tomato) with r(2) values ranging between 0.97 and 0.99. For water samples limits of detection ranged between 0.1 and 2 microg L(-1 )with relative standard deviations lower than 20%. Detection limits for tomato samples were between 0.003 and 0.025 mg kg(-1) with relative standard deviations around 25%. Finally, the SPME procedure has been applied to vegetable (tomato) and fruit (strawberry) samples obtained from an experimental plot treated with lambda-cyhalothrin, and in both cases the analyte was detected and quantified using a calibration curve prepared using blank matrix. SPME has been shown to be a simple extraction technique which has a number of advantages such as solvent-free extraction, simplicity, and compatibility with chromatographic analytical systems. Difficulties with the correct quantification in a complex matrix are also discussed.     

高效液相色谱-气相色谱在线联用同时测定土壤中饱和烃和芳香烃

为加强对土壤中石油烃类污染物的风险管控,生态环境部已将石油烃类列为土壤中的重点监测项目.石油烃源于石油与合成油,是涵盖一定碳数范围的碳氢化合物,主要分为饱和烃和芳香烃两大类.芳香烃通常是高度烷基化的单环、双环与多环芳烃,其对人和动物的毒性较饱和烃大很多,因此,仅仅测定土壤中总石油烃含量难以准确评估其环境毒性.目前环境领...     

Chemical Composition and <em>in Vitro</em> Evaluation of the Antioxidant and Antimicrobial Activities of <em>Eucalyptus gillii </em>Essential Oil and Extracts<em></em>

In this study, essential oil and various extracts (hexane, petroleum ether, acetone, ethanol, methanol and water) of Eucalyptus gilii were screened for their chemical composition, antimicrobial and antioxidant activities. The essential oil chemical composition was analyzed by gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detection (GC-FID), respectively. Thirty four compounds were identified, corresponding to 99.5% of the total essential oil. Tannins [104.9-251.3 g catechin equivalent (CE)/Kg dry mass], flavonoids [3.3-34.3 g quercetin equivalent (QE)/Kg dry mass], phenolics [4.7-216.6 g gallic acid equivalent (GAE)/Kg dry mass] and anthocyannins [1.2-45.3 mg cyanidin-3-glucoside equivalent (C3GE)/Kg dry mass] of various extracts were investigated. Free radical scavenging capacity of all samples was determinedt. In the 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay, the IC₅₀ of essential oil was 163.5 ± 10.7 mg/L and in the 2,2'-azinobis-3-ethylbenzothiazoline-6-sulphonate (ABTS) assay, it was 94.7 ± 7.1 mg/L. Among the various extracts, the water extract showed the best result (IC₅₀ = 11.4 ± 0.6 mg/L) in the DPPH assay which was comparable to vitamin C (IC₅₀ = 4.4 ± 0.2 mg/L). The antimicrobial activities were evaluated against different bacterial and fungal strains. Gram positive bacteria were found to be more sensitive to the essential oil and extracts than Gram negative ones. Anthocyanins seem to have a major effect on the growth of Bacillus subtilis (R² = 0.79). A significant antifungal activity was observed against the yeast and fungi. Correlations between chemical composition and antioxidant activities were studied and R² values were about 0.96 for the effect of phenolics on the DPPH assay.     

用于固相微萃取的乙烯基开链冠醚复合涂层的研制

固相微萃取 (SPME)是一种新型的样品预处理技术 [1] ,其核心是 SPME装置中萃取头上的固相涂层 .目前商用 SPME涂层的种类较少 ,热稳定性较差 (推荐使用温度 2 0 0～ 2 80℃ ) ,使用寿命较短(40～ 1 0 0次 ) ,价格偏高 ,限制了其推广应用 .因此发展高选择性、高稳定性和高效的固     

A highly thermal-resistant electrospun-based polyetherimide nanofibers coating for solid-phase microextraction

A high-temperature-resistant solid-phase microextraction (SPME) fiber was prepared based on polyetherimide (PEI) by the electrospinning method. The PEI polymeric solution was converted to nanofibers using high voltages and directly coated on a stainless steel SPME needle. The scanning electron microscopy images of PEI coating showed fibers with diameter range of 500–650 nm with a homogeneous and smooth surface morphology. The SPME nanofibers coating was optimized for PEI percentage, electrospinning voltage, and time. The extraction efficiency of the coating was investigated for headspace SPME of some environmentally important polycyclic aromatic hydrocarbons from aqueous samples followed by gas chromatography–mass spectrometry measurement. In addition, the important extraction parameters including extraction temperature, extraction time, ionic strength, as well as desorption temperature and time were investigated and optimized. The detection limits of the method under optimized conditions ranged from 1 to 5 ng L^?1 using time-scheduled selected ion monitoring mode. The relative standard deviations of the method were between 1.1 and 7.1 %, at a concentration level of 500 ng L^?1. The calibration curves of polycyclic aromatic hydrocarbons showed linearity in the range of 5–1000 ng L^?1. The developed method was successfully applied to real water samples and the relative recovery percentages obtained from the spiked water samples were from 84 to 98 % for all the selected analytes except for acenaphthene which was from 75 to 106 %.     

Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization

Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6–191 μg/L for nitrated and 0.3–8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2‐nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected.