Recoveries Of Polycyclic Aromatic Hydrocarbons Research Articles

Study on the Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Fingernail and Hair Samples by Gas Chromatography Mass Spectrometry (GC/MS)

Information about human exposure to polycyclic aromatic hydrocarbons (PAHs) in Vietnam is still very limited. In this study, an accurate method for the determination of 16 PAHs in human hair and fingernail samples was developed. The nail and hair samples were digested in sodium hydroxide solution. PAHs in the digested solutions were extracted using organic solvents such as hexane and dichloromethane. The extracts were cleaned up by using solid phase extraction (SPE) cartridges containing silica gel with dichloromethane/hexane mixture as elution solvent. PAHs were quantified by a gas chromatography/mass spectrometry (GC/MS) system operated in electron impact ionization and selected ion monitoring (EI/SIM) mode. The liquid-liquid extraction and SPE clean-up steps were investigated to obtain acceptable recovery of PAHs before application to nail and hair samples. Recovery of PAHs in spiked nail and hair samples ranged from 66% to 112%, indicating acceptable method accuracy. Concentrations of 16 PAHs in the nail and hair samples were 160 and 733 ng/g, respectively. Major PAHs found in the nail and hair samples were naphthalene, phenanthrene, fluoranthene, and pyrene. Additional studies on human biomonitoring of PAHs and their related compounds should be conducted in Vietnam.

The levels of polycyclic aromatic hydrocarbons in traditional cigarettes and E-cigarettes in Saudi Arabia markets: a comparative risk assessment study

BackgroundTwo validated and effective extraction techniques have been developed to ascertain the presence of polycyclic aromatic hydrocarbons (PAHs) in traditional cigarettes and E-cigarettes. PAHs are a class of chemicals that occur naturally, and these contaminants may cause cancer and other harmful effects in human beings. Traditional cigarettes and E-cigarettes contain many PAHs.MethodIn terms of linearity, limit of detection, limit of quantification, accuracy (%), and precision (%), the two in-house lab setups for 7PAHs extraction from traditional cigarettes and E-cigarette were validated using high-performance liquid chromatography-fluorescence detection.ResultsThe concentration of Σ7PAHs for traditional cigarettes and E-cigarettes ranged from 6.23 ± 0.04 ng/cig to 75.61 ± 0.02 ng/cig, and non-detectable to 3.56 ± 2.71 ng/puff. The PAHs recovery in traditional cigarettes and E-cigarettes ranged from 92.74–110.45%, and 97.20–111.74%. The toxicity of equivalent (TEQs) of carcinogens revealed that traditional cigarettes brands have higher TEQs than E-cigarettes.ConclusionThis study highlights the detection of 7PAHs levels and its risk assessment in product brands for traditional cigarettes and E-cigarettes marketed in Saudi Arabia. The results suggested that the developed methods are a precise and versatile approach for measuring 7PAHs in traditional cigarettes and E-cigarettes.

An ultrasound assisted dispersive micro solid-phase extraction and a composite ionic liquid-metal organic framework for sixteen polycyclic aromatic hydrocarbons analysis in fruit juice and environmental water samples

Aluminum-based metal organic framework composite containing ionic liquid was prepared and used as sorbent for extraction of sixteen polycyclic aromatic hydrocarbons in list of priority pollutants of United States Environmental Protection Agency before their analysis by gas chromatography/mass spectrometry. The dispersive micro solid-phase extraction method, known as a simple and fast method, was preferred as the extraction method. The optimized parameter conditions were 5 mL of sample solution, 10 min sonication by ultrasonic bath, 30 mg of sorbent, 30 °C extraction temperature, 0.1 mL of hexane as elution solvent with 5 min elution time. The suggested method presented that limit of detection and limit of quantification were in the range of 0.01–0.10 μg l-1, and 0.04–0.33 μg L-1, respectively. The intra-day and inter-day repeatability were within the ranges of 1.18–4.88 % and 1.02–5.06 %, respectively. The recoveries for polycyclic aromatic hydrocarbons in peach juice, cherry juice, tap water and rain water samples were obtained in the range of 84.9–99.9 % for spiked 5, 50 and 100 μg l-1 standard polycyclic aromatic hydrocarbons solution.

Solid phase extraction coupled with gas chromatography-triple quadrupole mass spectrometry for the rapid and simultaneous determination of forty-nine parent and halogenated polycyclic aromatic hydrocarbons in human serum

Halogenated polycyclic aromatic hydrocarbons (H-PAHs) are the emerging organic pollutants in environment, which are ubiquitous in the atmosphere, soil and water. Some H-PAH congeners have been proven to have dioxin-like toxicity. However, the research on the human internal exposure of H-PAHs is still limited. A simple and efficient analytical method is essential for the study of human internal exposure, so a method for the rapid and simultaneous determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 33 H-PAHs in human serum was established in this study. After 1.0 mL serum was extracted with ethyl acetate/acetonitrile (1:4) solution containing 1 % formic acid, samples were purified by Captiva EMR-Lipid solid phase extraction column, and then determined by gas chromatography tandem triple quadrupole mass spectrometer (GC-MS/MS). The results showed that the recoveries of PAHs and H-PAHs ranged from 71.2 % to 119 % and 68.8 % to 121 %, respectively. When 1.0 mL of serum sample is used, the method detection limit of PAHs and H-PAHs is 0.001–0.314 ng/mL. The method is simple and efficient, and suitable for the simultaneous determination of trace PAHs and H-PAHs in human serum. High concentrations of chlorinated polycyclic aromatic hydrocarbons were detected in pooled serum, of which 1,5-dichloranthracene was the main contributor congener, with a concentration of 204–328 ng/g lipid, which deserved more attention.

Enrichment and detection of polycyclic aromatic hydrocarbon in tea and coffee using phenyl-functionalized NiFe2O4@Ti3C2TX based magnetic solid-phase extraction

Polycyclic aromatic hydrocarbons (PAHs) are commonly found in various environmental matrices and have received significant attention due to their toxic effects on ecosystems and environmental health. In this study, a specific magnetic composite material derived from MXene, known as phenyl-functionalized NiFe2O4@Ti3C2TX, was designed and synthesized using a simple method. This composite material was used to develop an effective magnetic solid-phase extraction (MSPE) method for enriching trace polycyclic aromatic hydrocarbons (PAHs) in tea and coffee samples. The eluted PAHs were analyzed via gas chromatography–tandem mass spectrometry. Under optimal conditions, this method exhibited excellent linear relationships for 16 PAHs within the ranges of 0.001–25 and 0.0005–25 μg/L, with correlation coefficients exceeding 0.9979. The limits of detection for the target PAHs ranged from 0.1 to 0.3 ng/L. The effectiveness of the proposed method was evaluated by analyzing tea and coffee samples, and the satisfactory spiked recoveries of PAHs ranged from 84.5% to 112.6%.

Eco-friendly fabrication of novel hydrophobic CMC–C18@MWCNTs nano-sorbent for fat content removal in the analysis of polycyclic aromatic hydrocarbons in fatty-food samples

In this study, carbon nanohybrids was developed by hybridizing carboxymethyl cellulose (CMC) biopolymer with various amounts of multi-walled carbon nanotubes (MWCNTs: 0.2, 0.5, 1, 3, and 5%) in eco-friendly process to produce hydrophobic CMC–C18@MWCNTs, which was then used as a sorbent material for fat content in fatty food samples analysis. The hydrophobic biopolymers were synthesized using an ultrasound-assisted esterification process, and the physicochemical properties were analyzed using FT-IR, XRD, TGA, FE-SEM, and TEM. The performance of the hydrophobic nanocomposites was evaluated by assessing their ability to remove fat content during polycyclic aromatic hydrocarbon (PAHs) analysis in tuna samples. The results showed that CMC–C18–CNT0.2% provided the best peak shapes and highest recoveries for PAHs compounds, ranging between 74.3 and 89.7%, while CMC–C18–CNT5% had the lowest recoveries, ranging between 0 and 35%. Therefore, the lowest amount of MWCNTs was found to be the most efficient for removing fat content with providing high PAHs recovery, while increasing the MWCNTs percentage increased the hydrophobicity and removed PAHs analytes along with fat content. After the investigation, the method was validated using CMC–C18–CNT0.2% in three various levels: 2, 5 and 10 μg kg−1. The obtained results were satisfactory; the average recoveries for all PAHs compounds ranged between 74.3 to 89.7%, and the intra-day precision were estimated by coefficient of variation (%CV), where were less than 10% for all PAHs. The LOD and LOQ were lies between 0.33 to 0.89 μg kg−1 and 1.12 to 1.92 μg kg−1 respectively. For the calibration curve linearity, the correlation coefficient (r2) were higher than 0.999 for all PAHs. Overall, the hydrophobic CMC–C18@MWCNTs are a promising, modifiable, and useful material for fatty food analysis.

Length-controlled hydrophobic CF3-COF as a highly efficient absorbent coating for dual-mode solid-phase microextraction of sixteen polycyclic aromatic hydrocarbons in water samples

Polycyclic aromatic hydrocarbons (PAHs), a group of seriously hazardous environmental contaminants, have attracted extensive attention due to their carcinogenicity, genotoxicity, mutagenicity, and ubiquity. In this work, the excellent hydrophobic trifluoromethyl-enriched covalent organic framework (CF3-COF) was designed and synthesized as coating of solid-phase microextraction (SPME). The CF3-COF offered a high adsorption selectivity for PAHs, which could be attributed to the multiple interactions between the CF3-COF and PAHs, including hydrophobicity interaction, π-π and H bond interactions. Furthermore, headspace (HS) and direct immersion (DI) dual-mode solid-phase microextraction (HS/DI-SPME) were innovatively integrated as a dual-mode extraction by varying the length of SPME coating on stainless-steel, which could simultaneously and efficiently extract 16 PAHs with different volatile. Amazingly, the proposed strategy achieved fast adsorption for PAHs and shortened the adsorption equilibrium time to 15 min. By further integrating with gas chromatography tandem mass spectrometry (GC–MS/MS), PAHs could be detected in the range of 0.008–0.16 ng mL−1 with a quantitative limit of 0.029–0.47 ng mL−1, respectively. The recoveries of PAHs in water samples ranged from 80.84 to 117.67 %. This work indicates that the dual-mode CF3-COF-SPME is a promising candidate for the enrichment of multiple hazardous substances in complicated samples.

Polycyclic aromatic hydrocarbons in sewage-irrigated vegetables from industrial cities in Haryana, India.

The majority of Indians consume a lot of vegetables because of their health advantages. High concentrations of polycyclic aromatic hydrocarbons (PAHs) in vegetables may be seriously harmful to consumers' health. The method for identifying and measuring 16 USEPA polycyclic aromatic hydrocarbons (PAHs) in samples of sewage-irrigated vegetables from three industrial cities in Haryana, India, is described in this research. Ultrasonication, liquid-liquid extraction using n-hexane as a solvent, clean-up using a Florisil column, and reversed-phase high-performance liquid chromatography with a UV detector were all included in the process. The PAHs were successfully linearized (R2 > 0.99) at various doses. Results for PAH recovery ranged from 90 to about 100%. The limit of quantification was 0.002-0.580, and the limit of detection was 0.0006-0.174 µgkg-1. Data indicated that the highest mean concentrations of ∑16 PAHs were detected in Spinach (123.36 µgkg-1), in carrot (105.09 µgkg-1), and in cucumber (63.40 µgkg-1) among leafy, underground, and fruity vegetables, respectively.

Green preparation of magnetic pyrene-based hyper-cross-linked polymer using dual-purpose ferric chloride reagent for extraction of polycyclic aromatic hydrocarbons from natural water bodies

A magnetic hyper-cross-linked polymer Fe3O4/HCPPYR was prepared using pyrene as the monomer and formaldehyde dimethyl acetal (FDA) as the cross-linking agent. The objective of green chemistry was achieved by employing FeCl3 during the synthesis, as it played a dual role of a catalyst for the Friedel-Crafts reaction and an iron source for the synthesis of magnetic Fe3O4, thus maximizing efficiency and minimizing waste. Fe3O4/HCPPYR was applied as a sorbent for magnetic solid-phase extraction (MSPE) to extract fifteen polycyclic aromatic hydrocarbons (PAHs) from water. The effects of different parameters such as the quantity of adsorbent, the extraction time, the desorption conditions, the pH value and the effect of the salt concentration on the extraction efficiency were optimized. A simple and efficient method in combination with gas chromatography-mass spectrometry (GC–MS) (Fe3O4/HCPPYR−MSPE/GC–MS) was developed and successfully applied for the detection of PAHs in environmental water samples The analytical method showed LODs in the range of 0.004−0.06 µg L−1, which proved to be adequate for the detection all 15 PAHs at trace concentration. Spiked recoveries of PAHs in actual water samples ranged from 85.2 % to 118.5 % with relative standard deviations (RSDs) below 10.2%. These results indicate that the method has a good potential for reusability and possesses excellent sensitivity. This study showcased the potential of Fe3O4/HCPPYR composites in effectively removing organic pollutants from the aqueous environments, demonstrating their ability for water treatment applications.

Facile fabrication of naphthalene-functionalized magnetic nanoparticles for efficient extraction of polycyclic aromatic hydrocarbons from environmental water and fish samples

In this study, naphthalene-modified magnetic nanoparticles (Fe3O4@Nap) were simply prepared based on specific chelation interaction between phosphate groups and metal ions on Fe3O4 surface. The resultant Fe3O4@Nap were characterized by FTIR, BET, SEM, TEM, NAM, TGA, and VSM techniques. With Fe3O4@Nap as adsorbent, the polycyclic aromatic hydrocarbons (PAHs) were efficiently extracted by magnetic solid-phase extraction (MSPE) from environmental water and fish samples through the π-π interaction between modified naphthalene groups and PAHs, followed by their determination by GC–MS/MS. The key parameters influencing the extraction efficiency were investigated. Under the optimized conditions, the Fe3O4@Nap-based MSPE/GC-MS/MS method proposed in this paper was evaluated and applied for analyzing PAHs in environmental water and fish samples. And the proposed MSPE/GC-MS/MS method exhibited good linearities for water samples (in the range of 0.1–10 ng/mL, R2 >0.9945) and for fish samples (in the range of 1–100 ng/g, R2 > 0.9905). The limits of detection (LODs) for water and fish samples were 0.004–0.031 ng/mL and 0.07–0.28 ng/g, respectively. Additionally, this method exhibited desirable accuracy and precision. The PAH recovery values from water and fish samples ranged from 81.5% to 109.6% with inter- and intra-day relative standard deviations (RSDs) of less than 12.8%. The MSPE/GC-MS/MS method was successfully applied to the analysis of real environmental water and fish samples. Overall, the newly synthesized Fe3O4@Nap exhibited high sensitivity, specificity, reusability, repeatability, and it could efficiently extract PAHs from environmental water and fish samples by MSPE.

Measurement of Polycyclic Aromatic Hydrocarbons (PAHs) on Indoor Materials: Method Development.

Wildfire smoke penetrates indoors, and polycyclic aromatic hydrocarbons (PAHs) in smoke may accumulate on indoor materials. We developed two approaches for measuring PAHs on common indoor materials: (1) solvent-soaked wiping of solid materials (glass and drywall) and (2) direct extraction of porous/fleecy materials (mechanical air filter media and cotton sheets). Samples are extracted by sonication in dichloromethane and analyzed with gas chromatography-mass spectrometry. Extraction recoveries range from 50-83% for surrogate standards and for PAHs recovered from direct application to isopropanol-soaked wipes, in line with prior studies. We evaluate our methods with a total recovery metric, defined as the sampling and extraction recovery of PAHs from a test material spiked with known PAH mass. Total recovery is higher for "heavy" PAHs (HPAHs, 4 or more aromatic rings) than for "light" PAHs (LPAHs, 2-3 aromatic rings). For glass, the total recovery range is 44-77% for HPAHs and 0-30% for LPAHs. Total recoveries from painted drywall are <20% for all PAHs tested. For filter media and cotton, total recoveries of HPAHs are 37-67 and 19-57%, respectively. These data show acceptable HPAH total recovery on glass, cotton, and filter media; total recovery of LPAHs may be unacceptably low for indoor materials using methods developed here. Our data also indicate that extraction recovery of surrogate standards may overestimate the total recovery of PAHs from glass using solvent wipe sampling. The developed method enables future studies of accumulation of PAHs indoors, including potential longer-term exposure derived from contaminated indoor surfaces.

Optimization of the QuEChERS extraction method to determine Polycyclic Aromatic Hydrocarbons (PAHs) in powder aerosol particles collected by cyclone

Conventional methods for collecting and extracting aerosol particles are challenging in accurately characterizing particle-bound polycyclic aromatic hydrocarbons (PAHs) contamination and conducting cellular exposure studies. Therefore, developing direct aerosol sample collection and simple pretreatment analytical methods is necessary. This study describes the optimization of the QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method for the determination of PAHs in powder-form environmental standard materials (SRM1944) and proves it is also effective for analyzing PAHs in powder aerosol particle samples collected by cyclone. In this study, we used an I-optimal design response surface method combined with a desirability function to investigate the extraction effect of PAHs under different combinations of QuEChERS extraction factors, including extraction solvent, salt, and clean-up reagent. The optimized conditions of the method were determined using the 2-factor interaction (2FI) model combined with boundary conditions, resulting in acetonitrile/dichloromethane (7:1, v/v), Na2SO4/NaCl (1:1, w/w), and primary and secondary amine (PSA) as extraction solvents, extraction salts, and clean-up reagent, respectively. The optimized method showed good recoveries of PAHs reaching 76%–118% and 85%–121% for SRM1944 and standard solution. The results for cyclone-collected ambient powder aerosol particles extracted by the optimized QuEChERS illustrated that this improved procedure has good PAHs extraction efficiency as the traditional Soxhlet method, while reducing hazardous organic solvents usage, experimental cost (per mg sample) by 97% and sample pretreatment time. Overall, this combination of “powder aerosol particle collection and modified QuEChERS extraction” provides new insight on aerosol sample collection, extraction, and in vitro/in vivo exposure studies.

Optimization and Comparison of Microwave-Assisted Extraction, Supercritical Fluid Extraction, and Eucalyptus Oil-Assisted Extraction of Polycyclic Aromatic Hydrocarbons from Soil and Sediment.

Polycyclic aromatic hydrocarbons (PAHs) are persistent organic compounds of major concern that mainly accumulate in soils and sediments, and their extraction from environmental matrices remains a crucial step when determining the extent of contamination in soils and sediments. The objective of the present study was to compare the extraction of PAHs (phenanthrene, pyrene, chrysene, and benzo[a]pyrene) from spiked soil and sediment using supercritical fluid extraction (SFE) with ethanol as the modifier, microwave-assisted extraction (MAE), and eucalyptus oil-assisted extraction (EuAE). Recoveries of PAHs were comparable between the three methods, and >80% of applied pyrene, chrysene and benzo[a]pyrene were recovered. The most efficient method of extracting PAHs from naturally incurred soils with different levels of contamination was SFE. A longer extraction time was required for the EuAE method compared with SFE and MAE under optimized conditions. However, EuAE required lower extraction temperatures (15-20 °C) compared with SFE (80 °C) and MAE (110-120 °C), and consumed less solvent than SFE and MAE. Compared with hexane/acetone used in MAE, the use of ethanol in SFE and eucalyptus oil in EuAE can be considered as more sustainable approaches to efficiently extract PAHs from spiked/naturally contaminated soils and sediments. And, although less efficient for matrices containing higher carbon content, EuAE offered a cheap, low-tech approach to extracting PAHs. Environ Toxicol Chem 2023;42:982-994. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Dosing Methods to Enable Cell-Based In Vitro Testing of Complex Substances: A Case Study with a PAH Mixture.

Cell-based testing of multi-constituent substances and mixtures for their potential adverse health effects is difficult due to their complex composition and physical-chemical characteristics. Various extraction methods are typically used to enable studies in vitro; however, a limited number of solvents are biocompatible with in vitro studies and the extracts may not fully represent the original test article's composition. While the methods for dosing with "difficult-to-test" substances in aquatic toxicity studies are well defined and widely used, they are largely unsuited for small-volume (100 microliters or less) in vitro studies with mammalian cells. Therefore, we aimed to evaluate suitability of various scaled-down dosing methods for high-throughput in vitro testing by using a mixture of polycyclic aromatic hydrocarbons (PAH). Specifically, we compared passive dosing via silicone micro-O-rings, cell culture media-accommodated fraction, and traditional solvent (dimethyl sulfoxide) extraction procedures. Gas chromatography-tandem mass spectrometry (GC-MS/MS) was used to evaluate kinetics of PAH absorption to micro-O-rings, as well as recovery of PAH and the extent of protein binding in cell culture media with and without cells for each dosing method. Bioavailability of the mixture from different dosing methods was also evaluated by characterizing in vitro cytotoxicity of the PAH mixture using EA.hy926 and HepG2 human cell lines. Of the tested dosing methods, media accommodated fraction (MAF) was determined to be the most appropriate method for cell-based studies of PAH-containing complex substances and mixtures. This conclusion is based on the observation that the highest fraction of the starting materials can be delivered using media accommodated fraction approach into cell culture media and thus enable concentration-response in vitro testing.

Covalent organic framework@Ti3C2Tx composite as solid phase microextraction coating for the determination of polycyclic aromatic hydrocarbons in honey samples

In this study, covalent organic framework@MXene (COF@Ti3C2Tx) composites were synthesized and employed as solid phase microextraction coatings for isolation of polycyclic aromatic hydrocarbons (PAHs) from honey samples. The developed composites possessed unique structural characteristics and multiple interactions (π-π and hydrophobic interaction, etc.), which provided them with excellent extraction capacity towards the targeted PAHs. Under optimized conditions, the resultant COF@Ti3C2Tx-coating fiber-based HS-SPME/GC-FID method exhibited a wide linear range (2.0–2000 ng g−1), good linearities (r > 0.9964), and low limits of detection (0.20–0.60 ng g−1). The recoveries of PAHs in the honey samples were in the range of 73.2–112%, with RSDs less than 9.4%. In addition, the findings showed that the composite-based fiber offers a long lifetime, high enhancement factors (483–598), and excellent fiber-to-fiber reproducibility (RSDs <10.5%, n = 3). This work not only details the development of a multi-functional composite, but it also presents an effective strategy for the determination of trace PAHs in complex food matrix.

Polycyclic Aromatic Hydrocarbons from Bottled Water: A New Automated Solid Phase Extraction Method and Simulation of Cancer Risk

Considering the adverse effects of polycyclic aromatic hydrocarbons (PAHs) on human health and the complexity of their detection in water resources, this study was developed to assess the performance of a new automated device for the identification of PAHs in water based on the solid-phase extraction and to simulate the cancer risk of 16 priority PAHs by Monte Carlo technique. All operational modes of extraction were automatically performed using the proprietary software program. Three spiked aliquots of PAHs including 100, 500, and 1000 ng/L were used to evaluate the performance of the automated-solid phase extraction (SPE) apparatus. The time of extraction in the automatic-SPE apparatus was 50±4 minutes for simultaneous extraction of 4 water samples, which was four times faster than that of manual-SPE apparatus. The mean recoveries of PAHs were 89.22±4.94, 91.70±4.45, and 94.61±6.28% in spiked samples, with a mean of 91.84±5.22%. Except for naphthalene, all obtained recoveries were in an acceptable range (85-115%). The results of Monte Carlo simulation showed that the cancer risk attributable to eight detected PAHs including naphthalene, fluorene, phenanthrene (Phe), benzoanthracene, chrysene, benzo(k) fluoranthene, indeno(cd)pyrene, and dibenzo(a,h)anthracene ranged from 0.05E-6 to 0.11E-6, with the cancer risk of 0.012E-6 having the highest probability (P=0.82). Additionally, this simulation showed that 99% of the probability density of cancer risk was located within the range lower than 0.05E-6. Our results showed that the novel automated-SPE apparatus could be utilized for the extraction of PAHs from water resources with a good recovery (85%-115%), high operational speed, and potential for separation of solvents from the air in the drying step. Therefore, this device can be used for the extraction of trace PAHs and similar organic compounds from water resources.

Graphene oxide modified magnetic polyamidoamide dendrimers based magnetic solid phase extraction for sensitive measurement of polycyclic aromatic hydrocarbons

In this study, graphene oxide modified magnetic polyamidoamine dendrimers (MNPs@PAMAM-G2.0@GO) nanoparticles were successfully prepared by amidation method. The obtained MNPs@PAMAM-G2.0@GO nanocomposites were examined by fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), scanning electron microscope (SEM) and transmission electron microscopy (TEM), etc. MNPs@PAMAM-G2.0@GO exhibited excellent adsorption property and was investigated for magnetic solid phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) from water. The detection of extracted PAHs was accomplished by high performance liquid chromatography (HPLC) and gas chromatography tandem mass spectrometry (GC-MS/MS). The target PAHs included anthracene (ANT), pyrene (PYR), fluoranthene (FLT), carbazole (CB), 7-methylquinoline (7-MQL), 9-methylcarbazole (9-MCB), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DBT). Important operation parameters for MSPE that could affect the extraction efficiencies of PAHs were investigated in detail. Under optimal parameters, the constructed method demonstrated excellent linear range with 0.001–10 μg L−1 for analytes and low limits of detection within the range of 0.11–0.9 ng L−1. The spiked average recoveries of PAHs in natural water samples ranged from 92.5% to 105.2%. The promising results indicated that MNPs@PAMAM-G2.0@GO could be employed to efficiently extract PAHs from aqueous samples.

Liquid-liquid extraction combined with online cleanup for the simultaneous determination of PAHs by GC–MS/MS and their hydroxylated metabolites by LC-MS/MS in human fingernails

A method was developed for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and their hydroxylated metabolites (OH-PAHs) in human fingernails using liquid–liquid extraction and online purification. After surface decontamination by rinsing with acetone, the fingernails were digested with sodium hydroxide and subjected to liquid–liquid extraction with a mixture of n-hexane and methyl tertbutyl ether. The organic extract was then fractionated using a silica-based solid-phase extraction (SPE) cartridge to obtain a PAH fraction eluted with n-hexane/dichloromethane (v/v, 95:5) and an OH-PAH fraction eluted with dichloromethane/ethyl acetate (v/v, 50:50). The PAH fraction was directly injected into an online gel permeation chromatography-gas chromatography-triple quadrupole tandem mass spectrometry (GPC-GC–MS/MS) system, enabling rapid determination of 16 PAHs. A parallel online SPE liquid chromatography tandem mass spectrometry (LC-MS/MS) method was used to determine 12 OH-PAHs. Validation experiments showed that the recovery of PAH and OH-PAH were within range of 67.4%−105.1% (RSD ≤ 10.1%) and 72.8%−102.3% (RSD ≤ 10.9%), respectively, with limits of quantitation (LOQ) of 0.06–0.8 ng/g and 0.15–3.1 ng/g, respectively. Forty-two human fingernail samples from residents of Southern China were analyzed to establish background PAH and OH-PAH levels in this region. Several PAHs and OH-PAHs were detected, at concentrations of 97.5 to 3,687 ng/g for PAHs and 24.2 to 767 ng/g for OH-PAHs. The dominant homologues were two- and three-ring PAH isomers, notably naphthalene (Nap), fluorene (Flu), and phenanthrene (Phe), as well as the corresponding hydroxylated metabolites 2-OH-Nap, OH-Flu, and OH-Phe. Smoking, consuming barbecued food, and age had no significant effects on PAH exposure, but a larger sample would be required to confirm this finding. The online purification strategy presented here expedites cleanup and purification during analysis of human fingernails and should facilitate non-invasive biomonitoring of PAHs in humans, particularly when analyzing large numbers of samples.

Determination of polycyclic aromatic hydrocarbons using different extraction methods and HPLC-FLD detection in smoked and grilled meat products

Polycyclic aromatic hydrocarbons (PAHs) in meat products are formed, among others, as a by-product of thermal processing such as smoking or grilling. Due their highly toxic effects on the human organism, it is necessary to monitor PAH content in food products and develop appropriate analytical methods for their determination. The aim of this study was to compare PAH content in meat products subjected to smoking or grilling process. PAH content was determined using three different analytical methods, verified for efficiency using the external standard method. The results showed that smoking led to higher PAH contamination compared to grilling. Extraction by saponification and SPE method was the most effective for the detection and quantification of PAHs. The samples analyzed using this method showed the highest PAH content and recoveries. The results of the study showed a significant effect of the extraction method on the recovery levels and PAH content in meat.

Analysis of Polycyclic Aromatic Hydrocarbon in Airborne Particulate Matter Samples by Gas Chromatography in Combination with Tandem Mass Spectrometry (GC-MS/MS).

Polycyclic aromatic hydrocarbons (PAHs), the family of organic contaminations, have been shown to have negative effects on human health. However, until now, the comprehension on occurrence, distribution, and risk assessment of human exposure to PAHs has been limited in Vietnam. In this work, a capillary gas chromatography coupled with electron impact ionization tandem mass spectrometry (GC-EI-MS/MS) has been introduced for analysis of 16 PAHs in some particulate matter samples. PAHs have been separated on the TG 5 ms capillary gas chromatographic column and detected by tandem mass spectrometry in multiple reaction monitoring mode. The PAHs in the particulate matter (PM 2.5 and PM 10) samples were extracted by ultrasonic-assisted liquid extraction and cleaned up by an acidic silica gel solid phase extraction. The linearity range of all analyzed PAHs was from 5 to 2000 ng mL−1 with R2 ≥0.9990. Limit of detection (LOD) of PAHs in particulate matter sample was from 0.001 ng m−3 (Br-Naph) to 0.276 ng m−3 (Fln). The recovery of PAHs was investigated by international proficiency testing samples. The recoveries of PAHs in proficiency testing sample ranged from 79.3% (Chr) to 109.8% (IcdP). The in-house validated GC-EI-MS/MS method was then applied to analysis of some particulate matter samples that were collected in the Hanoi areas. The total concentrations of PAHs in several brands of samples collected from Hanoi were found in the range of 226.3 ng m−3–706.43 ng m−3. Among the studied compounds, naphthalene was found at high frequency and ranged from 106.5 ng m−3 to 631.1 ng m−3. The main distribution of the PAHs in particulate matter samples was two-ring and three-ring compounds.