Project description:A link between the aromatic character of polycyclic aromatic hydrocarbons and gas chromatography elution order in columns with a polysiloxane backbone in the stationary phase is reported for the first time. The aromatic character was calculated using a method that combines the π-Sextet Rule and the Pauling Ring Bond Orders to allow the establishment of the location and migration of aromatic sextets in PAH structures. One GC column with a polysiloxane - like backbone (Rxi-PAH) and three GC columns with a polysiloxane backbone (DB-5, SE-52, and LC-50), were used for the analysis. According to the results of this study, within an isomer group, PAHs that contain a lower number of rings affected by the aromatic sextets tend to elute earlier than PAHs that contain a higher number of rings affected by the aromatic sextets. The PAHs that follow the calculated elution order are 88 % in the Rxi-PAH column, 88 % in the DB-5 column, 93 % in the SE-52 column, and 85% in the LC-50 column. It is expected that future analyses with other aromatic compounds in GC columns with a polysiloxane backbone in the stationary phase will follow a GC elution order that agrees with the aromatic character of the molecules.
Project description:Assessing the potential carcinogenicity of human toxins represents an ongoing challenge. Chronic rodent bioassays predict human cancer risk with limited reliability, and are expensive and time-consuming. To identify alternative prediction methods, we evaluated a transcriptomics-based human in vitro model to classify carcinogens by their modes of action. The aim of this study was to determine the transcriptomic response and identify specific molecular signatures of polycyclic aromatic hydrocarbons (PAHs), which can be used as predictors of carcinogenicity of environmental toxins in human in vitro systems. We found that characteristic molecular signatures facilitate identification and prediction of carcinogens.
Project description:Natural gas extraction, often referred to as "fracking", has increased rapidly in the United States in recent years. To address potential health impacts, passive air samplers were deployed in a rural community heavily affected by the natural gas boom. Samplers were analyzed for 62 polycyclic aromatic hydrocarbons (PAHs). Results were grouped based on distance from each sampler to the nearest active well. Levels of benzo[a]pyrene, phenanthrene, and carcinogenic potency of PAH mixtures were highest when samplers were closest to active wells. PAH levels closest to natural gas activity were comparable to levels previously reported in rural areas in winter. Sourcing ratios indicated that PAHs were predominantly petrogenic, suggesting that PAH levels were influenced by direct releases from the earth. Quantitative human health risk assessment estimated the excess lifetime cancer risks associated with exposure to the measured PAHs. At sites closest to active wells, the risk estimated for maximum residential exposure was 0.04 in a million, which is below the U.S. Environmental Protection Agency's acceptable risk level. Overall, risk estimates decreased 30% when comparing results from samplers closest to active wells to those farthest from them. This work suggests that natural gas extraction is contributing PAHs to the air, at levels that would not be expected to increase cancer risk.
Project description:Polycyclic aromatic hydrocarbons (PAHs)-a large group of organic compounds-are extremely hazardous to human health. In this study, the 198 samples from six groups of daily food products in the Hanoi metropolitan area were collected and prepared by the QuEChERS sample treatment technique. The detection and identification of PAHs were obtained by gas chromatography⁻tandem mass spectrometry (GC⁻MS/MS) determination. The results demonstrated that the recovery of PAH compounds ranged approximately between 71% and 110% when the solvent evaporation condition was optimized using the nitrogen gas at a low temperature (1 °C). The in-house method was validated in terms of linearity, extractive condition, repeatability, recovery, limit of detection (LOD), and limit of quantification (LOQ). The ranges of average PAH levels were 9.3⁻9.6 µg/kg (for instant noodles), 0.22⁻2.48 µg/kg (for cakes) 0.91⁻4.83 µg/kg (dried vegetables), 5.14⁻23.32 µg/kg (teas), 4.82⁻24.35 µg/kg (coffees), and 1.43⁻25.2 µg/kg (grilled meats). The results indicated that the total concentrations of residual PAHs and benzo(a)pyrene in the instant noodles and grilled meat samples surpassed the maximum limits tolerated by the European Commission (35 µg/kg and 5 µg/kg, respectively) in many investigated samples.
Project description:Thermal desorption (TD) coupled with gas chromatography/mass spectrometry (TD-GC/MS) is a simple alternative that overcomes the main drawbacks of the solvent extraction-based method: long extraction times, high sample manipulation, and large amounts of solvent waste. This work describes the optimization of TD-GC/MS for the measurement of airborne polycyclic aromatic hydrocarbons (PAHs) in particulate phase. The performance of the method was tested by Standard Reference Material (SRM) 1649b urban dust and compared with the conventional method (Soxhlet extraction-GC/MS), showing a better recovery (mean of 97%), precision (mean of 12%), and accuracy (±25%) for the determination of 14 EPA PAHs. Furthermore, other 15 nonpriority PAHs were identified and quantified using their relative response factors (RRFs). Finally, the proposed method was successfully applied for the quantification of PAHs in real 8?h-samples (PM10), demonstrating its capability for determination of these compounds in short-term monitoring.
Project description:A gas chromatography-mass spectrometry (GC-MS) method was validated for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) from the FDA list of 93 harmful or potentially harmful constituents of mainstream cigarette smoke (MCS). Target analytes were extracted from total particulate matter using accelerated solvent extraction with a toluene/ethanol solvent mixture. Matrix artefacts were removed by two-step solid-phase extraction process. Three different GC-MS systems [GC-MS (single quadrupole), GC-MS/MS (triple quadrupole) and GC-HRMS (high resolution, magnetic sector)] using the same separation conditions were compared for the analysis of MCS of 3R4F Kentucky reference cigarettes generated under ISO and intense smoking regimes. The high mass resolution (m/∆m ≥ 10,000) and associated selectivity of detection by GC-HRMS provided the highest quality data for the target PAHs in MCS. Owing to the HR data acquisition mode enabling measurement of accurate mass, limits of quantification for PAHs were 5 to 15-fold lower for GC-HRMS than for GC-MS/MS and GC-MS. The presented study illustrates that the optimised sample preparation strategy followed by GC-HRMS analysis provides a fit-for-purpose and robust analytical approach allowing measurement of PAHs at (ultra)low concentrations in MCS. Furthermore, the study illustrates the importance and benefits of robust sample preparation and clean-up to compensate for limited selectivity when low-resolution MS is used.
Project description:The method for the determination of 16 priority polycyclic aromatic hydrocarbons (PAHs) in plant leaves has been studied extensively, yet the quantitativemethod for measuring non-priority PAHs in plant leaves is limited. A method for the simultaneous determination of 31 polycyclic aromatic hydrocarbons (PAHs) in plant leaves was established using an ultrasonic extraction-gas chromatography-mass spectrometry-internal standard method. The samples of plant leaves were extracted with ultrasonic extraction and purified with solid-phase extraction columns. The PAHs were separated by using gas chromatography-mass spectrometry equipped with a DB-EUPAH capillary column (20 m × 0.18 mm × 0.14 μm) with a selective ion monitoring (SIM) detection mode, and quantified with an internal standard. The method had good linearity in the range of 0.005~1.0 μg/mL with correlation coefficients greater than 0.99, and the method detection limit and maximum quantitative detection limit were in the ranges of 0.2~0.7 μg/kg and 0.8~2.8 μg/kg, respectively. The method was verified with spiked recovery experiments. The average spiked recovery ranged from 71.0% to 97.6% and relative standard deviations (n = 6) were less than 14%. Herein, we established a quantitativemethod for the simultaneous determination of priority and non-priority PAHs in plant leaves using GC-MS. The method is highly sensitive and qualitatively accurate, and it is suitable for the determination of PAHs in plant leaves.
Project description:Assessing the potential carcinogenicity of human toxins represents an ongoing challenge. Chronic rodent bioassays predict human cancer risk with limited reliability, and are expensive and time-consuming. To identify alternative prediction methods, we evaluated a transcriptomics-based human in vitro model to classify carcinogens by their modes of action. The aim of this study was to determine the transcriptomic response and identify specific molecular signatures of polycyclic aromatic hydrocarbons (PAHs), which can be used as predictors of carcinogenicity of environmental toxins in human in vitro systems. We found that characteristic molecular signatures facilitate identification and prediction of carcinogens. To evaluate the change in gene expression levels, human hepatocellular carcinoma (HepG2) cells were exposed to nine different PAHs (benzo[a]pyrene, dibenzo[a,h]anthracene, 3-methylcholanthrene, naphthalene, chrysene, phenanthrene, benzo[a]anthracene, benzo[k]fluoranthene, and indeno[1,2,3-c,d]pyrene) for 48 h. Gene expression analysis was conducted using a 44K whole human genome microarray (Agilent Technologies, USA).