Aromatic Hydrocarbons In Edible Oils Research Articles

Synchronous fluorescence spectra-based machine learning algorithm with quick and easy accessibility for simultaneous quantification of polycyclic aromatic hydrocarbons in edible oils

Polycyclic aromatic hydrocarbons (PAHs) are one of the leading causes of human cancer. Four typical PAHs (PAH4) including benzo(a)pyrene (BaP), benzo(b)fluoranthene (BbF), benzo(a)anthracene (BaA), and chrysene (Chr) have been regarded as reasonable indicators for the occurrence of PAHs in food. In this study, the constant wavelength synchronous fluorescence (CWSF) spectra of PAH4 mixtures were used as the data sets without preprocessing and directly combined with the back propagation neural network (BPNN) algorithm to establish a quantitative analysis method of PAH4. This method is capable of predicting the concentrations of PAH4 in edible oil samples without pre-separation. The detection limits for BaP, BbF, BaA, and Chr were 0.014, 0.068, 0.026, and 0.013 μg/kg, respectively. The recoveries in various oil samples for BaP, BbF, BaA, and Chr were 99.5 ± 2.1, 101.0 ± 4.6, 98.6 ± 3.2, and 98.5 ± 4.9 %, respectively. The proposed method has proved to be a powerful tool for the rapid detection of PAH4.

Fabrication and application of Zn5 functionalized copolymer monolithic column for pipette tip micro-solid phase extraction of 4 polycyclic aromatic hydrocarbons in edible oil

The contamination of polycyclic aromatic hydrocarbons (PAHs) in edible oil is a health threat. Thus, trace analysis of PAHs is of high necessity. Based on the efficient adsorption of PAHs on Zn5 metal cluster, a Zn5 functionalized copolymer monolithic column was rationally designed for pipette tip micro-solid phase extraction (μ-SPE). The modified Zn5 improved the adsorption selectivity and capacity of the monolith for naphthalene, phenanthrene, fluoranthene and pyrene. Chemical doping and copolymerization stabilized the monolith with a long life. Under optimal extraction conditions, a μ-SPE-high performance liquid chromatography with ultraviolet detector method was established for the detection of 4 PAHs in edible oils. The method yielded detection ranges of 0.15–250 μg L−1 (R2 > 0.997), detection limits of 0.050–1.5 μg L−1, satisfactory recoveries (86.3–101.5 %), and high precisions (RSDs < 7.9 %). The results indicated that the Zn5 functionalized copolymer monolithic column was an ideal separation medium for the detection of PAHs residues in edible oils.

Determination of polycyclic aromatic hydrocarbons in edible oil by magnetic solid phase extraction based on a mesoporous molybdenum disulfide/graphite prior to gas chromatography-mass spectrometry

In this work, a magnetic mesoporous molybdenum disulfide/graphite nanosheets (mm-MoS2/GN) was successfully synthesized and applied to magnetic solid phase extraction (MSPE) of 13 polycyclic aromatic hydrocarbons (PAHs) from edible oil samples. The prepared mm-MoS2/GN was characterized by FT-IR, XRD, VSM, BET, SEM and TEM. The influence of various parameters such as the adsorbent mass, adsorption/desorption time, and elution solvent through response surface methodology in MSPE was investigated. The porous and fluffy structure with rich active sites (π interactions, electrostatics, hydrogen bonds) and amphiphilicity properties of mm-MoS2/GN make it an ideal material for the separation and enrichment of trace PAHs in edible oils. Under optimal MSPE and GC-MS conditions, the linearity ranges of the proposed method were 1.0–100.0 μg·kg−1 with a satisfactory correlation coefficient above 0.9907. The limits of detection and quantification for 13 PAHs were 0.10–2.50 μg·kg−1 and 0.85–5.00 μg·kg−1, respectively. The intra- and inter-day precisions were less than 3.0 % and 3.6 %, respectively. The recoveries for spiked edible oil samples ranged from 70.2 % to 112.6 % with RSDs of less than 5.8 %. In this work, a novel, rapid, economic and effective method was proposed, and successfully applied to detect polycyclic aromatic hydrocarbons in several oil samples from local market.

Automated workflow utilizing saponification and improved epoxidation for the sensitive determination of mineral oil saturated and aromatic hydrocarbons in edible oils and fats

Refined edible oils and fats are known to contain olefins resisting the typical epoxidation used for the sample preparation of mineral oil saturated and aromatic hydrocarbons (MOSH and MOAH). These olefins can be misinterpreted as MOAH and are therefore an important reason for inconsistent results between laboratories. Collaborative trials confirm this assumption for low MOAH contents near the quantitation limits regularly. In the scope of this work, a new epoxidation approach was developed. Persistent olefins in refined oils could be successfully epoxidized with performic acid. The reaction kinetics was investigated using model substances for biogenic olefins and MOAH. It was rationalized why certain olefins resist epoxidation and which MOAH can potentially get lost. A prominent peak cluster in the MOAH fraction of refined palm oils could be identified by means of GC-MS and explained why it cannot be epoxidized. Based upon this, an automated and streamlined workflow for sample preparation and analysis was composed tackling major problems identified in previously published methods. Optimized and miniaturized saponification, extraction, epoxidation, and enrichment paired with online LC-GC-FID led to a robust method that was tested and validated for edible oils and fats (RSDR < 7% for MOSH and MOAH at values of 14.9 and 2.1 mg/kg, respectively). Due to increased sample amount and minimized blank values, quantitation limits below 1 mg/kg for MOSH and MOAH were achieved. The trueness of the method was verified by analyzing collaborative trial samples.

Measurement of polycyclic aromatic hydrocarbons in edible oils and potential health risk to consumers using Monte Carlo simulation, southwest Iran.

Persistent organic pollutants, such as polycyclic aromatic hydrocarbons, are hazardous trace contaminants frequently observed in food ingredients, such as edible oils. This study aimed to measure PAHs in forty brands of edible oils marketed in southwest Iran. Additionally, we characterized the daily intake of MOE and ILCR using Monte Carlo simulation. To analyze the content of PAHs, the liquid-liquid extraction method followed by GC-MS was utilized. The average concentration of PAHs was mostly lower than the maximum value for individual PAH (2 μg/Kg); however, the average concentration of fluorene (3.86 μg/Kg) and benzo(a)anthracene (3.13 μg/Kg) was more than the permitted level. The highest residual concentrations of PAHs were mostly observed in canola and corn oils. The daily intake of BaP and 4-PAH for 95% of consumers was 0.01 ng/kg BW/day and 0.04 ng/kg BW/day, respectively. Also, MOE was more than 10,000 for the percentiles of 5%, 50%, and 95%. The modeled ILCR showed that consumption of oil does not currently pose a cancer risk for Iranian consumers due to PAHs exposure. Concerning potential health risks, consumption of edible oils is safe; however, regular monitoring and assessment are required.

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Determination of Polycyclic Aromatic Hydrocarbons in Edible Oil by Magnetic Solid Phase Extraction Based on a Mesoporous Molybdenum Disulfide/Graphite Prior to Gas Chromatography-Mass Spectrometry

Determination of Polycyclic Aromatic Hydrocarbons in Edible Oil by Magnetic Solid Phase Extraction Based on a Mesoporous Molybdenum Disulfide/Graphite Prior to Gas Chromatography-Mass Spectrometry

Offline Solid-Phase Extraction and Separation of Mineral Oil Saturated Hydrocarbons and Mineral Oil Aromatic Hydrocarbons in Edible Oils, and Analysis via GC with a Flame Ionization Detector.

A method was developed for the determination of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in edible oils, achieving similar limits of quantification than those obtained by online extraction methodologies, i.e., 0.5 mg/kg. The isolation of MOSH and MOAH was performed in a silver nitrated silica gel stationary phase prior to their analysis by gas chromatography–flame ionization detector (GC-FID). To improve the sensitivity, the simulated on-column injection method, using a suitable liner, was optimized. The method was validated at 0.5, 10.0 and 17.9 mg/kg, and recoveries ranged from 80 to 110%. Intra and inter-day precision were evaluated at the same levels, and relative standard deviation (RSD) was lower than 20%. The method was applied to a total of 27 samples of different types of oil previously analyzed in an accredited laboratory, detecting MOSH up to 79.2 mg/kg and MOAH up to 22.4 mg/kg.

Quality alert from direct discrimination of polycyclic aromatic hydrocarbons in edible oil by liquid-interfacial surface-enhanced Raman spectroscopy

Edible oil is easy to be polluted by polycyclic aromatic hydrocarbons (PAHs) in production, processing, storage and use. Rapid screening of oil quality and safety is a huge demand in food industry and government regulation. Usually, sample pretreatment is needed for PAHs detection due to the complexity of the oil base but greatly limits the detection speed. Here we develop a liquid-interfacial surface-enhanced Raman spectroscopy (SERS) technology without sample pretreatment to realize the rapid and direct detection of ultra-trace PAHs in edible oil within 3 min. A quantitative analysis curve of benzopyrene (BaP) content in soybean oil is established in the range of 0.1 ppb–100 ppm with a high coefficient correlation (R2) of 0.9959 in curve fitting. It was found that only 4.5 h of frying would make the BaP content exceed the limit of 10 ppb in the Chinese Food Safety National Standard. Four common PAHs can be quickly identified in frying oil samples collected from special snack streets and the SERS profiles of soybean oil with adulteration of refined gutter oil could be well classified. This study paves a reliable method to rapid analyze edible oil with broad application prospects in the field of grain and oil safety.

Polycyclic aromatic hydrocarbons in edible oils: An overview on sample preparation, determination strategies, and relative abundance of prevalent compounds.

Polycyclic aromatic hydrocarbons (PAHs) are food contaminants whose presence in foodstuffs is especially alarming due to their carcinogenic character. These substances are highly lipophilic and thus, unsafe levels of these compounds have been found in edible fats and oils. Efficient methodologies to determine such molecules in lipidic matrixes are therefore essential. In this review, a detailed description of the analytical methods for the determination of PAHs in vegetable oils from the last 15 years has been provided. Particular emphasis has been placed on innovative sample treatments, which facilitate and shorten the pretreatment of the oils. Finally, results from recent investigations have been reviewed and studied in depth, in order to elucidate which PAHs are most commonly found in vegetable oils.

The effects of extracting procedures on occurrence of polycyclic aromatic hydrocarbons in edible oils.

Polycyclic aromatic hydrocarbons (PAHs) are one of the most hazardous naturally occurring chemical contaminants of food. Edible oils are easily contaminated by PAHs generated during high-temperature processing steps such as oil extraction and refining. In this study, the effects of different extraction methods on the levels of PAHs in sesame oils and red pepper seed oils were assessed. GC-MS was used to determine the levels of PAHs in edible oils. Sesame oils extracted from seeds by plate-pressing extraction method had lower levels of PAHs than those extracted by screw-expeller extraction method from sesame flour. Furthermore, the levels of PAHs increased by 62.2% when the extraction time was longer. Notably, the PAHs already present in oils could be effectively reduced by refining procedures such as sinking, centrifugation, filtration, and neutralization with alkali.

Determination of Polycyclic Aromatic Hydrocarbons in Edible Oil Using Fast and Sensitive Microwave-assisted Extraction and Dispersive Liquid–Liquid Microextraction Followed by Gas Chromatography-Mass Spectrometry

Edible oils as important fat-rich samples have the most probability in forming of polycyclic aromatic hydrocarbons. In this research an efficient, sensitive and fast microwave-assisted extraction and dispersive liquid-liquid microextraction (MAE-DLLME) followed by gas chromatography-mass spectrometry (GC-MS) was employed for isolation and determination of PAHs in edible oil. Effective parameters for extraction procedure including type and volume of extraction and disperser solvent, microwave time, NaCl amount and pH were optimized using response surface methodology (RSM) based on central composite design (CCD). In microwave procedure, PAHs extracted from oil sample with acetonitrile/acetone (50:50) and methanolic KOH in two steps. In microextraction stage, mixture of ethanol (disperser solvent), tetrachloroethylene (extraction solvent) and biphenyl (internal standard) was rapidly injected into the sample solution. After performing phase separation, sedimented phase was analyzed by GC-MS. For proposed method, the calibration curve was obtained in the range of 2–500 ng mL−1 with correlation coefficient (R2) 0.9346 to 0.9978. Enrichment factors were between 81 and 124 for PAHs and repeatability as relative standard deviations (RSDs) were 5.2% to 9.1% for all PAH compounds at a concentration of 10 ng mL−1. Limits of detection (LODs) and limits of quantitation (LOQs) were obtained in the range of 0.2–2.7 ng mL−1 and 0.6–9.1 ng mL−1, respectively. Comparison of this method with other analytical method showed that MAE-DLLME coupled with GC-MS is a powerful method for detecting PAHs in complex matrices. The validated method was applied for the determination of PAHs in real edible oil samples and acceptable results were obtained.

Multiresidue determination of polycyclic aromatic hydrocarbons in edible oils by liquid-liquid extraction–solid-phase extraction–gas chromatography–mass spectrometry

The presence of polycyclic aromatic hydrocarbons (PAHs) in edible oils is usually due to environmental contamination, manufacturing processes or the nature of the oil. Because oils constitute a very large family of foodstuffs that are ubiquitous in human diet, the presence of PAHs in them may have a considerable impact. In this work, we developed a method for determining EPA's 16 PAH priority pollutants using liquid–liquid and solid-phase extraction for their extraction and isolation, and gas chromatography–mass spectrometry for their quantification. The proposed method is highly sensitive, with limits of detection from 4 to 110 ng kg−1, accurate (PAH recoveries of 87–104%) and precise (relative standard deviation < 7.5%). Application to various types of oil (olive, sunflower, coconut, soybean and sesame) testified to its flexibility. Most of the samples studied contained more than three PAHs, albeit at concentrations below the legally allowed levels. Only two samples of refined sunflower oil contained no PAH at levels within the sensitivity range of the method.

Multi-Walled Carbon Nanotubes as Effective Sorbents for Rapid Analysis of Polycyclic Aromatic Hydrocarbons in Edible Oils Using Dispersive Solid-Phase Extraction (d-SPE) and Gas Chromatography—Tandem Mass Spectrometry (GC-MS/MS)

A method was developed for the analysis of four polycyclic aromatic hydrocarbons regulated in the European Union, namely, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene in edible oils. Multi-walled carbon nanotubes were applied for dispersive solid-phase extraction of analytes from the oils after dilution with n-hexane followed by elution of analytes with toluene under reflux conditions. Gas chromatography coupled to tandem mass spectrometry was used for quantitative determination of the analytes. The efficiency of four nanotube-based sorbents was evaluated. The performance characteristics of the method permitted reliable measurement of four regulated polycyclic aromatic hydrocarbons in oil samples according to the criteria stated in the Commission Regulation No. 836/2011 and considering the maximum levels (MLs) stated in the Commission Regulation (EU) No. 835/2011. The concentrations of the selected analytes in real-world samples determined by our developed method and by previously validated gel permeation chromatography method were found to be in a good agreement.

Determination of mineral oil aromatic hydrocarbons in edible oils and fats by online liquid chromatography–gas chromatography–flame ionization detection – Evaluation of automated removal strategies for biogenic olefins

The determination of mineral oil aromatic hydrocarbons (MOAH) in foodstuffs gained in importance over the last years as carcinogenicity cannot be excluded for certain MOAH. The existence of olefins in foodstuffs, such as edible oils and fats, can be problematic for the determination of MOAH by LC-GC-FID. Removal of these interfering substances by HPLC based on polarity differences is not possible. During gas chromatographic separation heavily overloaded peaks are observed rendering the detection of small mineral oil contaminations almost impossible. Therefore, removal of these olefins is necessary before subjection of the sample to LC-GC-FID. Epoxidation of olefins to increase their polarity proved to be a valuable tool in the past. Precision and trueness of the results as shown in a collaborative trial, however, are relying on exact reaction conditions. Additionally, it is known that certain MOAH are oxidized during epoxidation and therefore get lost. In the scope of this work, hydroboration, bromohydrin reaction, and epoxidation were examined for their potential for derivatization of unsaturated hydrocarbons with increased robustness and higher recovery of MOAH. Epoxidation by meta-chloroperoxybenzoic acid (mCPBA) delivered the best removal of olefins. Factors influencing this reaction were enlightened. Adaption of the reaction conditions and time-controlled automation increased the recovery of polycyclic MOAH. Good precision (RSDr <1.5%) and recovery (95–102%) for MOAH were also observed for sunflower and olive oils spiked with a lubricating mineral oil (at 24.5mg/kg of MOAH). The trueness of the method was verified by analyzing collaborative trial samples.

Determination of polycyclic aromatic hydrocarbons in edible oil by gel permeation chromatography and ultra-high performance liquid chromatography coupled with diode array detector and fluorescence detector

This paper develops an instrumental analytical approach for detection of fourteen polycyclic aromatic hydrocarbons (PAHs) in edible oil samples using gel permeation chromatography (GPC) and ultra-high performance liquid chromatography (UHPLC) coupled with diode array detector (DAD), and fluorescence detector (FLD). The GPC was used to remove triglycerides from edible oil samples. The extracted samples were then detected using UHPLC—DAD—FLD. In order to obtain good separation and high reproducibility, the UHPLC—DAD—FLD experimental condition was optimized. The PAHs including three groups of isomeric PAHs can be separated completely in 12 min using BEH Shield RP 18 column with a suitable gradient elution program. The mean recoveries were in the range of 73–110% with an acceptable reproducibility (RSD &lt; 10%, n = 3). During real sample analysis, the method can decrease the chance of false positives with both DAD and FLD being used simultaneously. The results indicate that the approach is simple, easy, and acceptably reproducible, thereby showing great potential as a method for detection of fourteen PAHs contained in edible oil samples.

Single-laboratory validation of a saponification method for the determination of four polycyclic aromatic hydrocarbons in edible oils by HPLC-fluorescence detection

ABSTRACTAn analytical method is reported for the determination of four polycyclic aromatic hydrocarbons (benzo[a]pyrene (BaP), benz[a]anthracene (BaA), benzo[b]fluoranthene (BbF) and chrysene (CHR)) in edible oils (sesame, maize, sunflower and olive oil) by high-performance liquid chromatography. Sample preparation is based on three steps including saponification, liquid–liquid partitioning and, finally, clean-up by solid phase extraction on 2 g of silica. Guidance on single-laboratory validation of the proposed analysis method was taken from the second edition of the Eurachem guide on method validation. The lower level of the working range of the method was determined by the limits of quantification of the individual analytes, and the upper level was equal to 5.0 µg kg−1. The limits of detection and quantification of the four PAHs ranged from 0.06 to 0.12 µg kg−1 and from 0.13 to 0.24 µg kg−1. Recoveries of more than 84.8% were achieved for all four PAHs at two concentration levels (2.5 and 5.0 µg kg−1), and expanded relative measurement uncertainties were below 20%. The performance of the validated method was in all aspects compliant with provisions set in European Union legislation for the performance of analytical methods employed in the official control of food. The applicability of the method to routine samples was evaluated based on a limited number of commercial edible oil samples.

One-step solvent extraction followed by liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry for the determination of polycyclic aromatic hydrocarbons in edible oils.

A method for rapid analysis of 16 polycyclic aromatic hydrocarbons (PAHs) in edible oils has been developed on the basis of a simplified solvent extraction and liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry performed in multiple reaction monitoring mode. The briefness of the experimental procedure, the use of milliliters of acetonitrile for extraction without any further cleanup process, the short analysis time, and the excellent sensitivity and selectivity demonstrated the advantages of this practical and environmentally friendly method. All the analytes exhibited satisfactory recoveries at three spiking levels (the recoveries ranged from 77.8 to 106.4%), and the relative standard deviations were lower than 10%. The limits of quantitation of this method for the 16 PAHs were in the range of 0.02-0.43 μg/kg. The validated method was successfully applied for the determination of PAHs in coconut oil reference material (BCR-458) and real edible oil samples. The results suggested that a large-scale investigation of the concentration of PAHs in vegetable oils in China is required.

Simultaneous determination of 24 polycyclic aromatic hydrocarbons in edible oil by tandem solid-phase extraction and gas chromatography coupled/tandem mass spectrometry.

An efficient and fast tandem SPE method followed by GC/MS/MS has been developed for the determination and the quantification of 24 polycyclic aromatic hydrocarbons (PAHs) in edible oil. This method includes the monitoring of 15 + 1 PAHs designated as a priority by the European Union in their 2005/108/EC recommendation and 16 PAHs listed by the U. S. Environmental Protection Agency. The sample preparation procedures were based on SPE in which PAH-dedicated cartridges with molecularly imprinted polymers and graphitized carbon black were used in series. The novel tandem SPE combination of selective extraction and purification of light and heavy PAHs provided highly purified analytes. Identification and quantification of 24 target PAHs were performed using GC/MS/MS with the isotope dilution approaches using D-labeled and (13)C-labeled PAHs. The advantages of GC/MS/MS as compared to other detection methods include high sensitivity, selectivity, and interpretation ability. The method showed satisfactory linearity (R(2) > 0.998) over the range assayed (0.5-200 μg/kg); the LODs ranged from 0.03 to 0.6 μg/kg, and LOQs from 0.1 to 2.0 μg/kg. The recoveries using this method at three spiked concentration levels (2, 10, and 50 μg/kg) ranged from 56.8 to 117.7%. The RSD was lower than 12.7% in all cases. The proposed analytical method has been successfully applied for the analysis of the 24 PAHs in edible oil.

Single laboratory validation of an environmentally friendly single extraction and cleanup method for quantitative determination of four priority polycyclic aromatic hydrocarbons in edible oils and fats

This paper reports a simple, rapid, reliable and environmentally friendly gas chromatography-mass spectrometry (GC-MS) method for analyzing polycyclic aromatic hydrocarbons (PAHs) in edible oils and fats.