Update on new trend and progress of the mechanism of polycyclic aromatic hydrocarbon biodegradation by Rhodococcus, based on the new understanding of relevant theories: a review.

Rapid industrial and societal developments have led to substantial increases in the use and exploitation of petroleum, and petroleum hydrocarbon pollution has become a serious threat to human health and the environment. Polycyclic aromatic hydrocarbons (PAHs) are primary components of petroleum hydrocarbons. In recent years, microbial remediation of PAHs pollution has been regarded as the most promising and cost-effective treatment measure because of its low cost, robust efficacy, and lack of secondary pollution. Rhodococcus bacteria are regarded as one of main microorganisms that can effectively degrade PAHs because of their wide distribution, broad degradation spectrum, and network-like evolution of degradation gene clusters. In this review, we focus on the biological characteristics of Rhodococcus; current trends in PAHs degradation based on knowledge maps; and the cellular structural, biochemical, and enzymatic basis of degradation mechanisms, along with whole genome and transcriptional regulation. These research advances provide clues for the prospects of Rhodococcus-based applications in environmental protection.

GC-MS/MS Method for Determination of Polycyclic Aromatic Hydrocarbons in Herbal Medicines.

Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic organic contaminants that have a highly carcinogenic and mutagenic nature. This study aimed to develop and validate a sensitive analytical method to determine 8 PAHs in 51 herbal medicines (HMs) using gas chromatography (GC)-tandem mass spectrometry (MS/MS). Liquid--liquid extraction and florisil SPE cartridge purification were basically adopted for pretreatment. For the samples containing essential oil, starch grain, etc., N,N-dimethyl formamide/water mixture (9:1, v/v) was added in the extraction step. The multiple reaction monitoring (MRM) conditions were newly obtained by the infusion of reference solutions of the targeted compounds at a concentration of 100 ng/mL into the GC-MS/MS system used in this study. The 51 items were classified according to whether or not they contained essential oil. Eight PAHs were not detected in 39 (8.3%) of the 459 samples monitored. The total content of 8 PAHs ranged from 0.45 µg/kg in Anemarrhenae Rhizoma to 270.94 µg/kg in Zingiberis Rhizoma. The average content of those ranged from 0.9 µg/kg in Araliae Continentalis Radix to 110.8 µg/kg in Coptidis Rhizoma Preparata cum Vinum. The results of this study prove that the proposed method is useful for determining 8 PAHs in HMs.

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.

Enhanced benzofluoranthrene removal in constructed wetlands with iron- modified biochar: Mediated by dissolved organic matter and microbial response.

Polycyclic aromatic hydrocarbons (PAHs) pose a high risk to ecosystems owing to their adverse environmental effects. The use of biochar in constructed wetlands (CWs) to remove PAH has received increased interest, but is frequently challenging because of saturation adsorption. To enhance the microbial degradation, electron acceptors are provided. This study aimed to remove a representative PAH, benzofluoranthrene (BbF), using iron-modified biochar as a supplement to the CW substrate. Results revealed that iron-mediated biochar based CWs increased the removal of BbF by 20.4 % and ammonium by 25.6 %. The BbF retained in substrate with biochar (36.6 % higher content) and further removed with iron modification (40.6 % lower content). Iron-modified biochar increased dissolved organic carbon content, particularly low-aromaticity, and low-molecular-weight organic matters (25.7 % higher tryptophan-like material), which contributed to PAH degradation by microorganisms. Microbial analysis confirmed that iron-mediated biochar enriched the abundance of microbes (e.g., Cellulomonas, Actinotalea, and Sphingomonas) and key enzymes (e.g., catA, lipV, and sdhA) that are involved in PAH degradation. Higher proportion of iron-reducing bacteria (e. g., Thiobacillus, Rhodobacter) played a significant role in driving microbial iron cycle, which was beneficial for PAHs removal. Based on the results, we confirmed that the use of iron-modified biochar in CWs enhance PAH removal.

Microbial degradation and transformation of benzo[a]pyrene by using a white-rot fungus Pleurotus eryngii F032.

Polycyclic aromatic hydrocarbons (PAHs) are environmentally recalcitrant contaminants formed from naturally or incomplete combustion of organic materials and some of them are difficult to degrade due to their hydrophobicity and persistency. Benzo [a]pyrene (BaP), is one of PAHs that having five fused benzene and reported as mutagenic, carcinogenic and teratogenic compounds. Biodegradation is one of promising techniques due to its relatively low economic cost and microorganism is a natural capacity to consume hydrocarbons. In this investigation, Pleurotus eryngii F032 was grown in 20 mL of modified mineral salt broth (MSB) supplemented with BaP under static and agitated culture. Within 20 days, static culture removed 59% of BaP, whereas agitated culture removed the highest amount (73%). To expedite BaP elimination, the mechanism and behavior of BaP biosorption and biotransformation by Pleurotus eryngii F032 were additionally examined by gas chromatography-mass spectrometer (GC-MS). The optimal conditions for P. eryngii F032 to eliminate BaP were 25 °C, a C/N ratio of 8, pH 3 and 0.2% inoculum concentration. At an initial BaP content of 10 mg/L, more than 50% was effectively eliminated within 20 days under these conditions. Salinity, glucose, and rhamnolipids were the most important factors impacting BaP biodegradation. GC-MS found degradation products such as BaP-3,6-quinone, indicating plausible metabolic routes. Finally, it may be assumed that the primary mechanism by which white-rot fungi eliminate BaP is by the utilization of biotransformation enzymes such as laccase to mineralize the PAHs. Hence, Pleurotus eryngii F032 could be an ideal candidate to treat PAHs contaminated soils.

A rapid gas chromatography quadrupole time-of-flight mass spectrometry method for the determination of polycyclic aromatic hydrocarbons and sulfur heterocycles in spilled crude oils.

Spilled crude oil samples contain various toxic compounds including polycyclic aromatic hydrocarbons (PAHs) as well as sulfur heterocycles (PASHs) and their related alkylated forms (APAHs and APASHs). In this study, a method was successfully developed employing a gas chromatography quadrupole time-of-flight (GC-QToF) mass spectrometer to quantitatively analyze both PAHs/APAHs and PASHs/APASHs in these samples. With GC-QToF, the monoisotopic mass of the compounds is distinguished, allowing the PASHs/APASHs to be extracted separately from the PAHs/APAHs in crude oil. A gas chromatography triple quadrupole (GC-MS/MS) mass spectrometer was also used to confirm that a GC-QToF is the preferred instrument for analyzing these compounds. With the use of PASH/APASH standards to determine response correction factors (RCFs) in relation to PAH standards, the developed method is capable of analyzing PAHs, APAHs, PASHs, and APASHs in a single injection. The use of RCFs allowed for the development of a practical polycyclic aromatic carbon (PAC) method for analyzing a total of 77 compounds of the 2 groups in crude oil. This newly developed method was applied to spilled crude oils, demonstrating its potential in toxicological study as well as oil spill forensic investigation.

Biodegradation Potential of Bacillus sp. PAH-2 on PAHs for Oil-Contaminated Seawater.

Microbial degradation is a useful tool for inhibiting or preventing polycyclic aromatic hydrocarbons (PAHs) widely distributed in marine environment after oil spill accidents. This study aimed to evaluate the potential and diversity of bacteria Bacillus sp. PAH-2 on Benzo (a) anthracene (BaA), Pyrene (Pyr), and Benzo (a) pyrene (BaP), their composite system, aromatic components system, and crude oil. The seven-day degradation rates against BaA, Pyr, and BaP were 20.6%, 12.83%, and 17.49%, respectively. Further degradation study of aromatic components demonstrated PAH-2 had a high degradation rate of substances with poor stability of molecular structure. In addition, the degradation of PAHs in crude oil suggested PAH-2 not only made good use of PAHs in such a more complex structure of pollutants but the saturated hydrocarbons in the crude oil also showed a good application potential.

Development of a syringe membrane-based microextraction method based on metal-organic framework mixed-matrix membranes for preconcentration/extraction of polycyclic aromatic hydrocarbons in tea infusion.

Inevitably, the residues of polycyclic aromatic hydrocarbons (PAHs) in tea leaves will be transferred to hot tea infusion, constituting a certain drinking risk; consequently, it is imperative to develop rapid, sensitive, and robust approaches for their trace-level detection. Herein, we developed a syringe membrane-based microextraction (SMME) method for preconcentration/extraction of PAHs in tea infusions. This method utilized metal-organic framework-mixed matrix membranes (MOF-MMMs) as adsorbents, which anchored the nanoparticles of MOFs onto the surface of PVDF membrane. The UiO-66 (Zr)-based MMM possessed high Brunauer-Emmett-Teller (BET) surface area (320.5 m2 g-1) and pore volume (0.18 cm3 g-1), thus enhancing extraction/adsorption efficiency. Under optimized conditions, the limits of detection for PAHs reached as low as 0.02-0.08 µg L-1 with extraction recoveries of 85.5-102.1%, and the inter-day and intra-day precision was lower than 8.4% in tea infusions. Consequently, the SMME/HPLC-DAD method shows a great potential in conventional monitoring of PAHs in tea samples.

High crystalline magnetic covalent organic framework with three-dimensional grapevine structure for ultrasensitive extraction of nitro-polycyclic aromatic hydrocarbons in food and environmental samples.

Developing and establishing an efficient pre-treatment approach for the precise extraction of nitrated-polycyclic aromatic hydrocarbons (N-PAHs) from real-life samples is critical for ensuring their safety. In this study, a novel crystalline magnetic covalent organic framework with a grapevine structure not a single core-shell, Fe3O4@TAPT-DMTA-COF, was fabricated via chemical bonding. Unchanging the reticulated structure and high crystallinity of TAPT-DMTA-COF, the combination made this material possess not only simple operation via magnetic decantation but also remarkable chemical stability. Fe3O4@TAPT-DMTA-COF had a large surface area (1578.45 m2/g), and rich electronegative triazine-groups, which makes it become a superior magnetic enrichment material for trace N-PAHs. For N-PAHs analysis, low limits of detection (LODs) (1.43-17.24 ng/L), excellent relative standard deviations (RSDs ≤ 11.52%), and wide linearity (10-5000 ng/L) were obtained. Real-life applications based on this composite have been successfully explored by capturing the N-PAHs emitted from food and environmental samples.

Air-assisted liquid-liquid microextraction based on the solidification of floating deep eutectic solvents for the simultaneous determination of bisphenols and polycyclic aromatic hydrocarbons in tea infusions via HPLC.

Deep eutectic solvents (DESs) are a new class of green "designer solvent"; its physicochemical properties can be easily tuned by adjusting DES' constituents, chemical ratio and water content. In this study, three hydrophobic DESs with low viscosity, low density, and melting points close to room temperature were designed and synthesized. Based on these DESs, an air-assisted liquid-liquid microextraction technique was developed based on the solidification of floating DESs for the simultaneous determination of bisphenols and polycyclic aromatic hydrocarbons (PAHs) via HPLC. The microextraction parameters were optimized via the Plackett-Burman design and response surface methodologies. The method shows satisfactory linearity (R2 ≥ 0.9928), a low limit of detection (0.16-0.75 µg L-1) and satisfactory precision (≤2.3%), and was successfully applied for the simultaneous determination of bisphenols and PAHs from tea infusions with satisfactory recoveries (82.0-116.6%). This method is simple, rapid, economical, environmentally compatible, dispersive solvent-frees and centrifugation-free, and has promising applications in food safety.

Comprehensive two-dimensional gas chromatography-high resolution mass spectrometry with complementary ionization methods in the study of 5000-year-old mummy.

RATIONALE: Mummification is one of the defining customs of ancient Egypt. The nuances of the embalming procedure and the composition of the embalming mixtures have attracted the attention of scientists and laypeople for a long time. Modern analytical tools make mummy studies more efficient. METHODS: Comprehensive two-dimensional gas chromatography-high resolution mass spectrometry (GCxGC/HRMS) with complementary ionization methods (electron ionization, positive chemical ionization, and electron capture negative ionization [ECNI]) with a Pegasus GC-HRT+4D instrument was used to identify embalming components in the mummy from the Pushkin Museum of Fine Arts acquired in 1913 in London at the de Rustafjaell sale. The mummy dates back to the late Predynastic period (direct accelerator mass spectrometry-dating 3356-3098 bc), being one of the oldest in the world. RESULTS: The results showed the complexity of the embalming mixtures that were already in use 5000 years ago. Several hundred organic compounds were identified in the mummy samples. Various types of hydrocarbons (triterpanes, steranes, isoprenoid, and polycyclic aromatic hydrocarbons) prove the presence of petroleum products. Iodinated compounds detected using ECNI define oils of marine origin, whereas esters of palmitic acid indicate the use of beeswax. The nature of the discovered components of conifer tar proves that the preliminary processing of conifer resins involved heating. GCxGC/HRMS also allowed a number of modern contaminants (phthalates, organophosphates, and even DDT) to be identified. CONCLUSIONS: Application of a powerful GCxGC/HRMS technique with complementary ionization methods allowed significant widening of the range of organic compounds used for mummification that could be identified. The complexity of the embalming mixtures supports the hypothesis of the high social status of the child made on the basis of the preliminary study of the mummy.

Influence of Plant Extract Addition to Marinades on Polycyclic Aromatic Hydrocarbon Formation in Grilled Pork Meat.

Marinating is one of the most common methods of pre-processing meat. Appropriate selection of marinade ingredients can influence the physicochemical properties of the meat and can reduce the level of polycyclic aromatic hydrocarbons (PAHs) in the final product. The effects of the inclusion of natural plant extracts such as bay leaf (BL), black pepper (BP), turmeric (TU), jalapeno pepper (JP) and tamarind paste (TA) in marinades on the physicochemical properties of grilled pork neck were studied. The addition of spice extracts to marinades increased the proportion of colour components L* and b*. The use of TU, TA, JP, MX and C marinades lowered the hardness and pH of the meat. The highest phenolic compound levels were observed in the case of the mixture of all extracts (MX) and JP marinades, and the highest total antioxidant capacity was exhibited by the BL and MX marinades. The highest PAH content was recorded in the CON marinade (Σ12PAH 98.48 ± 0.81 µg/kg) and the lowest in the JP marinade (4.76 ± 0.08 µg/kg), which had the strongest, statistically significant reducing effect (95% reduction) on PAH levels. Analysis of correlation coefficients showed a relationship between the total antioxidant capacity of the marinades and the PAH content in grilled pork.

Determination of PAH Benzo[a]anthracene, Chrysene, Benzo[b]flouranthene and Benzo[a]pyrene in Hydro Alcoholic Herbal Extracts with Fluorescence Detector Using Solid-Phase Extraction.

An appropriate purification and quantification method has been developed for polycyclic aromatic hydrocarbons (PAH) in hydro alcoholic herbal extracts. For this, Bacopa monnieri, Camellia sinensis, Withania somnifera and Andrographis paniculata samples were extracted with modified solid-phase extraction (SPE) and the PAH were quantified using liquid chromatography coupled to fluorescence detector. Purification of herbal extract using hexane and acetone in the ratio of 1:1 followed by treatment with QuEChERS salt (6 g MgSO4 and 1.5 g sodium acetate) improved the recovery rate of PAH. Silica SPE, which accomplishes solvent exchange to hexane by cleanup method, was developed to reduce the matrix effect and quality of the result obtained was increased. The developed method can be used for regular monitoring and analysis of PAH in natural extracts so as to prevent contamination.

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.

Emulsification of Surfactant on Oil Droplets by Molecular Dynamics Simulation.

Heavy oil in crude oil flooding is extremely difficult to extract due to its high viscosity and poor fluidity. In this paper, molecular dynamics simulation was used to study the emulsification behavior of sodium dodecyl sulfonate (SDSn) micelles on heavy oil droplets composed of asphaltenes (ASP) at the molecular level. Some analyzed techniques were used including root mean square displacement, hydrophile-hydrophobic area of an oil droplet, potential of mean force, and the number of hydrogen bonds between oil droplet and water phase. The simulated results showed that the asphaltene with carboxylate groups significantly enhances the hydration layer on the surface of oil droplets, and SDSn molecules can change the strength of the hydration layer around the surface of the oil droplets. The water bridge structure between both polar heads of the surfactant was commonly formed around the hydration layer of the emulsified oil droplet. During the emulsification of heavy oil, the ratio of hydrophilic hydrophobic surface area around an oil droplet is essential. Molecular dynamics method can be considered as a helpful tool for experimental techniques at the molecular level.

Diatom aggregation when exposed to crude oil and chemical dispersant: Potential impacts of ocean acidification.

Diatoms play a key role in the marine carbon cycle with their high primary productivity and release of exudates such as extracellular polymeric substances (EPS) and transparent exopolymeric particles (TEP). These exudates contribute to aggregates (marine snow) that rapidly transport organic material to the seafloor, potentially capturing contaminants like petroleum components. Ocean acidification (OA) impacts marine organisms, especially those that utilize inorganic carbon for photosynthesis and EPS production. Here we investigated the response of the diatom Thalassiosira pseudonana grown to present day and future ocean conditions in the presence of a water accommodated fraction (WAF and OAWAF) of oil and a diluted chemically enhanced WAF (DCEWAF and OADCEWAF). T. pseudonana responded to WAF/DCEWAF but not OA and no multiplicative effect of the two factors (i.e., OA and oil/dispersant) was observed. T. pseudonana released more colloidal EPS (< 0.7 µm to > 3 kDa) in the presence of WAF/DCEWAF/OAWAF/OADCEWAF than in the corresponding Controls. Colloidal EPS and particulate EPS in the oil/dispersant treatments have higher protein-to-carbohydrate ratios than those in the control treatments, and thus are likely stickier and have a greater potential to form aggregates of marine oil snow. More TEP was produced in response to WAF than in Controls; OA did not influence its production. Polyaromatic hydrocarbon (PAH) concentrations and distributions were significantly impacted by the presence of dispersants but not OA. PAHs especially Phenanthrenes, Anthracenes, Chrysenes, Fluorenes, Fluoranthenes, Pyrenes, Dibenzothiophenes and 1-Methylphenanthrene show major variations in the aggregate and surrounding seawater fraction of oil and oil plus dispersant treatments. Studies like this add to the current knowledge of the combined effects of aggregation, marine snow formation, and the potential impacts of oil spills under ocean acidification scenarios.

Direct Evidence of Salinity and pH Effects on the Interfacial Interactions of Asphaltene-Brine-Silica Systems.

The hydraulic fracturing technique remains essential to unlock fossil fuel from shale oil reservoirs. However, water imbibed by shale during hydraulic fracturing triggers environmental and technical challenges due to the low flowback water recovery. While it appears that the imbibition of fracturing fluid is a complex function of physico-chemical processes in particular capillary force which is associated with wettability of oil-brine-shale, the controlling factor(s) to govern the wettability is incomplete and the literature data in this context is missing. We thus measured the adsorption/desorption of asphaltenes on silica surface in the presence of brines using quartz crystal microbalance with dissipation (QCM-D). We detected zeta potential of asphaltene-brine and brine-silica systems and calculated the disjoining pressures of the asphaltene-brine-silica system in the case of different salinity. Moreover, we performed a geochemical study to quantify the variation of surface chemical species at asphaltene and silica surfaces with different pH values and used the chemical force microscope (CFM) method to quantify the effect of pH on intermolecular forces. Our results show that lowering salinity or raising pH reduced the adhesion force between asphaltene and silica surface. For example, at a pH value of 6.5, when the concentration of injected water is reduced from 1000 mM to 100 mM and 10 mM, the adhesion force decreased by approximately 58% and 66%, respectively. In addition, for the 100 mM NaCl solution, when the pH value increased from 4.5 to 6.5 and 9, the adhesion force decreased by approximately 56% and 87%, respectively. Decreased adhesion forces between asphaltene and the silica surface could promote the desorption of asphaltene from the silica surface, resulting in a negative zeta potential for both asphaltene-silica and brine-silica interfaces and a shift of wettability towards water-wet characteristic. During such a process, -NH+ number at asphaltene surfaces decreases and the bonds between -NH+ and >SiO- break down, to further interpret the formation of a thinner asphaltene adlayer on the rock surface. This study proposes a reliable theoretical basis for the application of hydraulic fracturing technology, and a facile and possible manipulation strategy to increase flowback water from unconventional reservoirs.

The True Value of Spirulina.

Algae products are attracting growing interest due to their pleasant taste and their high contents in protein, essential amino acids, vitamins, and minerals. Specifically, spirulina products are widely promoted for their high vitamin B12 content. So far, knowledge regarding the contamination with cyanotoxins, heavy metals, pesticides, or polycyclic aromatic hydrocarbons (PAHs) is scarce, although some studies reported high contaminant levels in spirulina products. The regular intake of spirulina, and very likely other algae products as well, as a dietary supplement in the gram range demands a closer monitoring of potentially harmful constituents.

Physicochemical properties and health risk assessment of polycyclic aromatic hydrocarbons of fragrant rapeseed oils in China.

BACKGROUND: Fragrant rapeseed oil is a type of hot-pressed oil in China. In this study, physicochemical properties, oxidative stability index (OSI), tocopherols, sterols, and polycyclic aromatic hydrocarbons (PAHs) in fragrant rapeseed oils were evaluated. Additionally, the cancer risk assessment pertaining to PAHs in fragrant rapeseed oil was investigated. RESULTS: Acid values (0.64-2.68 mg potassium hydroxide per gram), peroxide values (1.58-4.86 mmol kg-1 ), and color values (R = 2.6-5.8, Y = 35) of fragrant rapeseed oils were all within codex limits. Tocopherols and sterols ranged from 559.5 to 783.7 mg kg-1 and 4412.6 to 7859.8 mg kg-1 respectively. The OSI (110 °C) was between 4.8 and 15.9 h, with an average value of 10.8 h. Mean values of benzo[a]pyrene and PAH4 (chrysene, benz[a]anthracene, benzo[b]fluroranthene, and benzo[a]pyrene) were 2.32 µg kg-1 and 8.21 µg kg-1 respectively. The 95% dietary exposure of benzo[a]pyrene equivalent (BaPeq) contents from PAH4 were 0.3474 ng kg-1 day-1 , 0.3942 ng kg-1 day-1 , 1.8293 ng kg-1 day-1 , and 0.4294 ng kg-1 day-1 for male children, adolescents, adults, and seniors respectively. For females, these values were 0.3443 ng kg-1 day-1 , 0.3228 ng kg-1 day-1 , 1.8697 ng kg-1 day-1 , and 0.4084 ng kg-1 day-1 , respectively. Moreover, incremental lifetime cancer risk values at the cumulative probabilities of 91.3% and 91.6% for male adults and female adults respectively were higher than 1 × 10-5 . CONCLUSION: The results imply that the potential risk of cancer with PAHs in fragrant rapeseed oil should be a concern, especially for the health of adults. Fragrant rapeseed oil is still a product subject to contamination by PAHs. Limits for PAH4 of fragrant rapeseed oil should be included in Chinese regulations to improve safety. © 2020 Society of Chemical Industry.

In Vitro Bioavailability of the Hydrocarbon Fractions of Dimethyl Sulfoxide Extracts of Petroleum Substances.

Determining the in vitro bioavailable concentration is a critical, yet unmet need to refine in vitro-to-in vivo extrapolation for unknown or variable composition, complex reaction product or biological material (UVCB) substances. UVCBs such as petroleum substances are commonly subjected to dimethyl sulfoxide (DMSO) extraction in order to retrieve the bioactive polycyclic aromatic compound (PAC) portion for in vitro testing. In addition to DMSO extraction, protein binding in cell culture media and dilution can all influence in vitro bioavailable concentrations of aliphatic and aromatic compounds in petroleum substances. However, these in vitro factors have not been fully characterized. In this study, we aimed to fill in these data gaps by characterizing the effects of these processes using both a defined mixture of analytical standards containing aliphatic and aromatic hydrocarbons, as well as 4 refined petroleum products as prototypical examples of UVCBs. Each substance was extracted with DMSO, and the protein binding in cell culture media was measured by using solid-phase microextraction. Semiquantitative analysis for aliphatic and aromatic compounds was achieved via gas chromatography-mass spectrometry. Our results showed that DMSO selectively extracted PACs from test substances, and that chemical profiles of PACs across molecular classes remained consistent after extraction. With respect to protein binding, chemical profiles were retained at a lower dilution (higher concentration), but a greater dilution factor (ie, lower concentration) resulted in higher protein binding in cell medium, which in turn altered the ultimate chemical profile of bioavailable PACs. Overall, this case study demonstrates that extraction procedures, protein binding in cell culture media, and dilution factors prior to in vitro testing can all contribute to determining the final bioavailable concentrations of bioactive constituents of UVCBs in vitro. Thus, in vitro-to-in vivo extrapolation for UVCBs may require greater attention to the concentration-dependent and compound-specific differences in recovery and bioavailability.