Degradation of gaseous hydrocarbons in aerated stirred bioreactors inoculated with Rhodococcus erythropolis: Effect of the carbon source and SIFT-MS method development.

The study of microbial hydrocarbons removal is of great importance for the development of future bioremediation strategies. In this study, we evaluated the removal of a gaseous mixture containing toluene, m-xylene, ethylbenzene, cyclohexane, butane, pentane, hexane and heptane in aerated stirred bioreactors inoculated with Rhodococcus erythropolis and operated under non-sterile conditions. For the real-time measurement of hydrocarbons, a novel systematic approach was implemented using Selected-Ion Flow Tube Mass Spectrometry (SIFT-MS). The effect of the carbon source (∼9.5 ppmv) on (i) the bioreactors' performance (BR1: dosed with only cyclohexane as a single hydrocarbon versus BR2: dosed with a mixture of the 8 hydrocarbons) and (ii) the evolution of microbial communities over time were investigated. The results showed that cyclohexane reached a maximum removal efficiency (RE) of 53% ± 4% in BR1. In BR2, almost complete removal of toluene, m-xylene and ethylbenzene, being the most water-soluble and easy-to-degrade carbon sources, was observed. REs below 32% were obtained for the remaining compounds. By exposing the microbial consortium to only the five most recalcitrant hydrocarbons, REs between 45% ± 5% and 98% ± 1% were reached. In addition, we observed that airborne microorganisms populated the bioreactors and that the type of carbon source influenced the microbial communities developed. The abundance of species belonging to the genus Rhodococcus was below 10% in all bioreactors at the end of the experiments. This work provides fundamental insights to understand the complex behavior of gaseous hydrocarbon mixtures in bioreactors, along with a systematic approach for the development of SIFT-MS methods.

Profiles, exposure assessment and expanded screening of PAHs and their derivatives in one petroleum refinery facility of China.

This study investigated environmental distribution and human exposure of polycyclic aromatic hydrocarbons (PAHs) and their derivatives in one Chinese petroleum refinery facility. It was found that, following with high concentrations of 16 EPA PAHs (∑Parent-PAHs) in smelting subarea of studied petroleum refinery facility, total derivatives of PAHs [named as XPAHs, including nitro PAHs (NPAHs), chlorinated PAHs (Cl-PAHs), and brominated PAHs (Br-PAHs)] in gas (mean= 1.57 × 104 ng/m3), total suspended particulate (TSP) (mean= 4.33 × 103 ng/m3) and soil (mean= 4.37 × 103 ng/g) in this subarea had 1.76-6.19 times higher levels than those from other subareas of this facility, surrounding residential areas and reference areas, indicating that petroleum refining processes would lead apparent derivation of PAHs. Especially, compared with those in residential and reference areas, gas samples in the petrochemical areas had higher ∑NPAH/∑PAHs (mean=2.18), but lower ∑Cl-PAH/∑PAHs (mean=1.43 × 10-1) and ∑Br-PAH/∑PAHs ratios (mean=7.49 × 10-2), indicating the richer nitrification of PAHs than chlorination during petrochemical process. The occupational exposure to PAHs and XPAHs in this petroleum refinery facility were 24-343 times higher than non-occupational exposure, and the ILCR (1.04 × 10-4) for petrochemical workers was considered to be potential high risk. Furthermore, one expanded high-resolution screening through GC Orbitrap/MS was performed for soils from petrochemical area, and another 35 PAHs were found, including alkyl-PAHs, phenyl-PAHs and other species, indicating that profiles and risks of PAHs analogs in petrochemical areas deserve further expanded investigation.

Vibrational spectroscopy of interstellar PAHs: 1-cyanonaphthalene and 2-cyanonaphthalene.

In this work, we present a comprehensive experimental and theoretical study of the vibrational spectra of PAH molecules recently detected in the interstellar medium: 1-cyanonaphthalene and 2-cyanonaphthalene. The room temperature IR spectra of 1- and 2-cyanonaphthalene in the region 100-3100 cm-1 and their vibrational Raman spectra in the region 35-3100 cm-1 are reported here for the first time. A detailed spectral analysis is carried out using quantum chemical calculations employing the DFT methodology. Anharmonic corrections using the VPT2 method yield excellent agreement with the experimental spectra. A re-investigation of the vibrational spectrum of the parent molecule: naphthalene validates the experimental and theoretical methods used. A consistent set of assignments is reported for the fundamental bands of 1- and 2-cyanonapththalene. The experimental and theoretical data presented here would be useful inputs for modelling the role of cyanonaphthalene in astrophysical processes.

Preferential association of PBDEs and PAHs with mineral particles vs. dissolved organic carbon: Implications for groundwater contamination at e-waste sites.

Polybrominated biphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) are commonly detected contaminants at e-waste recycling sites. Against the conventional wisdom that PBDEs and PAHs are highly immobile and persist primarily in shallow surface soils, increasing evidence shows that these compounds can leach into the groundwater. Herein, we compare the leachabilities of PBDEs vs. PAHs from contaminated soils collected at an e-waste recycling site in Tianjin, China. Considerable amounts of BDE-209 (0.3-2 ng/L) and phenanthrene (42-106 ng/L), the most abundant PBDE and PAH at the site, are detected in the effluents of columns packed with contaminated soils, with the specific concentrations varying with hydrodynamic and solution chemistry conditions. Interestingly, the leaching potential of BDE-209 appears to be closely related to the release of colloidal mineral particles, whereas the leachability of phenanthrene correlates well with the concentration of dissolved organic carbon in the effluent, but showing essentially no correlation with the concentration of mineral particles. The surprisingly different trends of the leachability observed between BDE-209 and phenanthrene is counterintuitive, as PBDEs and PAHs often co-exist at e-waste recycling sites (particularly at the sites wherein incineration is being practiced) and share many similarities in terms of physicochemical properties. One possible explanation is that due to its extremely low solubility, BDE-209 predominantly exists in free-phase (i.e., as solid (nano)particles), whereas the more soluble phenanthrene is mainly sorbed to soil organic matter. Findings in this study underscore the need to better understand the mobility of highly hydrophobic organic contaminants at contaminated sites for improved risk management.

Carbonyl-amine condensation coupled ozonolysis of dipropylamine and styrene: Decay kinetics, reaction mechanism, secondary organic aerosol formation and cytotoxicity.

Oxidation of organic amines (OAs) or aromatic hydrocarbons (AHs) produces carbonyls, which further react with OAs to form carbonyl-amine condensation products, threatening environmental quality and human health. However, there is still a lack of systematic understanding of the carbonyl-amine condensation reaction processes of OAs or between OAs and AHs, and subsequent environmental health impact. This work systematically investigated the carbonyl-amine condensation coupled ozonolysis kinetics, reaction mechanism, secondary organic aerosol (SOA) formation and cytotoxicity from the mixture of dipropylamine (DPA) and styrene (STY) by a combined method of product mass spectrometry identification, particle property analysis and cell exposure evaluation. The results from ozonolysis of DPA and STY mixture revealed that STY inhibited the ozonolysis of DPA to different degrees to accelerate its own decay rate. The barycenter of carbonyl-amine condensation reactions was shifted from inside of DPA to between DPA and STY, which accelerated STY ozonolysis, but slowed down DPA ozonolysis. For the first time, ozonolysis of DPA and STY mixture to complex carbonyl-amine condensation products through the reactions of DPA with its carbonyl products, DPA with STY's carbonyl products and DPA's bond breakage product with STY's carbonyl products was confirmed. These condensation products significantly contributed to the formation and growth of SOA. The SOA containing particulate carbonyl-amine condensation products showed definite cytotoxicity. These findings are helpful to deeply and comprehensively understand the transformation, fate and environmental health effects of mixed organics in atmospheric environment.

Estimation of gaseous polycyclic aromatic hydrocarbons (PAHs) and characteristics of atmospheric PAHs at a traffic site in Kanazawa, Japan.

Size-fractionated particulate matter (PM2.5 and PM>2.5) was collected at a traffic site in Kanazawa, Japan in a seasonal sampling work in 2020. Nine polycyclic aromatic hydrocarbons (4- to 6-ring PAHs) were determined in fine and coarse particles. The gas/particle partitioning coefficients (Kp) of the PAHs were calculated from the supercooled liquid vapour pressure and octanol-air partitioning coefficient based on the relationships obtained in previous traffic pollution-related studies. Gaseous PAHs were estimated by Kp and the concentrations of PM and particulate PAHs. The concentrations of total PAHs were 32.5, 320.1 and 5646.2 pg/m3 in the PM>2.5, PM2.5 and gas phases, respectively. Significant seasonal trends in PAHs were observed (particle phase: lowest in summer, gas phase: lowest in spring, particle and gas phase: lowest in spring). Compared to 2019, the total PAH concentrations (in particles) decreased in 2020, especially in spring and summer, which might be due to reduced traffic trips during the COVID-19 outbreak. The incremental lifetime cancer risk (ILCR) calculated from the toxic equivalent concentrations relative to benzo[a]pyrene (BaPeq) was lower than the acceptable limit issued by the US Environmental Protection Agency, indicating a low cancer risk in long-term exposure to current PAH levels. It is notable that gaseous PAHs considerably contributed to BaPeq and ILCR (over 50%), which highlighted the significance of gaseous PAH monitoring for public health protection. This low-cost estimation method for gaseous PAHs can be expected to reliably and conveniently obtain PAH concentrations as a surrogate for traditional sampling in the future work.

Sublethal effects of early-life exposure to common and emerging contaminants in birds.

The plight of wild birds is becoming critical due to exposure to environmental contaminants. Although laboratory studies have provided insights into the developmental effects of chemical exposures, less is known about the adverse effects of environmental chemicals in developing wild birds. Early life stages are critical windows during which long-term organization of physiological, behavioral, and neurological systems can occur. Thus, contaminant exposure at early life stages can directly influence survival and reproductive success, with consequences for population stability and resilience in wild species. This review synthesizes existing knowledge regarding both short- and long-term effects of early-life exposure to widespread contaminants in birds. We focus especially on wild birds and on contaminants of concern within the Gulf of Mexico as an example of a habitat under anthropogenic stress from exposure to a complex mixture of chemicals and changing land uses that exacerbate existing vulnerabilities of wildlife in this region. Chemical contaminants for discussion in this review are based on avian mortality records from the Wildlife Health Information Sharing Partnership (WHISPers) database and on additional review of the literature regarding avian contaminants of concern for the northern Gulf of Mexico, and include oil and associated polycyclic aromatic hydrocarbons, dioxin and dioxin-like compounds, flame retardants, pesticides, heavy metals, and plastics. We provide an overview of effects in bird species at both the pre-hatching and post-hatching early life stages, discuss differences in sensitivities by route of exposure, life stage, and life history, and provide recommendations for future research. We find that additional research is needed on altricial species, post-hatching early-life exposure, long-term effects, and on ecologically relevant contaminant concentrations and routes of exposure. Given the increasing frequency and intensity of anthropogenic stressors encountered by wild animals, understanding both lethal and sublethal impacts of contaminants on the health of individuals and populations will be critical to inform restoration, management, and mitigation efforts.

The origin of selectivity in the trimerization of 1,3-cyclopentadiene from an activation strain perspective.

CONTEXT: Quantum chemical modeling (DFT-PBE0/cc-pVTZ) of the [4 + 2]-cycloaddition reaction of 1,3-cyclopentadiene (CPD) to (exo/endo)-dicyclopentadiene (DCPD) was carried out, resulting in 14 products-CPD trimers. According to calculations, exo-addition of CPD to the norbornene (NB) fragment of DCPD and trans-addition of CPD to the cyclopentene (CP) fragment of DCPD are kinetically preferred. Ring strain energies ERS were calculated for all trimers using the homodesmotic reaction approach. The least strained trimers are formed by exo-addition of CPD to the NB fragment of exo-DCPD, while the most strained ones are formed by endo-addition of CPD to the NB fragment of endo-DCPD. ERS values are in good agreement with thermodynamic stability of trimers. Analysis of activation energy using the activation strain model showed steric effects causing deformation of the DCPD molecule upon reaching the transition state to be the leading factor of the magnitude of the cycloaddition reaction activation barrier. Deformation of the DCPD molecule mostly occurs in two dihedral angles-the angle of escape of H atoms from the plane of the double bond involved in cycloaddition and the angle between the NB and CP fragments. The sum of deviations of these angles in the transition states (or products) structures is in good agreement with Gibbs activation energies of cycloaddition reactions of CPD to DCPD. METHODS: Quantum chemical calculations were carried out using density functional theory in Gaussian 09 software. Hybrid exchange-correlation PBE0 functional was used with cc-pVTZ basis set.

Hierarchically spherical assembly of carbon nanorods derived from metal-organic framework as solid-phase microextraction coating for nitrated polycyclic aromatic hydrocarbon analysis.

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are pervasive contaminants in aquatic environments. They are characterized by persistence, toxicity, bioaccumulation, and long-range transport, significantly threatening human health. The development of sensitive methods for nitro-PAH analysis in environmental samples is in great need. This study developed a novel carbonaceous SPME coating derived from metal-organic framework (MOF), namely a spherical assembly consisting of carbon nanorods with hierarchical porosity (HP-MOF-C), for the extraction and determination of nitro-PAHs in waters. The HP-MOF-C coated fiber demonstrated superior nitro-PAH extraction efficiencies, with enrichment factors 2∼70 times higher than commercial fibers. This enhancement was due to the strong hydrophobic, π-π electron coupling/stacking, and π-π electron donor-acceptor interactions between the carbonaceous framework of HP-MOF-C and the nitro-PAHs. Moreover, the unique hierarchical porous structure of HP-MOF-C accelerated the diffusion of nitro-PAHs, further facilitating their enrichment. The fiber also exhibited good thermal stability, remarkable chemical stabilities against common acid, base, and polar/non-polar solvents, and long service life (> 150 SPME cycles). The nitro-PAH determination method based on HP-MOF-C coating yielded wide linear ranges, low detection limits (0.4∼5.0 ng L-1), satisfactory repeatability and reproducibility, and good recoveries in real water samples. The proposed method was considered to be green according to the Analytical GREEnness assessment. The present study not only offers an efficient SPME coating for the enrichment of nitro-PAHs, but also provides insights into the design of porous coating materials.

Expanding the Landscape of Phosphorous-Based Open Shell Species: Stable Mono-, Di-, and Trianionic Radicals Based on a Contorted Triphosphaalkene.

The stepwise reduction of the highly contorted truxene-based triphosphaalkene 1 using KC8 led to the isolation of mono-, di-and tri-anionic species. The solid-state molecular structures of mono- and diradical anionic species were elucidated by single crystal X-ray diffractions, revealing elongated P-C bonds and a pronounced "indene" aromatization compared to the parent system. All three radical species displayed distinct Electron Paramagnetic Resonance (EPR) spectra, providing compelling evidence for the open-shell electronic configuration of both the diradical and triradical species-an observation unprecedented in any previously reported phosphorous-based anionic polyradicals. Mulliken spin density calculations revealed a dominant localization of radical spin on a single phosphorous atom in the monoanion. In the dianion, spin localization is observed on two phosphorous atoms (~34% each), with a minor contribution from the third phosphorous (0.13%), while the trianion demonstrates a uniform distribution of spin density (~30%) across each phosphorous atom.

Concentration of polycyclic aromatic hydrocarbons (PAHs) in bread and health risk assessment across the globe: A systematic review and meta-analysis.

Although bread is the principal food in most countries, polycyclic aromatic hydrocarbons (PAHs) may be present and pose a potential risk to consumers. The aim of this review is to provide a comprehensive report on the concentration and health risks associated with PAHs in bread around the world. Various databases, such as Scopus, PubMed, Science Direct, and Google Scholar, were searched from their beginnings until December 2023 for this systematic review, which included 34 potentially relevant articles with data relating to 1057 bread samples. Utilizing a multilevel regression modeling approach, the study evaluated various factors such as fuel type, bread type, and geographical location. Following the initial evaluation, in 26.47% and 20.28% of all studies, the levels of Bap and PAH4 were higher than the permissible limit values, respectively. Based on the isomer ratios, 55.88% of the studies associated the presence of PAHs in bread samples with pyrogenic/coal combustion sources. According to the carcinogenic risk results, bread consumers in all studies have been exposed to moderate or high levels of carcinogenicity. The most significant risk levels are associated with the consumption of bread in Egypt, Kuwait, Iran, and India. Moreover, meta-regression analysis demonstrated significantly higher toxicity equivalent quotient and cancer risk mean values in bread baked using fossil fuels compared to other sources (p < .05). The high concentrations of PAHs, especially Benzo[a]pyrene, in bread pose a serious public health risk. Stringent regulations and monitoring are crucial to reduce contamination. Further research is necessary to develop safe processing methods to remove PAHs in bread.

Potential of Coffee Cherry Pulp Extract against Polycyclic Aromatic Hydrocarbons in Air Pollution Induced Inflammation and Oxidative Stress for Topical Applications.

Airborne particulate matter (PM) contains polycyclic aromatic hydrocarbons (PAHs) as primary toxic components, causing oxidative damage and being associated with various inflammatory skin pathologies such as premature aging, atopic dermatitis, and psoriasis. Coffee cherry pulp (CCS) extract, rich in chlorogenic acid, caffeine, and theophylline, has demonstrated strong antioxidant properties. However, its specific anti-inflammatory effects and ability to protect macrophages against PAH-induced inflammation remain unexplored. Thus, this study aimed to evaluate the anti-inflammatory properties of CCS extract on RAW 264.7 macrophage cells exposed to atmospheric PAHs, compared to chlorogenic acid (CGA), caffeine (CAF), and theophylline (THP) standards. The CCS extract was assessed for its impact on the production of nitric oxide (NO) and expression of tumor necrosis factor-alpha (TNF-α), interleukin-6 (IL-6), inducible nitric oxide synthase (iNOS), and cyclooxygenase-2 (COX-2). Results showed that CCS extract exhibited significant antioxidant activities and effectively inhibited protease and lipoxygenase (LOX) activities. The PAH induced the increase in intracellular reactive oxygen species, NO, TNF-α, IL-6, iNOS, and COX-2, which were markedly suppressed by CCS extract in a dose-dependent manner, comparable to the effects of chlorogenic acid, caffeine, and theophylline. In conclusion, CCS extract inhibits PAH-induced inflammation by reducing pro-inflammatory cytokines and reactive oxygen species (ROS) production in RAW 264.7 cells. This effect is likely due to the synergistic effects of its bioactive compounds. Chlorogenic acid showed strong antioxidant and anti-inflammatory activities, while caffeine and theophylline enhanced anti-inflammatory activity. CCS extract did not irritate the hen's egg chorioallantoic membrane. Therefore, CCS extract shows its potential as a promising cosmeceutical ingredient for safely alleviating inflammatory skin diseases caused by air pollution.

In-tube solid-phase microextraction of polycyclic aromatic hydrocarbons from refinery water samples using UiO-66/polyacrylonitrile electrospun nanofibers followed by high-performance liquid chromatography-ultraviolet detection.

A simple and quick fiber-in-tube solid-phase microextraction (FIT-SPME) was introduced for the extraction and determination of nine polycyclic aromatic hydrocarbons followed by a high-performance liquid chromatography-ultraviolet detector in refinery water samples. For this purpose, a water-resistant metal-organic framework with a high surface area called UiO-66 has been applied in the form of an electrospun coating on stainless steel wires. After that, all the fibers were packed in the lumen of a stainless-steel tube to make the extraction phase. Both one variable at a time and experimental design methods have been used to optimize effective parameters on FIT-SPME. Under optimum conditions, the method demonstrated good linearity between 0.5 and 1000.0 µg/L with a coefficient of determination greater than 0.9906. Furthermore, the limits of detection values ranged from 0.2 to 1.5 µg/L. The intra-day and inter-day relative standard deviations were < 8.4% and < 9.7%, respectively. Lastly, the proposed method was applied to extract and determine analytes in four refinery water samples as well as surface water containing high total dissolved solids, and well waters where satisfactory results have been obtained.

Distribution, sources, and risk assessment of polycyclic aromatic hydrocarbons in surface soils and plants from industrial and agricultural areas, Junggar Basin, Xinjiang.

The contamination characteristics of Polycyclic Aromatic Hydrocarbons (PAHs) in different environmental functional areas are different. In this study, the contamination of PAHs in soils and common plants in typical mining and farmland areas in Xinjiang, China, was analyzed. The results showed that the contamination levels of PAHs in mining soils were significantly higher than those in farmland soils, and the mining soils were dominated by 4-5-ring PAHs and farmland soils by 3-4-ring PAHs. Analysis of their sources using a positive definite factor matrix model showed that PAHs in mining soils mainly originated from coal and natural gas combustion, and transportation processes; while farmland soils mainly came from biomass and coal combustion, and fossil fuel volatile spills. The cancer risk of PAHs in soils was evaluated using a combination of the Monte Carlo and the lifetime carcinogenic risk models, and the results showed that the overall level of cancer risk for mining soils was higher than that for farmland soils, and can put some people in high risk of cancer. For plant samples, except for individual crop samples, the contamination levels of mining plants and crops were similar, with 4-5-ring PAHs dominating in desert plants in mining areas and the highest proportion of 3-ring PAHs in crops in agricultural fields, and PAHs in both plants were mainly from biomass and coal combustion. The results of correlation analysis showed that 2-ring PAHs in crop roots were significantly positively correlated with it in corresponding soils, and some high-ring PAHs in crop leaves were significantly negatively correlated with it in corresponding soils. Therefore, there were significant differences in the pollution characteristics of PAHs in soils and common plants in mining and agricultural areas. Human health risks and ecological risks are mainly concentrated in mining areas, and appropriate intervention measures should be taken for pollution remediation.

Prenatal exposure to environmentally relevant levels of PAHs inhibits spermatogenesis in adult mice and the mechanism involved.

Polycyclic aromatic hydrocarbons (PAHs) are a class of contaminants that cannot be banned. Exposure to PAHs has been reported to alter spermatogenesis in mammals, but little is known about prenatal exposure to a mixture of PAHs on the reproductive toxicity of adult offspring. In this study, we investigated the associations between prenatal exposure to environmentally relevant levels of PAHs in mice and testicular dysfunction, including impaired spermatogenesis and steroid hormone dysfunction in male offspring on postnatal day 180. The percentage of testicular apoptotic cells was significantly increased, which was further verified by the up-regulated BAX protein. The expression of Ar and the Leydig cell marker Cyp11a1 was down-regulated, suggesting an impairment in the synthesis of steroid hormones. DNA hypermethylation of the Tnp1 and Sohlh2 promoters suppresses transcriptional expression, consequently altering the sperm production process. This study shows that prenatal exposure to PAHs may induce long-term reproductive toxicity.

A vortex-assisted MSPD method for the extraction of Polycyclic Aromatic Hydrocarbons from shrimp with determination by GC-MS/MS.

Polycyclic Aromatic Hydrocarbons (PAHs) are organic compounds with two or more condensed aromatic rings, formed from incomplete organic matter combustion. PAHs pose potential health risks due to their carcinogenic and mutagenic properties, accumulating in edible tissues of aquatic organisms, such as shrimp, which is extensively produced in the southern region of Rio Grande do Sul state (Brazil) and it is the most consumed seafood globally. Therefore, this study aimed to optimize and validate an analytical method for extracting 16 priority PAHs from shrimp samples using Vortex-Assisted Matrix Solid-Phase Dispersion (VA-MSPD) with determination by Gas Chromatography Tandem Mass Spectrometry (GC-MS/MS). The optimized method, which uses a reused solid support, was validated according to INMETRO and SANTE guidelines. PAHs demonstrated adequate linearity with correlation coefficients > 0.99. The matrix effect was assessed, and 12 out of the 16 PAHs showed a matrix effect of less than ±20%. The method's quantification limits ranged from 6.67 to 33.35 ng g-1. Accuracy and precision showed recovery values ranging from 55 to 115% with relative standard deviation (RSD) lower than 17% for all PAHs. In the applicability, 11 PAHs were detected, such as benzo[a]pyrene and benzo[b]fluoranthene, and the ∑PAHs ranged from 25.14 to 79.52 ng g-1, confirming the environmental contamination in the region and the need for monitoring these contaminants in shrimp destined for human consumption.

High phenanthrene degrading efficiency by different microbial compositions construction.

Microbial remediation has become the most promising technical means for the remediation of polycyclic aromatic hydrocarbons (PAHs) non-point source contaminated soil due to its low cost of treatment, complete degradation of pollutants, and in-situ remediation. In this study, in order to demonstrate the phenanthrene degrading microbial diversity, phenanthrene was chosen as the representative of PAHs and strains capable of degrading phenanthrene were isolated and screened from the sedimentation sludge and the bottom sludge of oil tank trucks, and high throughput sequencing was used to check the dominant strains with a good degrading effect on phenanthrene. Results showed even more than 50% of phenanthrene was degraded in all samples, the composition of PAH-degrading bacteria was diverse, and different environments constructed different functional microbial groups, which resulted in the microbial adapting to the diversity of the environment. Finally, a series of bacterial species with phenanthrene-degrading functions such as Achromobacter, Pseudomonas, Pseudochelatococcus, Bosea was enriched after nine transferring process. Overall, our study offers value information for the enrichment of functional degrading microbes of phenanthrene or other pollutants that more concern should be paid in not only the degradation rate, but also the diversity variation of microbial community composition.

Interactions between polycyclic aromatic hydrocarbons and genetic variants in the cGAS-STING pathway affect the risk of colorectal cancer.

The cGAS-STING pathway plays an essential role in the activation of tumor immune cells. Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants with potential carcinogenicity, and their exposure is associated with the development of colorectal cancer. However, the impacts of genetic factors in the cGAS‒STING pathway and gene‒environment interactions on colorectal cancer remain understudied. We used logistic regression models and interaction analysis to evaluate the impact of genetic variants on colorectal cancer risk and gene‒environment interactions. We analysed the expression patterns of candidate genes based on the RNA-seq data. Molecular biology experiments were performed to investigate the impact of PAHs exposure on candidate gene expression and the progression of colorectal cancer. We identified the susceptibility locus rs3750511 in the cGAS‒STING pathway, which is associated with colorectal cancer risk. A negative interaction between TRAF2 rs3750511 and PAHs exposure was also identified. Single-cell RNA-seq analysis revealed significantly elevated expression of TRAF2 in colorectal cancer tissues compared with normal tissues, especially in T cells. BPDE exposure increased TRAF2 expression and the malignant phenotype of colorectal cancer cells. The treatment also further increased the expression of the TRAF2 downstream gene NF-κB and decreased the expression of Caspase8. Our results suggest that the genetic variant of rs3750511 affects the expression of TRAF2, thereby increasing the risk of colorectal cancer through interaction with PAHs. Our study provides new insights into the influence of gene‒environment interactions on the risk of developing colorectal cancer.

Determination of hydroxypolycyclic aromatic hydrocarbons in urine by electromembrane extraction coupled with liquid chromatography.

Polycyclic aromatic hydrocarbons (PAHs) have been classified as the earliest discovered class of environmental carcinogens, seriously endangering human health and ecological safety, and the hydroxylpolycyclic aromatic hydrocarbons (OH-PAHs) in human urine are considered as the main biomarkers to evaluate the exposure levels of PAHs in human body. Therefore, it is necessary to develop an accurate and sensitive method for the determination of urinary OH-PAHs. Herein, we proposed electromembrane extraction (EME) as a simple, effective and ecofriendly sample pretreatment technique for selective extraction, purification and enrichment of four typical OH-PAHs (2-naphthol, 2- and 3-phenanthrol, 2-hydroxyfluorene) in human urine for the first time. Under the optimum conditions, an analytical method of EME coupled with HPLC was established, which provided wide linear ranges for four OH-PAHs from 1 to 500 ng mL-1 with low LODs of 0.05-0.3 ng mL-1. The average recoveries of four OH-PAHs at three spiked levels in human urine were 81.6-102.5% with RSDs all below 9.4%. The present method has been successfully applied for the sensitive determination of trace four OH-PAHs in urine samples from non-smokers and smokers with a maximum concentration of 2.24 and 3.56 ng mL-1, respectively, which showed a great potential for the analysis of trace OH-PAHs in biological samples.

Yarrowia lipolytica growth, lipids, and protease production in medium with higher alkanes and alkenes.

Two strains of Yarrowia lipolytica (CBS 2075 and DSM 8218) were first studied in bioreactor batch cultures, under different controlled dissolved oxygen concentrations (DOC), to assess their ability to assimilate aliphatic hydrocarbons (HC) as a carbon source in a mixture containing 2 g·L-1 of each alkane (dodecane and hexadecane), and 2 g·L-1 hexadecene. Both strains grew in the HC mixture without a lag phase, and for both strains, 30 % DOC was sufficient to reach the maximum values of biomass and lipids. To enhance lipid-rich biomass and enzyme production, a pulse fed-batch strategy was tested, for the first time, with the addition of one or three pulses of concentrated HC medium. The addition of three pulses of the HC mixture (total of 24 g·L-1 HC) did not hinder cell proliferation, and high protease (> 3000 U·L-1) and lipids concentrations of 3.4 g·L-1 and 4.3 g·L-1 were achieved in Y. lipolytica CBS 2075 and DSM 8218 cultures, respectively. Lipids from the CBS 2075 strain are rich in C16:0 and C18:1, resembling the composition of palm oil, considered suitable for the biodiesel industry. Lipids from the DSM 8218 strain were predominantly composed of C16:0 and C16:1, the latter being a valuable monounsaturated fatty acid used in the pharmaceutical industry. Y. lipolytica cells exhibited high intrinsic surface hydrophobicity (> 69 %), which increased in the presence of HC. A reduction in surface tension was observed in both Y. lipolytica cultures, suggesting the production of extracellular biosurfactants, even at low amounts. This study marks a significant advancement in the valorization of HC for producing high-value products by exploring the hydrophobic compounds metabolism of Y. lipolytica.