Passive sampling coupled to ultraviolet irradiation: a useful analytical approach for studying oxygenated polycyclic aromatic hydrocarbon formation in bioavailable mixtures.
Ontology highlight
ABSTRACT:
SUBMITTER: Forsberg ND
PROVIDER: S-EPMC3963818 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Antiaromatic and open-shell molecules are attractive because of their distinct electronic and magnetic behaviour. However, their increased reactivity creates a challenge for probing their properties. Here, we describe the on-surface and in-solution generation and characterisation of a highly reactive antiaromatic molecule: indeno[1,2-b]fluorene (IF). In solution, we generated IF by KI-induced dehalogenation of a dibromo-substituted precursor molecule and found that IF survives for minutes at ambient conditions. Using atom manipulation at low temperatures we generated IF on Cu(111) and on bilayer NaCl. On these surfaces, we characterised IF by bond-order analysis using non-contact atomic force microscopy with CO-functionalised tips and by orbital imaging using scanning tunnelling microscopy. We found that the closed-shell configuration and antiaromatic character predicted for gas-phase IF are preserved on the NaCl film. On Cu(111), we observed significant bond-order reorganisation within the s-indacene moiety because of chemisorption, highlighting the importance of molecule surface interactions on the ?-electron distribution.
| S-EPMC5864723 | biostudies-literature
Project description:Exposure to polycyclic aromatic hydrocarbons (PAHs) in the food chain is the major human health hazard associated with the Deepwater Horizon oil spill. Phenanthrene is a representative PAH present in crude oil, and it undergoes biological transformation, photooxidation, and chemical oxidation to produce its signature oxygenated derivative, phenanthrene-9,10-quinone. We report the downstream metabolic fate of phenanthrene-9,10-quinone in HepG2 cells. The structures of the metabolites were identified by HPLC-UV-fluorescence detection and LC-MS/MS. O-mono-Glucuronosyl-phenanthrene-9,10-catechol was identified, as reported previously. A novel bis-conjugate, O-mono-methyl-O-mono-sulfonated-phenanthrene-9,10-catechol, was discovered for the first time, and evidence for both of its precursor mono conjugates was obtained. The identities of these four metabolites were unequivocally validated by comparison to authentic enzymatically synthesized standards. Evidence was also obtained for a minor metabolic pathway of phenanthrene-9,10-quinone involving bis-hydroxylation followed by O-mono-sulfonation. The identification of 9,10-catechol conjugates supports metabolic detoxification of phenanthrene-9,10-quinone through interception of redox cycling by UGT, COMT, and SULT isozymes and indicates the possible use of phenanthrene-9,10-catechol conjugates as biomarkers of human exposure to oxygenated PAH.
| S-EPMC4028327 | biostudies-literature
Project description:Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during, and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water-air boundary was determined. This is the first report of vapor phase and flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 1 and 24 ng/m(3) and 0.3 and 27 ng/m(3), respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air-water flux of 13 individual PAHs were strongly associated with the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi in the summer, each nominally 10,000 ng/m(2)/day. Acenaphthene was the PAH with the highest observed volatilization rate of 6800 ng/m(2)/day in September 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air-water chemical flux determinations with passive sampling technology.
| S-EPMC4291772 | biostudies-literature
Project description:Polycyclic aromatic hydrocarbons (PAHs) are found throughout the interstellar medium and are important markers for the evolution of galaxies and both star and planet formation. They are also widely regarded as a major source of carbon, which has implications in the search for extraterrestrial life. Herein we construct a melting point phase diagram for a series of phenanthrene/pyrene binary mixtures to identify the eutectic composition (75 mol % phenanthrene) and its melting point (83 °C). The molten oil obtained on heating this eutectic composition to 90 °C in aqueous solution is homogenized in the presence of a water-soluble polymeric emulsifier. On cooling to 20 °C, polydisperse spherical phenanthrene/pyrene hybrid microparticles are obtained. Varying the stirring rate and emulsifier type enables the mean microparticle diameter to be adjusted from 11 to 279 μm. Importantly, the phenanthrene content of individual microparticles remains constant during processing, as expected for the eutectic composition. These new hybrid microparticles form impact craters and undergo partial fragmentation when fired into a metal target at 1 km s-1 using a light gas gun. When fired into an aerogel target at the same speed, microparticles are located at the ends of characteristic "carrot tracks". Autofluorescence is observed in both types of experiments, which at first sight suggests minimal degradation. However, Raman microscopy analysis of the aerogel-captured microparticles indicates prominent pyrene signals but no trace of the more volatile phenanthrene component. Such differential ablation during aerogel capture is expected to inform the in situ analysis of PAH-rich cosmic dust in future space missions.
| S-EPMC11295189 | biostudies-literature
Project description:The current work sought to develop predictive models between time-weighted average polycyclic aromatic hydrocarbon (PAH) concentrations in the freely dissolved phase and those present in resident aquatic organisms. We deployed semipermeable membrane passive sampling devices (SPMDs) and collected resident crayfish (Pacifastacus leniusculus) at nine locations within and outside of the Portland Harbor Superfund Mega-site in Portland, OR. Study results show that crayfish and aqueous phase samples collected within the Mega-site had PAH profiles enriched in high molecular weight PAHs and that freely dissolved PAH profiles tended to be more populated by low molecular weight PAHs compared to crayfish tissues. Results also show that of several modeling approaches, a two-factor partial least-squares (PLS) calibration model using detection limit substitution provided the best predictive power for estimating PAH concentrations in crayfish, where the model explained ?72% of the variation in the data set and provided predictions within ?3× of measured values. Importantly, PLS calibration provided a means to estimate PAH concentrations in tissues when concentrations were below detection in the freely dissolved phase. The impact of measurements below detection limits is discussed.
| S-EPMC4046869 | biostudies-other
Project description:Complex mixtures of polycyclic aromatic hydrocarbons (PAHs) are difficult to resolve because of the high degree of overlap in compound vapor pressures, boiling points, and mass spectral fragmentation patterns. The objective of this research was to improve the separation of complex PAH mixtures (including 97 different parent, alkyl-, nitro-, oxy-, thio-, chloro-, bromo-, and high molecular weight PAHs) using GC × GC/ToF-MS by maximizing the orthogonality of different GC column combinations and improving the separation of PAHs from the sample matrix interferences, including unresolved complex mixtures (UCM). Four different combinations of nonpolar, polar, liquid crystal, and nanostationary phase columns were tested. Each column combination was optimized and evaluated for orthogonality using a method based on conditional entropy that considers the quantitative peak distribution in the entire 2D space. Finally, an atmospheric particulate matter with diameter <2.5 ?m (PM(2.5)) sample from Beijing, China, a soil sample from St. Maries Creosote Superfund Site, and a sediment sample from the Portland Harbor Superfund Site were analyzed for complex mixtures of PAHs. The highest chromatographic resolution, lowest synentropy, highest orthogonality, and lowest interference from UCM were achieved using a 10 m × 0.15 mm × 0.10 ?m LC-50 liquid crystal column in the first dimension and a 1.2 m × 0.10 mm × 0.10 ?m NSP-35 nanostationary phase column in the second dimension. In addition, the use of this column combination in GC × GC/ToF-MS resulted in significantly shorter analysis times (176 min) for complex PAH mixtures compared to 1D GC/MS (257 min), as well as potentially reduced sample preparation time.
| S-EPMC3423902 | biostudies-literature
Project description:UnlabelledPolycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants that are hazardous to human health. It has been demonstrated that members of the Mycobacterium genus are among the most effective degraders of PAHs, but few studies have focused on the degradation of PAH mixtures. In this study, single and mixed PAH metabolism was investigated in four phylogenetically distinct Mycobacterium species with respect to (i) parent compound degradation, (ii) bacterial growth, (iii) catabolic gene expression, and (iv) metabolite production. Synergistic and antagonistic effects on four model PAH compounds (benzo[a]pyrene, pyrene, fluoranthene, and phenanthrene) characterized degradation of mixtures in a strain- and mixture-dependent manner. The mixture of pyrene and phenanthrene, in particular, resulted in antagonized degradation by three out of four bacterial species, and further studies were narrowed to investigate the degradation of this mixture. Antagonistic effects persisted over time and were correlated with reduced bacterial growth. Antagonized degradation of PAH was not caused by preferential degradation of secondary PAHs, nor were mixture compounds or concentrations toxic to cells growing on sugars. Reverse transcription-PCR (RT-PCR) studies of the characterized catabolic pathway of phenanthrene showed that in one organism, antagonism of mixture degradation was associated with downregulated gene expression. Metabolite profiling revealed that antagonism in mixture degradation was associated with the shunting of substrate through alternative pathways not used during the degradation of single PAHs. The results of this study demonstrate metabolic differences between single and mixed PAH degradation with consequences for risk assessment and bioremediation of PAH-contaminated sites.ImportanceMycobacterium species are promising organisms for environmental bioremediation because of their ubiquitous presence in soils and their ability to catabolize aromatic compounds. PAHs can be degraded effectively as single compounds, but mixed substrates often are subject to degradative inhibition, which may explain the persistence of these pollutants in soils. Single and mixed PAH degradation by diverse Mycobacterium species was compared, with associated bacterial growth, gene expression, and metabolite production. The results demonstrate that antagonism characterized degradation in a strain- and mixture-dependent manner. One strain that was versatile in its pathway use of single chemicals also efficiently degraded the mixture, whereas antagonism in other the strains was associated with altered metabolic profiles, indicating unusual pathway use. The impacts of this work on risk assessment and bioremediation modeling studies indicate the need to account for mixture-generated intermediates and to recognize mixture degradation as a property distinct from that of PAH substrate range.
| S-EPMC4959237 | biostudies-literature
Project description:Atmospheric concentrations of flame retardants, polycyclic aromatic hydrocarbons, and pesticides were measured using passive air samplers equipped with polyurethane foam disks to find spatial information in and around Chicago, Illinois. Samplers were deployed around the greater Chicago area for intervals of 6 weeks from 2012 to 2013 (inclusive). Volumes were calculated using passive sampling theory and were based on meteorology and the compounds' octanol-air partition coefficients. Geometric mean concentrations of total polybrominated diphenyl ethers ranged from 11 to 150 pg/m3, and tributyl phosphate, tris(2-chloroethyl)phosphate, tris(1-chloro-2-propyl)phosphate, and triphenyl phosphate concentrations were in the ranges of 54-290, 32-340, 130-580, and 170-580 pg/m3, respectively. The summed concentrations of 16 PAHs ranged from 8700 to 52,000 pg/m3 over the sampling area, and DDT, chlordane, and endosulfan concentrations were in the ranges of 2.7-9.9, 8.2-66, and 16-85 pg/m3, respectively. Sampling sites were split into two groups depending on their distances from the Illinois Institute of Technology campus in Chicago. With a few exceptions, the concentrations of most compound groups in the city's center were the same or slightly higher than those measured >45 km away. The data also showed that the concentrations measured with a passive atmospheric sampling system are in good agreement with those measured with an active, high-volume, sampling system. Given that the sampling times are different (passive, 43 days; active, 1 day), and that both of these measured concentrations cover about 5 orders of magnitude, the agreement between these passive and active sampling methods is excellent.
| S-EPMC6314031 | biostudies-literature
Project description:Polycyclic aromatic hydrocarbons and polychlorinated biphenyls are commonly categorized as persistent organic pollutants. In order to analyze these pollutants, customized stationary phases are increasingly being developed and synthesized for solid-phase extraction. In this work, we tested a new solventless solid-phase extraction approach based on the use of a Magic Chemisorber® (Frontier Lab) which consists of a bead-covered polydimethylsiloxane stationary phase with a thickness of 500 µm. These devices are directly immersed into aqueous samples and then introduced into a pyrolysis-gas chromatography-mass spectrometry system equipped with a cryofocusing system for the thermal desorption and analysis of the adsorbed species. Our new method performs better than the most recent solid-phase extraction devices, with limits of detection lower than 2.7 ng/L and limits of quantification lower than 9.0 ng/L. The method was tested on standard compounds and on an environmental sample, showing the potential to characterize other chemical species besides the persistent organic pollutants, such as phthalate plasticizers and antioxidants.
| S-EPMC9477944 | biostudies-literature
Project description:Naphthalene and phenanthrene are transformed by enzymes encoded by the pah gene cluster of Pseudomonas putida OUS82. The pahA and pahB genes, which encode the first and second enzymes, dioxygenase and cis-dihydrodiol dehydrogenase, respectively, were identified and sequenced. The DNA sequences showed that pahA and pahB were clustered and that pahA consisted of four cistrons, pahAa, pahAb, pahAc, and pahAd, which encode ferredoxin reductase, ferredoxin, and two subunits of the iron-sulfur protein, respectively.
| S-EPMC205371 | biostudies-other