Polycyclic Aromatic Hydrocarbons Signatures Research Articles

The need for spatially resolved observations of polycyclic aromatic hydrocarbons in protoplanetary discs

Context. The signatures of polycyclic aromatic hydrocarbons (PAHs) have been observed in protoplanetary discs, and their emission features obtained from spectral energy distributions (SED) have been used in the literature to characterise their size and determine their abundance. Aims. Two simple disc models (uniform PAH distribution against a PAH gap in the inner disc) are compared to investigate the difference of their SED and obtainable information. Methods. We used the radiative transfer code RADMC-3D to model the SED of two protoplanetary discs orbiting a typical Herbig star, one of which features a depletion of PAHs in the inner disc. We further created artificial images of the discs at face-on view to extract radial profiles of the PAH emission in the infrared. Results. We find that the extracted PAH features from an SED provide limited information about the PAHs in protoplanetary disc environments, except for the ionisation state. The distribution of PAHs in a protoplanetary disc influences the total observed PAH luminosity in a non-linear fashion and alters the relative strength between the 3.3 µm and 11.3 µm features. Furthermore, we produced radial profiles at the 3 µm, 6 µm and, 11 µm PAH emission features and find that they follow a double power-law profile where the slope reflects the radiative environment (single photon regime vs. multi-photon regime) in which the PAHs lie. Conclusions. Using spatially resolved techniques such as IFU or imaging in the era of the James Webb Space Telescope, we find that multi-wavelength radial emission profiles will not only provide information on the spatial distribution of the PAHs, but may also provide information on their size and underlying UV environment, which is crucial for photo-evaporative disc wind models.

Mass spectrometric analysis of unprecedented high levels of carbonaceous aerosol particles long-range transported from wildfires in the Siberian Arctic

Abstract. Wildfires in Siberia generate large amounts of aerosols, which may be transported over long distances and pose a threat to the sensitive ecosystem of the Arctic. Particulate matter (PM) of aged wildfire plumes originating from Yakutia in August 2021 was collected in Nadym and on Bely Island (both in northwestern Siberia). An advanced analysis of the chemical composition of aerosol particles was conducted through a multi-wavelength thermal–optical carbon analyzer (TOCA) coupled to resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) as well as through ultra-high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). In Nadym, concentrations of organic carbon (OC) and elemental carbon (EC) peaked at 100 and 40 µg m−3, respectively, associated with Angström absorption exponents for 405 and 808 nm (AAE405/808) between 1.5 and 3.3. The weekly average on Bely Island peaked at 8.9 µg m−3 of OC and 0.3 µg m−3 of EC and AAE405/808 close to unity. In particular, ambient aerosol in Nadym had a distinct biomass burning profile with pyrolysis products from carbohydrates, such as cellulose and hemicellulose, as well as lignin and resinoic acids. However, temporarily higher concentrations of five- and six-ring polycyclic aromatic hydrocarbons (PAHs), different from the PAH signature of biomass burning, suggest a contribution of regional gas flaring. FT-ICR MS with electrospray ionization (ESI) revealed a complex mixture of highly functionalized compounds, containing up to 20 oxygen atoms, as well as nitrogen- and sulfur-containing moieties. Concentrations of biomass burning markers on Bely Island were substantially lower than in Nadym, flanked by the appearance of unique compounds with higher oxygen content, higher molecular weight, and lower aromaticity. Back-trajectory analysis and satellite-derived aerosol optical depth suggested long-range transport of aerosol from the center of a Yakutian wildfire plume to Nadym and from the plume periphery to Bely Island. Owing to lower aerosol concentrations in the plume periphery than in its center, it is demonstrated how dilution affects the chemical plume composition during atmospheric aging.

Polycyclic Aromatic Hydrocarbons as Fuel-dependent Markers in Ship Engine Emissions using Single-Particle Mass Spectrometry

We investigated the fuel-dependent single-particle mass spectrometric signatures of polycyclic aromatic hydrocarbons (PAHs) from the emissions of a research ship engine operating on marine gas oil (MGO), hydrotreated vegetable oil...

Wildfire in the geological record: Application of Quaternary methods to deep time studies

For hundreds of millions of years wildfire has influenced, and been influenced by, plant evolution, biogeochemical cycling, and climate. Wildfire has even been implicated as one of the causative agents of mass extinctions. The deep time geologic record offers demonstrated, but underdeveloped, potential to advance knowledge on the role of wildfire in the Earth system. Herein, we present and discuss the geologic history of wildfire and methods for its reconstruction. We argue that application of the numeric approaches to wildfire reconstruction often used in Quaternary studies would advance understanding of deep time wildfire. Application of numeric methods increases statistical rigour, with the intent of reducing bias and increasing accuracy. For example, numeric methods offer a means to robustly calibrate the provenance and taphonomy of particles used to reconstruct wildfire, and to quantify uncertainties. Statistical methods should be used to assess the fidelity of new chemical proxies of wildfire, such as the types, amounts, distributions, and isotope signatures of polycyclic aromatic hydrocarbons, to represent source area and fuel type.

Brown Coal and Logwood Combustion in a Modern Heating Appliance: The Impact of Combustion Quality and Fuel on Organic Aerosol Composition.

Residential heating with solid fuels is one of the major drivers for poor air quality in Central and Eastern Europe, and coal is still one of the major fuels in countries, such as Poland, the Czech Republic, and Hungary. In this work, emissions from a single-room heater fueled with brown coal briquettes (BCBs) and spruce logs (SLs) were analyzed for signatures of inorganic as well as semivolatile aromatic and low-volatile organic constituents. High variations in organic carbon (OC) emissions of BCB emissions, ranging from 5 to 22 mg MJ-1, were associated to variations in carbon monoxide (CO) emissions, ranging from 900 to 1900 mg MJ-1. Residential BCB combustion turned out to be an equally important source of levoglucosan, an established biomass burning marker, as spruce logwood combustion, but showed distinct higher ratios to manosan and galactosan. Signatures of polycyclic aromatic hydrocarbons emitted by BCB combustion exhibited defunctionalization and desubstitution with increasing combustion quality. Lastly, the concept of island and archipelago structural motifs adapted from petroleomics is used to describe the fraction low-volatile organic compounds in particulate emissions, where a transition from archipelago to island motifs in relation with decreasing CO emissions was observed in BCB emissions, while emissions from SL combustion exhibited the island motif.

Chemical signatures of polycyclic aromatic hydrocarbons in the emissions from in situ oil burns.

This study characterized the parent and alkylated polycyclic aromatic hydrocarbons (PAHs) in gaseous and particulate emissions from the in situ burning (ISB) of oils. The experimental results indicate that the burning of the heavy oil produced the most PAH emissions because of its longest burning time. In addition, the parent PAHs mainly exist in the particulate phase, while alkylated PAHs mostly accumulate in the gaseous phase. In particular, the diagnostic-ratios of PAHs with great stability in both gaseous and particulate emissions from ISB are identified by comparing the laboratory and field data. The presences of bell-, slope- and V-shaped distribution patterns of alkylated PAHs in the emissions precisely indicate their sources to be petrogenic and pyrogenic processes occurring during ISB. The formation of 2-methylanthracene during ISB is confirmed. The overall findings are expected to provide a prospective protocol to characterize PAH pollution from ISB emissions in case of oil spills.

Single-particle characterization of polycyclic aromatic hydrocarbons in background air in northern Europe

Abstract. We investigated the distribution of polycyclic aromatic hydrocarbons (PAHs) on individual ambient aerosol particles at the Swedish western coast in a pristine environment for 10 d in October 2019. The measurements were carried out using new technology with single-particle mass spectrometry (SPMS) that reveals both the inorganic particle composition as well as the particle-bound PAHs (Schade et al., 2019). More than 290 000 particles were characterized; 4412 of them reveal PAH signatures. Most of the PAH-containing particles were internal mixtures of carbonaceous material, secondary nitrate and metals from distant sources in central and eastern Europe. We characterize the aerosol with respect to the inorganic composition, comparable to conventional SPMS, before we discuss the distribution of PAHs within this particle ensemble. Vice versa, we analyze the single-particle PAH spectra for characteristic patterns and discuss the inorganic composition, origin and atmospheric processing of the respective particles. The study period comprised different meteorological situations: clean air conditions with winds from the North Sea/Kattegat and little terrestrial air pollution, long-range transport from eastern Europe and southern Sweden, and transport of aerosols from central Europe over the sea. For all meteorological conditions, PAHs were detected in particles whose inorganic content indicates traffic emissions, such as combinations of soot, iron and calcium as well as in particles with biomass-burning signatures. However, there were variations in their amounts, dependent on the geographic origin. Because of strong mixing, rapid degradation and speciation limits, e.g., for PAHs of the same nominal mass, the application of diagnostic ratios for source apportionment is limited under the conditions of our study. Nevertheless, the combination with the inorganic content and meteorological data provides unique insights into the particles' origin, aging and mixing state. We exemplarily show how the observation of PAH profiles and inorganic secondary components on a single-particle level can open a new door to investigate aerosol aging processes. To our best knowledge, we herewith present the first comprehensive study on the single-particle distribution of PAHs in ambient air as well as the first set of combined data on PAHs and inorganic composition on a single-particle level.

Polycyclic aromatic hydrocarbon growth in a benzene discharge explored by IR-UV action spectroscopy.

Infrared signatures of polycyclic aromatic hydrocarbons (PAHs) are detected towards many phases of stellar evolution. PAHs are major players in the carbon chemistry of the interstellar medium, forming the connection between small hydrocarbons and large fullerenes. However, as details on the formation of PAHs in these environments are still unclear, modeling their abundance and chemistry has remained far from trivial. By combining molecular beam mass-selective IR spectroscopy and calculated IR spectra, we analyze the discharge of benzene and identify resulting products including larger PAHs, radicals and intermediates that serve as promising candidates for radio astronomical searches. The identification of various reaction products indicates that different gas-phase reaction mechanisms leading to PAH growth must occur under the same conditions to account for all observed PAH-related species, thereby revealing the complex and interconnected network of PAH formation pathways. The results of this study highlight key (exothermic) reactions that need to be included in astrochemical models describing the carbon chemistry in our universe.

Levels and Compositions of Polycyclic Aromatic Hydrocarbons in Rainwater and Their Implication for Aquatic Environments in Urban Area in Saitama, Japan

In this study, we investigated concentrations and profiles of polycyclic aromatic hydrocarbons (PAHs) in rainwater and surface water samples collected in Saitama, an urban city located in Japan. The volume-weighted mean concentration of total PAHs in rainwater samples (dissolved + particulate) was 108.8 ng L−1 with a range of 17.6–192.9 ng L−1. Two and three benzene ring PAHs were predominantly detected, occupying 67.0% of the total concentration in rainwater samples. Individual PAH concentrations were negatively correlated with their K ow, suggesting that low-molecular-weight PAHs are preferentially scavenged owing to the higher hydrophilicity. The toxic equivalent calculated based on the relative potencies of individual PAHs showed high toxic contributions by chrysene and benz[a]anthracene in the rainwater samples. Those PAHs levels in rainwater were comparable or higher than those in adjacent river water. Correlation coefficient of PAH signatures between rainwater and surface water samples was high particularly in the dissolved phase, supporting the source/sink relationships of PAHs between wet deposition samples and receiving waters. The mean deposition flux of PAHs was 2000 ng m−2 and considered to increase with precipitation amounts.

The [formula omitted] absorption in Titan’s stratosphere: Contribution of ethane, propane, butane and complex hydrogenated organics

The complex organic chemistry harbored by the atmosphere of Titan has been investigated in depth by Cassini observations. Among them, a series of solar occultations performed by the VIMS instrument throughout the 13 years of Cassini revealed a strong absorption centered at ∼3.4μm. Several molecules present in Titan’s atmosphere generate spectral features in that wavelength region, but their individual contributions are difficult to disentangle. In this work, we quantify the contribution of the various molecular species to the 3.4μm band using a radiative transfer model. Ethane and propane are significant components of the band but they are insufficient to reproduce perfectly its shape. Polycyclic Aromatic Hydrocarbons (PAHs) and more complex polyaromatic hydrocarbons like Hydrogenated Amorphous Carbons (HACs) are the most plausible candidates because they are rich in C-H bonds. PAHs signature have already been detected above ∼900 km, and they are recognized as precursors of aerosol particles. High similarities between individual spectra impede the derivation of abundances.

Destruction and multiple ionization of PAHs by X-rays in circumnuclear regions of AGNs

ABSTRACT The infrared signatures of polycyclic aromatic hydrocarbons (PAHs) are observed in a variety of astrophysical objects, including the circumnuclear medium of active galactic nuclei (AGNs). These are sources of highly energetic photons (0.2–10 keV), exposing the PAHs to a harsh environment. In this work, we examined experimentally the photoionization and photostability of naphthalene (C10H8), anthracene (C14H10), 2-methyl-anthracene (C14H9CH3), and pyrene (C16H10) upon interaction with photons of 275, 310, and 2500 eV. The measurements were performed at the Brazilian Synchrotron Light Laboratory using time-of-flight mass-spectrometry. We determined the absolute photoionization and photodissociation cross-sections as a function of the incident photon energy; the production rates of singly, doubly, and triply charged ions; and the molecular half-lives in regions surrounding AGNs. Even considering moderate X-ray optical depth values (τ = 4.45) due to attenuation by the dusty torus, the half-lives are not long enough to account for PAH detection. Our results suggest that a more sophisticated interplay between PAHs and dust grains should be present in order to circumvent molecular destruction. We could not see any significant difference in the half-life values by increasing the size of the PAH carbon backbone, NC, from 10 to 16. However, we show that the multiple photoionization rates are significantly greater than the single ones, irrespective of the AGN source. We suggest that an enrichment of multiply charged ions caused by X-rays can occur in AGNs.

Fully anharmonic infrared cascade spectra of polycyclic aromatic hydrocarbons.

The infrared (IR) emission of polycyclic aromatic hydrocarbons (PAHs) permeates our universe; astronomers have detected the IR signatures of PAHs around many interstellar objects. The IR emission of interstellar PAHs differs from their emission as seen under conditions on Earth as they emit through a collisionless cascade down through their excited vibrational states from high internal energies. The difficulty in reproducing interstellar conditions in the laboratory results in a reliance on theoretical techniques. However, the size and complexity of PAHs require careful consideration when producing the theoretical spectra. In this work, we outline the theoretical methods necessary to lead to fully theoretical IR cascade spectra of PAHs including: an anharmonic second order vibrational perturbation theory treatment, the inclusion of Fermi resonances through polyads, and the calculation of anharmonic temperature band shifts and broadenings (including resonances) through a Wang-Landau approach. We also suggest a simplified scheme to calculate vibrational emission spectra that retain the essential characteristics of the full IR cascade treatment and can directly transform low temperature absorption spectra in IR cascade spectra. Additionally we show that past astronomical models were in error in assuming a 15 cm-1 correction was needed to account for anharmonic emission effects.

Fine particulate-bound polycyclic aromatic hydrocarbons in vehicles in Rome, Italy.

Urban commuters are exposed to elevated levels of air pollutants, especially in heavily polluted areas and traffic congested roads. In order to assess the contribution of commuting to citizens' exposure, measurements of fine particulate (PM2.5) and polycyclic aromatic hydrocarbons (PAHs) were carried out in cars, busses, and metro trains, within the LIFE+ EXPAH Project. Monitoring campaigns were performed in Rome, Italy, from April 2011 to August 2012. Inside the busses, the concentration of total PAHs ranged from 2.7 to 6.6ng/m3 during the winter and from 0.34 to 1.51ng/m3 in the summer. In cars, internal concentrations were in the range 2.2-7.3 and 0.46-0.82ng/m3, respectively, in the 2-year time. Analogous differences between seasons were observed examining the benzo[a]pyrene-equivalent carcinogenicity. In the metro trains, total PAHs ranged from 1.19 to 2.35ng/m3 and PM2.5 ranged from 17 to 31μg/m3. The PM2.5 concentration in all transport modes ranged from 10 to 160μg/m3 during the cold season and 15-48μg/m3 during the warm time. The average inside-to-outside ratio (R I/O) was found to exceed 1.0 for PM2.5 only in busses, probably due to dust re-suspension caused by crowding and passenger activity. The molecular PAH signature suggests that vehicle emissions and biomass combustion were the major sources of commuters' exposure to these toxicants in Rome. According to linear regression analysis, the PAH concentrations inside the vehicles were linked to those detected outside. Statistically significant differences (p<0.05) were found between the in-vehicle locations and the urban pollution network stations, with higher PAH values detected, on the average, in these latter.

Application of PMF receptor model merging with PAHs signatures for source apportionment of black carbon in the continental shelf surface sediments of the Bohai and Yellow Seas, China

AbstractBlack carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are byproducts generated from the incomplete combustion of organic materials, including fossil fuels and biomass. The similar production processes shared by BC and PAHs provide the possibility to infer the BC sources using the PAHs signatures. This study successfully utilized data sets of BC and PAHs analyzed from the continental shelf surface sediments of the Bohai and Yellow Seas to a standard receptor model of positive matrix factorization (PMF) to apportion the sources of BC in the sediment matrix. Results showed that combustion of fossil fuels (i.e., coal and oil/petroleum) accounted for an average level of 83 ± 5% of the total BC preserved, which was significantly higher than that from the biomass burning (17 ± 5%). The spatial distributions of the fossil BC concentrations and percentages differed significantly from those of the biomass BC, implying their different geochemical behaviors in the continental shelf regimes and further emphasizing the importance to effectively differentiate between fossil BC and biomass BC. In addition to the relative proportions of the BC subtypes (char‐BC/soot‐BC), the regional‐specific hydrodynamic conditions, including the cold cyclonic eddy, resuspension and coastal current, also exerted a significant influence on these spatial variations.

Visualization of soot inception in turbulent pressurized flames by simultaneous measurement of laser-induced fluorescence of polycyclic aromatic hydrocarbons and laser-induced incandescence, and correlation to OH distributions

Distributions of polycyclic aromatic hydrocarbons (PAH) and their correlation with soot formation were studied in ethylene–air swirl flames stabilized in a gas turbine model combustor at increased pressure. The combustor can be operated with secondary air injection to study the influence of soot oxidation. We employed PAH laser-induced fluorescence using UV excitation simultaneously with IR-excited laser-induced incandescence to identify soot. PAH signatures typically appear discontinuous unlike OH, yet similar to soot but exhibit more uniform intensity and larger size. The correlation of both diagnostics allowed identification of a wide range of soot formation progress, including isolated soot or PAH, as well as PAH transitioning into soot. The occurrence of soot, PAH and OH and their spatial variations are strongly dependent on the properties of the flow field. In the bottom part of the inner recirculation zone and for the reference case, a rich flame with additional oxidation air, soot levels are relatively high, while PAH intensities in this region are minimal. This correlates well with high temperatures in this region published recently, which are unfavorable for soot formation as the precursors, PAH, decompose. Consequently, soot presence here is attributed to transport. In contrast to OH and soot distributions which change significantly upon addition of secondary air downstream of the primary combustion zone, PAH distributions for both cases look relatively similar. This is attributed to a downstream consumption of PAH by different processes. Without oxidation air, PAH completely transform into soot, while additional oxidation air leads to their oxidation.

Atmospheric sources and soil filtering of PAH content in karst seepage waters

The analysis of PAHs (polycyclic aromatic hydrocarbons) in karst environments has provided an assessment of the vulnerability of karst water and the study of PAH records in stalagmites. The major source of PAHs has generally been considered to be the soil. In this study, we report the quantification of PAHs in the ecosystem compartments of a mountain karst system over a snow-melting period and the spring to summer dry period. PAH profiles in karst seepage waters were consistently similar to those in wet deposits, following the change in PAH profiles between winter and summer periods. However, PAH signatures of atmospheric wet deposits were modulated by a loss of the high molecular weight PAHs, which appear to accumulate in soils. A PAH mass balance was calculated during a summer storm event. This mass balance suggests that dry deposits and canopy throughfall could account for the PAH abundance in karst seepage waters. This study demonstrates the ability of organic hydrophobic compounds to be directly transferred from the atmosphere or canopy into seepage waters, giving new emphasis to the study of PAHs recorded in stalagmites.

Solvent-Extractable Polycyclic Aromatic Hydrocarbons in Biochar: Influence of Pyrolysis Temperature and Feedstock

Despite the increasing agricultural use of biochar as a way of combining the utilization of biomass for energy production with the removal of CO(2) from the atmosphere, it is not known how variations in pyrolysis temperature and feedstock type affect concentration and composition of polycyclic aromatic hydrocarbons (PAHs) that inevitably form and associate with biochar. To close this knowledge gap, we quantified 11 unsubstituted three- to five-ring PAHs as well as alkylated forms of phenanthrene and anthracene in grass and wood chars produced in 100 °C increments across a temperature range (100 to 700 °C). Our results show that solvent-extractable PAH concentrations in biochars produced at heat treatment temperatures (HTTs) of 400 and 500 °C greatly exceed those observed at higher and lower temperature, supporting a low HTT solid-phase formation mechanism operable at temperatures commonly used for industrial biochar production. The maximum extractable yield of 'pyrolytic' unsubstituted PAHs for grass (22 μg g(-1) at HTT = 500 °C) greatly exceeds the value for wood (5.9 μg g(-1)). Moreover, PAH signatures (e.g., total monomethylphenanthrene to phenanthrene ratios, MP/P ~2-3) at intermediate temperatures (400 °C) resemble those of fossil oils rather than that commonly attributed to pyrolytic products. Further research is needed to characterize the PAH evolution in modern pyrolysis reactors and assess the fate of biochar-bound PAHs in soils and sediments. Various commonly applied PAH ratios and indicator compounds show promise as markers for specific feedstock materials and pyrolysis conditions of biochars in environmental systems.

FLUORESCENT ANALYSIS OF PHOTOSYNTHETIC MICROBES AND POLYCYCLIC AROMATIC HYDROCARBONS LINKED TO OPTICAL REMOTE SENSING

Abstract. Fluorescence analysis, being a non-invasive technique, has become one of the most powerful and widely used techniques for microbiologists and chemists to study various types of sample from photosynthetic microbes to hydrocarbons. The work reported here focuses on experimental results of fluorescent features of photosynthetic microbial species (cyanobacteria) and also five different crude oil samples. The cyanobacteria samples were collected from the Baltic Sea at the end of July 2011 and were associated with cyanobacterial bloom events, and the crude oil samples were from various oil spill events. The aim of the study was to find fluorescent biosignatures of cyanobacteria (initially a species specific to the Baltic Sea) and the fingerprints of crude oil; oil spills can be difficult to differentiate from biogenic films when using Synthetic Aperture Radar (SAR) or sunglint contaminated optical imagery. All samples were measured using a Perkin Elmer LS55 Luminescence spectrometer over a broad range of excitation and emission wavelength from ultraviolet (UV) to near infrared (NIR). The results are presented in Excitation Emission Matrices (EEMs) that exhibit the fluorescent features of each sample. In the EEM of the seawater sample containing cyanobacteria, there is an intense emission peak from tryptophan with fluorescent excitation and emission peaks at 285 and 345 nm respectively. In addition, fluorescent signatures of phycocyanin and chlorophyll-a are present with excitation and emission centre wavelengths at 555 nm, 645 nm and 390 nm, 685 nm, respectively. Additionally, the fluorescence signatures of Polycyclic Aromatic Hydrocarbons (PAHs) are present in the EEMs of crude oil samples with excitation and emission peaks at 285 nm and 425 nm. This study underpins further research on how to distinguish cyanobacteria species by their fluorescence signatures and the potential role that PAHs play in detection of cyanobacteria fluorescence features.

Identification of molecular signatures predicting the carcinogenicity of polycyclic aromatic hydrocarbons (PAHs)

Assessing the potential carcinogenicity of human toxins represents an ongoing challenge. Chronic rodent bioassays predict human cancer risk with limited reliability, and are expensive and time-consuming. To identify alternative prediction methods, we evaluated a transcriptomics-based human in vitro model to classify carcinogens by their modes of action. The aim of this study was to determine the transcriptomic response and identify specific molecular signatures of polycyclic aromatic hydrocarbons (PAHs), which can be used as predictors of carcinogenicity of environmental toxins in human in vitro systems. We found that characteristic molecular signatures facilitate identification and prediction of carcinogens. To evaluate the change in gene expression levels, human hepatocellular carcinoma (HepG2) cells were exposed to nine different PAHs (benzo[a]pyrene, dibenzo[a,h]anthracene, 3-methylcholanthrene, naphthalene, chrysene, phenanthrene, benzo[a]anthracene, benzo[k]fluoranthene, and indeno[1,2,3-c,d]pyrene) for 48h.Unsupervised gene expression analysis resulted in a characteristic molecular signature for each toxin, and a supervised analysis identified 31 outlier genes as distinct molecular signatures distinguishing carcinogens from noncarcinogens. Further analysis and multi-classification revealed 430 genes as surrogate markers for predicting carcinogenic potencies of each PAH with 100% accuracy. Our results suggest that these expression signatures can be used as predictable and discernible surrogate markers for detecting and predicting PAH exposure, and their carcinogenic potential. Furthermore, the use of these markers can be more widely applied in combination with traditional techniques for assessing and predicting toxic exposure to PAHs.

Combustion-derived substances in deep basins of Puget Sound: Historical inputs from fossil fuel and biomass combustion

Reconstructions of 250 years historical inputs of two distinct types of black carbon (soot/graphitic black carbon (GBC) and char-BC) were conducted on sediment cores from two basins of the Puget Sound, WA. Signatures of polycyclic aromatic hydrocarbons (PAHs) were also used to support the historical reconstructions of BC to this system. Down-core maxima in GBC and combustion-derived PAHs occurred in the 1940s in the cores from the Puget Sound Main Basin, whereas in Hood Canal such peak was observed in the 1970s, showing basin-specific differences in inputs of combustion byproducts. This system showed relatively higher inputs from softwood combustion than the northeastern U.S. The historical variations in char-BC concentrations were consistent with shifts in climate indices, suggesting an influence of climate oscillations on wildfire events. Environmental loading of combustion byproducts thus appears as a complex function of urbanization, fuel usage, combustion technology, environmental policies, and climate conditions.