Depletion Of Polycyclic Aromatic Hydrocarbons Research Articles

A seawater field study of crude and fuel oil depletion in Northern Norway at two different seasons – Chemistry and bacterial communities

After marine oil spills, natural processes like photooxidation and biodegradation can remove the oil from the environment. However, these processes are strongly influenced by environmental conditions. To achieve a greater understanding of how seasonal variations in temperature, light exposure and the bacterial community affect oil depletion in the marine environment, we performed two field experiments during the spring and autumn. Field systems equipped with a thin oil film of Statfjord, Grane or ULSFO were deployed in northern Norway. Depletion of the total extractable matter was faster during the spring than during the autumn. Statfjord showed faster depletion of n-alkanes during spring, while depletion of polycyclic aromatic hydrocarbons varied between the seasons based on the degree of alkyl-substitutions. ULSFO displayed the overall slowest depletion. Biodegradation of the oils was associated with high abundances of unassigned bacteria during the spring but was governed by Alcanivorax, Cycloclasticus, Oleibacter and Oleispira during the autumn.

Air-sea exchange of PAHs in the Taiwan Strait: Seasonal dynamics and regulation mechanisms revealed by machine learning approach

In this study, to understand the seasonal dynamics of air-sea exchange and its regulation mechanisms, we investigated polycyclic aromatic hydrocarbons (PAHs) at the air-sea interface in the western Taiwan Strait in combination with measurements and machine learning (ML) predictions. For 3-ring PAHs and most of 4- to 6-ring, volatilization and deposition fluxes were observed, respectively. Seasonal variations in air-sea exchange flux suggest the influence of monsoon transitions. Results of interpretable ML approach (XGBoost) indicated that volatilization of 3-ring PAHs was significantly controlled by dissolved PAH concentrations (contributed 24.0 %), and the gaseous deposition of 4- to 6-ring PAHs was related to more contaminated air masses originating from North China during the northeast monsoon. Henry’s law constant emerged as a secondary factor, influencing the intensity of air-sea exchange, particularly for low molecular weight PAHs. Among environmental parameters, notably high wind speed emerges as the primary factor and biological pump’s depletion of PAHs in surface seawater amplifies the gaseous deposition process. The distinct dynamics of exchanges at the air-water interface for PAHs in the western TWS can be attributed to variations in primary emission intensities, biological activity, and the inconsistent pathways of long-range atmospheric transport, particularly within the context of the monsoon transition.

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.

Chemodynamics of Polycyclic Aromatic Hydrocarbons and Their Alkylated and Nitrated Derivatives in the Yellow Sea and East China Sea.

The occurrence of continuously released polycyclic aromatic hydrocarbons (PAHs) in marginal seas is regulated by hydrological and biogeochemical processes; however, scarce knowledge is about their derivatives in marine environments. In this study, the dissolved and particulate PAHs and their alkylated/nitrated derivatives (A-PAHs/N-PAHs) in surface seawater of the southwestern Yellow Sea (YS) and northwestern East China Sea (ECS) during September 2022 were comprehensively discussed. Results confirm higher levels of Σ26PAHs (9.3-70 ng/L) and Σ43A-PAHs (13-76 ng/L) than Σ20N-PAHs (0.80-6.6 ng/L). The spatial heterogeneity of contaminants was regulated by substantial riverine runoff and ocean currents. Lagrangian Coherent Structure analysis further revealed the existence of a transport barrier at the shelf break of the southwestern YS where contaminants hardly crossed and tended to accumulate. The relationship between dissolved compounds and chlorophyll a indicated both biodegradation and the biological pump contributed to the depletion of PAHs and A-PAHs from surface seawater while the biological pump was the major driver for N-PAHs, despite their complicated water-particle partition behavior due to variations in physicochemical properties in the presence of nitro groups. Source identification demonstrated that pyrogenic and petrogenic sources dominated the YS and ECS, respectively, while photochemical transformations appeared more active in the YS.

Turbulent processing of PAHs in protoplanetary discs

Context. Polycyclic aromatic hydrocarbons (PAHs) have been detected in numerous circumstellar discs. Despite the correlation between stellar temperature and low PAH detections rates, the diversity of PAH detections and non-detections at similar stellar properties is not well understood. Aims. We propose the continuous processing of PAHs through clustering, adsorption on dust grains, and their reverse-processes as key mechanisms to reduce the emission-capable PAH abundance in protoplanetary discs. This cycle of processing is driven by vertical turbulence in the disc mixing PAHs between the disc midplane and the photosphere. Methods. We used a theoretical Monte Carlo model for photodesorption in the photosphere and a coagulation code in the disc midplane to estimate the relevance and timescale of these processes in a Herbig Ae/Be disc environment. By combining these components in a 1D vertical model, we calculated the gas-phase depletion of PAHs that stick as clusters on dust grains. Results. Our results show that the clustering of gas-phase PAHs is very efficient, and that clusters with more than 100 monomers can grow for years before they are able to freeze out in the disc midplane. Once a PAH cluster is frozen on the dust grain surface, the large heat capacity of these clusters prevents them from evaporating off the grains in UV-rich environments such as the photosphere. Therefore, the clustering of PAHs followed by freeze-out can lead to a depletion of gas-phase PAHs in protoplanetary discs. We find that this mechanism is more efficient when the PAH species has fewer carbon atoms. In contrast, PAH monomers and very small clusters consisting of a few monomers can easily detach from the grain by absorption of a single UV photon. Evaluated over the lifetime of protoplanetary discs, we find a depletion of PAHs by a factor that ranges between 50 and 1000 compared to the standard ISM abundance of PAHs in the inner disc through turbulent processing. Conclusions. Through these processes, we favour PAHs smaller than circumovalene (C66H20) as the major gas-phase emitters of the disc photosphere as larger PAH monomers cannot photodesorb from the grain surface. These gas-phase PAHs co-exist with large PAH clusters sticking on dust grains. We find a close relation between the amount of PAHs frozen out on dust grains and the dust population, as well as the strength of the vertical turbulence.

PAH depletion in weathered oil slicks estimated from modeled age-at-sea during the Deepwater Horizon oil spill

During time-periods oil slicks are in the marine environment (age-at-sea), weathering causes significant changes in composition and mass loss (depletion) of oil spill chemicals including the more toxic polycyclic aromatic hydrocarbons (PAHs). The goal of this study was to estimate the age-at-sea of weathered oil slicks using the oil spill module of the Connectivity Modeling System and to use this age to interpret PAH concentration measurements. Percent depletion (PD) for each measurement was computed as the percentage difference between the original and measured PAH concentration in the crude oil and weathered oil slicks, normalized upon the mass losses relative to hopane. Mean PD increased with estimated age-at-sea for all PAHs. Less PD was observed for alkylated than for parent PAHs, likely due to decreasing vapor pressure with increasing degree of alkylation. We conclude that estimated age-at-sea can be used to explain PAH depletion in weathered oil slicks. We propose PAH vapor pressure can be coupled with the model to expand capacity for predicting concentration distributions of individual parent and alkylated PAHs in weathered oil along the coastline. This new module will advance the science supporting oil spill response by providing more certain estimates of health risks from oil spills.

Changes in Chemical Composition and Copepod Toxicity during Petroleum Photo-oxidation.

Photoproducts can be formed rapidly in the initial phase of a marine oil spill. However, their toxicity is not well understood. In this study, oil was irradiated, chemically characterized, and tested for toxicity in three copepod species (Acartia tonsa, Temora longicornis, and Calanus finmarchicus). Irradiation led to a depletion of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in oil residues, along with an enrichment in aromatic and aliphatic oil photoproducts. Target lipid model-based calculations of PAH toxicity units predicted that PAH toxicities were lower in water-accommodated fractions (WAFs) of irradiated oil residues ("irradiated WAFs") than in WAFs of dark-control samples ("dark WAFs"). In contrast, biomimetic extraction (BE) measurements showed increased bioaccumulation potential of dissolved constituents of irradiated WAFs compared to dark WAFs, mainly driven by photoproducts present in irradiated oil. In line with the BE results, copepod mortality increased in irradiated WAFs compared to dark WAFs. However, low copepod toxicities were observed for WAFs produced with photo-oxidized oil slicks collected during the Deepwater Horizon oil spill. The results of this study suggest that while oil photoproducts have the potential to be a significant source of copepod toxicity, dilution and dispersion of these higher solubility products appear to help mitigate their toxicity at sea.

Changes in Urban Gas-Phase Persistent Organic Pollutants During the COVID-19 Lockdown in Barcelona

The composition of polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), and organophosphate flame retardants (OPFRs) present in the gas-phase fraction of the atmosphere of Barcelona was analyzed during the SARS-CoV-2 coronavirus disease (COVID-19) lockdown and prior to this period. The changes in daily concentrations of CO, NO, NO2, O3 and particulate matter smaller than 10 μm (PM10) were considered for comparison. Bayesian analysis considering serial dependencies and seasonality showed statistically significant decreases of CO, NO, NO2, and PM10 (between −28 and −76%) and O3 increases (+45%) during lockdown. However, the lockdown concentration decreases of PeCB (−90.5%, from 8.5 to 0.8 pg m–3), HCB (−79%, 25.5–5.4 pg m–3) and some PAHs, such as benz[a]anthracene (−87%, 120–17 pg m–3) and pyrene (−81%, 3,500–680 pg m–3), were even stronger. The PAH depletion ranged between −68 and −87% that could be primarily associated with the strong reduction of traffic mobility during this period (−80%). Besides traffic reduction, the observed air quality improvements could be related to lower generation of solid urban residues (−25%) and the subsequent decrease of urban waste incineration (between −25 and −28%). Tributyl phosphate also showed a reduction in concentration during lockdown but the other OPFRs were seemingly not affected by this restriction, possibly as a result of the uniform release from the emission sources, e.g., construction material, industrial applications, and household products.

An Infrared Study of the Dust Properties and Geometry of the Arched Filaments H ii Region with SOFIA/FORCAST

Abstract Massive stellar clusters provide radiation ( ) and winds (∼1000 km s−1) that act to heat dust and shape their surrounding environment. In this paper, the Arched Filaments in the Galactic center were studied to better understand the influence of the Arches cluster on its nearby interstellar medium (ISM). The Arched Filaments were observed with the Faint Object InfraRed CAMera for the SOFIA Telescope at 19.7, 25.2, 31.5, and 37.1 μm. Color–temperature maps of the region created with the 25.2 and 37.1 μm data reveal relatively uniform dust temperatures (70–100 K) over the extent of the filaments (∼25 pc). Distances between the cluster and the filaments were calculated assuming equilibrium heating of standard-size ISM dust grains (∼0.1 μm). The distances inferred by this method are in conflict with the projected distance between the filaments and the cluster, although this inconsistency can be explained if the characteristic grain size in the filaments is smaller (∼0.01 μm) than typical values. DustEM models of selected locations within the filaments show evidence of depleted abundances of polycyclic aromatic hydrocarbons (PAHs) by factors of ∼1.6–10 by mass compared to the diffuse ISM. The evidence for both PAH depletion and a smaller characteristic grain size points to processing of the ISM within the filaments. We argue that the eroding of dust grains within the filaments is not likely attributable to the radiation or winds from the Arches cluster, but may be related to the physical conditions in the Galactic center.

Phytomediated biostimulation of the autochthonous bacterial community for the acceleration of the depletion of polycyclic aromatic hydrocarbons in contaminated sediments.

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic contaminants causing hazards to organisms including humans. The objective of the study was to validate the vegetation of dredged sediments with Phragmites australis as an exploitable biostimulation approach to accelerate the depletion of PAHs in nitrogen spiked sediments. Vegetation with Phragmites australis resulted in being an efficient biostimulation approach for the depletion of an aged PAHs contamination (229.67 ± 15.56 μg PAHs/g dry weight of sediment) in dredged sediments. Phragmites australis accelerated the oxidation of the PAHs by rhizodegradation. The phytobased approach resulted in 58.47% of PAHs depletion. The effects of the treatment have been analyzed in terms of both contaminant depletion and changes in relative abundance of the metabolically active Gram positive and Gram negative PAHs degraders. The metabolically active degraders were quantified both in the sediments and in the root endospheric microbial community. Quantitative real-time PCR reactions have been performed on the retrotranscribed transcripts encoding the Gram positive and Gram negative large α subunit (RHDα) of the aromatic ring hydroxylating dioxygenases. The Gram positive degraders resulted in being selectively favored by vegetation with Phragmites australis and mandatory for the depletion of the six ring condensed indeno[1,2,3-cd]pyrene and benzo[g,h,i]perylene.

Biodegradation of high-molecular-weight polycyclic aromatic hydrocarbons by a wood-degrading consortium at low temperatures

This study evaluates the ability of two bacterial consortia (C2PL05 and BOS08), extracted from very different environments, to degrade low- (naphthalene, phenanthrene, anthracene) and high- (pyrene, perylene) molecular-weight polycyclic aromatic hydrocarbons (PAHs) at high (15-25°C) and low (5-15°C) temperature ranges. C2PL05 was isolated from a soil in an area chronically and heavily contaminated with petroleum hydrocarbons and BOS08 from decomposing wood in an unpolluted forest, free of PAHs. Bacterial consortia were described by cultivable and noncultivable techniques (denaturing gradient gel electrophoresis). Fungal DNA was not observed within the wood-decomposing consortium and fungal activity was therefore negligible during most of the PAH degradation process. PAH-degrading bacterial populations, measured by most probable number enumeration, increased during the exponential phase. Toxicity estimated by the Microtox method was reduced to low levels and final PAH depletion, determined by HPLC, confirmed the high degree (54% and 99%, respectively) of low- and high-molecular-weight PAH degradation capacity of the two consortia. PAH-degrading capacity was also confirmed at low temperatures, and especially by consortium BOS08 not previously exposed to those toxic compounds, where strains of Acinetobacter sp., Pseudomonas sp., Ralstonia sp. and Microbacterium sp. were identified.

Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM

Polycyclic aromatic hydrocarbons (PAHs) are often found in oily wastewaters. Their presence is usually the result of human activities and has a negative effect on the environment. One important step in addressing this problem is to evaluate the effectiveness of PAH removal by biological processes since these are the most cost-effective treatments known today. Many techniques are presently available for PAH determination in wastewaters. Solid phase microextracion (SPME) is known to be one of the most effective techniques for this purpose. When analyzing complex matrices with substances such as natural organic matter (NOM) and non-aqueous phase liquids (NAPL), it is important to differentiate the free dissolved PAH from matrix-bonded PAH. PAHs associated with the bonded fraction are less susceptible to biological treatment. The present study concerns the development of a simple and suitable methodology for the determination of the freely dissolved and the total fraction of PAHs present in oily wastewaters. The methodology was then applied to an oily wastewater from a fuel station retention basin. Headspace SPME was used for analyzing PAH since the presence of a complex or dirty matrix in direct contact with the fiber may damage it. Four model PAHs-anthracene, fluorene, phenanthrene, and pyrene-were analyzed by GC-MS. Negligible depletion SPME technique was used to determine the free fraction. Total PAH was determined by enhancing the mass transfer from the bonded phase to the freely dissolved phase by temperature optimization and the use of the method of standard additions. The PAH absorption kinetics were determined in order to define the optimal sampling conditions for this method. The fitting of the experimental data to a mathematical model was accomplished using Berkeley Madonna software. Humic acid and silicon oil were used as model NOM and NAPL, respectively, to study the effect of these compounds on the decrease of SPME response. Then, the method was evaluated with wastewater from a fuel station spill retention basin. The SPME kinetic parameters-k (1) (uptake rate), k (2) (desorption rate), and K (SPME) (partition coefficient)-were determined from experimental data modeling. The determination of the free fraction required 15-min sampling to ensure that PAH depletion from sample was below 1%. For total PAH, a 30-min extraction at 100 degrees C ensured the maximum signal response in the GC-MS. For the determination of free and total PAHs, extractions were performed before reaching the SPME equilibrium. The wastewater used in this study had no free fraction of the analyzed PAHs. However, the four studied PAHs were found when the method for total PAH was used. The addition of NOM and NAPL dramatically decreased the efficiency of the SPME. This decrease was the result of a greater partition of the PAHs to the NAPL and NOM phases. This fact was also observed in the analysis of the fuel station spill retention basin, where no free PAH was measured. However, using the method of standard addition for the determination of total PAH, it was possible to quantify all four PAHs. The method developed in the present study was found to be adequate to differentiate between free and total PAH present in oily wastewater. It was determined that the presence of NOM and NAPL had a negative effect on SPME efficiency. The presence of binding substances had a great influence on SPME kinetics. Therefore, it is of extreme importance to determine their degree of interference when analyzing oily wastewaters or results can otherwise be erroneous. Other factors influencing the total PAH determinations should be considered in further studies.

Detailed modeling of PAH and soot formation in a laminar premixed benzene/oxygen/argon low-pressure flame

Combustion-generated polycyclic aromatic hydrocarbons (PAH) and soot particles are of significant environmental concern whereas controlled combustion is of increasing interest for the synthesis of carbonaceous nanostructures such as fullerenic material. Improved understanding of chemical and physical processes involved in PAH and soot formation is required to correlate operating conditions with emission characteristics. A detailed kinetic model describing the formation and consumption of PAH and soot in fuel-rich hydrocarbon combustion has been developed. Using a sectional approach, large PAH and carbonaceous particles with diameters of up to ≈70 nm are defined as classes (BINs) covering given mass ranges. Numbers of carbon and hydrogen atoms corresponding to their average masses are assigned to each BIN, accounting for a decrease in H/C ratios with increasing particle size. The model has been successfully tested for a rich premixed benzene/oxygen/argon flame ( ϕ = 2.4, 10% argon, v = 25 cm s −1, 5.33 kPa). Model predictions are compared with published experimental data including mole fraction profiles of individual PAH and concentration as well as number density profiles of soot. Reactions of PAH radicals with PAH and between PAH radicals were found to be the dominant pathway to soot nuclei. Surface growth contributes ≈75% to the final particle mass, and reaction of acetylene with particle radicals is the major growth pathway. Surface growth reactions are involved in PAH depletion in the postflame zone. Particle coagulation involving BINs and BIN radicals significantly contributes to the formation of progressively larger particles whereas oxidation by OH plays a non-negligible role in their depletion.

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) by Cladosporium sphaerospermum isolated from an aged PAH contaminated soil

The ability of a Deuteromycete fungus, Cladosporium sphaerospermum, previously isolated from soil of an aged gas manufacturing plant, to degrade polycyclic aromatic hydrocarbons was investigated. This strain was able to degrade PAHs in non-sterile soils (average 23%), including high molecular weight PAHs, after 4 weeks of incubation. In a microcosm experiment, PAH depletion was clearly correlated to fungal establishment. In liquid culture, this strain degraded rapidly benzo( a)pyrene during its early exponential phase of growth (18% after 4 days of incubation). Among extracellular ligninolytic enzyme activities tested, only laccase activity was detected in liquid culture in the absence or in presence of benzo( a)pyrene. C. sphaerospermum might be a potential candidate for an effective bioremediation of aged PAH-contaminated soils.

Formation mechanism of polycyclic aromatic hydrocarbons and fullerenes in premixed benzene flames

A better understanding of the formation of polycyclic aromatic hydrocarbons (PAH) and fullerenes is of practical interest due to the apparent environmental health effects of many PAH and potential industrial applications of fullerenes. In the present work, a kinetic model describing the growth of PAH up to coronene (C24H12) and of C60 and C70 fullerenes is developed. Comparison of the model predictions with concentration profiles in a nearly sooting low-pressure premixed, laminar, one-dimensional benzene/oxygen/argon flame (equivalence ratio φ = 1.8, pressure = 2.67 kPa) measured by Bittner using a molecular beam system coupled to mass spectrometry shows reasonably good predictive capability for stable and radical intermediates and growth species up to C16H10 isomers. Cyclopentadienyl is found to be a key species for naphthalene formation. The further growth process is based on H abstraction and acetylene addition but also the contribution of small PAH is considered. Good to fair agreement between model predictions and experimental data for larger PAH including the different C16H10 isomers obtained by gas chromatography coupled to mass spectrometry and high performance liquid chromatography could be achieved for PAH in a sooting low-pressure premixed, laminar, one-dimensional benzene/oxygen/argon flame (φ = 2.4, 5.33 kPa). C60 and C70 fullerenes are underpredicted, and possible reasons such as uncertainties in rate coefficients or the existence of other formation pathways are discussed. PAH depletion in the burnt gas is not reproduced by the model and is believed to involve supplementary sinks such as reactions involving PAH and growing soot particles.

Bioremediation of a polycyclic aromatic hydrocarbon‐contaminated soil by using different aerobic batch bioreactor systems

The intrinsic depuration capability of a soil contaminated by polycyclic aromatic hydrocarbons (PAHs) originating from a contaminated industrial site was evaluated in this study by using different aerobic batch bioreactors: a slurry‐phase bioreactor, a blade‐agitated bioreactor, and a rotary vessel bioreactor. For each bioreactor, the disappearance of 14 target PAHs and of the total extractable organic matter was monitored. The three treatments exhibited rapid and extensive removal of the PAHs, which disappeared at different degradation rates according to their molecular weight and aromaticity degree. PAHs with two, three, and four aromatic rings were degraded in sequence, with average rates that generally decreased as the number of molecule rings increased. A slight increase in the bacterial biomass concentration and significant CO2 production were also observed during the time course of the treatments. Among the three treatments, the slurry‐phase system provides the most effective and fastest removal of the PAHs and the organic extractable matter. However, the semisolid‐phase systems exhibited PAH depletion, capabilities higher than those reported in the literature for soils with similar particle size distribution in solid‐phase conditions.