Partitioning Of Polycyclic Aromatic Hydrocarbons Research Articles

Variations of source-specific risks for inhalable particles-bound PAHs during long-term air pollution controls in a Chinese megacity: Impact of gas/particle partitioning

Gas/particle (G/P) partitioning is a determining factor that drives the behavior of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere. To comprehend the variations and impacts of PAHs G/P partitioning on inhalation risks from different sources, atmospheric PAHs in Chengdu were studied from January 2009 to January 2021. Chengdu's air quality demonstrated improvement, with a noticeable decline in PM10 (from 238 to 103 μg m−3), PM10-bound PAHs mass concentrations (from 0.08 to 0.01 μg m−3), as well as PAHs inhalation non-cancer (from 63.5 to 7.1) and cancer risks (from 6.2 × 10−5 to 7.7 × 10−6). Decreasing trends were also observed in the concentrations of organic carbon (OC) and the values of absorptive G/P partitioning coefficient (Kp, OM) from 2009 to 2020, indicating a slight decrease in the PM absorptive capacity. A positive matrix factorization (PMF) model utilized three distinct datasets: PMFpp (particle-phase PAHs only), PMFtot (total PAHs concentrations), and PMFpp/gas (particle-phase in parallel with gas-phase PAHs). PMFpp and PMFpp/gas provide reasonable source apportionment and source-specific risk results. However, daily variations in source contributions of PMFtot were found to be unreasonable. PMFpp/gas and PMFtot could identify a source of low molecular weight PAHs (LPAHs) related to temperature, and a significantly positive correlation between LPAHs and temperature was discovered. Gas/particle partitioning of PAHs showed a notable impact on source-specific risks associated with coal and biomass combustion (CC&BC). The findings contribute to our understanding of the variation in PAHs G/P partitioning and the PM absorptive capacity resulting from effective air pollution control in China. Additionally, they offer prerequisite information for incorporating semi-volatile organic compounds in source apportionment and source-specific risk assessment.

Drivers distinguishing of PAHs heterogeneity in surface soil of China using deep learning coupled with geo-statistical approach

Although numerous studies have reported the influencing factors of polycyclic aromatic hydrocarbons (PAHs) in surface soil from source, process or soil perspectives, the mechanism of PAHs heterogeneity in surface soil are still not well understood. In this study, the effects of 16 PAHs in surface soil of China sampled between 2003 and 2020 with their 17 “source-process-sink” factors at 1 km resolution (N = 660)) were explored using deep learning (eXtreme Gradient Boosting) to mine key information from complex dataset under the optimized parameters (i.e., learning rate = 0.05, maximum depth = 5, sub-sample = 0.8). It was observed that top five factors of 16 PAH had the largest cumulative contribution (i.e., from 84.8% to 98.1%) on their soil concentrations. PAH emission was the predominant driver, and its effect on soil PAH increases with increasing logKow. Soil was the second driver, in which clay can promote the partition of PAHs with low or middle logKow. However, sand can accumulate those congeners with high logKow. Moreover, the deep learning plus geo-statistical models (with low deviation for testing dataset (N = 283)) were capable of predicting soil PAH concentrations using their drivers with high accuracy. This study improved the understanding of the environmental fate and spatial variability of soil PAHs, as well as provided a novel technique (i.e., deep learning coupled with geo-statistics) for accurate prediction of soil pollutants.

Spatial distribution and partition of polycyclic aromatic hydrocarbons (PAHs) in the water and sediment of the southern Bohai Sea: Yellow River and PAH property influences

The marginal Bohai Sea, connected to the northwestern Pacific Ocean, is threatened by human activity. The Yellow River, the second largest river in China, drains large amounts of water, silts, and polycyclic aromatic hydrocarbons (PAHs) into the southern Bohai Sea; however, to what extent the Yellow River inputs influence the spatial distributions and partitions of PAHs in the southern Bohai Sea is not well known. Therefore, this study collected surface water, bottom water, and sediment samples from the southern Bohai Sea and analyzed them to examine the spatial distributions and partitions of 15 priority PAHs. The results showed that PAH concentrations ranged from 26.9 to 50.1 ng L–1 in surface water, 18.8 to 44.1 ng L–1 in bottom water, and 7.4 to 143.9 ng g–1 in sediment, with higher proportions of four-, five-, and six-ring PAHs in sediment than in water. PAH inputs from the Yellow River and sea coastal currents determined the spatial distribution of PAH concentrations in water and sediment, with an overall decrease from the estuary to the southeast. However, the solid dilution effect of input silts from the Yellow River and the liquid dilution effect of water from the Yellow River and Yellow Sea led to lower PAH concentrations in the water and sediment of the southern Bohai Sea than those in other areas of the Bohai Sea. PAH exchange between the atmosphere and seawater led to significantly higher individual PAH concentrations (except for acenaphthylene) in the surface water than in the bottom water, with ratios significantly related to the PAH n-octanol-water partition coefficient, organic carbon-water partition coefficient, and Henry's law constants. These parameters also determined PAH partitioning between the bottom water and sediment. Individual and total PAH concentrations in the sediment were significantly correlated with organic matter, clay, and silt contents. Therefore, the partitions and spatial distributions of PAHs in the southern Bohai Sea comprehensively depend on PAH properties, PAH inputs from the Yellow River and the atmosphere, sea currents, and seawater and sediment properties. The ecological risks posed by individual PAHs in both water and sediment were negligible or acceptable.

Black carbon, soil organic matter molecular signatures under different land uses in Shenyang, China and relationship with PAHs

The content, composition and molecular signatures of soil organic matter (SOM) have important influences on the cycle of soil organic carbon (SOC) and the partitioning of polycyclic aromatic hydrocarbons (PAHs) in soil. Seventy-nine soil samples from farmland, forest and urban areas were collected in Shenyang, China to investigate black carbon (BC) content, SOM molecular signatures varied with land use patterns, as well as the relationship with PAHs. The content of BC in urban soils was significantly higher than that of farmland and forest. BC was a key contributor of urban SOM which accounted for 0.35 ± 0.31 of SOC in urban soil. Based on BC/SOC ratio, the main sources of BC were identified as fossil fuel combustion for urban soils, while for farmland and forest soils, it is the mixed results of fossil fuel combustion and biomass burning. All categories of PAHs in urban soils showed the highest level compared to farmland and forest soils. Pearson's correlation analysis results showed there were significant positive correlations between BC and PAHs categories in urban soils, indicating the important role of BC in the accumulation of PAHs in soil. SOM from each of the two different land use patterns can be distinguished by molecular signatures. Urban SOM had abundant molecular markers derived from condensed organic carbon inputs, which was consistent with the BC/SOC value. Farmland SOM had abundant carbon from vegetation and microorganisms, and forest SOM was rich in organic carbon from fresh plant materials. The markers enriched in urban SOM showed significant correlations with most PAHs categories, highlighting the affinity of urban SOM for PAHs at the molecular level. This study contributed to understanding the impact of land management methods on SOM molecular composition signatures and its influence on PAHs occurrence in soil, providing a theoretical basis for regional soil pollution management.

Spatiotemporal distribution and particle–water partitioning of polycyclic aromatic hydrocarbons in Bohai Sea, China

The Bohai Sea is one of the most polluted marine areas in China with polycyclic aromatic hydrocarbons (PAHs) due to its unique hydrological and geographical environment. To investigate differences in PAH concentrations, composition, and particle–water partitioning before and after the rainy reason, water samples were collected during two surveying voyages covering most of the area of the Bohai Sea. Total and dissolved PAH concentrations were higher during the June voyage (total PAHs: 32.29 ± 15.18 ng/L, dissolved PAHs: 31.25 ± 15.26 ng/L) than the August voyage (total PAHs: 15.98 ± 6.39 ng/L, dissolved PAHs: 11.21 ± 5.59 ng/L). The opposite trend was observed for particulate PAHs (June: 1.04 ± 1.01 ng/L, August: 4.78 ± 2.96 ng/L). Among particulate PAHs, an unusually high proportion (65.07%) of low-molecular-weight (LMW) PAHs was observed during the August voyage, which was significantly higher than the proportion during the June voyage (21.86%). This high proportion was inconsistent with the general distribution of PAHs in the aquatic environment according to their physicochemical properties. The excess LMW PAHs adsorbed on suspended particulate matter arose mainly from soil affected by the petrochemical industry of the Bohai Economic Rim, and were carried with particles on runoff into the Bohai Sea during the rainy season. An estimated 5.49 t of LMW PAHs transitioned from the particulate phase to the dissolved phase during the rainy season. This transfer of LMW PAHs from coastal soil to the water column may be an important source of PAHs in the Bohai Sea.

Different sorption behaviours of pyrene onto polyethylene microplastics in a binary system with water and a ternary system with water and sediment

Microplastics (MPs) and polycyclic aromatic hydrocarbons (PAHs) are two ubiquitous coexisting pollutants that pose potential threats to the environment and organisms and have attracted increasing attention in recent years. However, the interaction between these two pollutants in water, with and without sediment, and the associated mechanisms have not been fully understood. This study aims to explore differences in the sorption behaviours of pyrene at environmentally realistic concentrations by polyethylene MPs (PE-MPs) in binary (water-MPs) and ternary (water-MPs-sediment) systems and to elucidate the role of sediment in the sorption process. Kinetic and isothermal studies show that sediment acted as a “sponge” to adsorb the vast majority of pyrene at the beginning of the sorption experiment in the ternary system, which behaved differently than in the binary system. The sediment-sorbed pyrene was then gradually released but re-adsorbed by PE-MPs, while the concentration of pyrene in water remained at a steady low level. These findings reveal that PE-MPs exhibited a higher pyrene affinity than sediment and being potential pyrene carriers in aqueous systems. Through sorption kinetics and isotherm models study, it was found that pseudo-second-order (PSO) kinetics (0.9773), Elovich (0.9314) and Henry’s (0.9850) models has the highest R2 value, indicating that chemisorption and hydrophobic interactions were attributed to the sorption process. The present study also demonstrates the competition between sediment and MPs in adsorption of pyrene, and highlights the impact of sediment and MPs in the partitioning of PAHs in aquatic environments, which may change the fate of pollution carried by MPs.

Polycyclic aromatic hydrocarbons in Fildes Peninsula, maritime Antarctica: Effects of human disturbance

This study provides the first data on the distribution, sources, and transport dynamics of polycyclic aromatic hydrocarbons (PAHs) in Fildes Peninsula, Antarctica via summertime analyses of lakes, seawater, snow, and air in 2013. Relatively high PAH levels and similar composition profiles (dominance of two- and three-ring PAHs) in the investigated marine and terrestrial environmental matrices were found, indicating substantial primary emissions of petrogenic PAHs. This result was corroborated by nonequilibrium partitioning of atmospheric PAHs caused by release of anthropically-derived lighter PAHs and air mass movement trajectories mainly originated from the Antarctic marginal seas. Notable geographical disparities of PAH pollution in the various types of samples consistently suggested impacts of station-related activities, rather than long-range atmospheric transport, on PAHs in Fildes Peninsula. The lack for temperature dependence for gas-phase concentrations and various molecular diagnostic ratios of atmospheric PAHs demonstrated that the impact of local anthropogenic inputs on air PAH variability supersedes the re-emission effect. The derived air–water and air–snow exchanges of PAHs in this remote region indicated a disequilibrium state, partially associated with intense local emissions of PAHs. PAH outgassing from, and absorption into, lake and marine waters were both observed, probably due to differences in anthropogenic influences among sites, while the net deposition of gaseous PAHs into snow prevailed. The results of this study shed lights on the major importance of native anthropogenic sources in the footprint and fate of PAHs in the Fildes Peninsula, which merits further monitoring.

Fine particles and pyrogenic carbon fractions regulate PAH partitioning and burial in a eutrophic shallow lake

Aquatic particles and organic carbon (OC) regulate the occurrence and transport of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) in water-suspended particle-sediment interfaces. Conventional studies on the mechanisms regulating the relationships between PAHs and total particles/OC have ignored micro-scale regulatory factors such as particle size and OC composition. Field research in the eutrophic shallow Lake Taihu, China, revealed that the fine particle fractions 2.7–10 μm in diameter had stronger PAH adsorption capacity and significantly regulated PAH particle size distribution and water-particle partitioning. Selective PAH biodegradation by planktonic microorganisms probably significantly weakened the capacity of the coarse fractions to regulate PAHs. OC fragments at different temperature gradients had markedly different influences on the particle size distribution of PAHs. High-temperature pyrogenic OC fractions (part of black carbon) were the principal OC regulatory factors for medium-to high-molecular-weight PAHs. However, the OC fragments did not directly affect the particle distribution of low-molecular-weight PAHs. During particle deposition and burial, microbial PAH utilization and efficiency probably regulated the burial potential of various hydrophobic PAH species. Biodegradation of relatively less hydrophobic PAHs with octanol-water partition coefficients (log Kow) < 5.8 showed an increasing trend with decreasing PAH hydrophobicity. Biological pump action of the relatively higher hydrophobic PAH species (log Kow > 5.8) showed a decreasing trend with increasing PAH hydrophobicity. The discoveries of the present work further clarified the mechanisms of PAH partitioning and burial in a eutrophic shallow lake and collectively provides a valuable reference for modeling the transport and dispersal mechanisms of hydrophobic, particle-bound organic contaminants in other aquatic ecosystems.

Gas-PM2.5 partitioning, health risks, and sources of atmospheric PAHs in a northern China city: Impact of domestic heating

The diurnal variation, gas-particle partitioning, health risks, and sources of polycyclic aromatic hydrocarbons (PAHs) were investigated in a northern basin city of China in winter, 2020. The mean concentrations of particulate and gaseous PAHs were 87.90 ng m−3 and 69.65 ng m−3, respectively, and their concentrations were considerably enhanced during the domestic heating period. The relationship between the gas-particle partitioning coefficient of PAHs (KP) and subcooled liquid vapor pressure of PAHs (PL0) indicated organic absorption as the mechanism for this partitioning. However, the dual sorption model confirmed adsorption onto elemental carbon (EC). The health risks indicated by several equivalent parameters showed an important health effect of PAHs, especially of particulate PAHs bound onto PM2.5 during the heating period. Environmentally persistent free radicals (EPFRs) were also studied as an auxiliary parameter to evaluate the health impact of PAHs. According to the diagnostic ratios of PAHs and PMF model results, petroleum volatilization and coal combustion were the dominant sources of particulate PAHs during the non-heating and heating periods, respectively. The source apportionment results can help efficiently control PAHs and their health risks.

Atmospheric chemistry and cancer risk assessment of Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs over a semi-arid site in the Indo-Gangetic plain.

Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs were collected over a year at a traffic dominated site in Agra, to determine the dominant partitioning mechanism. During the entire sampling period, total PAHs and Nitro-PAHs were 3465±3802 and 26.1±25.9ngm-3 respectively. The gas-particle partitioning behavior of PAHs was studied by applying the Pankow model, Absorption model, and Dual model. Amongst all the partitioning models, the Dual model fits well and indicates that the partitioning of PAHs at the traffic site in Agra depends on both the physical adsorption of PAHs on the Total Suspended Particulate (TSP) surface and absorption of PAHs into the organic layer present on the TSP surface. Pankow model indicates that PAHs are emitted from the source close to the sampling point and due to this PAHs do not get enough time to get partitioned in between both the phases. Incremental lifetime Cancer Risk (ILCR) shows that adults and children are more prone to cancer risk in comparison to infants for both PAHs and Nitro-PAHs. Cancer risk by inhalation was minimum in comparison to both ingestion and dermal exposure. Nitro-PAHs in the particulate phase were high enough to exceed the minimum permissible limit (10-6) of causing cancer by ingestion and dermal exposure.

A numerical modeling framework for simulating the key in-stream fate processes of PAH decay in Muskeg River Watershed, Alberta, Canada

Most previous water quality studies oversimplified in-stream processes for modeling the fate and transport of critical organic contaminants, such as Polycyclic Aromatic Hydrocarbons (PAHs). Taking four selected PAHs as representative organic contaminants, we developed a numerical modeling framework using a Water Quality Analysis Simulation Program 8 (WASP8) and a well-established watershed model, i.e., Soil and Water Assessment Tool (SWAT) to: (1) address the influence of in-stream processes, including direct photolysis, volatilization, partitioning of PAHs to suspended solids, and DOC complexation processes on PAH concentrations; and (2) establish relationships between spatiotemporal distribution of environmental factors (e.g., ice coverage, water temperature, wind, and light attenuation), in-stream processes, and PAH concentrations at a watershed scale. Using calibrated SWAT and WASP8 models, we evaluated the impacts of seasonal changes in environmental factors on in-stream processes in the Muskeg River watershed, which is part of the Athabasca Oil Sands Region (AOSR), the third-largest crude oil reserves of the world in western Canada. Among four selected PAHs, simulation results suggest that Naphthalene primarily decay in the water through volatilization or direct photolysis. For Phenanthrene, Pyrene, and Chrysene, DOC complexation, volatilization, and direct photolysis all contribute to their decay in the water, with a strong dependence on seasonality. Model simulations indicated that direct photolysis and volatilization rates are meager in cold seasons, mainly due to low river temperature and ice coverage. However, these processes gradually resume when entering the warm season. In summary, the model simulation results suggest that critical in-stream processes such as direct photolysis, volatilization, and partitioning and their relationship with environmental factors should be considered when simulating the fate and transport of organic contaminants in the river systems. Our results also reveal that the relationship between environmental factors and fate processes affecting PAH concentrations can vary across a watershed and in different seasons.

Gas-particle partitioning of polycyclic aromatic hydrocarbons from oil combustion involving condensate, diesel and heavy oil

This study focuses on the gas-particle (G-P) partitioning of 16 polycyclic aromatic hydrocarbons (PAHs) from oil combustion, which is one of the important contributors of anthropogenic PAHs but has been rarely studied. The combustions of different types of oils involving ultra-light to heavy oils were investigated, and the PAH partitioning mechanism was determined by the widely used Junge-Pankow adsorption model, Koa absorption model, and dual sorption model, respectively. The results show that the source-specific diagnostic ratios of Ant/(Ant+Phe) are between 0.09 and 0.24, the estimated regression slopes of G-P partition coefficients (KP) of the total PAHs on their sub-cooled liquid vapor pressures (PLO) are in the range of − 0.34 to − 0.25, and the predicted fractions of PAHs in the particle phase (φ) by Koa absorption model are close to the measured values, while the log KPvalues of the LMW PAHs from the combustions of diesel and heavy oil are better represented by the dual sorption model. Our findings indicate that PAHs are derived from mixed sources that include the unburned original oil and combustion products, and the PAH partitioning mechanism is governed by the process of absorption into organic matter because of the unburned oil, but both adsorption and absorption exist simultaneously in the lighter PAHs from the combustions of heavier oils (i.e., diesel and heavy oil). Based on these findings, the understanding of the fate and transport of PAH emissions and the optimization of the emergency responses to accidents such as marine oil spills would be potentially improved.

Polycyclic Aromatic Hydrocarbons in the Marine Atmosphere from the Western Pacific to the Southern Ocean: Spatial Variability, Gas/Particle Partitioning, and Source Apportionment.

The spatial variability of polycyclic aromatic hydrocarbons (PAHs) in the marine atmosphere contributes to the understanding of the global sources, fate, and impact of this contaminant. Few studies conducted to measure PAHs in the oceanic atmosphere have covered a large scale, especially in the Southern Ocean. In this study, high-volume air samples were taken along a cross-section from China to Antarctica and analyzed for gaseous and particulate PAHs. The data revealed the spatial distribution, gas-particle partitioning, and source contributions of PAHs in the Pacific, Indian, and Southern Oceans. The median concentration (gaseous + particulate) of ∑24PAHs was 3900 pg/m3 in the Pacific Ocean, 2000 pg/m3 in the Indian Ocean, and 1200 pg/m3 in the Southern Ocean. A clear latitudinal gradient was observed for airborne PAHs from the western Pacific to the Southern Ocean. Back trajectories (BTs) analysis showed that air masses predominantly originated from populated land had significantly higher concentrations of PAHs than those from the oceans or Antarctic continents/islands. The air mass origins and temperature have significant influences on the gas-particle partitioning of PAHs. Source analysis by positive matrix factorization (PMF) showed that the highest contribution to PAHs was from coal combustion emissions (52%), followed by engine combustion emissions (27%) and wood combustion emissions (21%). A higher contribution of PAHs from wood combustion was found in the eastern coastal region of Australia. In contrast, engine combustion emissions primarily influenced the sites in Southeast Asia.

Multimedia distribution of polycyclic aromatic hydrocarbons in the Wang Lake Wetland, China

The Wang Lake Wetland is a highly valued area that is protected due to its high biodiversity. The wetland has a complicated hydrological regime and is subject to frequent human disturbance. We hypothesize that fluctuating hydrology and human activities have varied contributions to the temporal and spatial variations of polycyclic aromatic hydrocarbons (PAHs) in the wetland. Soil (SS), sediment (SD), and water, to acquire dissolved phase (DP) and suspended particulate matter (SPM), samples were collected from eight locations during low- and high-flow periods to elucidate multimedia phase distribution and transport of PAHs. Following the onset of the rainy season, the concentration of SPM-associated PAHs increased significantly, while the DP PAHs remained stable. Individual PAH ratios showed that, although pyrogenic sources are common, petrogenic derived compounds are the main source of PAHs in the Wang Lake Wetland. During the high-flow period, the empirical values for logarithms of the organic carbon-normalized partition coefficients (log KOC) of individual PAH-congeners were lower than the corresponding field-observed log KOC values from the SPM-DP and SD-DP systems, reflecting the complexity in evaluating multi-phase PAH partitioning. During the high-flow period, temperature-driven changes may have changed the sediment from a sink to a source for some high molecular weight PAHs. It was determined that human activities governed the PAH loading in the low-flow period, whereas during high-flow conditions, increased rainfall, higher temperatures, and fishery activity are the main factors controlling PAH input to the Wang Lake Wetland.

Emission Characteristics of Gas-and Particle-Phase Polycyclic Aromatic Hydrocarbons from Cooking

Polycyclic aromatic hydrocarbons (PAHs) play a key role in the formation of secondary organic areole and ozone. This study sampled three commercial Chinese restaurants and a food plant in Shenzhen to analyze the emission characteristics of PAHs, especially the alkyl PAHs in both gas and particle phases. The results showed that the ρ(total PAHs)in the particle and gas phase were (1381.6±140.5) ng·m-3, (1030.2±116.4) ng·m-3, (908.3±111.9) ng·m-3, and (838.0±93.5) ng·m-3 in the food plant, Sichuan, Cantonese, and Zhejiang restaurants, respectively. More than 60% of the PAHs were distributed in the gas phase, especially the lower molecular weight PAHs (lower than Chrysene). The gas phase proportion of naphthalene was the highest, with over 75% of it distributed in the gas phase. However, the PAHs with a higher molecular weight than that of benzo(b)fluorescence were mainly distributed in the particle phase. The total concentration of alkyl PAHs emitted from cooking was much lower than that of the corresponding parent PAHs, and the distribution characteristics of alkyl PAHs were quite different from those of other emission sources. The linear fitting of lgKp and lgPL showed that the slopes of the three commercial restaurants ranged from -0.25 to -0.28, whereas for the food plant, the value was -0.18, which indicates that the gas-particle partitioning of PAHs were not in equilibrium.

Non-equilibrium influence on G/P partitioning of PAHs: Evidence from the diurnal and nocturnal variation

Gas/particle (G/P) partitioning is an important behavior for the atmospheric transport of polycyclic aromatic hydrocarbons (PAHs). In this study, paired daytime and nighttime air samples were collected for one year in order to study the diurnal and nocturnal variations of concentration and G/P partitioning of PAHs. Higher PAHs concentrations in total phase were observed in nighttime. The geomean (GM) concentrations of Σ15PAHs in total phase were 69.6 and 52.8 ng/m3 in nighttime and daytime, respectively. More obviously diurnal and nocturnal variations were observed in non-heating season, with the GM ratios of Σ15PAHs in nighttime to daytime of 1.65 and 1.06 in non-heating season and heating season, respectively. The results could be attributed to emission sources and meteorological conditions. The values of particulate phase fraction (ϕP) and G/P partitioning quotient (log KP) were used to quantify the phase distribution of PAHs. For most high molecular weight PAHs, the values of ϕP and log KP in nighttime were higher than those in daytime, which could be mainly attributed to the lower temperature in nighttime. However, for the three light molecular weight PAHs (Acy, Ace and Flu), higher values of ϕP and log KP were observed in daytime. The regression of log KP against log KOA for the three PAHs in daytime differed from those in nighttime. The chemical losses of PAHs in different phases might be responsible for the result. These findings suggested that the chemical loss of PAHs in gas phase should be considered for the G/P partitioning process.

Differential accumulation of polycyclic aromatic hydrocarbons (PAHs) in three earthworm ecotypes: Implications for exposure assessment on historically contaminated soils

This study compared accumulation of the 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) in three different earthworm ecotypes, Amynthas sp., Eisenia fetida, and Lumbricus terrestris, in four historically (> 50 years) contaminated manufactured gas plant (MGP) soils using bioassays. Epi-endogeic deep burrowing and soil ingesting Amynthas sp. accumulated significantly more ∑16 PAHs than any other species (upto 8.7 times more), and epigeic surface dwelling E. fetida showed the lowest ∑16 PAH accumulation. Results indicated the importance of earthworm habit and physiology on PAH partitioning into earthworm lipids. Exposure to soil borne PAHs via the gut, as compared with passive diffusion from pore water, was important in species tested, being most evident in burrowing species Amynthas sp. and L. terrestris and for the desorption-resistant higher molecular weight (HMW) PAHs. Biota-soil accumulation factors (BSAF) were low, as influenced by aging, sequestration and strong PAH sorption to secondary sorptive phases in the historically contaminated soils. Bioconcentration factors (BCFs) calculated from freely dissolved pore water PAH concentrations derived from polyoxymethylene solid-phase extractions (POM) were species specific, indicating stronger relationships with octanol-water partition coefficient (KOW) for Amynthas sp. and L. terrestris than for E. fetida. Modelling demonstrated that KOW values were not a reliable proxy for BCF in equilibrium partitioning theory (EqPT) to predict bioavailability for the range of earthworms tested, being less accurate for E. fetida compared to the burrowing species. The study showed that including burrowing and soil feeding earthworm species, such as Amynthas sp. and L. terrestris, in standard testing would benefit regulatory decisions for more accurate quantification of PAH bioavailability in ecological risk assessment on historically contaminated soils.

The effects of molecular weight and orientation on the membrane permeation and partitioning of polycyclic aromatic hydrocarbons: a computational study.

Membrane permeation and the partitioning of polycyclic aromatic hydrocarbons (PAHs) are crucial aspects affecting their carcinogenicity and mutagenicity. However, a clear understanding of these processes is still rare due to the difficulty of determining the details experimentally. Here, the interactions between PAHs and lipid bilayers were studied by molecular simulations, mainly to check the influence of molecular weight and orientation. The liposome-water partition coefficient (KLW), transmembrane time (τ), and permeability coefficient (P) of the PAHs were calculated by integrating free energy profiles from umbrella sampling. For selected PAHs, the membrane adsorption is a spontaneous process. The preferred location is near the CC bond and the orientation is related to the molecular structure. The P values of all the PAHs are basically the same order of magnitude, which means that the molecular weight contributes little to the process. As for KLW and τ, they show obvious increases with different molecular weights. Unconstrained simulations showed that a flat orientation on the membrane surface would prevent PAHs from being transported through the membrane. Highly hydrophobic driving forces are not always good for the absorption of PAHs, especially the formation of aggregates. In addition, the orientations and energetic barriers of PAHs near the midplane of the lipid bilayer explain the different transitions of high- and low-weight PAHs. This work provides molecular level details relating to the interactions of PAHs with lipid membranes, with significance for understanding the health effects of PAHs.

Modelling of gas-particle partitioning of PAHs according to ab/adsorption approach

The new approach of the study was to assess the consistency between the gas?particle partition coefficients of 16 EPA (Environmental Protection Agency) polycyclic aromatic hydrocarbons (PAHs) predicted by the Dachs?Eisenreich ab/adsorption model and the experimental results obtained within the field measurements. A total number of 29 air samples was obtained at 9 locations in Serbia. High volume air sampler was applied, with quartz filters for collecting the atmospheric particles and polyurethane foam filters (PUF) for retaining the free gas molecules of PAHs. The results predicted by the model and the experimental data were compared. The deviations between the measured and predicted f (fraction) values were less than one order of magnitude for Flo, Phe, Ant, Flu, Pyr, B(a)A and Chr. For the PAHs with high molecular mass, B(b)F, B(k)F, B(a)P, I(1,2,3-cd)P, D(ah)A and B(ghi)P, very good agreement was confirmed, except for the data measured at the Oil refinery in Pancevo. The applied model underestimated the concentrations of PAHs in gasphase for the low-molecular mass PAHs.

On-site measured emission factors of polycyclic aromatic hydrocarbons for different types of marine vessels

A portable emission sampling system was used to perform on-site measurements of the emission factors (EFs; quantities of pollutants emitted per unit of energy consumed) of 29 polycyclic aromatic hydrocarbons (PAHs) for five types of marine vessels using light diesel in Hainan Province, China. Both gaseous- and particulate-phase PAHs from vessel emissions were sampled and measured using gas chromatography coupled with mass spectrometry (GC-MS), and the PAH EFs were calculated based on the carbon mass balance method. The average EFs of gaseous- and particulate-phase PAHs were 6.2 ± 7.8 and 17 ± 26 mg/kg, with naphthalene (NAP) and phenanthrene (PHE) dominating the gaseous- and particulate-phase PAH emissions, respectively. Among the five types of vessels, the EFs for small fishing boats were significantly higher than those for other types of vessels, and the lowest EFs were found for tug boats. Composition profiles and typical isomer ratios of PAHs were calculated for five types of vessels. Particulate-phase PAHs accounted for 63 ± 16% of the total emissions of 29 PAH species, and the particulate/gaseous-phase partitioning of PAHs was dominated by organic carbon (OC) absorption rather than black carbon (BC) adsorption. Emission factors of PAHs under different activity conditions were measured and calculated, and relatively higher EFs were found in the maneuvering mode for medium fishing boats and in the operating mode for engineering vessels. No significant differences were found among the PAH composition profiles under different activity conditions.