Gas-phase Polycyclic Aromatic Hydrocarbons Research Articles

Effects of metal-loaded ZSM-5 catalysts on gas-phase products and PAHs formation characteristics during the co-pyrolysis of plastic with biomass

With the urbanization and population growth, the disposal of plastic waste has become a significant challenge, as the traditional methods often result in pollution and resource wastage. Pyrolysis technology offers a sustainable solution by converting the waste plastics into valuable gas or liquid fuels. The co-pyrolysis of plastics and biomass is an effective approach for synergistically managing these two types of solid waste. The polyethylene (PE) and salix psammophila (SP) was used to investigate the gas production characteristics and polycyclic aromatic hydrocarbons (PAHs) formation during the co-pyrolysis. Additionally, Cu/ZSM-5, Co/ZSM-5, and Ni/ZSM-5 catalysts were employed to investigate the effects of different metal-loaded catalysts on the co-pyrolysis process. The results indicate that, with the increase of the pyrolysis temperature, the yield of gas-phase products gradually increases, solid residue decreases, and liquid-phase products initially increase before declining, reaching their maximum at 500 °C. The synergistic effect promotes the formation of C2Hm (C2H2, C2H4, C2H6) and CH4, leading to the increase of the gas-phase product yields compared to the individual pyrolysis. The addition of catalysts further enhances the gas production: Cu/ZSM-5 boosts H2 yield, Co/ZSM-5 shows selectivity for CH4 and C2Hm, and Ni/ZSM-5 exhibits better selectivity for CO and H2. Under the various pyrolysis conditions, aromatic compounds and aliphatic hydrocarbons consistently dominate the liquid-phase products. With the increase of the pyrolysis temperature, the proportion of aliphatic hydrocarbons decreases, while the proportion of aromatic compounds increases. The addition of catalysts reduces the proportions of both aliphatic and aromatic compounds. PAHs generation is temperature-dependent, significantly increasing at 700 °C. At the low pyrolysis temperatures, the co-pyrolysis reduces PAHs yield, but at high temperatures, PAHs formation increases. The addition of catalysts decreases PAHs yield and toxicity equivalency. Cu/ZSM-5 promotes the cracking of two-ring PAHs, reducing two-ring PAHs yield. Co and Ni catalysts enhance the selective aromatization of small hydrocarbon molecules, forming low-ring PAHs and limiting PAHs aggregation. Overall, Ni/ZSM-5 demonstrates the best performance in enhancing gas production and reducing PAHs emissions, followed by Co/ZSM-5 and Cu/ZSM-5.

Kinetic insights and pollution mitigation in waste tire pyrolysis: Targeting sulfur, nitrogen, and PAHs emissions

Waste tires have potential to be used for generation of fuel via thermal degradation because of their non-biodegradable nature. Nevertheless, the formation of various pollutants such as sulfur-based and nitrogen-based are inevitable due to presence of nitrogen and sulfur containing compounds during waste tires production. The main purpose was to examine the effect of variating heating rates on pollutants release because heating rate is an important parameter which influences the pollutants releasing profile. Moreover, Ar and CO2 as reaction medium were used to identify their behavior for restraining the PAHs in gas phase. The present study investigates the influence of heating rates and carrier gas environment (Argon and CO2) to reduce the pollutants emission. Thermogravimetry-Mass Spectrum coupled with Fourier transform infrared spectrometer was used to evaluate the thermal degradation and pollutants formation. The major degradation of waste tires occurred between 300 and 500 ℃. The sulfur-based (H2S, CS2, COS, SO2, and CH3SH), nitrogen-based (NH3, HNCO, NO, and HCN) and 9 series of PAHs pollutants were detected. The higher heating rates promoted the pollutants emission. The degradation of compounds having sulfur content formed -SH radials and -SH helped in further release of sulfur based-pollutants. The NH3 releasing profile started after 200 ℃ and released till around 800 ℃ for 30 ⁰C/min and 40 ⁰C/min but its emission was very low after 600 ⁰C for heating rates 5 ⁰C/min, 10 ⁰C/min, and 20 ⁰C/min. The aromatic compounds fraction was more at higher heating rate due to short residence time for pyrolytic products to go through secondary reaction. The 5 ℃/min and 10 ℃/min were considered favorable heating rates in terms of achieving lowest activation energy in both gas environments. The thermodynamic parameters analysis suggested that waste tires pyrolysis was non-spontaneous and endothermic reaction as well as feedstocks showed potential to be utilized for waste conversion.

Modeling polycyclic aromatic hydrocarbons (PAHs) concentrations from wildfires in California

In recent years, wildfires in California have increased in frequency and intensity due to climate change and prolonged drought. The air pollutants released by wildfires cause significant health consequences, among which polycyclic aromatic hydrocarbons (PAHs) are particularly toxic. Estimating PAH emissions from wildfires is challenging due to variability in vegetation types. In this study, we estimate PAH emission rates across California at a high resolution, based on laboratory-measured PAH emission rates from 22 different vegetation types and detailed vegetation mapping. By combining these estimates with biomass burning data from the NCAR Fire Inventory, the Community Multiscale Air Quality Modeling System simulates PAH concentrations for the 2017 fire season. The modeling results compare favorably to measurements from three PAH monitoring sites in California. The peak PAH emissions from wildfire events are up to be 80 times higher in the gas phase and 32 times higher in the particle phase compared to a case without fire emissions. The population-weighted PAH concentrations from the fire case (0.053 µg/m3) are 47 % higher compared to a non-fire case (0.036 µg/m3) in the particle phase and 11 % higher in the gas phase (9.82 ppt compared to 8.83 ppt) during the study period. While highly depended on the meteorological condition, the simulated spatial distribution indicates that gas-phase PAHs are less likely to travel long distances from the fire source and are prone to aging into the particle phase during transport. Consequently, populations are more likely to be exposed to particle-phase PAHs during wildfire events. This finding has important implications for understanding the health impacts of wildfire-induced PAH concentrations, as particle-phase PAHs may have different toxicological effects compared to gas-phase PAHs.

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.

Prediction of soot for pressurized turbulent kerosene-air diffusion flames using method of moments

ABSTRACT A comprehensive CFD model is developed to predict soot for a turbulent kerosene-air diffusion flame. The method of moments (MOM) soot model has better prediction capability with meaningful soot behavioral predictions than semi-empirical models. The coupled model is primarily validated with experimental measurements from the literature in the form of major species concentration, flame temperature, and soot volume fraction. A surrogate mix comprising 80% n-decane and 20% toluene on a liquid volume basis constitutes kerosene fuel. The 20% aromatic content is able to reproduce the sooting behavior with considerable accuracy. The model can replicate CO, CO2, CH4, C2H2, C2H4, and C6H6 concentrations, flame temperature, soot volume fraction, and soot aggregation parameters for a laminar JetA-1 flame at atmospheric pressure. The reproduction of flame temperature and major species concentrations for a laminar kerosene flame validates the applicability of the gas-phase kinetic mechanism and PAH formation pathway for the reacting flow system. The model also performs appreciably for measurements of a turbulent kerosene flame at higher operating pressures up to 6.44 bar. The peak soot volume fraction matches significantly well with the measurements for all the flames. The predicted peak soot volume fractions are 8.8, 27.3, 68, and 82 ppm compared to measured values of 9.3, 28.3, 63, and 67 ppm at pressures 1, 2.7, 4.81, and 6.44 bar, respectively. However, the location of the peak soot has a slight discrepancy at low pressures till 2.7 bar, showing the predicted peak earlier compared to a later appearance in the measurements. The simulated peak flame temperatures are 1377, 1393, 1412, and 1477 K as operating pressure increases from 1 to 2.7, 4.81, and 6.44 bar. The thermal absorbance from soot and species radiation plays a vital role in predicting the flame temperature. Soot radiation reduces flame temperature by ~ 500 K compared to gaseous radiation (CO2, H2O, CO, CH4, etc.), reducing approximately 100 K. The predictive soot number density, mean diameter, surface area, primary particle count in soot aggregates, and primary particle diameter carry a substantial dependency on the operating pressure.

Investigations into the transition to sustainable alternative fuels in a South African underground platinum mine

Adverse environmental impacts associated with the use of fossil fuels and the over-dependence thereon has made energy security and sustainability a critical issue worldwide particularly for key energy intensive economic sectors which are heavily dependent on diesel. We thus investigated the feasibility of a transition to two different alternative fuels namely, rapeseed methyl ester (RME) biodiesel and gas-to-liquid fuel (GTL), in the platinum mining industry in South Africa. Load haul dump vehicles are the most abundant workhorses underground and were the selected vehicles to test alternative fuels at 100% without any engine modification. Potential reduction of harmful unregulated polycyclic aromatic hydrocarbon (PAH) emissions was the focus of the research due to their adverse impacts on the environment, human health and engine operations. Quantitative collection of gas and particle phase PAHs was made possible using portable denuder devices followed by analysis by two-dimensional gas chromatography coupled to time-of-flight mass spectrometry. Results showed that total PAH emissions from a high idling vehicle decreased dramatically when diesel was substituted with both biofuels (total gas phase PAH concentrations of 34; 14 and 9 µg m-3 for diesel, GTL and RME, respectively) and no substantial hinderance on engine performance was reported. This novel sector specific study on unmodified heavy duty working vehicles can potentially translate into a real-world, immediate solution, as not only would the selected biofuels be able to directly replace diesel, but both have high potential of being locally produced in South Africa and assist in the promotion of a circular economy.

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.

128 Exposure to soot, Measured as Black Carbon and PAH, in Swedish Chimney Sweeps

Abstract The overall aim of our research is to study chimney sweeps exposure to soot to be able to give recommendations on how to effectively reduce the exposure. To do this a suitable method to study soot exposure is required. In this study we use a new method to study the personal airborne exposure to soot measured as black carbon (BC). BC is measured with a AethLabs MA200 micro aethalometer with a flow rate of 100 mL/min and sampling time of 1 min. By using a direct-reading instrument we aim to identify variability in exposure levels during the workday, and potential work tasks contributing to elevated exposure to soot. The study includes 20 chimney sweeps performing black sweeping in Sweden and BC is measured for eight workdays for each individual. During these days individuals also fill out a diary of work tasks performed. To assess the value of the BC levels, airborne polycyclic aromatic hydrocarbon (PAH) is also measured with personal sampler for particulate- and gas phase PAH. PAH is measured in parallel with BC during one workday. Preliminary results show variability of BC levels between different individuals as well as different workdays for the same individual. We are also able to link BC levels with work tasks from the diaries. Significantly elevated PAH levels and especially the particle-bound PAHs, including the carcinogenic benzo(a)pyrene, were observed in most samples.

Hydrocarbons in the atmospheric gas phase of a coastal city in Tunisia: Levels, gas–particle partitioning, and health risk assessment

Many studies have focused on aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (AHs and PAHs) in different environmental compartments, especially atmospheric particles (aerosols), due to their adverse effects on the environment and human health. However, much less information is currently available on the content of AHs and PAHs in the atmospheric gas phase, which is a major reservoir of volatile and photoreactive compounds. Here, for the first time, we assessed the levels, gas–particle partitioning, human health risks and seasonal variations of AHs and PAHs in the atmospheric gas-phase of Bizerte city (Tunisia, North Africa) over a one-year period (March 2015–January 2016). Σ34PAH concentration in the gas phase over the period ranged from 6.7 to 90.6 ng m−3 and on average was 2.5 times higher in the cold season than in the warm season. Σ28AH concentration in the gas phase over the period ranged from 14.0 to 35.9 ng m−3, with no clear seasonal variations. In the gas phase, hydrocarbons were dominated by low-molecular-weight (LMW) compounds, i.e. 3- and 4-ring for PAHs and < n-C24 for AHs. Gas-phase concentrations of PAHs and AHs accounted for up to 80 % of the total (gas + particle phases) atmospheric concentrations of PAHs and AHs. Further analysis of gas–particle partitioning showed that LMW hydrocarbons preferential accumulated in the gas phase, and that gas–particle partitioning was not in equilibrium but dominated by absorption processes into the aerosol organic matter. Benzo[a]pyrene toxic equivalency quotient (BaP-TEQ) in the gas phase represented on average 37 % of the total atmospheric BaP-TEQ concentration, which was always higher in the cold season. Atmospheric gas is a significant factor in the risks of cancer associated with inhalation of ambient air. The Monte Carlo simulation-based exposure assessment model predicted that outdoor air exposure to PAHs does not pose a cancer risk to infants, but the children, adolescent, and adult populations may face a lower cancer risk during the warm season and a higher risk in the cold season.

In situ investigation of N deposit effects on polycyclic aromatic hydrocarbons (PAHs) photolysis in snow

As snow is an ideal scavenger of polycyclic aromatic hydrocarbons (PAHs) for both particulate- and gas-phase PAHs, a large amount of PAHs are accumulated in snowpacks. These PAHs could be released from seasonal snowpacks into environment over a short time during the snow melting period, causing a flush of contaminants. Understanding the fate of PAHs in snow therefore is important to evaluate the contaminant flush during snow melting. However, as an important natural process, PAH photolysis in snow is still unclear, especially in the context of global climate change. Therefore, photolysis of the 16 PAHs, which are listed as priority controlled pollutants by United States Environmental Protection Agency (US EPA), was investigated with N deposit in field in snow in this study. A mixture of the 16 US EPA priority PAHs and nitrate/ammonia were spiked into sealed quartzose bottles containing snow samples in field. The bottles were then exposed to solar radiation in field for 6 h. Experimental results showed that >50% of PAHs were lost during 6 h photolysis, mostly occurred in the first hour. Generally, HMW PAHs were photolyzed faster than LMW PAHs, though the photolysis rate did not strictly increase with molecular weight. Low concentrations of nitrate can enhance photolysis of Ant and Pyr, while photolysis of investigated PAHs was inhibited with nitrate concentration increasing. In contrast, both low and high concentration of ammonium can inhibit PAH photolysis. The inhibiting effect of both nitrate and ammonia on photolysis of HMW PAH is stronger than that of LMW PAHs, indicating direct photolysis of PAHs is the main pathway of PAH degradation in snow in situ. This study firstly showed the effect of N deposition on PAH photolysis in snow. Under current increasing N deposition in northeast China, this study implied that more PAHs in snow could be preserved during winter and released shortly during snowmelt, resulting in high ecological risk in spring.

Emission factors for polycyclic aromatic hydrocarbons from laboratory biomass-burning and their chemical transformations during aging in an oxidation flow reactor

Atmospheric polycyclic aromatic hydrocarbons (PAHs) can be emitted from different combustion sources including domestic biomass burning, internal combustion engines, and biomass burning (BB) in wild, prescribed, and agricultural fires. With climate warming and consequent global increases in frequency and severity of wildfires, BB is a dominant source of PAHs emitted into the atmosphere.In this study, six globally and regionally important and representative fuels (Alaskan peat, Moscow peat, Pskov peat, eucalyptus, Malaysian peat, and Malaysian agricultural peat) were burned under controlled conditions in the combustion chamber facility at the Desert Research Institute (DRI, Reno, NV, USA). Gas- and particle-phase BB emissions were aged in an oxidation flow reactor (OFR) to mimic five to sevendays of atmospheric aging. To sample gas- and particle-phase BB emissions, fresh and OFR-aged biomass-burning aerosols were collected on Teflon-impregnated glass fiber filters (TIGF) in tandem with XAD resin media for organic carbon speciation. The objectives of this study were to i) quantify the emission factors for 113 PAHs emitted from the combustion of the six selected fuels, ii) characterize the distribution of PAH compounds between gas and particle phases for these fuels, iii) identify the changes in PAHs during OFR-aging, and iv) evaluate toxicity potential with characterized compounds.We found that combustion emissions of gas-phase PAHs were more abundant (>80 % by mass) than particle-phase PAHs, for emissions from all combusted fuels. The mass fraction of substituted napthalenes in Moscow peat and Malaysian peat emissions were ∼70 % & 84 %, respectively, whereas in Eucalyptus the same fraction was <50 %, which indicates that these substituted compounds can be used as tracers for peat emissions. Mass concentrations of gas- and particle-phase PAHs were reduced by ∼70 % after OFR oxidation. However, the understanding of the fate of PAHs during OFR oxidation requires further investigations. Our results also indicate that the PAH toxicity of BB samples would be underestimated by 10–100 times if only the BaPeq for the 16 US EPA priority PAHs in the particle phase are included.

Gas Particle Partitioning of PAHs Emissions from Typical Solid Fuel Combustions as Well as Their Health Risk Assessment in Rural Guanzhong Plain, China.

Air pollutants from the incomplete combustion of rural solid fuels are seriously harmful to both air quality and human health. To quantify the health effects of different fuel-stove combinations, gas and particle partitioning of twenty-nine species of polycyclic aromatic hydrocarbons (PAHs) emitted from seven fuel-stove combinations were examined in this study, and the benzo (a) pyrene toxicity equivalent (BaPeq) and cancer risks were estimated accordingly. The results showed that the gas phase PAHs (accounting for 68-78% of the total PAHs) had higher emission factors (EFs) than particulate ones. For all combustion combinations, pPAHs accounted for the highest proportion (84.5% to 99.3%) in both the gas and particulate phases, followed by aPAHs (0.63-14.7%), while the proportions of nPAHs and oPAHs were much lower (2-4 orders of magnitude) than pPAHs. For BaPeq, particulate phase PAHs dominated the BaPeq rather than gas ones, which may be due to the greater abundance of 5-ring particle PAHs. Gas and particle pPAHs were both predominant in the BaPeq, with proportions of 95.2-98.6% for all combustion combinations. Cancer risk results showed a descending order of bituminous coal combustion (0.003-0.05), biomass burning (0.002-0.01), and clean briquette coal combustion (10-5-0.001), indicating that local residents caused a severe health threat by solid fuel combustion (the threshold: 10-4). The results also highlighted that clean briquette coal could reduce cancer risks by 1-2 orders of magnitude compared to bulk coal and biomass. For oPAH, BcdPQ (6H-benzo(c,d)pyrene-6-one) had the highest cancer risk, ranging from 4.83 × 10-5 to 2.45 × 10-4, which were even higher than the total of aPAHs and nPAHs. The dramatically high toxicity and cancer risk of PAHs from solid fuel combustion strengthened the necessity and urgency of clean heating innovation in Guanzhong Plain and in similar places.

Environmental and health risk implications of unregulated emissions from advanced biofuels in a Euro 6 engine

The use of conventional and advanced biofuels is part of the efforts to reduce greenhouse gases and harmful exhaust gaseous emissions. This study investigates the unregulated emissions in gas and particles from a Euro 6b diesel engine, operated with four unconventional and advanced biofuels (two hydrogenated terpenic biofuels, a polyoxymethylene dimethyl ether, and a glycerol-derived biofuel), blended with diesel fuel and pure hydrotreated vegetable oil as base biofuel. The engine was operated following WLTC starting from cold-engine conditions. Gas phase samples were collected at each phase of the driving cycle and particulate matter (PM) samples were collected from a dilution tunnel at the end of the driving cycle. A total of 16 PAH and 13 carbonyls were analyzed. In addition, the apoptotic index induced by gas and particle emissions was determined. In the gaseous phase, the total PAH and carbonyl emission factors were higher at the low-speed phase for all fuels. Gas-phase PAH emission factors exceeded particle-bound PAH. Carbonyl emission factors ranged from 0.12 ± 0.012 to 25.3 ± 4.2 mg/km, markedly exceeding gaseous PAH emissions, which ranged from 20.7 ± 1.5 to 51.7 ± 8.9 μg/km. Diesel fuel exhibited the highest carbonyl emissions and its blend with 20% of hydrogenated turpentine exhibited the highest PAH emissions at the end of the WLTC, both due to high emissions at the low-speed phase. Although particle-bound PAH comprise only a small fraction of total PAH emissions, both phases (gas and particles) contributed approximately equal to the toxicity associated with carcinogenic PAH. The apoptotic cells percentage increased in a dose-dependent manner and was significantly higher in cells exposed to gas phase-derived samples. The apoptotic index induced by particulate matter samples did not show a concentration-response effect for any of the fuels.

Cancer risk assessment and source apportionment of the gas- and particulate-phase of the polycyclic aromatic hydrocarbons in a metropolitan region in Brazil

A risk assessment and a source apportionment of the particulate- and gas-phase PAHs were conducted in a high vehicular traffic and industrialized region in southeastern Brazil. Higher concentrations of PAHs were found during summer, being likely driven by the contributions of PAHs in the vapor phase caused by fire outbreaks during this period. Isomer ratio diagnostic and Principal Component Analysis (PCA) identified four potential sources in the region, in which the Positive Matrix Factorization (PMF) model confirmed and apportioned as gasoline-related (31.8%), diesel-related (25.1%), biomass burning (23.4%), and mixed sources (19.6%). The overall cancer risk had a tolerable value, with ∑CR = 4.6 × 10−5, being ingestion the major via of exposure (64% of the ∑CR), followed by dermal contact (33% of the ∑CR) and inhalation (3%). Mixed sources contributed up to 45% of the overall cancer risk (∑CR), followed by gasoline-related (up to 35%), diesel-related (up to 15%), and biomass burning (up to 10%). The risk assessment for individual PAH species allowed identifying higher CR associated with BaP, DBA, BbF, BaA, and BkF, species associated with gasoline-related and industrial sources. Higher risks were associated with PM2.5-bound PAHs exposure, mainly via ingestion and dermal contact, highlighting the need for measures of mitigation and control of PM2.5 in the region.

Development of a Fully Reversible PAH Clustering Model

Physical clustering of Polycyclic Aromatic Hydrocarbon (PAH) molecules is subject to many studies as a part of understanding the complex clustering behavior and formation of carbon nanoparticles, such as soot and carbon black. A new fully reversible PAH clustering (FRPC) model is introduced to account for the full reversibility of PAH inception and molecular adsorption. Instead of assessing the performance of the new FRPC in a flame simulation as is typically done, a simplified system is utilized such that PAH clustering can be isolated from all other particle processes. The chosen simplified system consists of a 0D homogeneous reactor of PAHs at certain temperatures and has previously been investigated using molecular dynamics. The results from the FRPC model display excellent performance when compared to the molecular dynamic results. It is found that reversible rates play a significant role for smaller PAHs and at higher temperatures where the conditions are closer to an equilibrium between the gas-phase and condensed-phase PAHs. It is demonstrated that efficiency-based models are ill-suited to model PAH clustering due to the lack of explicitly modeling the reverse rates of clustering. The newly developed FRPC model represents the first step in a piece-wise development of a carbon nanoparticle formation model. ▪

Analysis of gaseous polycyclic aromatic hydrocarbon emissions from cooking devices in selected rural and urban kitchens in Bomet and Narok counties of Kenya.

Traditional combustion devices and fuels such as charcoal, wood and biomass, are widely utilised in rural and urban households in Africa. Incomplete combustion can generate air pollutants which are of human toxicological importance, including polycyclic aromatic hydrocarbons (PAHs). In this study, portable multi-channel polydimethylsiloxane rubber traps were used to sample gas phase emissions from cooking devices used in urban and rural households in Bomet and Narok counties of Kenya. A wide range of total PAH concentrations was found in samples collected (0.82 - 173.69 µg/m3), which could be attributed to the differences in fuel type, combustion device, climate, and nature of households. Wood combustion using the 3-stone device had the highest average total PAH concentration of ~71 µg/m3. Narok had higher indoor total gas phase PAH concentrations averaging 35.88 µg/m3 in urban and 70.84 µg/m3 in rural households, compared to Bomet county (2.91 µg/m3 in urban and 9.09 µg/m3 in rural households). Ambient total gas phase PAH concentrations were more similar (Narok: 1.26 - 6.28 µg/m3 and Bomet: 2.44 - 6.30 µg/m3). Although the 3-stone device and burning of wood accounted for higher PAH emissions, the charcoal burning jiko stove produced the highest toxic equivalence quotient. Monitoring of PAHs emitted by these cooking devices and fuels is critical to public health and sustainable pollution mitigation.

Changes and distribution of gas-phase polycyclic aromatic hydrocarbons and organochlorine compounds in a high-mountain gradient over a three-year period (Pyrenees, 2017–2020)

The atmospheric gas-phase concentrations of several polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), hexachlorobenzene (HCB), and pentachlorobenzene (PeCB) were measured in six high-mountain sites in the Pyrenees (1619–2453 m). Polyurethane foam passive air samplers were used for this purpose, providing continuous records spanning over three years (2017–2020). The mean concentrations of ∑PCBs, HCB, and PeCB, 13 ± 4 pg m−3, 44 ± 18 pg m−3, and 23 ± 20 pg m−3, respectively, were of the order of those reported in other mountain sites and similar to those measured 20 years ago in the same area, evidencing the persistence of these compounds despite the international regulatory actions. The mean concentration of ∑PAHs was 631 ± 238 pg m−3, representing between two- and three-times lower values than 20 years ago in the same area, but still in the range of other mountain regions. Statistically significant increases in gas-phase concentrations at higher temperatures were observed for most compounds. The experimental phase-change pseudo-enthalpies calculated from the slopes of the regressions between the natural logarithm of the concentrations and the reciprocal of temperature were lower than the reference values for nearly all compounds. This difference suggested a main contribution of long-range atmospheric transport of the gas-phase PAH and organochlorine concentrations in this mountain area. However, the less volatile compounds such as benz[a]anthracene, PCB138, and PCB180 showed a closer similarity between experimental and laboratory enthalpies, indicating that a significant portion of the variations in concentration of these compounds originated from temperature-dependent diffusive exchange by re-volatilization from local surfaces. The concentrations found in these sentinel ecosystems demonstrate that long-range transport of organic pollutants remains a risk in remote continental environments.

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.

Comparison of indoor and outdoor polycyclic aromatic hydrocarbons from multiple urban residences in Northern China: Coastal versus inland area

Passive air and dust samples were simultaneously collected from urban residences in three functional areas at a coastal site (Weihai) and an inland site (Heze) in Northern China. Samples were concurrently collected in bedrooms, kitchens, and an adjacent outdoor area for each home during the non-heating and heating seasons. Nineteen polycyclic aromatic hydrocarbons (PAHs) were studied by gas chromatography-mass spectrometry (GC-MS). The higher concentrations of PAHs occurred in inland than coastal and industrial area than other districts. The PAHs were more concentrated in outdoor air samples in both cities, but the opposite trend was observed in the dust samples. Compared with bedrooms, higher concentrations of gas-phase PAHs occurred in kitchen. PHE (36.4%) and FLU (18.0%) were the dominant PAHs measured in air samples, whereas middle molecular weight PAHs (34.0%) and high molecular weight PAHs (44.3%) were greater in dust bound PAHs. The I/O ratios of 2–3 rings PAHs in the air were greater than 4–7 rings in both cites indicating that indoor sources had a greater impact on low molecular weight PAHs. The positive matrix factorization (PMF) model identified vehicle exhaust and biomass/coal combustion as the main PAH sources in both outdoor air and dust samples while cooking and solvent use contributed more to indoor samples. Dermal contact with dust accounted for 79.1–85.1% of the total incremental lifetime cancer risk (ILCR) in the study area. Children's ingestion risk was 1.34 and 1.37 times that of adults for both indoor and outdoor sampling areas, respectively.

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.