Sources Of Aromatic Hydrocarbons Research Articles

A novel biomass pyrogenic index and its application coupled with black carbon for improving polycyclic aromatic hydrocarbon source identification.

To accurately subdivide the sources of polycyclic aromatic hydrocarbons (PAHs), the composition characteristics of 36 total polycyclic hydrocarbons (T-PAHs; 16 parent PAHs and 20 alkylated PAHs [A-PAHs]) in biomass-residue samples were analyzed. A novel biomass pyrogenic index (BPI) was defined based on A-PAH-fingerprinting differences between biomass-combustion and petroleum sources of PAHs and the sum of the concentrations of pyrene, fluoranthene, benzo[a]anthracene, and alkylated homologs) divided by the ∑value of EPA PAHs with 2-3 rings. BPIs of < 0.5 and > 0.5 indicated that the PAHs originated mainly from biomass combustion and petroleum, respectively. And the ∑targeted A-PAH pairs influencing the BPI/black carbon (BC) ratio was used to identify PAH sources in surface-sediment samples, using 0.5 as the threshold to distinguish between different sources across the strait. The columnar sediments were used to verify the accuracy of two source-identification methods. The results revealed that the main PAH sources changed since 2005, which is highly consistent with those obtained using positive matrix factors and a changing trend in the main types of local energy use. These results highlight the significance of A-PAHs in accurately identifying PAH sources and suggest that applying compositional differences in BC from different sources for PAH-source identification merits further study.

Simple lignin-based, light-driven shape memory polymers with excellent mechanical properties and wide range of glass transition temperatures

Lignin is the most abundant biomass source of aromatic hydrocarbons but, at present, is not effectively utilized. The development of simple and efficient methods for producing lignin-based polymers to replace petroleum-based products is an important strategy for promoting environmentally friendly and sustainable materials and controlling carbon emissions. In this work, lignin-based, light-driven shape memory polymers (ELIDs) with improved mechanical properties have been prepared from enzymatic hydrolysis lignin, itaconic acid and 1,12-dodecanediol, without any chemical modification of the lignin. The polymers contain large proportions of lignin (20–40 wt%, designated ELID20 to ELID40) and their mechanical properties are dependent on the lignin content. Maximum tensile strength (46.9 MPa) was achieved with ELID30, maximum elongation at break (93.7 %) was achieved with ELID20 and highest fracture energy (10.75 J cm−3) was achieved with ELID25. These excellent mechanical properties are accompanied by good thermal stability and a wide range of glass transition temperatures (21.2–157.3 °C), supporting a broad range of applications. The shape fixation rate (Rf) and shape recovery rate (Rr) were highest for ELID30 (98.7 % and 97.4 %, respectively). Under 1 sun simulated solar irradiation, ELID20 reached a temperature exceeding the glass transition temperature in 15 s and, under 3 sun simulated solar irradiation, ELID30 reached a temperature of 130 °C and shape recovered in 60 s. The excellent mechanical properties and good light-driven shape memory of ELIDs provide inspiration for the development and utilization of lignin-based polymers.

A multivariate approach to polycyclic aromatic hydrocarbon source apportionment in Connecticut, USA using compound-specific isotopic compositions

A multivariate approach to polycyclic aromatic hydrocarbon source apportionment in Connecticut, USA using compound-specific isotopic compositions

Geochemical investigation of hydrocarbon generation potential of coal from Raniganj Basin, India

Methane content in a coal seam is a necessary parameter for evaluating coal bed gas, and it poses an environmental risk to underground coal mining activities. Keeping in pace with comprehensive studies of coal bed gas, 12 coal samples were selected from the Sitarampur block of Raniganj Coalfield for analysis. The Petrographic examination illustrated that significant values of reactive macerals present in samples demonstrate that organic matter is dominated by the prominent source of aromatic hydrocarbons with a minor proportion of aliphatic hydrocarbon, which falls in the region of (Type III) kerogen, confirms the suitability for the potential of hydrocarbon generation. “A” factor (aliphatic/aromatic bands) and “C” factor (carbonyl/carboxyl bands) value concluded that the sample has the lowest aromaticity and the highest hydrocarbon-generating potential, which was also validated by the Van Krevelen diagram. The Van Krevelen diagram plots between the H/C and O/C ratio indicate that coal samples lie in the type III kerogen, and bituminous coal (gas prone zone) is present in the block, which is confirmed by the cross-plot between desorbed and total gas (cc/g). The in situ gas content values are high enough to produce methane from coal beds. The overall study concludes that the Sitarampur block from Raniganj Coalfield is suitable for hydrocarbon generation and extraction.

Polycyclic aromatic hydrocarbon source fingerprints in the environmental samples of Anzali-South of Caspian Sea.

The major emission sources of polycyclic aromatic hydrocarbons (PAHs) in Anzali city, apportionment of these sources and transfer of PAHs through street dust and runoff to rivers and finally the Caspian Sea, were studied. PAHs in environmental samples including street dust, runoff, and river sediment samples as well as in major sources of hydrocarbons in urban area including vehicles exhaust, gasoline and diesel fuels, engine oils of automobiles and boats, asphalt, and tire debris were extracted by Soxhlet and liquid-liquid extraction in solid and liquid phase and were analyzed by GC-MS. Significance of each source in PAH emission in the area was identified by chemical fingerprinting. According to the spatial distribution of PAHs in receptor samples stations of street dust and runoff located in the center of the city with high traffic of vehicles had higher concentrations of PAHs than stations in the out bonds of the city. In the river sediment samples, the stations located in the port area had the highest concentrations of PAHs. Results of chemical fingerprinting showed that especially in street dust and runoff samples, the isometric patterns of PAHs were rather similar to those in the proposed major sources, showing that they may have been originated from them, especially from asphalt and tire. On the contrary, river sediment samples were confirmed to receive inputs from other unknown independent sources.

Lionfish (Pterois volitans) as biomonitoring species for oil pollution effects in coral reef ecosystems

With oil spills, and other sources of aromatic hydrocarbons, being a continuous threat to coral reef systems, and most reef fish species being protected or difficult to collect, the use of the invasive lionfish (Pterois volitans) might be a good model species to monitor biomarkers in potentially exposed fish in the Caribbean and western Atlantic. The rapid expansion of lionfish in the Caribbean and western Atlantic, and the unregulated fishing for this species, would make the lionfish a suitable candidate as biomonitoring species for oil pollution effects. However, to date little has been published about the responses of lionfish to environmental pollutants. For this study lionfish were collected in the Florida Keys a few weeks after Hurricane Irma, which sank numerous boats resulting in leaks of oil and fuel, and during the winter and early spring after that. Several biomarkers indicative of exposure to PAHs (bile fluorescence, cytochrome P450-1A induction, glutathione S-transferase activity) were measured. To establish if these biomarkers are inducible in PAH exposed lionfish, dosing experiments with different concentrations of High Energy Water Accommodated Fraction of crude oil were performed. The results revealed no significant effects in the biomarkers in the field collected fish, while the exposure experiments demonstrated that lionfish did show strong effects in the measured biomarkers, even at the lowest concentration tested (0.3% HEWAF, or 25 μg/l ƩPAH50). Based on its widespread distribution, relative ease of collection, and significant biomarker responses in the controlled dosing experiment, it is concluded that lionfish has good potential to be used as a standardized biomonitoring species for oil pollution in its neotropical realm.

Direct Growth of Substrate-Adhered Graphene on Flexible Polymer Substrates for Soft Electronics

This article describes a novel method of growing graphene directly on a flexible substrate at low temperatures using plasma-enhanced chemical vapor deposition with a solid aromatic hydrocarbon source, 1,2,3,4-tetraphenylnaphthalene (TPN), which acts as the feedstock for graphene growth. TPN is embedded with copper ions that are reduced under the growth conditions to copper nanoparticles that catalyze the graphene growth and then evaporate to leave pristine graphene. Strong covalent bonds between the TPN film and the flexible substrate, prepared by depositing an aluminum oxide (Al2O3) layer on a colorless polyimide layer, are generated by exposing the TPN film to ultraviolet/ozone. The TPN/substrate interfacial adhesive bonds impede the sublimation of TPN from the flexible substrate at the growth temperature, and TPN can convert directly to graphene. The synthesized substrate-adhered graphene shows excellent bending stability, with small electrical resistance changes (the resistance R during bending over i...

Monocyclic aromatic hydrocarbons production from catalytic cracking of pine wood-derived pyrolytic vapors over Ce-Mo2N/HZSM-5 catalyst

A series of Mo2N/HZSM-5 and transition metal modified Mo2N/HZSM-5 catalysts were prepared for the catalytic upgrading of pine wood-derived pyrolytic vapors for the selective production of monocyclic aromatic hydrocarbons (MAHs), while restraining the formation of polycyclic aromatic hydrocarbons (PAHs). Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were performed to determine the effects of several factors on selective MAHs production, including Mo2N loading on HZSM-5, transition metal (Fe, Ce, La, Cu, Cr) modification of Mo2N/HZSM-5, pyrolysis temperature, and catalyst-to-biomass ratio. In addition, quantitative experiments were conducted to determine the actual yields of major aromatic hydrocarbons and the source of aromatic hydrocarbons from basic biomass components. Results indicated that among the various catalysts, the Ce-10%Mo2N/HZSM-5 exhibited the best performance on promoting the formation of MAHs and restraining the generation of PAHs. Under the optimal conditions, the actual yields of MAHs and PAHs from Ce-10%Mo2N/HZSM-5 catalytic process were 99.8mg/g and 7.5mg/g, while those from HZSM catalyst were only 77.2mg/g and 23.7mg/g respectively. Furthermore, the possible catalytic mechanism of the Ce-Mo2N/HZSM-5 catalyst was proposed based on the catalyst characterization.

Characterization and Sources of Aromatic Hydrocarbons (BTEX) in the Atmosphere of Two Urban Sites Located in Yucatan Peninsula in Mexico

Benzene, toluene, ethylbenzene, p-xylene, O3, NOx, CO, PM2.5 and meteorological parameters were measured in urban air of two sites in Merida, Yucatan, Mexico during 2016–2017. Samples were collected using 1.5 h time intervals at three different sampling periods before being analyzed by gas chromatography with flame ionization detection. The highest concentrations of BTEX occurred during midday and afternoon in spring and summer seasons. Mean concentrations of, BTEX for the Cholul and SEDUMA sites, respectively, were 40.91 μg/m3 and 32.86 μg/m3 for benzene; 6.87 μg/m3 and 3.29 μg/m3 for toluene; 13.87 μg/m3 and 8.29 μg/m3 for p-xylene; and 6.23 μg/m3 and 4.48 μg/m3 for ethylbenzene. The toluene/benzene and xylene/ethylbenzene concentration ratios indicated that BTEX levels at both sites were influenced by local and fresh emissions (vehicular traffic). Bivariate and multivariate analyses were performed in order to correlate BTEX concentrations with criteria air pollutants to infer their possible sources. Health risk assessment revealed that exposure to benzene exceeded the recommended value for the integrated lifetime cancer risk. These results suggest that Merida’s population is exposed to cancer risk, and changes in the existing environmental policies should therefore be applied to improve air quality.

Pyrolysis mechanism of microalgae Nannochloropsis sp. based on model compounds and their interaction

Pyrolysis is one of important pathways to convert microalgae to liquid biofuels and key components of microalgae have different chemical composition and structure, which provides a barrier for large-scale microalgae-based liquid biofuel application. Microalgae component pyrolysis mechanism should be researched to optimal pyrolysis process parameters. In this study, single pyrolysis and co-pyrolysis of microalgal components (model compounds castor oil, soybean protein and glucose) were conducted to reveal interaction between them by thermogrametric analysis and bio-crude evaluation. Castor oil (model compound of lipid) has higher pyrolysis temperature than other model compounds and has the maximum contribution to bio-crude formation. Bio-crude from soybean protein has higher N-heterocyclic compounds as well as phenols, which could be important aromatic hydrocarbon source during biorefineries and alternative aviation biofuel production. Potential interaction pathways based on model compounds are recommended including further decomposition of Maillard reaction products (MRPs) and surfactant synthesis, which indicate that glucose played an important role on pyrolysis of microalgal protein and lipid components. The results should provide necessary information for microalgae pyrolysis process optimization and large-scale pyrolysis reactor design.

From diverse polycyclic aromatic molecules to interconnected graphene nanocapsules for supercapacitors

3D interconnected graphene nanocapsules (IGNCs) were prepared by a template strategy coupled with in-situ chemical activation technique via using diverse polycyclic aromatic molecules as building blocks for supercapacitors. Benefiting from the synergistic effects of nano-MgO-template and in-situ KOH activation, the 3D IGNCs feature seemingly incompatible advantages of conductive and porous properties, possessing interconnected thin networks for high electron conduction, short hierarchical pores for fast ion transport, and abundant accessible active sites for ion adsorption. The specific surface area, pore size and pore volume mainly depend on the mass of raw materials and the annealing temperatures. When evaluated as electrodes for supercapacitors, IGNCs exhibit remarkably enhanced electrochemical characteristics such as high capacitance, good rate performance and cycle stability. This work opens up a facile way for high-efficiency preparation of 3D IGNCs from diverse aromatic hydrocarbon sources for energy storage to substitute conventional porous carbons.

Extraction of aromatic hydrocarbons from pyrolysis gasoline using tetrathiocyanatocobaltate-based ionic liquids: Experimental study and simulation

The pyrolysis gasoline is one of the main sources of aromatic hydrocarbons as a result of their high content in these compounds. Organic solvents such as sulfolane are currently employed in the extraction of aromatic but the ionic liquids (ILs) have been recently proposed as potential replacement. In this work, we have studied the use of the bis(1-ethyl-3-methylimidazolium) tetrathiocyanatocobaltate ([emim]2[Co(SCN)4]) and bis(1-butyl-3-methylimidazolium) tetrathiocyanatocobaltate ([bmim]2[Co(SCN)4]) ILs in the extraction of aromatic hydrocarbons from pyrolysis gasoline. The extractive properties of both tetrathiocyanatocobaltate-based ILs were compared to those of other promising ILs and sulfolane, showing the highest values. To perform the simulation of the whole process, we have experimentally studied the liquid-liquid extraction of aromatics from pyrolysis gasoline and the recovery of the extracted hydrocarbons from the ILs. In addition, a thermophysical characterization of the ionic solvents was performed measuring their densities, viscosities, thermal stabilities, maximum operation temperatures, and specific heats. Employing the experimental data, the extractor was simulated using the Kremser equation whereas the recovery section formed by flash distillation units was simulated using a new algorithm specifically design to the case of a high concentration of non-volatile compounds.

ZnO template strategy for the synthesis of 3D interconnected graphene nanocapsules from coal tar pitch as supercapacitor electrode materials

Abstract 3D interconnected graphene nanocapsules (GNCs) were prepared from diverse aromatic hydrocarbons by a nano-ZnO-template strategy coupled with in-situ KOH activation technique. The as-made graphene networks feature thin carbonaceous shells with well-balanced micropores and mesopores. Such 3D porous networks provide freeways for good electron conduction, short pores for ion fast transport, and abundant micropores for ion adsorption. As the electrodes in supercapacitors, the unique 3D GNCs show a high capacitance of 277 F g −1 at 0.05 A g −1 , a good rate performance of 194 F g −1 at 20 A g −1 , and an excellent cycle stability with over 97.4% capacitance retention after 15000 cycles in 6 M KOH electrolyte. This synthesis strategy paves a universal way for mass production of 3D graphene materials from diverse aromatic hydrocarbon sources including coal tar pitch and petroleum pitch for high performance supercapacitors as well as support and sorbent.

Particulate-bound polycyclic aromatic hydrocarbon sources and determinants in residential homes

Human exposure to polycyclic aromatic hydrocarbons (PAHs) in indoor environments can be particularly relevant because people spend most of their time inside buildings, especially in homes. This study aimed to investigate the most important particle-bound PAH sources and exposure determinants in PM2.5 samples collected in 19 homes located in northern Italy. Complementary information about ion content in PM10 was also collected in 12 of these homes. Three methods were used for the identification of PAH sources and determinants: diagnostic ratios with principal component and hierarchical cluster analyses (PCA and HCA), chemical mass balance (CMB) and linear mixed models (LMMs). This combined and tiered approach allowed the infiltration of outdoor PAHs into indoor environments to be identified as the most important source in winter, with a relevant role played by biomass burning and traffic exhausts to be identified as a general source of PAHs in both seasons. Tobacco smoke exhibited an important impact on PAH levels in smokers' homes, whereas in the whole sample, cooking food and natural gas sources played a minor or negligible role. Nitrate, sulfate and ammonium were the main inorganic constituents of indoor PM10 owing to the secondary formation of ammonium sulfates and nitrates.

Sustained deposition of contaminants from the Deepwater Horizon spill

The 2010 Deepwater Horizon oil spill resulted in 1.6-2.6 × 10(10) grams of petrocarbon accumulation on the seafloor. Data from a deep sediment trap, deployed 7.4 km SW of the well between August 2010 and October 2011, disclose that the sinking of spill-associated substances, mediated by marine particles, especially phytoplankton, continued at least 5 mo following the capping of the well. In August/September 2010, an exceptionally large diatom bloom sedimentation event coincided with elevated sinking rates of oil-derived hydrocarbons, black carbon, and two key components of drilling mud, barium and olefins. Barium remained in the water column for months and even entered pelagic food webs. Both saturated and polycyclic aromatic hydrocarbon source indicators corroborate a predominant contribution of crude oil to the sinking hydrocarbons. Cosedimentation with diatoms accumulated contaminants that were dispersed in the water column and transported them downward, where they were concentrated into the upper centimeters of the seafloor, potentially leading to sustained impact on benthic ecosystems.

Effect of Polycyclic Aromatic Hydrocarbon Source Materials and Soil Components on Partitioning and Dermal Uptake.

The bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soils can be influenced by the source material they are emitted within, the properties of the receiving soil, weathering processes, and the concentration of PAHs. In this study 30 contaminated soils were constructed with common PAH sources (fuel oil, soot, coal tar based skeet particles) and direct spike with a solvent added to different types and contents of soil organic matter and minerals to achieve PAH concentrations spanning 4 orders of magnitude. Source material had the greatest impact on PAH partitioning. Soils containing skeet generally exhibited the highest KD values, followed by soot, fuel oil, and solvent spiked soils. Among all soil compositions, the presence of 2% charcoal had the largest enhancement of KD. Partitioning behavior could not be predicted by an organic carbon and black carbon partitioning model. Including independently measured partitioning behavior of the soil components and PAH sources allowed better prediction but still suffered from issues of interaction (oil sorption in peat) and highly nonlinear partitioning with depletion (for skeet). Dermal absorption of PAHs measured using pig skin was directly related to the freely dissolved aqueous concentration in soil and not the total concentration in the soil. Overall, we show that PAH source materials have a dominating influence on partitioning, highlighting the importance of using native field soils in bioavailability and risk assessments.

Problems in the fingerprints based polycyclic aromatic hydrocarbons source apportionment analysis and a practical solution

This work intended to explain the challenges of the fingerprints based source apportionment method for polycyclic aromatic hydrocarbons (PAH) in the aquatic environment, and to illustrate a practical and robust solution. The PAH data detected in the sediment cores from the Illinois River provide the basis of this study. Principal component analysis (PCA) separates PAH compounds into two groups reflecting their possible airborne transport patterns; but it is not able to suggest specific sources. Not all positive matrix factorization (PMF) determined sources are distinguishable due to the variability of source fingerprints. However, they constitute useful suggestions for inputs for a Bayesian chemical mass balance (CMB) analysis. The Bayesian CMB analysis takes into account the measurement errors as well as the variations of source fingerprints, and provides a credible source apportionment. Major PAH sources for Illinois River sediments are traffic (35%), coke oven (24%), coal combustion (18%), and wood combustion (14%).

Combination of Unmix and positive matrix factorization model identifying contributions to carcinogenicity and mutagenicity for polycyclic aromatic hydrocarbons sources in Liaohe delta reed wetland soils, China

Surface soils were collected from Liaohe delta, China, the largest reed wetland in the world dominated by common reed (Phragmites australis). Samples were analyzed for sixteen priority polycyclic aromatic hydrocarbons (PAHs) by GC/MS. The potential source patterns and source contributions to seven carcinogenic PAH congeners were performed by combining of Unmix and positive matrix factorization (PMF) model with the formula of toxic equivalent quantity (TEQBaP) and mutagenic equivalent quantity (MEQBaP), respectively. Four source categories, including petrogenic source, biomass burning, diesel emission and coal combustion, were identified by Unmix and PMF models. For both Unmix and PMF model, the mixed sources (gasoline and diesel engine emission) contributed the most to the TEQBaP and MEQBaP, while petrogenic source, the largest contributor for PAHs, made lower contribution to TEQBaP and MEQBaP. Minor source contribution difference was found between two models, which might be attributed to uncertainties model parameters and species variables. Hence, it is very essential to use combined source apportionment techniques for quantitatively identifying PAHs sources and estimated their carcinogenicity and mutagenicity.

Evaluation of aromatic oxidation reactions in seven chemical mechanisms with an outdoor chamber

Environmental context Regulatory air quality models used to develop strategies to reduce ozone and other pollutants must be able to accurately predict ozone produced from aromatic hydrocarbons. In urban areas, major sources of aromatic hydrocarbons are gasoline and diesel-powered vehicles. Our findings show that the representation of aromatic hydrocarbon chemistry in air quality models is an area of high uncertainty Abstract Simulations using seven chemical mechanisms are intercompared against O3, NOx and hydrocarbon data from photooxidation experiments conducted at the University of North Carolina outdoor smog chamber. The mechanisms include CB4–2002, CB05, CB05-TU, a CB05 variant with semi-explicit aromatic chemistry (CB05RMK), SAPRC07, CS07 and MCMv3.1. The experiments include aromatics, unsaturated dicarbonyls and volatile organic compound (VOC) mixtures representing a wide range of urban environments with relevant hydrocarbon species. In chamber simulations the sunlight is characterised using new solar radiation modelling software. A new heterogeneous chamber wall mechanism is also presented with revised chamber wall chemical processes. Simulations from all mechanisms, except MCMv3.1, show median peak O3 concentration relative errors of less than 25% for both aromatic and VOC mixture experiments. Although MCMv3.1 largely overpredicts peak O3 levels, it performs relatively better in predicting the peak NO2 concentration. For aromatic experiments, all mechanisms except CB4–2002, largely underpredict the NO–NO2 crossover time and over-predict both the absolute NO degradation slope and the slope of NO2 concentration rise. This suggests a major problem of a faster and earlier NO to NO2 oxidation rate across all the newer mechanisms. Results from individual aromatic and unsaturated dicarbonyl experiments illustrate the unique photooxidation chemistry and O3 production of several aromatic ring-opening products. The representation of these products as a single mechanism species in CB4–2002, CB05 and CB05-TU is not adequate to capture the O3 temporal profile. In summary, future updates to chemical mechanisms should focus on the chemistry of aromatic ring-opening products.

Comparison of aromatics released via hydropyrolysis with their solvent extractable counterpart for biodegraded Nigeria crude oil

The molecular profiles of aromatics generated through hydropyrolysis with the free (maltene) counterpart were compared, with a view to assessing the effectiveness of using molecular information for the aromatics bound in asphaltene matrix for polycyclic aromatic hydrocarbon source apportionment studies. The results obtained from gas chromatograph-mass spectrometry (GC-MS) total and selected ion molecular profiles of free and bound aromatics for Nigeria crude oil shows that the solvent extractible aromatics has either been heavily biodegraded or covered by humic materials arising from microbial activity and will therefore need further purification to resolve the aromatic hydrocarbons present. However, the aromatics released via hydropyrolysis (trapped in asphaltene matrix) are still preserved. The molecular profile of asphaltene derived aromatics is highly dominated by both alkylated parent and parent polycyclic aromatic hydrocarbons such as methyl fluoranthene and pyrene, benzo (b/k) fluoranthene. Key words: Crude oil, aromatics, hydropyrolysis.