Half-life Of Polycyclic Aromatic Hydrocarbons Research Articles

Distributions of PAHs, NPAHs, OPAHs, BrPAHs, and ClPAHs in air, bulk deposition, soil, and water in the Shandong Peninsula, China: Urban-rural gradient, interface exchange, and long-range transport

A systematic study of the movement of PAHs (Polycyclic aromatic hydrocarbons) and their derivatives through air, soil, and water is key to understanding the exchange and transport mechanisms of these pollutants in the environment and for ultimately improving environmental quality. PAHs and their derivatives, such as nitrated PAHs (NPAHs), oxygenated PAHs (OPAHs), brominated PAHs (BrPAHs) and chlorinated PAHs (ClPAHs), were analyzed in air, bulk deposition, soil, and water samples collected from urban, rural, field, and background sites on the eastern coast of China. The goal was to investigate and discuss their spatiotemporal variations, exchange fluxes, and transport potential. The concentrations of PAHs and their derivatives in the air and bulk deposition displayed distinct seasonal patterns, with higher concentrations observed during the winter and spring and lower concentrations during the summer and autumn. NPAHs exhibited the opposite trend. Significant urban-rural gradients were observed for most of the PAHs and their derivatives. According to the air-soil fugacity calculations, 2–3 ring PAHs, BrPAHs, and ClPAHs were found to volatilize from the soil into the air, while 4–7 ring PAHs, OPAHs, and NPAHs deposited from the air into the soil. The air-water fugacity of the PAHs and their derivatives indicated that surface water was an important source for the ambient atmosphere in Qingdao. The characteristic travel distances (CTDs) and persistence (Pov) for atmospheric transport were much lower than that for the water samples, which may be due to the longer half-lives of PAHs and their derivatives in water. NPAHs and ClPAHs with long transport distances and strong persistence in water could lead to a significant impact on marine pollution.

Optimization of the photocatalytic degradation process of aromatic organic compounds applied to mangrove sediment

Polycyclic aromatic hydrocarbons (PAHs) are part of a class of organic compounds resistant to natural degradation. In this way, heterogeneous photocatalysis becomes useful to degrade persistent organic pollutants, however it can be influenced by environmental variables (i.e.: organic matter) and experimental factors such as: mass of the photocatalyst and irradiation time. The objective of this research was to use a factorial design 2k as a function of the multiple response (MR) to evaluate simultaneously experimental conditions for the photodegradation of polycyclic aromatic hydrocarbons in contaminated mangrove sediment and its application in oil from Potiguar Basin in Brazil. The sediment samples collected in Belmonte city (Southern Bahia state) were contaminated with 0.25 mg kg−1 of Acenaphthene, Anthracene, Benzo[a]Anthracene, Indene[1,2,3cd]pyrene, Dibenzo[ah]anthracene, Benzo[ghi]pyrene. Factors such as mass of the photocatalyst and irradiation time were evaluated in factorial design 22, with triplicate from the central point, to 1g of the PAH contaminated sediment. After performing the experiments, it was found that the best experimental condition for the degradation of all PAHs indicated by MR was the central point (0.5 g of photocatalyst and 12h of irradiation). For such conditions, the half-life of PAHs varied from 3.51 to 9.37 h and the degradation speed constant between 0.0740 to 0.1973 h−1. The comparison of the optimized methodology between photolysis tests and heterogeneous photocatalysis was performed using the Kruskal-Wallis test, which indicated a difference for the reference solution, where heterogeneous photocatalysis was more efficient in the degradation of PAHs. The optimized methodology was apply in samples contaminated with crude oil from Potiguar Basin, no significant difference was observed in the aromatic fraction, using for the Kruskal-Wallis test. Heterogeneous photocatalysis has shown to be a promising remediation technique to remedy aromatic organic compounds in mangrove sediments.

Modelling PAHs Transfer from Polluted Soil to Herbaceous Species in Phytoremediation Attempts

To address the soil–plant transfer modelling of 13 US-EPA Polycyclic Aromatic Hydrocarbons (PAHs), a mechanistic model—MM_19—has been developed based on the fugacity concept. For that, the Mackay_97 model has been improved in terms of reconsidering the losses related to the transport and transformation mechanisms taking place in the compartments—roots and aboveground shoots—of the three short-life species (Eleusine indica, Cynodon dactylon and Alternanthera sessilis). Model input parameters consist of both experimental and literature data, including the initial soil and air PAHs content, flowrates, PAHs physico-chemical properties, retention times and transport half-lives of PAHs inside plant species. Using in situ weather data and Penman’s law, xylem flows were estimated as the evapotranspiration for each plant. Model calibration was performed using a Generalized Reduced Gradient (GRG) nonlinear optimization solver method. Sensitivity analysis showed that the phloem flow was the most sensitive among all tested parameters. According to the Nash–Sutcliffe efficiency (NSE), the MM_19 model is more efficient than the Mackay_97 model for all three plant species. Finally, the impact of PAHs physico-chemical parameters on their sol-plant transfer was discussed in terms of slight, intermediate and high molecules weight. The NSE values showed that the MM_19 model is more efficient than the Mackay_97 model. Indeed, comparisons between experimental and simulated results in the MM_19 model showed similarities for each compartment of the plant species. Thus, the MM_19 model can be used to predict the soil–plant transfer of organic pollutants.

Biodegradation of aged polycyclic aromatic hydrocarbons in agricultural soil by Paracoccus sp. LXC combined with humic acid and spent mushroom substrate.

Paracoccus sp. LXC combined with humic acid (HA) and spent mushroom substrate (SMS) obtained from Auricularia auricular and Sarcomyxa edulis was tested for the remediation of agricultural soil contaminated with aged polycyclic aromatic hydrocarbons (PAHs). The biomass and diversity of bacteria and fungi and the soil enzyme activity were analyzed. PAH removal and dissipation kinetics were examined. The highest degradation rate of PAHs was 56.5% when soil was amended with Paracoccus sp. LXC combined with HA and unsterilized SMS from A. auricular. The half-life of PAHs decreased from 2323.3 days in natural attenuation to 66.6-277.2 days in amended treatments. Soil treated with Paracoccus sp. LXC combined with HA and SMS from A. auricular acquired high contents of organic matter and nutrients. HA and SMS aided the growth of PAH-degrading bacteria and promoted the diversity of bacteria but not of fungi. The degradation rate of PAHs was mainly correlated positively with soil laccase activity. Low- and middle-molecular-weight PAHs were significantly removed by Paracoccus sp. LXC, HA and SMS. High-molecular-weight PAHs were removed by SMS but not by Paracoccus sp. LXC. Biodegradation by Paracoccus sp. LXC combined with HA and SMS is a promising choice for remediating aged PAH-contaminated agricultural soils.

Association of atmospheric concentrations of polycyclic aromatic hydrocarbons with their urinary metabolites in children and adolescents.

This study aims to determine the atmospheric concentrations of particulate matter 2.5 (PM2.5)-bounded polycyclic aromatic hydrocarbons (PAHs) and their association with their urinary metabolites in children and adolescents. This study was conducted from October 2014 to March 2016 in Isfahan, Iran. We measured 16 species of PAHs bounded to PM2.5 by gas chromatography mass spectrometry (GC/MS) from 7 parts of the city. Moreover, PAH urinary metabolites were measured in 186 children and adolescents, randomly selected from households. Urinary metabolites consisted of 1-hydroxy naphthalene (1-naphthol), 2-hydroxy naphthalene (2-naphthol), 9-hydroxy phenanthrene (9-phenanthrol), and 1-hydroxy pyrene using GC/MS. Considering the short half-lives of PAHs, we measured the metabolites twice with 4 to 6months of time interval. We found that the ambient concentrations of PAHs were significantly associated with their urinary metabolites. 1-hydroxy naphthalene and 2-hydroxy naphthalene concentrations showed an increase of 1.049 (95% CI: 1.030, 1.069) and 1.047 (95% CI: 1.025, 1.066) for each unit increase (1ng/m3) in ambient naphthalene. Similarly, 1-hydroxy pyrene showed an increase of 1.009 (95% CI: 1.006-1.011) for each unit increase (1ng/m3) in ambient pyrene concentration after adjustment for body mass index, physical activity level, urinary creatinine, age, and sex. The association of urinary 9-hydroxyphenanthrene and ambient phenantherene was significant in the crude model; however after adjustment for the abovementioned covariates, it was no more significant. We found significant correlations between exposure to ambient PM2.5-bounded PAHs and their urinary excretion. Considering the adverse health effects of PAHs in the pediatric age group, biomonitoring of PAHs should be underscored; preventive measures need to be intensified.

Study of Kinetics Mechanism of PAHs Photodegradation in Solution

As a typical group of persistent organic pollutants, polycyclic aromatic hydrocarbons (PAHs) are widely distributed and persistent in ecological environment via environmental media (e.g. air, soil, water, suspended solids, organisms, etc.), causing great damage to organisms. Its fate and transportation from surface water to aquifers has attracted more and more attention. As PAHs in surface water or in topsoil will undergo photochemical reactions, a self-designed cylindrical photodegradation reactor has been designed to study the photodegradation of PAHs in aqueous solutions in this study. The results have shown that PAHs degrade rapidly under the lighting conditions. Pseudo-first-order kinetics was observed for degradation of fluorene (FLU), phenanthrene (PHE) and pyrene (PYR), as indicated by linear relations between ln (C0/Ct) and time. The reaction kinetics constants of FLU, PHE and PYR were 0.031, 0.045, 0.017 min-1 respectively, and the photolysis half-lives of PAHs are only several minutes (FLU, 4.17min; PHE, 3.79min; PYR 4.77min). Their photolysis rates following the decreasing order PHE > FLU > PYR is due to their different absorption spectrum and peak values under the UV-light.

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O<sub>3</sub>, NO<sub>2</sub>, H<sub>2</sub>O, OH and NO<sub>3</sub>

Abstract. We present a kinetic double-layer surface model (K2-SURF) that describes the degradation of polycyclic aromatic hydrocarbons (PAHs) on aerosol particles exposed to ozone, nitrogen dioxide, water vapor, hydroxyl and nitrate radicals. The model is based on multiple experimental studies of PAH degradation and on the PRA framework (Pöschl-Rudich-Ammann, 2007) for aerosol and cloud surface chemistry and gas-particle interactions. For a wide range of substrates, including solid and liquid organic and inorganic substances (soot, silica, sodium chloride, octanol/decanol, organic acids, etc.), the concentration- and time-dependence of the heterogeneous reaction between PAHs and O3 can be efficiently described with a Langmuir-Hinshelwood-type mechanism. Depending on the substrate material, the Langmuir adsorption constants for O3 vary over three orders of magnitude (Kads,O3 ≈ 10−15–10−13 cm3), and the second-order rate coefficients for the surface layer reaction of O3 with different PAH vary over two orders of magnitude (kSLR,PAH,O3 ≈ 10−18–10−17 cm2 s−1). The available data indicate that the Langmuir adsorption constants for NO2 are similar to those of O3, while those of H2O are several orders of magnitude smaller (Kads,H2O ≈ 10−18–10−17 cm3). The desorption lifetimes and adsorption enthalpies inferred from the Langmuir adsorption constants suggest chemisorption of NO2 and O3 and physisorption of H2O. Note, however, that the exact reaction mechanisms, rate limiting steps and possible intermediates still remain to be resolved (e.g., surface diffusion and formation of O atoms or O3− ions at the surface). The K2-SURF model enables the calculation of ozone uptake coefficients, γO3, and of PAH concentrations in the quasi-static particle surface layer. Competitive adsorption and chemical transformation of the surface (aging) lead to a strong non-linear dependence of γO3 on time and gas phase composition, with different characteristics under dilute atmospheric and concentrated laboratory conditions. Under typical ambient conditions, γO3 of PAH-coated aerosol particles are expected to be in the range of 10−6–10−5. At ambient temperatures, NO2 alone does not efficiently degrade PAHs, but it was found to accelerate the degradation of PAHs exposed to O3. The accelerating effect can be attributed to highly reactive NO3 radicals formed in the gas phase or on the surface. Estimated second-order rate coefficients for O3-NO2 and PAH-NO3 surface layer reactions are in the range of 10−17–10−16 cm2 s−1 and 10−15–10−12 cm2 s−1, respectively. The chemical half-life of PAHs is expected to range from a few minutes on the surface of soot to multiple hours on organic and inorganic solid particles and days on liquid particles. On soot, the degradation of particle-bound PAHs in the atmosphere appears to be dominated by a surface layer reaction with adsorbed ozone. On other substrates, it is likely dominated by gas-surface reactions with OH or NO3 radicals (Eley-Rideal-type mechanism). To our knowledge, K2-SURF is the first atmospheric process model describing multiple types of parallel and sequential surface reactions between multiple gaseous and particle-bound chemical species. It illustrates how the general equations of the PRA framework can be simplified and adapted for specific reaction systems, and we suggest that it may serve as a basis for the development of a general master mechanism of aerosol and cloud surface chemistry.

Modeling and prediction of photolysis half-lives of polycyclic aromatic hydrocarbons in aerosols by quantum chemical descriptors

Quantitative structure-property relationship (QSPR) modeling is a powerful approach for predicting environmental fate parameters of organic pollutants with their structure descriptors. This study reports QSPR models for photolysis half-lives of polycyclic aromatic hydrocarbons (PAHs) in aerosols. Quantum chemical descriptors computed with density functional theory at B3LYP/6-31G(d) level and partial least squares (PLS) analysis with optimizing procedure were used for generating QSPR models. The correlation coefficient of the optimal model was 0.993, and the fitting results showed this optimal model had high fitting precision and good predictability. The predicted photolysis half-lives by the optimal model are very close to those observed. The PLS assistant analysis indicated that PAHs with large electronic spatial extent tend to be photolyzed faster, while PAHs with high molecular total energy and small Mulliken atomic charges on the most negative carbon atom tend to be photolyzed slower in aerosols.

Influence of UV-B Radiation and Temperature on Photodegradation of PAHs: Preliminary Results

The joint impact of UV-B radiation and temperature on photodegradation of polycyclic aromatic hydrocarbons (PAHs) sorbed to an organic solvent was assessed in this study. This approach was experimentally performed in a laboratory investigation by means of comparison of two different environments: Atlantic (Lancaster, UK) and Mediterranean (Tarragona, Catalonia, Spain) climatic conditions. The concentration of 10 PAHs contained in a tetradecane solution was compared under two different temperatures (10 and 20°C) and UV-B doses (6.5 and 22.5 kJ m−2 day−1). No photodegradation was observed for the heaviest hydrocarbons (benzo(a)anthracene, chrysene, benzo(a)pyrene, dibenzo(g,h,i)perylene and coronene). In general terms, the half-life of PAHs was highly dependent on their molecular weight. Significant faster photodegradation rates were detected specially for light PAHs. It indicates that a synergistic effect occurred when both temperature and UV-B dose increased. This synergism might have a great implication on the long-range transport of environmental organic pollutants taking into account that low-latitude areas are the hottest and most irradiated of the planet.

QSPR STUDY ON DIRECT PHOTOLYSIS HALF-LIVES OF PAHs IN WATER SURFACE

Quantitative structure-property relationship (QSPR) modeling is a helpful approach used to correlate the properties of pollutants with their structure descriptors. In this paper a QSPR model for direct photolysis half-lives of polycyclic aromatic hydrocarbons (PAHs) under sunlight on the water surface was developed using density functional theory (DFT) and direct photolysis half-lives of seven PAHs without reported observed values were predicted. The quantum chemical descriptors used in this study were computed at the level of B3LYP/6–311+G(d) and analyzed by partial least squares (PLS) method. The obtained QSPR model with a correlation coefficient of 0.963 was more significant than that derived from semi-empirical molecular orbital algorithm in literatures. It was found that the eigenvalues of the frontier molecular orbital (E HOMO , E LUMO , E NLUMO and E NHOMO ) are important in governing the photolysis half-lives of PAHs in water surface, while the molecular weight (MW) and molecular total energy (TE) also have great effects on photolysis half-lives. The importance of E NLUMO and E NHOMO in the model complicates the photolytic mechanism of PAHs and they might become two useful descriptors in QSPR study on photolysis.

Is it possible to develop a QSPR model for direct photolysis half-lives of PAHs under irradiation of sunlight?

By the use of the partial least squares method and 11 fundamental quantum chemical descriptors computed from the PM3 Hamiltonian, a Quantitative Structure–Property Relationship model was obtained for direct photolysis half-lives of selected polycyclic aromatic hydrocarbons (PAHs) under irradiation of sunlight. Direct photolysis half-lives for some other PAHs without reported values were predicted. It was concluded from the model that the main factors affecting photolysis half-lives of PAHs under irradiation of sunlight are PAH absolute hardness and electronegativity, which are related to the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital, ( E lumo− E homo) and ( E lumo+ E homo), respectively. Increasing E homo and the average molecular polarizability ( α) values of the PAHs leads to decrease of photolysis half-lives. Increasing ( E lumo- E homo) and E lumo values of the PAHs leads to an increase of the PAH photolysis half-lives.

Diurnal and seasonal modelling of the tropospheric half-lives of polycyclic aromatic hydrocarbons

The half-lives of polycyclic aromatic hydrocarbons (PAH) were calculated under different conditions of location, season, and time of day, based on the reaction of PAH with the hydroxyl radical OH as the major sink. The calculations required a method of estimating the diurnal variation in the concentration of OH, which is not normally available experimentally. For naphthalene as a prototype PAH, the half-lives were of the order of several hours, but varied by more than an order of magnitude with season and geographical location. The previously developed model applicable to rural atmospheres was modified to estimate the half-lives of PAH in the urban troposphere by including of the reaction of OH with NO2 as a major urban sink for OH. The half-lives of several PAH were estimated for North York, Ontario, under different conditions of NO2 and ozone concentrations during a period of high tropospheric air pollution in July 1988.

A model to evaluate half-lives of PAHs naturally occurring on airborne particulate.

Constant decay of polycyclic aromatic hydrocarbons (PAHs) adsorbed onto airborne particulate collected in glass fibre filters and exposed to sunlight ranged from 1.8 to 4.4 X 10(-3) (min-1), corresponding respectively to a half-life of 100 and 425 min. Half-life of PAHs appeared to be positively correlated with filter loading. Experimental results showed that decay of PAHs adsorbed on airborne particulate was induced by two concomitant reactions; a photochemical reaction involving the outer layers of collected particulate, and a "dark" reaction that may occur in the inner layers. The constant decays of these two reactions were calculated using a simplified mathematical model. The authors suggest the use of this model to compare chemical stability of airborne PAHs exposed, during their permanence in the atmosphere, to different physical (light intensity, temperature, humidity) as well as chemical conditions (oxidant concentration, chemical composition of particulate).