Studies on photochemistry of aromatic hydrocarbons V: Photochemical reaction of chlorobenzene with nitrogen oxides in air

The investigations on the photochemical reaction of chlorobenzene with nitrogen oxides in air were carried out using the reaction vessels made of Pyrex glass and quartz, respectively. The irradiation of chlorobenzene in the Pyrex glass vessel gave m-chloronitrobenzene, 2-chloro-6-nitrophenol, 2-chloro-4-nitrophenol and 4-chloro-2-nitrophenol, while the irradiation of chlorobenzene in the quartz vessel resulted in m-chloronitrobenzene, p-nitrophenol, 2-chloro-4-nitrophenol, 3-chloro-2-nitrophenol, 3-chloro-6-nitrophenol and 3-chloro-4-nitrophenol.The formation mechanism of these chloronitrophenols was considered using the theory of the nitro-nitrite rearrangement of chloronitrobenzenes.     

Behavior and prediction of photochemical degradation of chlorinated polycyclic aromatic hydrocarbons in cyclohexane

The photochemical degradation of 11 chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and the corresponding 5 parent PAHs was examined to simulate the compound’s fate on aerosol surfaces. All the ClPAHs and PAHs decayed according to the first-order reaction rate kinetics. The photolysis rates of ClPAHs varied greatly according to the skeleton of PAHs; the rates of chlorophenanthrenes (ClPhes) and 1-chloropyrene were higher than those of corresponding parent PAHs, whereas chlorofluoranthenes, 7-chlorobenz[a]anthracene and 6-chlorobenzo[a]pyrene were more stable under irradiation compared to respective parent PAH. Considering the photoproducts of ClPhes detected, the oxidation could occur immediately at positions of the highest frontier electron density. Finally, the quantitative structure-property relationship models were developed for direct photolysis half-lives and average quantum yields of the ClPAHs and parent PAHs, in which the significant factors affecting photolysis were E_LUMO+1, total energy and surface area, and E_LUMO, E_LUMO − E_HOMO and total energy, respectively.     

Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC/NO_x) mixtures irradiated in the presence of fine (<2.5 μm) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO_x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 μm⁻³, followed by 1.09±0.27% for p-xylene at 6.4 μg m⁻³, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 μg m⁻³. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas–aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.     

The mobile source effect on curbside 1,3-butadiene,benzene, and particle-bound polycyclic aromatic hydrocarbons assessed at a tollbooth

On-road mobile sources contribute substantially to ambient air concentrations of the carcinogens 1,3-butadiene, benzene, and polycyclic aromatic hydrocarbons (PAHs). The current study measured benzene and 1,3-butadiene at the Baltimore Harbor Tunnel tollbooth over 3-hr intervals on seven weekdays (n = 56). Particle-bound PAH was measured on a subset of three days. The 3-hr outdoor 1,3-butadiene levels varied according to time of day and traffic volume. The minimum occurred at night (12 a.m.-3 a.m.) with a mean of 2 microg/m3 (SD = 1.3, n = 7), while the maximum occurred during the morning rush hour (6 a.m.-9 a.m.) with a mean of 11.9 microg/m3 (SD = 4.6, n = 7). The corresponding traffic counts were 1413 (SD = 144) and 16,893 (SD = 692), respectively. During the same intervals, mean benzene concentration varied from 3 microg/m3 (SD = 3.1, n = 7) to 22.3 microg/m3 (SD = 7.6, n = 7). Median PAH concentrations ranged from 9 to 199 ng/m3. Using multivariate regression, a significant association (p < 0.001) between traffic and curbside concentration was observed. Much of the pollutant variability (1,3-butadiene 62%, benzene 77%, and PAH 85%) was explained by traffic volume, class, and meteorology. Results suggest > 2-axle vehicles emit 60, 32, and 9 times more PAH, 1,3-butadiene, and benzene, respectively, than do 2-axle vehicles. This study provides a model for estimating curbside pollution levels associated with traffic that may be relevant to exposures in the urban environment.     

Uptake of polycyclic aromatic hydrocarbons by Trifolium pretense L. from water in the presence of a nonionic surfactant

A greenhouse study examined plant uptake of phenanthrene and pyrene, as representatives of polycyclic aromatic hydrocarbons (PAHs), from an aqueous solution containing a nonionic surfactant Tween 80. The uptake was conducted with 1.0 mg l(-1) phenanthrene and 0.12 mg l(-1) pyrene under a wide range of Tween 80 concentrations (0-105.6 mg l(-1)). Tween 80 at the test concentrations did not show any apparent phytotoxity toward the growth of red clover (Trifolium pretense L.). At concentrations generally lower than 13.2 mg l(-1), Tween 80 enhanced the plant uptake based on the concentrations and PCFs (plant concentration factors) of these two PAHs. When present at higher concentrations, Tween 80 inhibited the uptake of both PAH compounds by the tested plant. The maximal plant uptake was observed at 6.6 mg l(-1) Tween 80, in which PAH concentrations and PCFs were 18-115% higher than those in Tween 80-free controls. The total mass removal (off-take) of phenanthrene and pyrene by root or shoot increased initially and decreased thereafter with the increase in Tween 80 concentrations. Although shoot biomass was evidently larger than root, the off-take was much higher in root than shoot because of the larger root concentrations of these chemicals. Results from this study show promises for the potential efficacy of enhanced phytoremediation in PAH contaminated sites using surfactant amendment.     

Influence of secondary formation on atmospheric occurrences of oxygenated polycyclic aromatic hydrocarbons in airborne particles

Temporal and spatial variations in concentrations of particle-associated polycyclic aromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives (nitro-PAHs and oxy-PAHs) were investigated to assess the influence of secondary formation on atmospheric occurrences of oxy-PAHs associated with particulate matter in downtown Tokyo, Japan. The daily variation in concentration of 1,8-naphthalic anhydride (1,8-NA) in summer 2007 was similar to that for 2-nitrofluoranthene (2-NF), a representative secondary formed nitro-PAH, while the variation for benzanthrone (BA) was similar to PAHs. In addition, the concentrations of polycyclic aromatic compounds (PACs) associated with airborne particulate matter decreased in the order of PAHs > BA > 9-fluorenone (9-FO) or 9,10-anthraquinone (9,10-AQ) > 1,8-NA with an increase in distance from the roadside, whereas 2-NF was constant. These results suggest that a considerable fraction of some oxy-PAHs such as 1,8-NA associated with airborne particulate matter in downtown Tokyo originates from atmospheric secondary formation.     

The impact of natural and anthropogenic hydrocarbons on the tropospheric budget of carbon monoxide

A method to quantify the relative contributions of surface sources and photochemical production of atmospheric carbon monoxide has been implemented in a three-dimensional chemical-transport model. The impact of biogenic and anthropogenic hydrocarbons has been calculated. The oxidation of isoprene contributes to about 10% of the global tropospheric burden of carbon monoxide, with a maximum contribution over southern America and Africa. Oxidation of methane and terpenes contribute to 28 and 2%, respectively, of the tropospheric burden of CO. The oxidation of the other hydrocarbons, which include ethane, propane, ethylene, propylene and the surrogate hydrocarbon representing other hydrocarbons results in 12% of the CO tropospheric burden, among which 69% results from the oxidation of hydrocarbons of biologic origin. The overall global CO yield from the oxidation of isoprene is estimated to be 23% on a carbon basis. Comparisons between model results and the few available observations of isoprene, terpenes and their oxidation products show that there is no evidence that the current global isoprene emissions proposed in the IGAC/GEIA emissions data base are substantially overestimated, as suggested by previous studies.     

能量注入对放电等离子体去除气相苯系物的影响

采用正极性高压直流供电和串齿线放电极--管式接地极构成的放电等离子体反应器,研究了苯系物(苯、甲苯和对二甲苯)去除效率与供电电压之间的关系,以及放电极齿轮数对苯系物去除效率、COx(CO2 CO)生成量和能量效率的影响.研究结果表明,苯系物的去除效率、COx生成量皆随电压升高而增大.随着电压升高,能量效率先升后降,当电压为11 kV左右时,能量效率最高.对应放电齿轮数为31的苯系物去除效率、COx生成量和能量效率皆高于放电齿轮数为55或7,这表明对应特定的等离子体反应器,有一最佳放电齿数匹配.     

Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity

To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.     

A comparative study on the uptake of polycyclic aromatic hydrocarbons by Anodonta californiensis

Uptake of polycyclic aromatic hydrocarbons (PAHs) by the freshwater bivalve mollusc Anodonta californiensis was examined in the presence and absence of surfactant in order to gain further insight into mixture toxicity and to predict whether certain mixtures have negative and/or positive effects on aquatic organisms. In the presence of surfactant, the uptake of anthracene or chrysene was higher than that of naphthalene, given the same concentration in the solution. In the absence of surfactant, the trend was similar, but the uptakes were increased by approximately 100% compared to those in the presence of surfactant. On the uptake of naphthalene, the presence of anthracene showed only minor influence. The uptake of anthracene was affected by both naphthalene and chrysene. The uptake of chrysene was influenced by neither naphthalene nor anthracene. There was no observable displacement of divalent cations from the surface of the gill membrane by any of the PAHs studied.     

Modeling the formation,decay, and partitioning of semivolatile nitro-polycyclic aromatic hydrocarbons (nitronaphthalenes) in the atmosphere

A nitronaphthalene kinetics mechanism has been implemented and added to the photochemical smog mechanism, Carbon Bond-4. This mechanism was used to simulate the formation, decay, and partitioning of 1- and 2-nitronaphthalene and compare it to outdoor smog chamber data. The results suggest that these types of mechanisms can be used to model nitronaphthalene formation and decay in regional airmasses. The partitioning experiments were conducted at night. The sampling system consisted of two Teflon impregnated glass fiber filters followed by a gas-phase denuder. Evidence is provided that partitioning equilibrium is maintained even when the gas-phase components are decaying rapidly under sunlight. The photolysis rate constants were determined relative to k_NO2 to be 0.07×k_NO2 and 0.005×k_NO2 for 1- and 2-nitronaphthalene, respectively. Our results confirm that gas-phase photolysis is the major degradation pathway for 1-nitronaphthalene, whereas for 2-nitronaphthalene other pathways may also be important. The photochemical formation of nitronaphthalenes was studied using a mixture of naphthalene, propylene, NO_x, and diesel particles. 2-nitronaphthalene was observed to build up to higher levels than 1-nitronaphthalene, as the photodegradation of the latter was faster. Additionally, as a part of this study 1-nitronaphthalene has been identified and quantified in diesel exhaust.     

Biogenic polycyclic aromatic hydrocarbons in sediments of the San Joaquin River in California (USA), and current paradigms on their formation

Biogenic perylene and higher plant pentacyclic triterpenoid-derived alkylated and partially aromatized tetra- and pentacyclic derivatives of chrysene (3,4,7-trimethyl- and 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, THC) and picene (1,2,9-trimethyl- and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene, THP) were two- to four-fold more abundant than pyrogenic PAH in two sediment cores from the San Joaquin River in Northern California (USA). In a core from Venice Cut (VC), located in the river, PAH concentrations varied little downcore and the whole-core PAH concentration (biogenics?+?pyrogenics) was 250.6?±?73.7 ng g^?1 dw; biogenic PAH constituted 67?±?4 % of total PAH. THC were 26?±?9 % of total biogenic PAH, THP were 36?±?7 %, and perylene was 38?±?7 %. PAH distributions in a core from Franks Tract (FT), a former wetland that was converted to an agricultural tract in the late 1800s and flooded in 1938, were more variable. Surface sediments were dominated by pyrogenic PAH so that biogenic PAH were only ~30 % of total PAH. Deeper in the core, biogenic PAH constituted 60–93 % of total PAH; THC, THP and perylene were 31?±?28 %, 24?±?32 %, and 45?±?36 % of biogenic PAH. At 100–103 cm depth, THP constituted 80 % of biogenic PAH and at 120–123 cm perylene was 95 % of biogenic PAH. Current concepts related to precursors and transformation processes responsible for the diagenetic generation of perylene and triterpenoid-derived PAH are discussed. Distributions of biogenic PAH in VC and FT sediments suggest that they may not form diagenetically within these sediments but rather might be delivered pre-formed from the river’s watershed.     

Aliphatic and polycyclic aromatic hydrocarbons in the surface sediments from the Eastern Aegean: assessment and source recognition of petroleum hydrocarbons

Materials and methods  

Aliphatic and polycyclic aromatic hydrocarbons (PAHs) were determined in surficial sediments from the Aegean Sea in the Eastern Mediterranean in 2008.