Roadside BTEX and other gaseous air pollutants in relation to emission sources

Hourly concentrations of benzene, toluene, ethylbenzene, m,p-xylenes, and o-xylene (BTEX) plus CO, NO_x, SO₂ were monitored at roadsides simultaneously with the traffic volume during the dry season of 2004, in Hanoi, Vietnam. The selected three streets included Truong Chinh (TC) with high traffic volume, Dien Bien Phu (DBP) with low traffic volume, and Nguyen Trai (NT) with high traffic volume running through an industrial estate. BTEX were sampled by SKC charcoal tubes and analyzed by GC–FID. Geometric means of hourly benzene, toluene, ethylbenzene, m,p-xylenes and o-xylene are, respectively, 65, 62, 15, 43, and 22 μg m⁻³ in TC street; 30, 38, 9, 26, and 13 μg m⁻³ in DBP street; and 123, 87, 24, 56, and 30 μg m⁻³ in NT street. Levels of other gaseous pollutants including CO, NO_x, and SO₂, measured by automatic instruments, were low and not exceeding the Vietnam national ambient air quality standards. BTEX levels were comparatively analyzed for different downwind distances (3–50 m) from the street, between peak hours and off-peak hours, as well as between weekdays and weekend. Results of principal component analysis suggest that the gaseous pollutants are associated with different vehicle types.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.     

Atmospheric BTEX-concentrations in an area with intensive street traffic

The major threat to clean air in developed and industrializing countries is now posed by traffic emissions. The effects of traffic road modifications on the air quality are, however, rarely reported in the literature. The aim of this study was to determine the influence of the modernization and renovation of a traffic artery in the region of Mortsel (Antwerp, Belgium) on the concentration of volatile organic compounds such as: benzene, toluene, ethylbenzene and m-, p-, o-xylenes (BTEX). The original goal of the reconstruction works was to reduce the traffic lanes of one of the busiest streets in Antwerp, in order to discourage the road traffic and in consequence also to improve the air quality in this region. The average concentrations of BTEX before these works in 2003 were: 1.6, 7.0, 0.9, 2.3, and 0.9 μg/m³, for benzene, toluene, ethylbenzene, m + p xylenes, and o-xylene, respectively. However, after the completion of the works, in 2005, they were slightly higher: 2.5, 9.5, 1.6, 3.4, and 1.3 μg/m³, respectively. The scatter plots of benzene against toluene, ethylbenzene and xylenes in 2003 and 2005 showed very good correlations. This fact indicated that all of the measured compounds originated from the same source, namely the road traffic. Moreover, the data obtained from an air-monitoring station at less than 6 km distance from the sampling site (operated by the Flemish Environment Agency, and located in Borgerhout, Antwerp), confirmed the lack of influence of background concentrations of BTEX. The obtained results led to the conclusion that the reduction of the number of traffic lanes had apparently increased the traffic jams and also increased the emission from cars. Therefore, these modernization works had even a negative impact on the local concentration of traffic-related pollutants as BTEX.     

Dilution and aerosol dynamics within a diesel car exhaust plume—CFD simulations of on-road measurement conditions

Vehicle particle emissions are studied extensively because of their health effects, contribution to ambient PM levels and possible impact on climate. The aim of this work was to obtain a better understanding of secondary particle formation and growth in a diluting vehicle exhaust plume using 3-d information of simulations together with measurements. Detailed coupled computational fluid dynamics (CFD) and aerosol dynamics simulations have been conducted for H₂SO₄–H₂O and soot particles based on measurements within a vehicle exhaust plume under real conditions on public roads.Turbulent diffusion of soot and nucleation particles is responsible for the measured decrease of number concentrations within the diesel car exhaust plume and decreases coagulation rates. Particle size distribution measurements at 0.45 and 0.9 m distance to the tailpipe indicate a consistent soot mode (particle diameter D_p∼50 nm) at variable operating conditions. Soot mode number concentrations reached up to 10¹³ m⁻³ depending on operating conditions and mixing.For nucleation particles the simulations showed a strong sensitivity to the spatial dilution pattern, related cooling and exhaust H₂SO_4(g). The highest simulated nucleation rates were about 0.05–0.1 m from the axis of the plume. The simulated particle number concentration pattern is in approximate accordance with measured concentrations, along the jet centreline and 0.45 and 0.9 m from the tailpipe. Although the test car was run with ultralow sulphur fuel, high nucleation particle (D_p⩽15 nm) concentrations (>10¹³ m⁻³) were measured under driving conditions of strong acceleration or the combination of high vehicle speed (>140 km h⁻¹) and high engine rotational speed (>3800 revolutions per minute (rpm)).Strong mixing and cooling caused rapid nucleation immediately behind the tailpipe, so that the highest particle number concentrations were recorded at a distance, x=0.45 m behind the tailpipe. The simulated growth of H₂SO₄–H₂O nucleation particles was unrealistically low compared with measurements. The possible role of low and semi-volatile organic components on the growth processes is discussed. Simulations for simplified H₂SO₄–H₂O–octane–gasoil aerosol resulted in sufficient growth of nucleation particles.     

Quantifying RDX biodegradation in groundwater using δ15N isotope analysis

Isotope analysis was used to examine the extent of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) biodegradation in groundwater along a ca. 1.35-km contamination plume. Biodegradation was proposed as a natural attenuating remediation method for the contaminated aquifer. By isotope analysis of RDX, the extent of biodegradation was found to reach up to 99.5% of the initial mass at a distance of 1.15–1.35 km down gradient from the contamination sources. A range of first-order biodegradation rates was calculated based on the degradation extents, with average half-life values ranging between 4.4 and 12.8 years for RDX biodegradation in the upper 15 m of the aquifer, assuming purely aerobic biodegradation, and between 10.9 and 31.2 years, assuming purely anaerobic biodegradation. Based on the geochemical data, an aerobic biodegradation pathway was suggested as the dominant attenuation process at the site. The calculated biodegradation rate was correlated with depth, showing decreasing degradation rates in deeper groundwater layers. Exceptionally low first-order kinetic constants were found in a borehole penetrating the bottom of the aquifer, with half life ranging between 85.0 to 161.5 years, assuming purely aerobic biodegradation, and between 207.5 and 394.3 years, assuming purely anaerobic biodegradation.The study showed that stable isotope fractionation analysis is a suitable tool to detect biodegradation of RDX in the environment. Our findings clearly indicated that RDX is naturally biodegraded in the contaminated aquifer. To the best of our knowledge, this is the first reported use of RDX isotope analysis to quantify its biodegradation in contaminated aquifers.     

The estimation of historical CO2 trajectories is indeterminate: Comment on “A new look at atmospheric carbon dioxide”

A paper by Hofmann et al. (2009, this journal) is critiqued. It is shown that their exponential model for characterizing CO₂ trajectories for historical data is not estimated properly. An exponential model is properly estimated and is shown to fit over the entire 51 year period of available data. Further, the entire problem of estimating models for the CO₂ historical data is shown to be ill-posed because alternate model forms fit the data equally well. To illustrate this point the past 51 years of CO₂ data were analyzed using three different time-dependent models that capture the historical pattern of CO₂ increase. All three fit with R² > 0.98, are visually indistinguishable when overlaid, and match each other during the calibration period with R² > 0.999. Projecting the models forward to 2100, the exponential model comes quite close to the Intergovernmental Panel on Climate Change (IPCC) best estimate of 836 ppmv. The other two models project values far below the IPCC low estimates. The problem of characterizing historical CO₂ levels is thus indeterminate, because multiple models fit the data equally well but forecast very different future trajectories.     

Gas-phase absorption cross sections of 24 monocyclic aromatic hydrocarbons in the UV and IR spectral ranges

Absorption cross sections of 24 volatile and non-volatile derivatives of benzene in the ultraviolet (UV) and the infrared (IR) regions of the electromagnetic spectrum have been determined using a 1080 l quartz cell. For the UV a 0.5 m Czerny-Turner spectrometer coupled with a photodiode array detector (spectral resolution 0.15 nm) was used. IR spectra were recorded with an FT-IR spectrometer (Bruker IFS-88, spectral resolution 1 cm^-1). Absolute absorption cross sections and the instrument function are given for the UV, while for the IR, absorption cross sections and integrated band intensities are reported.The study focused primarily on the atmospherically relevant methylated benzenes (benzene, toluene, o-xylene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, styrene) and their ring retaining oxidation products (benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4,6-trimethylphenol and (E,Z)- and (E,E)-2,4-hexadienedial).The UV absorption cross sections reported here can be used for the evaluation of DOAS spectra (Differential Optical Absorption Spectroscopy) for measurements of the above compounds in the atmosphere and in reaction chambers, while the IR absorption cross sections will primarily be useful in laboratory studies on atmospheric chemistry, where FT-IR spectrometry is an important tool.     

Emission strengths for primary pollutants as estimated from an aircraft study of Hong Kong air quality

An aircraft study of air quality in the Hong Kong region during the fall of 1994 has allowed for an estimation of the daytime source strengths for CO and NO_y from the Hong Kong metropolitan center. Emission rate estimates for the Hong Kong urban plume for NO_y and CO were 5.4×10e(25) molecules s^-1 and 1.8×10e(26) molecules s^-1 as determined for the case study of 18 October. All emission rate estimates have uncertainties of a factor of 2. On one occasion a distinct plume emanating from Shenzhen in the People’s Republic of China was encountered. While plume delimitation was insufficient for source strength calculations, transect integrals did allow for a CO/NO_y ratio of about 16 to be determined. The CO/NO_y ratio for the Hong Kong urban plume was about 3.3. The difference in these ratios indicates differences in the overall combustion processes and efficiencies taking place within Hong Kong and the PRC.     

Decadal reductions of traffic emissions on a transit route in Austria – results of the Tauerntunnel experiment 1997

Real-world emissions of a traffic fleet on a transit route in Austria were determined in the Tauerntunnel experiment in October 1997. The total number of vehicles and the average speed was nearly the same on both measuring days (465 vehicles 30 min⁻¹ and 76 km h⁻¹ on the workday, 477 and 78 km h⁻¹ on Sunday). The average workday fleet contained 17.6% heavy-duty vehicles (HDV) and the average Sunday fleet 2.8% HDV resulting in up to four times higher emission rates per vehicle per km on the workday than on Sunday for most of the regulated components (CO₂, CO, NO_x, SO₂, and particulate matter-PM10). Emission rates of NMVOC accounted for 200 mg vehicle⁻¹ km⁻¹ on both days. The relative contributions of light-duty vehicles (LDV) and HDV to the total emissions indicated that aldehydes, BTEX (benzene, toluene, ethylbenzene, xylenes), and alkanes are mainly produced by LDV, while HDV dominated emissions of CO, NO_x, SO₂, and PM10. Emissions of NO_x caused by HDV were 16,100 mg vehicle⁻¹ km⁻¹ (as NO₂). Produced by LDV they were much lower at 360 mg vehicle⁻¹ km⁻¹. Comparing the emission rates to the results that were obtained by the 1988 experiment at the same place significant changes in the emission levels of hydrocarbons and CO, which accounted 1997 to only 10% of the levels in 1988, were noticed. However, the decrease of PM has been modest leading to values of 80 and 60% of the levels in 1988 on the workday and on Sunday, respectively. Emission rates of NO_x determined on the workday in 1997 were 3130 mg vehicle⁻¹ km⁻¹ and even higher than in 1988 (2630 mg vehicle⁻¹ km⁻¹), presumable due to the increase of the HD-traffic.     

The evolution of photochemical smog in a power plant plume

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study – Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west–northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50–60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O₃ that peaked at 120 ppbv at a short distance (15–25 km) downwind of Nashville. Ozone productivity (the ratio of excess O₃ to NO_y and NO_z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.     

Trace gas variations at Cape Point,South Africa,during May 1997 following a regional biomass burning episode

During the continuous monitoring of atmospheric parameters at the station Cape Point (34°S, 18°E), a smoke plume originating from a controlled fire of 30-yr-old fynbos was observed on 6 May 1997. For this episode, which was associated with a nocturnal inversion and offshore airflow, atmospheric parameters (solar radiation and meteorological data) were considered and the levels of various trace gases compared with those measured at Cape Point in maritime air. Concentration maxima in the morning of 6 May for CO₂, CO, CH₄ and O₃ amounted to 370.3 ppm, 491 ppb, 1730 ppb and 47 ppb, respectively, whilst the mixing ratios of several halocarbons (F-11, F-12, F-113, CCl₄ and CH₃CCl₃) remained at background levels. In the case of CO, the maritime background level for this period was exceeded by a factor of 9.8. Differences in ozone levels of up to 5 ppb between air intakes at 4 and 30 m above the station (located at 230 m above sea level) indicated stratification of the air advected to Cape Point during the plume event. Aerosols within the smoke plume caused the signal of global solar radiation and UV–A to be attenuated from 52.4 to 13.0 mW cm⁻² and from 2.3 to 1.3 mW cm⁻², respectively, 5 h after the trace gases had reached their maxima. Emission ratios (ERs) calculated for CO and CH₄ relative to CO₂ mixing ratios amounted to 0.042 and 0.0040, respectively, representing one of the first results for fires involving fynbos. The CO ER is somewhat lower than those given in the literature for African savanna fires (average ER=0.048), whilst for CH₄ the ER falls within the range of ERs reported for the flaming (0.0030) and smouldering phases (0.0055) of savanna fires. Non-methane hydrocarbon (NMHC) data obtained from a grab sample collected during the plume event were compared to background levels. The highest ERs (ΔNMHC/ΔCH₄) have been obtained for the C₂–C₃ hydrocarbons (e.g. ethene at 229.3 ppt ppb⁻¹), whilst the C₄–C₇ hydrocarbons were characterised by the lowest ERs (e.g. n-hexane at 1.0 and n-pentane at 0.8 ppt ppb⁻¹).     

Volatile organic compounds in roadside microenvironments of metropolitan Hong Kong

The characteristics and concentrations of volatile organic compounds (VOCs) in the roadside microenvironments of metropolitan Hong Kong were investigated. The VOC concentrations, especially toluene, benzene and chlorinated VOCs in Hong Kong were high when compared with those in most developed cities. The average and maximum concentration of toluene was 74.9 and 320.0 μg m⁻³, respectively. The respective values for benzene were 25.9 and 128.6 μg m⁻³. The chlorinated VOCs were dominated by trichloroethylene and tetrachloroethylene. The maximum concentrations of these two species reached 248.2 and 144.0 μg m⁻³, respectively. There were strong variations in the spatial fluctuation and characteristic of VOC concentrations. The highest VOC concentrations were found in the industrial district, which were followed by those in the commercial district, the central business district and finally the residential district. The highest concentrations of most VOC species, especially chlorinated VOC were found in the industrial and commercial districts. The average benzene/toluene ratio in Hong Kong was 0.5 suggesting that vehicular emission was the dominant VOC source in most areas of Hong Kong. There were strong deviations in benzene/toluene, benzene/ethylbenzene and benzene/(m+p-xylene) ratios in the commercial district, and highly chlorinated VOC in the industrial and commercial districts. These suggest that there were other benzene and VOC sources overlying on the high background VOC concentrations in these districts. The common usage of organic solvents in the building and construction industries, and in the small industries in the industrial and commercial districts were believed to be important sources of VOC in Hong Kong.     

Aromatic hydrocarbons at urban,sub-urban,rural (8°52′N; 67°19′W) and remote sites in Venezuela

Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C₉-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000.Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C₉-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (∼20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed.At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10⁶ molecules/cm³ was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene.At the remote “La Gran Sabana” region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that “urban” air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene.Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.     

Extent of H-atom abstraction from OH + p-cymene and upper limits to the formation of cresols from OH + m-xylene and OH + p-cymene

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH + m-xylene and <2% for formation of each cresol isomer from OH + p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH₃)₂ group) in the OH + p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH₃ and CH(CH₃)₂ groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10^?12 cm³ molecule^?1 s^?1 at 297 ± 2 K.     

Effect of copper(II) on biodegradation of benzo[a]pyrene by Stenotrophomonas maltophilia

Benzo[a]pyrene (BaP) biodegradation by Stenotrophomonas maltophilia was studied under the influence of co-existed Cu(II) ions. About 45% degradation was achieved within 3 d when dealing with 1 mg L^?1 BaP under initial natural pH at 30 °C; degradation reached 48% in 2 d at 35 °C. Efficacy of BaP biodegradation reached the highest point at pH 4. In the presence of 10 mg L^?1 Cu(II) ions, the BaP removal ratio was 45% on 7th day, and maintained stable from 7 to 14 d at 30 °C under natural pH. The favorable temperature and pH for BaP removal was 25 °C and 6.0 respectively, when Cu(II) ions coexisted in the solutions. Experiments on cometabolism indicated that S. maltophilia performed best when sucrose was used as an additional carbon source. GC–MS analysis revealed that the five rings of BaP opened, producing compounds with one or two rings which were more bioavailable.     

Comparing the desorption and biodegradation of low concentrations of phenanthrene sorbed to activated carbon,biochar and compost

Carbonaceous soil amendments are applied to contaminated soils and sediments to strongly sorb hydrophobic organic contaminants (HOCs) and reduce their freely dissolved concentrations. This limits biouptake and toxicity, but also biodegradation. To investigate whether HOCs sorbed to such amendments can be degraded at all, the desorption and biodegradation of low concentrations of ¹⁴C-labelled phenanthrene (?5 μg L^?1) freshly sorbed to suspensions of the pure soil amendments activated carbon (AC), biochar (charcoal) and compost were compared. Firstly, the maximum abiotic desorption of phenanthrene from soil amendment suspensions in water, minimal salts medium (MSM) or tryptic soy broth (TSB) into a dominating silicone sink were measured. Highest fractions remained sorbed to AC (84 ± 2.3%, 87 ± 4.1%, and 53 ± 1.2% for water, MSM and TSB, respectively), followed by charcoal (35 ± 2.2%, 32 ± 1.7%, and 12 ± 0.3%, respectively) and compost (1.3 ± 0.21%, similar for all media). Secondly, the mineralization of phenanthrene sorbed to AC, charcoal and compost by Sphingomonas sp. 10-1 (DSM 12247) was determined. In contrast to the amounts desorbed, phenanthrene mineralization was similar for all the soil amendments at about 56 ± 11% of the initially applied radioactivity. Furthermore, HPLC analyses showed only minor amounts (<5%) of residual phenanthrene remaining in the suspensions, indicating almost complete biodegradation. Fitting the data to a coupled desorption and biodegradation model revealed that desorption did not limit biodegradation for any of the amendments, and that degradation could proceed due to the high numbers of bacteria and/or the production of biosurfactants or biofilms. Therefore, reduced desorption of phenanthrene from AC or charcoal did not inhibit its biodegradation, which implies that under the experimental conditions these amendments can reduce freely dissolved concentration without hindering biodegradation. In contrast, phenanthrene sorbed to compost was fully desorbed and biodegraded.     

Modelling plume rise and dispersion from pool fires

This paper describes an investigation into the behaviour of smoke plumes from pool fires, and the subsequent generation of empirical models to predict plume rise and dispersion from such a combustion source. Synchronous video records of plumes were taken from a series of small-scale (0.06–0.25m²) outdoor methanol/toluene pool fire experiments, and used to produce sets of images from which plume dimensions could be derived. Three models were used as a basis for the multiple regression analysis of the data set, in order to produce new equations for improved prediction. Actual plume observations from a large (20.7 m×14.2 m) aviation fuel pool fire were also used to test the predictions. The two theoretically based models were found to give a better representation of plume rise and dispersion than the empirical model based on measurements of small-scale fires. It is concluded that theoretical models tested on small-scale fires (heat output ≈70 kW) can be used to predict plume behaviour from much larger combustion sources (heat output ≈70 MW) under near neutral atmospheric conditions.     

Urban roadside aromatic hydrocarbons in three cities of the Pearl River Delta,People's Republic of China

Urban roadside levels of benzene, toluene, ethylbenzene and xylenes (BTEX) were investigated in three typical cities (Guangzhou, Macau and Nanhai) in the Pearl River Delta Region of south China. Air samples were collected at typical ground level microenvironments by multi-bed adsorbent tubes. The BTEX concentrations were determined by thermal desorption–gas chromatography–mass selective detector (TD–GC–MSD) technique. The mean concentrations of benzene, toluene, ethylbenzene and xylenes were, respectively, 51.5, 77.3, 17.8 and 81.6 μg/m³ in Guangzhou, 34.9, 85.9, 24.1, 95.6 μg/m³ in Macau, and 20.0, 39.1, 3.0 and 14.2 μg/m³ in Nanhai. The relative concentration distribution pattern and mutual correlation analysis indicated that in Macau BTEX were predominantly traffic-related while in Guangzhou benzene had sources other than vehicle emission. In Nanhai, both benzene and toluene had different sources other than vehicle emission. The samples collected from Guangzhou showed that BTEX had significant higher concentrations in November than those in July.     

Evaluation of the UNC toluene-SOA mechanism with respect to other chamber studies and key model parameters

In a companion paper by Hu et al. [2007. A kinetic mechanism for predicting secondary organic aerosol formation from toluene oxidation in the presence of NO_x and natural sunlight. Atmospheric Environment, doi:10.1016/j.atmosenv.2007.04.025], a kinetic mechanism was developed from data generated in the University of North Carolina's (UNC) 270 m³ dual outdoor aerosol smog chamber, to predict secondary organic aerosol (SOA) formation from toluene oxidation in the atmosphere. In this paper, experimental data sets from European Photoreactor (EUPHORE), smog chambers at the California Institute of Technology (Caltech), and the UNC 300 m³ dual-outdoor gas phase chamber were used to evaluate the toluene mechanism. The model simulates SOA formation for the ‘low-NO_x’ and ‘mid-NO_x’ experiments from EUPHORE chambers reasonably well, but over-predicts SOA mass concentrations for the ‘high-NO_x’ run. The model well simulates the SOA mass concentrations observed from the Caltech chambers. Experiments with the three key toluene products, 1,4-butenedial, 4-oxo-2-pentenal and o-cresol in the presence of oxides of nitrogen (NO_x) are also simulated by the developed mechanism. The model well predicts the NO_x time–concentration profiles and the decay of these two carbonyls, but underestimates ozone (O₃) formation for 4-oxo-2-pentenal. It well simulates SOA formation from 1,4-butenedial but overestimates (possibly due to experimental problems) the measured aerosol mass concentrations from 4-oxo-2-pentenal. The model underestimates SOA production from o-cresol, mostly due to its under-prediction of o-cresol decay. The effects of varying temperature, relative humidity, glyoxal uptake, organic nitrate yields, and background seed aerosol concentrations, were also investigated.