Gas/particle partitioning behaviour of azaarenes in an urban atmosphere

The gas/particle partitioning of azaarenes in the Liverpool urban atmosphere was measured from May 1995 to April 1996. This period included one of the hottest summers and coldest winters recorded in the UK. The changes of the relative proportions of particulate and vapour phases showed a strong seasonal variation in which over 80% of azaarene compounds are associated with the particles in the winter and over 60% of azaarene compounds exist as vapour phase during the summer. The results are fitted into a gas/particle partitioning equation. Calculated vapour pressures, vaporization and desorption enthalpies are also given. Azaarene partitioning behaviour is modelled at a variety of aerosol concentrations and over a temperature range which includes normal ambient temperatures. It is hypothesised that three ring azaarene species are more likely to undergo changes in the relative proportions of particle and vapour phase material than either two or four ring compounds.     

Seasonal and particle size-dependent variations in gas/particle partitioning of PCDD/Fs

This study monitored particle size-dependent variations in atmospheric polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Two gas/particle partitioning models, the subcooled liquid vapor pressure (P(L)(0)) and the octanol-air partition coefficient (K(OA)) model, were applied to each particle sizes. The regression coefficients of each fraction against the gas/particle partition coefficient (K(P)) were similar for separated particles within the same sample set but differed for particles collected during different periods. Gas/particle partitioning calculated from the integral of fractions was similar to that of size-segregated particles and previously measured bulk values. Despite the different behaviors and production mechanisms of atmospheric particles of different sizes, PCDD/F partitioning of each size range was controlled by meteorological conditions such as atmospheric temperature, O(3) and UV, which reflects no source related with certain particle size ranges but mixed urban sources within this city. Our observations emphasize that when assessing environmental and health effects, the movement of PCDD/Fs in air should be considered in conjunction with particle size in addition to the bulk aerosol.     

Concentrations and gas/particle partitioning of PCBs in Chicago

Thirty seven air samples were collected in Chicago, IL from June to October 1995 and analyzed for gas and particle concentrations of polychlorinated biphenyls (PCBs). Lower molecular weight (MW) PCBs dominated the samples and on average 95% of the Sigma50PCB concentration (gas+particulate) was in the vapor phase. Sigma50PCB concentrations were classified based on prevailing winds (lake and land). The Sigma50PCB concentration varied between 0.42 and 5.21 ng/m3 (1.80+/-1.70 ng/m3) for lake and 0.53 and 8.31 ng/m3 (2.41+/-2.15 ng/m3) for land wind directions. Back trajectory analyses suggested that SW of Chicago can be an important local or regional source sector for PCBs. Partitioning between gas and particulate phases was modeled using the Junge-Pankow model. The measured particle phase concentrations for low MW PCBs were lower than those predicted by the model while the opposite was observed for high MW PCBs. Plots of gas/particle partition coefficient (log Kp) vs. subcooled liquid vapor pressure (log pL(0)) had reasonable correlations for individual samples but the slope varied among the samples. Samples that originated from over the lake had higher slopes than samples that originated from over the land.     

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans in atmosphere; evaluation of predicting models

The gas/particle partitioning of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) was measured at three sites for a year in order to monitor the variation of PCDD/Fs levels and describe their partitioning. The air concentrations of PCDD/Fs ranged from 71 to 1161 fg I-TEQ/m³ and large changes in these levels did not correlate with seasonal changes during this study. Different homolog patterns were observed in the gas/particle phase. High chlorinated dioxin/furans dominated the particle phase while low chlorinated dioxin/furans dominated the gas phase. The high correlation coefficient between log [(PCDD/Fs_vap)(TSP)/(PCDD/Fs_pat)] and 1/T was observed in lower chlorinated dioxin/furans unlike in OCDD/F. The slope of homolog ranged from −0.410 to −1.025 and that of 2,3,7,8-substituted isomers ranged from −0.379 to −0.772 in plots of the log partition coefficient (K_p) versus the log subcooled vapor pressure (P_L°).The octanol/air partition coefficient (K_oa)-based model of PCDD/Fs is more compatible with experimental data than those of the Junge–Pankow model that tends to overestimate results, even though both models include some level of uncertainty. However, both models can underestimate the particle phase of PCDD/Fs, especially when the ambient air temperature is extremely low in winter.     

Gas/particle partitioning of polycyclic aromatic hydrocarbons in coastal atmosphere of the north Yellow Sea, China

Samples of gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) were collected at three sampling stations (Xiaomai Island, Laohutan, and Zhangzi Island) in the north Yellow Sea, China during November 2008 and September 2009 to study their atmospheric transport potential and the gas/particle distributions. The composition of PAHs was dominated by gaseous compounds. The percentages of the particle-phase PAHs to the total concentrations were found to be higher during the heating period than the non-heating period. The ratios of naphthalene and acenaphthene to phenanthrene, chrysene and dibenzo(a,h)anthracene showed an increasing trend from Xiaomai Island to Zhangzi Island, which can be called as the local atmospheric distillation of PAHs. Gas/particle partitioning coefficients (K _p) and their relationship with the sub-cooled liquid vapor pressures (pº_L) of PAHs were investigated. The regressions of logK _p versus logpº_L gave significant correlations for all samples of the three sites with r ² values in the range 0.56–0.66 (p?<?0.01). Both Junge–Pankow adsorption model and octanol–air partition coefficient absorption model tended to underestimate the sorption for most PAHs, but the absorption model appeared to be more suitable for predicting the particle fraction of PAHs than the Junge–Pankow model.     

Experimental testing of an annular denuder and filter system to measure gas–particle partitioning of semivolatile bifunctional carbonyls in the atmosphere

An annular denuder and filter-pack system was tested in combination with the use of the in-tube and on-fiber O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA)-derivatization technique to simultaneously sample and measure gaseous and particulate concentrations of semivolatile bifunctional carbonyl compounds in the atmosphere. Ozone was denuded from the sampling air to avoid oxidation and PFBHA was used as the sorbent by coating the sampling denuders and impregnating the filters. The collection efficiency of the system was evaluated under different conditions in photochemical smog chamber experiments and in field samplings of urban and suburban atmospheres. The effects of concentration level, temperature, and humidity on the collection efficiency were assessed. The system showed average collection efficiencies in one denuder from 81% for pyruvic acid and 82% for glyoxylic acid to 87% for hydroxyacetone and dihydroxyacetone. The capacity of the filters to collect the gaseous fraction that cannot be collected in the denuders was also evaluated, and the system allows a correction for this artifact. The application of this method to chamber experiments and field samplings offers an easy-to-apply technique with good results that can be used to evaluate the partition mechanisms of these compounds in the atmosphere.     

The gas/particle partitioning of polycyclic aromatic hydrocarbons collected at a sub-Arctic site in Canada

Polycyclic aromatic hydrocarbons (PAH) were measured in air samples at a remote air monitoring site established in the Yukon Territory, Canada as part of a global project (International Polar Year; IPY) to study the potential for atmospheric long-range transport of anthropogenic pollutants to the Arctic. Gas- and particle-phase PAH were collected in polyurethane foam plugs and on glass fibre filters respectively from August 2007 to October 2009. PAH concentrations were found to be highest in the winter months and lowest in summer. The gas/particle partitioning coefficients of 3–5 ringed PAH were computed and seasonal averages were compared. In the summer time, lower molecular mass PAH exhibited relatively higher partitioning into the particle-phase. This particle-phase partitioning led to the shallowest slopes being recorded during summer for the log–log correlation plots between the PAH partition coefficients and their sub-cooled vapour pressures. Air mass back trajectories suggest that local impacts may be more important during the summer time which is marked by increased camping activities at camping sites in the proximity of the sampling station. In conclusion, both summer and wintertime variations in PAH concentrations and gas/particle partitioning are considered to be source- and phototransformation-dependent rather than dependent on temperature-driven shifts in equilibrium partitioning.     

Henry's law constant, octanol-air partition coefficient and supercooled liquid vapor pressure of carbazole as a function of temperature: application to gas/particle partitioning in the atmosphere

The Henry's law constant for carbazole was experimentally determined between 5 and 35 degrees C using a gas-stripping technique. The following equation was obtained for dimensionless Henry's law constant (H') versus temperature (T, K): ln H' = -3982(T,K)(-1) + 1.01. Temperature-dependent octanol-air partition coefficients (KOA) and supercooled liquid vapor pressures (PL,Pa) of carbazole were also determined using the GC retention time method. The temperature dependence of KOA and PL were explained by the following: log KOA = 4076/(T,K) - 5.65, log PL(Pa) = -3948(T,K)(- 1) + 11.48.The gas and particle-phase carbazole concentrations measured previously in Chicago, IL in 1995 was used for gas/particle partitioning modeling. Octanol based absorptive partitioning model consistently underpredicted the gas/particle partition coefficients (Kp) for all sampling periods. However, overall there was a good agreement between the measured Kp and soot-based model predictions.     

Particle-size distribution and gas/particle partitioning of atmospheric polybrominated diphenyl ethers in urban areas of Greece

Ambient concentrations, gas/particle partitioning and particle-size distribution of polybrominated diphenyl ethers (PBDEs) were investigated in two urban areas (Athens and Heraklion) of Greece. Atmospheric (gas + particle) concentrations of ∑PBDE varied from 21 to 30 pg m⁻³ in the center of Athens and from 4 to 44 pg m⁻³ in the suburbs of Heraklion. A predominance of particulate PBDEs was observed in Athens (71-76% in particles), whereas the opposite was evident in Heraklion (69-92% in gas phase). In both urban areas, PBDE particle-size distribution featured a distinct enrichment in smaller particles. A similar trend was also observed in aerosols of a background marine site. For all sampling sites, more than 46% of ∑PBDE was associated with particles of <0.57 μm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system.     

Models for gas/particle partitioning,transformation and air/water surface exchange of PCBs and PCDD/Fs in CMAQ

We have added the capability to simulate polychlorinated biphenyls (PCBs) and polychlorinated dibenzo [p] dioxins and polychlorinated dibenzo-furans (PCDD/Fs) to the Community Multiscale Air Quality (CMAQ) modeling system, thus taking advantage of the latter's capability to simulate atmospheric advection, diffusion, gas-phase chemistry, cloud/precipitation, and aerosol processes. The modifications reported here include the addition to the CMAQ system of two gas/particle partitioning models options: the Junge–Pankow adsorption model and the K_OA absorption model, as well as chemical transformations and atmosphere/water surface exchange processes for these semi-volatile organics. Simulations for the purpose of model testing and validation were conducted for the years 2000 and 2002 on a domain covering most of North America. Both partitioning models give reasonable results when compared with available measurements. The model predictions of deposition and air concentrations also agree well with measurements. The modeling results also indicate that the long-range transport is important and anthropogenic emissions of PCBs and PCDD/Fs are dominant although surface exchange of PCBs may be important for some clean locations.     

The effect of temperature on the gas–particle partitioning of reactive mercury in atmospheric aerosols

Measurements of gas–particle-partitioning coefficients for reactive mercury in dry urban and laboratory aerosol were found to strongly depend on ambient temperature. Samples of atmospheric and laboratory aerosols (defined as both the gas and particle phases) were collected using filter and absorbent methods and analyzed for reactive mercury using thermal desorption combined with cold vapor atomic fluorescence spectroscopy. Synthetic ambient aerosols were generated in the laboratory from ammonium sulfate and adipic acid mixed with mercuric chloride in a purpose-built aerosol reactor. The aerosol reactor was operated in a temperature-controlled laboratory. Linear relationships between the logarithm of inverse gas–particle partitioning and inverse temperature were observed and parameterized for use in the atmospheric modeling of reactive mercury. Reactive mercury was observed to partition from the particle to the gas phase as ambient temperature increased. Good agreement between measurements made using urban and laboratory aerosols was seen after gas–particle-partitioning coefficients were normalized for surface area instead of mass. Thermodynamic analyses of the urban and laboratory gas–particle-partitioning measurements revealed that the strength of interaction between reactive mercury and particle surfaces was suggestive of chemisorption. Gas–particle-partitioning coefficients made with the Tekran ambient mercury analyzer (AMA) also showed a dependence on temperature. However, the Tekran AMA partitioning coefficients did not agree well with partitioning coefficients measured using the filter-based methods. The disagreement is consistent with the 50 °C operational temperature of the Tekran AMA.     

On-road measurements of ultrafine particle concentration profiles and their size distributions inside the longest highway tunnel in Southeast Asia

This study measured ultrafine particle (UFP) levels and their size distributions in the Hsuehshan tunnel from August 12 to 19, 2009, using a Fast Mobility Particle Sizer. Measurement results demonstrate that traffic volume, the slope of the tunnel (downhill or uphill) and the ventilation system affected UFP levels inside the tunnel. Average UFP levels were about 1.0 × 10⁵–3.0 × 10⁵ particles cm^?3 at normal traffic volume. A traffic jam in the tunnel could raise UFP levels to over 1.0 × 10⁶ particles cm^?3. UFP levels at the uphill bore were significantly higher than those at the downhill bore due to high UFP levels exhausted from vehicles going uphill at high engine load conditions. UFP levels eventually diluted 10–50% with fresh air from tunnel air shafts. Gas-to-particle condensation conversion markedly produced nucleation mode particles at the tunnel entrance section. Observations also showed Aitken mode particles markedly formed by coagulation growth of nucleation mode particles in the tunnel middle section and exit section. That is, the particle size distributions changed significantly inside the tunnel. Measurement results suggest that particles in the Aitken mode in the long tunnel governed UFP levels.     

Occurrence of gaseous and particulate polycyclic aromatic hydrocarbons in the urban atmosphere: study of sources and ambient temperature effect on the gas/particle concentration and distribution

The presence of polycyclic aromatic hydrocarbons (PAHs) in an urban region (Heraklion, Greece) and processes that govern their atmospheric fate were studied from November 2000 until February 2002. Sixteen samples were collected, by using an artifact-free sampling device, on a monthly basis and the concentration of PAHs in gas and particulate phase was determined. The most abundant members (gas + particles) were phenanthrene (20.0+/-7.0 ng m(-3)), fluoranthene (6.5+/-1.7 ng m(-3)), pyrene (6.6+/-2.4 ng m(-3)), and chrysene (3.1+/-1.5 ng m(-3)). Total concentration (gas+particulate) of PAH ranged from 44.3 to 129.2 ng m(-3), with a mean concentration of 79.3 ng m(-3). Total concentration of PAHs in gas phase ranged from 31.4 to 84.7 ng m(-3) with non-observable seasonal variation. Conversely, maximum PAH concentrations in the particulate phase occurred during winter months. Particulate concentration varied from 11.4 to 44.9 ng m(-3), with an average of 25.2 ng m(-3). PAH distribution between gas and particulate phase was in agreement with the sub-cooled vapor pressure. Shift in gas/particle distribution due to difference in ambient temperature elucidated to some extent the seasonal variation of the concentration of PAHs in particles.     

Semivolatile PAH and n-alkane gas/particle partitioning using the dual model: up-to-date coefficients and comparison with experimental data

The gas/particle partitioning coefficient K _p , of a semivolatile compound is a key parameter for its atmospheric fate. The most complete method of predicting K _p for polycyclic aromatic hydrocarbons (PAHs) is offered by the dual model, as it describes both the adsorption on soot and absorption into organic matter processes. However, experimental and model data exist almost exclusively for PAHs. In order to bridge this gap, experimental data on the phase partitioning of both PAHs and n-alkanes were collected at an urban and a remote site. Moreover, all the necessary parameters (e.g., octanol–air and soot–air partitioning coefficients) for the dual model have been collected and updated or (if missing) estimated for the first time. The results point out that both absorption and adsorption seem to contribute to the partitioning of PAHs and n-alkanes. However, it seems that the dual model always underestimates the particle sorption not only for PAHs but also for n-alkanes.     

Characterization of gas/particle concentrations and partitioning of polychlorinated biphenyls (PCBs) measured in an urban site of Turkey

Air concentrations of polychlorinated biphenyls (PCBs) in both gas and particle phases were measured in an urban site (BUTAL-Merinos) of the city of Bursa, Turkey between August 2004 and May 2005. The mean of total (particle+gas) PCB concentrations was about 491.8+/-189.4pg/m(3). The main contributors for PCBs in the sampling site were the local sources and long-range atmospheric transport supported by back trajectory analysis. Lower molecular weight PCB congeners generally dominated in the samples. The particle phase of the measured PCBs accounted for 15% of the total PCB concentrations. Gas/particle distribution was investigated using different approaches such as log K(P)-log P(L)(o), log K(P)-log K(OA) and the Junge-Pankow model. Regression analysis among log K(P), log P(L)(o) and log K(OA) exhibited significant correlation at p<0.05. Correlation between PCB homologs and meteorological parameters was formed to investigate the possible relationships.     

Regional modelling of anthropogenic sulphur in Southeast Asia

A co-operative research project between the Malaysian Meteorological Service (MMS) and the Swedish Meteorological and Hydrological Institute (SMHI) focussing on the usage of an atmospheric transport and chemistry model, has just been initiated. Here, we describe the main features of the dispersion model and discuss a first set of calculations in light of available measurements of sulphuric species in Southeast Asia. According to our results, anthropogenic sulphur concentrations and depositions are particularly high near the large cities of the region, around a metal smelter in the southern Philippines, and in a region extending from northern Vietnam into southeastern China. These areas coincide with the high-emissions regions of Southeast Asia and we tentatively conclude that regional transport of acidifying species is not as far-reaching as in the mid-latitudes. From our calculations, and from supporting measurements we conclude that most of rural Southeast Asia is not yet severely affected by anthropogenic sulphur, but given the rapid rate of economical development in this region the situation may deteriorate quickly. Areas that are particularly at risk include the large cities, northern Vietnam, most of central Thailand, most of peninsular Malaysia, eastern Sumatra and parts of Java, all of which receive total-sulphur depositions in excess of 0.5 g S m⁻² yr⁻¹. Our model simulates sulphate in precipitation in accordance with measurements, but it has a tendency to overestimate atmospheric SO₂. It remains to be investigated whether this is a problem in the model formulation or a result of unrepresentative sampling. An immediate continuation of this study should be performed with higher spatial resolution than the currently used 100×100 km². Other imperfections in this model study, which should be addressed in future work, include parameterised vertical transport in deep convective clouds, the influence of natural emissions (primarily from volcanoes) on the concentration and deposition of sulphuric species, and the year-to-year variability of the driving meteorological conditions.     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.     

Characteristics of polycyclic aromatic hydrocarbons in ambient air of a tropical mega-area,Ho Chi Minh City,Vietnam: concentration,distribution, gas/particle partitioning,potential sources and cancer risk assessment

Environmental Science and Pollution Research - This is the first investigation on overall characteristics of 25 polycyclic aromatic hydrocarbons (PAHs) (15 PAHs regulated by US-EPA (excluding...