Gas/particle partitioning model
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Twenty-five biogenic and anthropogenic secondary organic aerosol (SOA) markers have been measured over a one-year period in both gaseous and PM10 phases in the Paris region (France). Seasonal and chemical patterns were similar to those previously observed in Europe, but significantly different from the ones observed in America and Asia due to dissimilarities in source precursor emissions. Nitroaromatic compounds showed higher concentrations in winter due to larger emissions of their precursors originating from biomass combustion used for residential heating purposes. Among the biogenic markers, only isoprene SOA marker concentrations increased in summer while pinene SOA markers did not display any clear seasonal trend. The measured SOA markers, usually considered as semi-volatiles, were mainly associated to the particulate phase, except for the nitrophenols and nitroguaiacols, and their gas/particle partitioning (GPP) showed a low temperature and OM concentrations dependency. An evaluation of their GPP with thermodynamic model predictions suggested that apart from equilibrium partitioning between organic phase and air, the GPP of the markers is affected by processes suppressing volatility from a mixed organic and inorganic phase, such as enhanced dissolution in aerosol aqueous phase and non-equilibrium conditions. SOA marker concentrations were used to apportion secondary organic carbon (SOC) sources applying both, an improved version of the SOA-tracer method and positive matrix factorization (PMF) Total SOC estimations agreed very well between both models, except in summer and during a highly processed Springtime PM pollution event in which systematic underestimation by the SOA tracer method was evidenced. As a first approach, the SOA-tracer method could provide a reliable estimation of the average SOC concentrations, but it is limited due to the lack of markers for aged SOA together with missing SOA/SOC conversion fractions for several sources.
- Klíčová slova
- Aerosol, Gas/particle partitioning, PMF, SOA, Source apportionment, Tracers,
- Publikační typ
- časopisecké články MeSH
21 PAHs, 27 oxy-PAHs and 32 nitro-PAHs were measured every third day over a year in both gaseous (G) and particulate PM10 (P) phases in ambient air of Grenoble (France). Mean total concentrations (G+P) of PAHs and oxy-PAHs were in the same range and about 10ngm(-3). Nitro-PAHs were 50 to 100 times less concentrated averaging 100pgm(-3). Polycyclic aromatic compound (PAC) concentrations were 5 to 7 times higher in "cold" period (October to March) than in "warm" period (April to September). Seasonal variations may be explained by higher primary emissions from residential heating, especially biomass burning in "cold" season. Meteorological conditions and influence of the geomorphology around Grenoble, with the formation of thermal inversion layers leading to the stagnation of pollutants, were additional key parameters. Maximum individual PAC concentrations were observed during two PM10 pollution events in December and February-March. Chemical processes and secondary formation of oxy- and nitro-PAH were probably enhanced by the accumulation of the pollutants during these events. PAC gas/particle partitioning depended on compound molecular weight and vapour pressure. Gas/particle partitioning of oxy- and nitro-PAHs were evaluated using a multi-phase poly-parameter linear free energy relationship model. The PAC cancer risk was assessed using toxic equivalency factors available in the literature (19 PAHs, 10 nitro-PAHs and 1 oxy-PAH). Overall, particle-bound PACs contributed about 76% of the cancer risk. While PAHs accounted for most of the total PAC cancer risk, oxy- and nitro-PAHs could account for up to 24%. The risk quantification across substance classes is limited by toxicological data availability.
- Klíčová slova
- Aerosol, Air quality, Gas/particle partitioning model, NPAH, OPAH, PAH,
- MeSH
- látky znečišťující vzduch analýza MeSH
- monitorování životního prostředí MeSH
- nádory epidemiologie MeSH
- pevné částice analýza MeSH
- plyny analýza MeSH
- polycyklické aromatické uhlovodíky analýza MeSH
- riziko MeSH
- roční období MeSH
- velkoměsta MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Francie epidemiologie MeSH
- velkoměsta MeSH
- Názvy látek
- látky znečišťující vzduch MeSH
- pevné částice MeSH
- plyny MeSH
- polycyklické aromatické uhlovodíky MeSH
A model for gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs) was evaluated using polyparameter linear free energy relationships (ppLFERs) following a multiphase aerosol scenario. The model differentiates between various organic (i.e., liquid water-soluble (WS)/organic soluble (OS) organic matter (OM), and solid/semisolid organic polymers) and inorganic phases of the particulate matter (PM). Dimethyl sulfoxide and polyurethane were assigned as surrogates to simulate absorption into the above-mentioned organic phases, respectively, whereas soot, ammonium sulfate, and ammonium chloride simulated adsorption processes onto PM. The model was tested for gas and PM samples collected from urban and nonurban sites in Europe and the Mediterranean, and the output was compared with those calculated using single-parameter linear free energy relationship (spLFER) models, namely Junge-Pankow, Finizio, and Dachs-Eisenreich. The ppLFER model on average predicted 96 ± 3% of the observed partitioning constants for semivolatile PAHs, fluoranthene, and pyrene, within 1 order of magnitude accuracy with root-mean-square errors (RMSE) of 0.35-0.59 across the sites. This was a substantial improvement compared to Finizio and Dachs-Eisenreich models (37 ± 17 and 46 ± 18% and RMSE of 1.03-1.40 and 0.94-1.36, respectively). The Junge-Pankow model performed better among spLFERs but at the same time showed an overall tendency for overestimating the partitioning constants. The ppLFER model demonstrated the best overall performance without indicating a substantial intersite variability. The ppLFER analysis with the parametrization applied in this study suggests that the absorption into WSOSOM could dominate the overall partitioning process, while adsorption onto salts could be neglected.
- MeSH
- látky znečišťující vzduch * MeSH
- monitorování životního prostředí MeSH
- pevné částice MeSH
- plyny MeSH
- polycyklické aromatické uhlovodíky * MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- látky znečišťující vzduch * MeSH
- pevné částice MeSH
- plyny MeSH
- polycyklické aromatické uhlovodíky * MeSH
Gas-particle partitioning is one of the key factors that affect the environmental fate of semivolatile organic chemicals. Many organophosphate esters (OPEs) have been reported to primarily partition to particles in the atmosphere. However, because of the wide range of their physicochemical properties, it is unlikely that OPEs are mainly in the particle phase "as a class". We compared gas-particle partitioning predictions for 32 OPEs made by the commonly used OECD POV and LRTP Screening Tool ("the Tool") with the partitioning models of Junge-Pankow (J-P) and Harner-Bidleman (H-B), as well as recently measured data on OPE gas-particle partitioning. The results indicate that half of the tested OPEs partition into the gas phase. Partitioning into the gas phase seems to be determined by an octanol-air partition coefficient (log KOA) < 10 and a subcooled liquid vapor pressure (log PL) > -5 (PL in Pa), as well as the total suspended particle concentration (TSP) in the sampling area. The uncertainty of the physicochemical property data of the OPEs did not change this estimate. Furthermore, the predictions by the Tool, J-P- and H-B-models agreed with recently measured OPE gas-particle partitioning.
The occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑7PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m-3, respectively) were found at the remote site Finokalia. Partitioning coefficients, K P, were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (P L°) and the octanol-air partition coefficient (K OA), were investigated. The equilibrium adsorption (P L°-based) and absorption (K OA-based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log K OA, were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95-1.5, 1.5-3.0, 3.0-7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log P L° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources.
- Klíčová slova
- Absorption/adsorption models, Aerosol mass size distribution, Gas/particle partitioning, Long-range transport,
- MeSH
- adsorpce MeSH
- halogenované difenylethery analýza MeSH
- látky znečišťující vzduch analýza MeSH
- monitorování životního prostředí * MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Řecko MeSH
- Názvy látek
- halogenované difenylethery MeSH
- látky znečišťující vzduch MeSH
Polycyclic aromatic hydrocarbons (PAHs) were monitored at 20 sites in semi-rural, urban, and industrial areas of Ulsan, the largest industrial city in South Korea, for one year. The target compounds were the 16 priority PAHs designated by the US Environmental Protection Agency except for naphthalene, acenaphthene, and acenaphthylene. Gaseous PAHs collected using polyurethane foam-based passive air samplers (PUF-PASs) and particulate PAHs predicted using gas/particle partitioning models were used to estimate the human health risks. The mean total cancer risk through inhalation intake and dermal absorption for all target age groups (children, adolescents, adults, and lifetime) ranged from 0.10 × 10-7 to 2.62 × 10-7, lower than the acceptable risk level (10-6), thus representing a safe level for residents. The cancer risk through dermal absorption and inhalation intake was predicted to be highest in winter, mostly due to the higher concentrations of PAHs, especially high-molecular-weight species with greater toxicity. Additionally, gaseous and particulate PAHs contributed more to dermal absorption and inhalation intake, respectively. As a consequence of local emissions and advection, the risks were higher in the industrial and semi-rural areas. This study suggests that human health risks can be cost-effectively mapped on a local scale using passive air sampling.
- Klíčová slova
- PAHs, PAS, Risk assessment, Ulsan, gas/particle partitioning model,
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1-30 ng m(-3) (corresponding to 15-35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2-11 pg m(-3) (4-26 % of the total) and of DDT compounds were 2-12 pg m(-3) (4-23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 μm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM0.95) were 73-90 %, 34-71 % and 36-81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3-29.7)×10(-6) cm(-1) (44-70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.
- MeSH
- aerosoly analýza MeSH
- atmosféra chemie MeSH
- chlorované uhlovodíky analýza MeSH
- inhalační expozice analýza MeSH
- látky znečišťující vzduch analýza MeSH
- lidé MeSH
- monitorování životního prostředí MeSH
- pesticidy analýza MeSH
- pevné částice analýza MeSH
- polychlorované bifenyly analýza MeSH
- polycyklické aromatické uhlovodíky analýza MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- aerosoly MeSH
- chlorované uhlovodíky MeSH
- látky znečišťující vzduch MeSH
- pesticidy MeSH
- pevné částice MeSH
- polychlorované bifenyly MeSH
- polycyklické aromatické uhlovodíky MeSH
BACKGROUND: Air pollution, which represents a major environmental risk to human health, comprises a complex mixture of compounds where only little is known about its specific toxicities. OBJECTIVES: This study examined the specific toxicities associated with ambient air pollutant mixtures with respect to gas/particle partitioning, particulate matter (PM) size, pollutant polarity and bioaccessibility from PM, and evaluated the contribution of PAHs and their oxygenated and nitrated derivatives (OPAHs, NPAHs). METHODS: Air samples (gas phase, PM10 and size-segregated PM), were collected at urban (in winter and summer) and background (winter) sites in the Czech Republic. The total and bioaccessible concentrations were addressed using organic solvent extraction and simulated lung fluid extraction, respectively. Organic extracts were also further fractionated according to polarity. Aryl hydrocarbon receptor (AhR)-mediated activity, anti-/estrogenicity, anti-/androgenicity, thyroid receptor (TR)-mediated activity and cytotoxicity for bronchial cells were determined by human cell-based in vitro bioassays. The contribution of studied compounds to observed effects was assessed by both modelling and reconstructing the mixtures. RESULTS: Significant effects were detected in the sub-micrometre size fraction of PM (estrogenicity, androgenicity, TR- and AhR-mediated activities) and in the gas phase (TR-mediated activity, antiandrogenicity). Compounds interacting with TR showed high bioaccessibility to simulated lung fluid. Relatively lower bioaccessibility was observed for estrogenicity and AhR-mediated activity. However, the toxicity testing of reconstructed mixtures revealed that the targeted pollutants are not the main contributors, except for urban PM air pollution in winter, where they accounted for 5-88% of several effects detected in the original complex environmental samples. DISCUSSION: Studied toxicities were mostly driven by polar compounds largely attributed to the easily inhalable PM1, which is of high relevance for human health risk assessment. Except of parent PAHs in some cases, the targeted compounds contributed to the detected effects mostly to a relatively low extent implying huge data gaps in terms of endocrine disruptive potencies of targeted substances and the significance of other polar compounds present in ambient air.
- Klíčová slova
- Air pollutant mixture, Bioassay, Endocrine disruption, Human health, PAHs, OPAHs, NPAHs, Toxic potential,
- MeSH
- látky znečišťující vzduch * analýza toxicita MeSH
- látky znečišťující životní prostředí * MeSH
- lidé MeSH
- monitorování životního prostředí MeSH
- pevné částice analýza toxicita MeSH
- polycyklické aromatické uhlovodíky * analýza toxicita MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
- Názvy látek
- látky znečišťující vzduch * MeSH
- látky znečišťující životní prostředí * MeSH
- pevné částice MeSH
- polycyklické aromatické uhlovodíky * MeSH
