Partitioning Of Semivolatile Organic Compounds Research Articles

Slopes and intercepts from log-log correlations of gas/particle quotient and octanol-air partition coefficient (vapor-pressure) for semi-volatile organic compounds: II. Theoretical predictions vs. monitoring

The logarithm of gas/particle (G/P) partition quotient (logKP) has been found to have a linear relationship with logKOA (octanol-air partition coefficient) with slope mo and intercept bo and logPL (subcooled liquid vapor pressure) with slope mp and intercept bp. In the sister paper of the present work, analytical equations to predict the slope mo and intercept bo based on logKOA and predict the slope mp and intercept bp based on logPL are developed using steady state theory. In this work, the equations are evaluated using world-wide monitoring data (262 pairs for mo and bo values and 292 pairs for mp and bp values produced from more than 10,000 monitiring data worldwide) for selected seven groups of semi-volatile organic compounds (SVOCs), including polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins and polychorinated dibenzofurans (PCDD/Fs), polyclorinated biphenyl (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated naphthalenes (PCNs), organochlorinated pesticides (OCPs), novel brominated flame retardants (NBFRs), and other selected halogenated flame retardants. The slopes and intercepts predicted by the steady state equations reproduce the trends observed in monitoring regression results for the seven SVOC groups, with 44.4% of the variation of monitoring mo values accounted for by logKOA and 48.2% of the variation of monitoring mp values accounted for by logPL. Theoretically, the values of mo can be any value between 0 and 1 dependent on the values of KOA, and are not constrained to 1 as in equilibrium theory. Likewise, the values of mp can be any value between 0 and -1 dependent on the values of PL, and not constrained to −1 predicted by the equilibrium theory. The influence of sampling artifacts on the G/P partitioning of SVOCs has most likely been overemphasized by the equilibrium theory. Thus, the equilibrium approach should be abandoned in favor of the steady state approach for calculating the G/P partition quotients for SVOCs with high KOA values (>1011.38) or low PL values (<10−4.92).

Semivolatile organic compounds in French schools: Partitioning between the gas phase, airborne particles and settled dust.

The indoor environmental quality in classrooms can largely affect children's daily exposure to indoor chemicals in schools. To date, there has not been a comprehensive study of the concentrations of semivolatile organic compounds (SVOCs) in French schools. Therefore, the French Observatory for Indoor Air Quality (OQAI) performed a field study of SVOCs in 308 nurseries and elementary schools between June 2013 and June 2017. The concentrations of 52 SVOCs, including phthalates, polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), synthetic musks, and pesticides, were measured in air and settled dust (40 SVOCs in both air and dust, 12 in either air or dust). The results showed that phthalates had the highest concentrations among the SVOCs in both the air and dust. Other SVOCs, including tributyl phosphate, fluorene, phenanthrene, gamma-hexachlorocyclohexane (gamma-HCH, lindane), galaxolide, and tonalide, also showed high concentrations in both the air and dust. Theoretical equations were developed to estimate the SVOC partitioning between the air and settled dust from either the octanol/air partition coefficient or the boiling point of the SVOCs. The regression constants of the equations were determined using the data set of the present study for phthalates and PAHs.

Particle-Phase Diffusion Modulates Partitioning of Semivolatile Organic Compounds to Aged Secondary Organic Aerosol.

The diffusivity of semivolatile organic compounds (SVOCs) in the bulk particle phase of a viscous atmospheric secondary organic aerosol (SOA) can have a profound impact on aerosol growth and size distribution dynamics. Here, we investigate the bulk diffusivity of SVOCs formed from photo-oxidation of isoprene as they partition to a bimodal aerosol consisting of an Aitken (potassium sulfate) and accumulation mode (aged α-pinene SOA) particles as a function of relative humidity (RH). The model analysis of the observed size distribution evolution shows that liquid-like diffusion coefficient values of Db > 10-10 cm2 s-1 fail to explain the growth of the Aitken mode. Instead, much lower values of Db between2.5 × 10-15 cm2 s-1 at 32% RH and 8 × 10-15 cm2 s-1 at 82% RH were needed to successfully reproduce the growth of both modes. The diffusivity within the aged α-pinene SOA remains appreciably slow even at 80% RH, resulting in hindered partitioning of SVOCs to large viscous particles and allowing smaller and relatively less viscous particles to effectively absorb the available SVOCs and grow much faster than would be possible otherwise. These results have important implications for modeling SOA formation and growth in the ambient atmosphere.

Gas/particle partitioning of semi-volatile organic compounds in the atmosphere: Transition from unsteady to steady state

We derive differential equations to determine the kinetics of gas/particle partitioning of semi-volatile organic compounds (SVOCs). These equations model the transient states from initiation of sorption to particles (non-steady state) through the establishment of steady state. Two hypothetical scenarios are examined: (1) exchange of SVOCs between gas- and particle-phases alone; and (2) both gas/particle partitioning and wet and dry deposition of particles. The differential equations show that, under Scenario 1, a steady state is reached as an equilibrium between gas- and particle-phases, whereas under Scenario 2, the attained steady state is not in equilibrium. Our model shows that SVOCs in atmosphere where particle deposition is occurring reach a steady non-equilibrium state sooner than they would reach equilibrium under Scenario 1. We infer that SVOCs in the atmosphere will reach steady state instead of equilibrium between gaseous and particulate phases in circumstances where wet and dry deposition of particles cannot be neglected. In addition, our study indicates that the time for SVOCs to reach steady state in the atmosphere is fast, most likely within minutes or hours, suggesting that SVOCs are in steady or quasi-steady state in the atmosphere. Our analysis also reveals that gas/particle partitioning and particle deposition of SVOCs are dependent on each other.

Modeling the bioaccessibility of inhaled semivolatile organic compounds in the human respiratory tract.

The bioaccessibility of semivolatile organic compounds (SVOCs) via inhalation has rarely been studied, as indicated by the literature. There is no model to calculate the SVOC bioaccessibility following inhalation, and measurement data have focused on only a few polycyclic aromatic hydrocarbons (PAHs) in the particle phase. The present work developed a mechanistic model to address the mass transfer of inhaled SVOCs among the gas, particle and mucus phases in the human respiratory tract. The model considers (1) the SVOC partitioning between the gas and particle phases as well as between the gas and mucus phases and (2) the deposition of gas- and particle-phase SVOCs in the mucus of the respiratory tract. Based on the model, the inhalation bioaccessibility for 72 SVOCs was calculated. The SVOCs were measured in French dwellings at the nationwide scale, and their median concentrations in both the gas and particle phases were used for the bioaccessibility calculations. The results show that the inhalation bioaccessibility varies considerably from one compound to another, e.g., between 0.62 and 1.00 for phthalates, between 0.71 and 0.79 for polybrominated diphenyl ethers (PBDEs), between 0.48 and 0.56 for polychlorinated biphenyls (PCBs), between 0.48 and 1.00 for different chemical families of pesticides and between 0.48 and 0.90 for PAHs.

Volatility measurements of 1, 2, 6-hexanetriol in levitated viscous aerosol particles

The partitioning of semi-volatile organic compounds (SVOCs) between particle and gas phases is a primary focus in the study of the formation and lifetime of secondary organic aerosols (SOAs). To predict the temporal and spatial distribution of SOAs, it is essential to retrieve the fundamental parameters of SVOCs that govern the distribution of organic compounds between the condensed and gas phases. In the present work, the volatility of 1,2,6-hexanetriol in sucrose/1,2,6-hexanetriol/water mixed aerosol droplets was studied by employing optical tweezers coupled with cavity-enhanced Raman spectroscopy. The radii and refractive indexes of the levitated droplets were determined in real time using the wavelength positions of stimulated Raman spectra, and the effective vapor pressures of 1,2,6-hexanetriol at different relative humidity (RH) were obtained according to Maxwell equation. For the droplets with sucrose/1,2,6-hexanetriol molar ratio of 1:1, the effective vapor pressure of 1,2,6-hexanetriol decreased with the decrease of RH. When the RH decreased from 70% to 10%, the effective vapor pressure of 1,2,6-hexanetriol decreased from (2.16±0.229)×10−4Pa to (6.72 ±0.7)×10−6Pa. Compared to the vapor pressure of pure 1,2,6-hexanetriol (1.16 ± 0.025) ×10−4Pa~(3.82±1.16) ×10−4Pa, the evaporation of 1,2,6-hexanetriol in the mixed droplet was suppressed by sucrose, especially at low RH. For the mixed droplets with sucrose/1,2,6-hexanetriol molar ratio of 3:1, 1:3, a similar phenomenon was observed. Besides, for the mixed droplets under constant RH, the effective vapor pressure of 1,2,6-hexanetriol decreased with the sucrose increasing, and the presence of 1,2,6-hexanetriol caused viscosity decline of sucrose in the meantime. To characterize the water mass transfer of mixed droplets at different RH, the characteristic time ratios between the droplet radius and the RH were calculated. Compared to the characteristic time ratio of pure sucrose droplets, the characteristic time ratio of the mixed droplets apparently decreased. And for constant RH, the characteristic time of sucrose/1,2,6-hexanetriol/H2O decreased with the increase of 1,2,6-hexanetriol. In general, we report the studies of both volatility and molecular diffusion process in the aerosol phase for the sucrose/1,2,6-hexanetriol/H2O ternary system, these results may provide a theoretical basis for subsequent research concerning the volatility of SVOCs in super viscous aerosols.

Improving new particle formation simulation by coupling a volatility-basis set (VBS) organic aerosol module in NAQPMS+APM

We developed a new modeling framework to simulate aerosol microphysics by incorporating a volatility basis-set (VBS) organic aerosol (OA) module into a three-dimensional (3-D) atmospheric transport model, namely, Nested Air Quality Prediction Modeling System with an Advanced Particle Microphysics (NAQPMS + APM). The new model calculates not only the condensation of sulfuric acid, nitrate, and ammonium and the coagulation of five types of particles (namely secondary, sea salt, dust, black carbon and organic carbon particles) but also the condensation of low-volatility organic vapors and the equilibrium partitioning of semi-volatile organic compounds. The new model was applied to simulate new particle formation (NPF) in summer in Beijing. The new model could noticeably improve the NPF simulation. On comparing the simulation with observation, the ion-mediated nucleation scheme was found to underestimate nucleation rates in summer in Beijing. By incorporating a nucleation formula involving the participation of organic compounds, NPF events could be reproduced satisfactorily. Reasonably calculating nucleation rates is essential for successfully simulating NPF. Accounting for the condensation of anthropogenic low-volatility organic vapors and the volatility of primary OA (POA) can improve the temporal variation of the number concentrations of particles in Aitken and accumulation modes. On a regional scale, anthropogenic low-volatility secondary organic gases (LV-SOGs) and the volatility of POA have large impacts on the aerosol number concentration and cloud condensation nuclei (CCN) concentration. Both anthropogenic LV-SOGs and volatility of POA must be considered to quantify the contribution of NPF to the aerosol number concentration and CCN concentration.

Sampling artifacts in denuders during phase partitioning measurements of semi-volatile organic compounds

The partitioning of semi-volatile organic compounds (SVOCs) between the gas and particle phase plays an important role in understanding the formation of secondary organic aerosols (SOAs) in the atmosphere. There are uncertainties and problems associated with measurements during the simultaneous sampling of both gas and particle phases. In recent studies, diffusion denuders have been used for separate sampling of gas and particle phases of organic compounds. The removal of the gaseous species in the denuder distorts the gas–particle equilibrium and leads to the dissociation of the particulate phase during the sampling. This phenomenon is particularly true for volatile organic species and leads to significant error in determining gas-to-particle phase partitioning of organic aerosols due to underestimation of the particle phase. In this study, a model for simultaneous gas diffusion and aerosol decomposition/evaporation in the parallel plate denuder was developed to investigate the effects of sampling artifacts on gas–particle partitioning measurements of SVOCs. The model equations were cast into dimensionless form for generalization, and the effects of governing dimensionless groups on the denuder sampling artifacts were evaluated by performing a sensitivity analysis. Also, regression correlations for denuder sampling artifacts as the function of governing dimensionless groups were obtained. It was observed that the sampling of SVOCs could result in substantial particulate phase loss due to evaporation in the denuder, resulting in significant errors in the phase partitioning measurements. Also, the operating conditions for the denuder, so that the denuder sampling artifacts lie within tolerable limits, were evaluated.Copyright © 2018 American Association for Aerosol Research

Semi-volatile organic compounds in French dwellings: An estimation of concentrations in the gas phase and particulate phase from settled dust

Semi-volatile organic compounds (SVOCs) are present in the gas phase, particulate phase and settled dust in the indoor environment, resulting in human exposure through different pathways. Sometimes, SVOCs are only measured in a single phase because of practical and/or financial constraints. A probabilistic method proposed by Wei et al. for the prediction of the SVOC concentration in the gas phase from the SVOC concentration in the particulate phase was extended to model the equilibrium SVOC concentrations in both the gas and particulate phases from the SVOC concentration measured in settled dust. This approach, based on the theory of SVOC partitioning among the gas phase, particulate phase, and settled dust incorporating Monte Carlo simulation, was validated using measured data from the literature and applied to the prediction of the concentrations of 48 SVOCs in both the gas and particulate phases in 3.6 million French dwellings where at least one child aged 6 months to 6 years lived. The median gas-phase concentration of 15 SVOCs, i.e., 5 phthalates, 2 organochlorine pesticides, 4 polycyclic aromatic hydrocarbons (PAHs), 2 synthetic musks, dichlorvos, and tributyl phosphate, was found to be higher than 1 ng/m3. The median concentration of 5 phthalates in the particulate phase was higher than 1 ng/m3. The impacts of some physical parameters, such as the molar mass and boiling point, on the SVOC partitioning among the different phases were quantified. The partitioning depends on the activity coefficient, vapor pressure at the boiling point, entropy of evaporation of the SVOCs, and the fraction of organic matter in particles. Thus, the partitioning may differ from one chemical family to another. The empirical equations based on regressions allow quick estimation of SVOC partitioning among the gas phase, particulate phase, and settled dust from the molar mass and boiling point.

Predicting Dermal Exposure to Gas-Phase Semivolatile Organic Compounds (SVOCs): A Further Study of SVOC Mass Transfer between Clothing and Skin Surface Lipids.

Dermal exposure to indoor gas-phase semivolatile organic compounds (SVOCs) has recently received a great deal of attention, and this has included evaluating the role of clothing in this process. Several models have been developed to assess dermal exposure to SVOCs, based on the transient mass transfer of SVOCs from air to dermal capillaries. Assumptions of these models are either that clothing completely retards SVOC transport, or that there is an air gap of constant thickness between the clothing and the surface of the skin, which may lead to errors in the model calculations. To solve this problem, we tried to describe SVOC transport between clothing and epidermis by considering two parallel processes: partitioning of SVOCs by direct contact (ignored in existing models), and Fickian diffusion through the air gap. Predictions from the present model agree well with the experimental data found in the literature (dermal uptake of diethyl phthalate (DEP) and di- n-butyl phthalate (DnBP) of a clothed participant). This study provides a useful tool to accurately assess dermal exposure to indoor SVOCs, especially for evaluating the effects of clothing on dermal exposure.

Mass accommodation coefficients of fresh and aged biomass-burning emissions

ABSTRACTMost chemical transport models treat the partitioning of semi-volatile organic compounds (SVOCs) with the assumption of instantaneous thermodynamic equilibrium. However, the mass accommodation coefficients, α, of biomass-burning organic aerosol (BBOA) are largely unconstrained. During the FLAME-IV campaign, we thermally perturbed aged and fresh BBOA with a variable residence time thermodenuder and measured the resulting change in particle mass concentration to restore equilibrium. We used this equilibration profile to retrieve an effective α for components of BBOA that dictated this profile and found that the mass accommodation coefficients lie within the range 0.1 ≪ α ⩽ 1. A simple plume dilution model shows a maximum of only a 7% difference between a dynamical and an instantaneous equilibrium partitioning model using our best-estimate value for α. This supports continued use of the equilibrium assumption to treat partitioning of biomass-burning emissions in chemical-transport models.Copyright © ...

Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air

Indoor semivolatile organic compounds (SVOCs) originate from indoor and outdoor sources. These SVOCs partition among different phases and available surfaces, which increases their residence time indoors to several years. SVOCs may also react with indoor oxidants, such as hydroxyl radicals (OH), nitrate radicals (NO3), and ozone. In the present study, the second-order reaction rate constants of 72 SVOCs in indoor air (gas and particle phases) at room temperature and ambient air pressure were retrieved from the literature. The pseudo–first-order reaction rate constants of these SVOCs were calculated for the indoor concentration ranges of OH, NO3, and ozone. Then, the extent to which the chemical reaction had a meaningful impact on the removal of SVOCs from the indoor environment was quantitatively analyzed. The orders of magnitude of the second-order rate constant ranged between 10−15 and 10−10 cm3/(molecule·s) for OH/SVOC reactions, 10−17 and 10−12 cm3/(molecule·s) for NO3/SVOC reactions, and 10−20 and 10−16 cm3/(molecule·s) for ozone/SVOC reactions in indoor air. Assuming that the highest indoor reactant concentrations were 1.8 × 106 molecules/cm3 (7.3 × 10−5 ppb) for OH, 2.5 × 108 molecules/cm3 (10−2 ppb) for NO3, and 1.4 × 1012 molecules/cm3 (58 ppb) for ozone, the highest pseudo–first-order rate constants in the gas phase for the studied reactions of OH/SVOCs (n = 72), NO3/SVOCs (n = 3), and ozone/SVOCs (n = 14) reached 1.5 h−1 (OH/benzo[a]pyrene), 0.41 h−1 (NO3/acenaphthene), and 1.0 h−1 (ozone/aldrin and ozone/heptachlor), respectively. The pseudo–first-order rate constants in the particle phase for the studied reactions of OH/SVOCs (n = 13), NO3/SVOCs (n = 6), and ozone/SVOCs (n = 14) at the high indoor reactant concentrations reached 0.09 h−1 (OH/DEHP), 5.8 h−1 (NO3/pyrene), and 11 h−1 (ozone/benzo[a]pyrene), respectively. These results indicate that the chemical reactions of some SVOCs in indoor air have a meaningful impact compared to the air exchange rate, which should be considered in future studies on indoor air quality modeling.

Adsorption of Phthalates on Impervious Indoor Surfaces.

Sorption of semivolatile organic compounds (SVOCs) onto interior surfaces, often referred to as the "sink effect", and their subsequent re-emission significantly affect the fate and transport of indoor SVOCs and the resulting human exposure. Unfortunately, experimental challenges and the large number of SVOC/surface combinations have impeded progress in understanding sorption of SVOCs on indoor surfaces. An experimental approach based on a diffusion model was thus developed to determine the surface/air partition coefficient K of di-2-ethylhexyl phthalate (DEHP) on typical impervious surfaces including aluminum, steel, glass, and acrylic. The results indicate that surface roughness plays an important role in the adsorption process. Although larger data sets are needed, the ability to predict K could be greatly improved by establishing the nature of the relationship between surface roughness and K for clean indoor surfaces. Furthermore, different surfaces exhibit nearly identical K values after being exposed to kitchen grime with values that are close to those reported for the octanol/air partition coefficient. This strongly supports the idea that interactions between gas-phase DEHP and soiled surfaces have been reduced to interactions with an organic film. Collectively, the results provide an improved understanding of equilibrium partitioning of SVOCs on impervious surfaces.

Lability of secondary organic particulate matter

The energy flows in Earth's natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representative of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic compared with biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate Dorg for the biogenic case is at least 103 times greater than that of the anthropogenic case. These differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PM in Earth's atmosphere.

Seasonal fate and gas/particle partitioning of semi-volatile organic compounds in indoor and outdoor air

Fifty-eight semi-volatile organic compounds (SVOCs) were investigated simultaneously in three indoor (apartment, nursery and office building) and one outdoor environment in the centre of Paris (France). All of these compounds except tetrabromobisphenol A were quantified in the gaseous and particulate phases in all three environments, and at a frequency of 100% for the predominant compounds of each SVOC class. Phthalic acid esters (PAEs) were the most abundant group (di-iso-butyl phthalate: 29–661 ng m−3, diethyl phthalate: 15–542 ng m−3), followed by 4-nonylphenol (1.4–81 ng m−3), parabens (methylparaben: 0.03–2.5 ng m−3), hexachlorobenzene (HCB) (0.002–0.26 ng m−3) and pentachlorobenzene (PeCB) (0.001–0.23 ng m−3). Polycyclic aromatic hydrocarbons (as ∑8PAHs) ranged from 0.17 to 5.40 ng m−3, polychlorinated biphenyls (as ∑7PCBi) from 0.06 to 4.70 ng.m3 and polybromodiphenyl ethers (as ∑8PBDEs) from 0.002 to 0.40 ng m−3. For most pollutants, significantly higher concentrations were observed in the nursery compared to the apartment and office. Overall, the indoor air concentrations were up to ten times higher than outdoor air concentrations. Seasonal variations were observed for PAEs, PCBs and PAHs. SVOCs were predominantly identified in the gaseous phase (>90%), except for some high-molecular-weight PAEs, PAHs and PCBs.

Distributions of the particle/gas and dust/gas partition coefficients for seventy-two semi-volatile organic compounds in indoor environment

Particle/gas and dust/gas partition coefficients (Kp and Kd) are two key parameters that address the partitioning of semi-volatile organic compounds (SVOCs) between gas-phase, airborne particles, and settled dust in indoor environment. A number of empirical equations to calculate the values of Kp and Kd have been reported in the literature. Therefore, the difficulty lies in the selection of a specific empirical equation in a given situation. In this study, we retrieved from the literature 38 empirical equations for calculating Kp and Kd values from the SVOC saturation vapor pressure and octanol/air partition coefficient. These values were calculated for 72 SVOCs: 9 phthalates, 9 polybrominated diphenyl ethers (PBDEs), 11 polychlorinated biphenyls (PCBs), 22 biocides, 14 polycyclic aromatic hydrocarbons (PAHs), 3 alkylphenols, 2 synthetic musks, tributylphosphate, and bisphenol A. The mean and median values of log10Kp or log10Kd for most SVOCs were of the same order of magnitude. The distribution of log10Kp values was fitted to either a normal distribution (for 27 SVOCs) or a log-normal distribution (for 45 SVOCs). This work provides a reference distribution of the log10Kp for 72 SVOCs, and its use may reduce the bias associated with the selection of a specific value or equation.

Nighttime aqueous-phase secondary organic aerosols in Los Angeles and its implication for fine particulate matter composition and oxidative potential

Recent investigations suggest that aqueous phase oxidation of hydrophilic organic compounds can be a significant source of secondary organic aerosols (SOA) in the atmosphere. Here we investigate the possibility of nighttime aqueous phase formation of SOA in Los Angeles during winter, through examination of trends in fine particulate matter (PM2.5) carbonaceous content during two contrasting seasons. Distinctive winter and summer trends were observed for the diurnal variation of organic carbon (OC) and secondary organic carbon (SOC), with elevated levels during the nighttime in winter, suggesting an enhanced formation of SOA during that period. The nighttime ratio of SOC to OC was positively associated with the relative humidity (RH) at high RH levels (above 70%), which is when the liquid water content of the ambient aerosol would be high and could facilitate dissolution of hydrophilic primary organic compounds into the aqueous phase. Time-integrated collection and analysis of wintertime particles at three time periods of the day (morning, 6:00 a.m.–9:00 a.m.; afternoon, 11:00 a.m.–3:00 p.m.; night, 8:00 p.m.–4:00 a.m.) revealed higher levels of water soluble organic carbon (WSOC) and organic acids during the night and afternoon periods compared to the morning period, indicating that the SOA formation in winter continues throughout the nighttime. Furthermore, diurnal trends in concentrations of semi-volatile organic compounds (SVOCs) from primary emissions showed that partitioning of SVOCs from the gas to the particle phase due to the decreased nighttime temperatures cannot explain the substantial OC and SOC increase at night. The oxidative potential of the collected particles (quantified using a biological macrophage-based reactive oxygen species assay, in addition to the dithiothreitol assay) was comparable during afternoon and nighttime periods, but higher (by at least ∼30%) compared to the morning period, suggesting that SOA formation processes possibly enhance the toxicity of the ambient particles compared to mobile-source dominated primary emissions in the Los Angeles area.

Characteristics of atmospheric particulate mercury in size-fractionated particles during haze days in Shanghai

Atmospheric particulate mercury (PHg) is recognized as a global pollutant that requires regulation because of its significant impacts on both human health and wildlife. The haze episodes that occur frequently in China could influence the transport and fate of PHg. To examine the characteristics of PHg during haze and non-haze days, size-fractioned particles were collected using thirteen-stage Nano-MOUDI samplers (10 nm–18 μm) during a severe haze episode (from December 2013 to January 2014) in Shanghai. The PHg concentration on haze days (4.11 ± 0.53 ng m−3) was three times higher than on non-haze days (1.34 ± 0.15 ng m−3). The ratio of the PHg concentration to total gaseous mercury (TGM) ranged from 0.42 during haze days to 0.21 during non-haze days, which was possibly due to the elevated concentration of particles for gaseous elemental mercury (GEM) adsorption, elevated sulfate and nitrate contributing to GEM oxidation, and the catalytic effect of elevated water-soluble inorganic metal ions. PHg/PM10 during haze days (0.019 ± 0.004 ng/μg) was lower than during non-haze days (0.024 ± 0.002 ng/μg), and PHg/PM10 was significantly reduced with an increasing concentration of PM10, which implied a relatively lower growth velocity of mercury than other compositions on particles during haze days, especially in the diameter range of 0.018–0.032 μm.During haze days, each size-fractioned PHg concentration was higher than the corresponding fraction on non-haze days, and the dominant particle size was in the accumulation mode, with constant accumulation to a particle size of 0.56–1.0 μm. The mass size distribution of PHg was bimodal with peaks at 0.32–0.56 μm and 3.1–6.2 μm on non-haze days, and 0.56–1.0 μm and 3.1–6.2 μm on haze days. There was a clear trend that the dominant size for PHg in the fine modes shifted from 0.32–0.56 μm during non-haze days to 0.56–1.0 μm on haze days, which revealed the higher growth velocity of PHg on haze days due to the condensation and accumulation of Hg in particles. Traffic emissions and coal combustion may contribute to the high concentrations of Hg, because PHg of every size was found to correlate positively with SO2, NO2, and CO. A correlation was found between every mode of PHg and relative humidity, which affected the gas-particle partitioning of semi-volatile organic compounds, resulting in effective partitioning into aerosols. The strong correlations between Hg and water-soluble ions implied the oxidation of elemental Hg was the main gas-to-particle chemical transformation process.

Modeling and analysis of sampling artifacts in measurements of gas-particle partitioning of semivolatile organic contaminants using filter-sorbent samplers

Measurements of gas/particle partition coefficients for semivolatile organic compounds (SVOCs) using filter-sorbent samplers can be biased if a fraction of gas-phase mass is measured erroneously as particle-phase due to sorption of SVOC gases to the filter, or, if a fraction of particle-phase mass is measured erroneously as gas-phase due to penetration of particles into the sorbent. A fundamental mechanistic model to characterize the air sampling process with filter-sorbent samplers for SVOCs was developed and partially validated. The potential sampling artifacts associated with measurements of gas-particle partitioning were examined for 19 SVOCs. Positive sampling bias (i.e., overestimation of gas/particle partition coefficients) was observed for almost all the SVOCs. For certain compounds, the measured partition coefficient was several orders of magnitude greater than the presumed value. It was found that the sampling artifacts can be ignored when the value of log[Kf/(Kp⋅Cp,a)] is less than 7. By normalizing the model, general factors that influence the sampling artifacts were investigated. Correlations were obtained between the dimensionless time required for the gas-phase SVOCs within the filter to reach steady state (Ts,s∗) and the chemical Vp values, which can be used to estimate appropriate sampling time. The potential errors between measured and actual gas/particle partition coefficients of SVOCs as a function of sampling velocity and time were calculated and plotted for a range of SVOCs (vapor pressures: 10−8 ∼ 10−3 Pa). These plots were useful in identifying bias from the sampling in previously-completed field measurements. Penetration of particles into the sorbent may result in significant underestimation of the partition coefficient for particles in the size range between 10 nm and 2 μm. For most of the selected compounds, backup filters can be used to correct artifacts effectively. However, for some compounds with very low vapor pressure, the artifacts remained or became even larger than they were without the backup filter. Thus, the option of backup filters must be considered carefully in field measurements of the gas/particle partitioning of SVOCs. The results of this work will allow researchers to predict potential artifacts associated with SVOC gas/particle partitioning as functions of compounds, the concentration of particles, the distribution of particle sizes, sampling velocity, and sampling time.

Atmospheric gas-particle partitioning versus gaseous/particle-bound deposition of SVOCs: Why they are not equivalent

Semi-volatile organic compounds (SVOCs) can be particle-bound or in the gas phase in the atmosphere, depending on the (temperature dependent) gas-particle partitioning of the chemicals and the fraction of particles in air. Several studies linked gas-particle partitioning of SVOCs in the atmosphere directly to the gaseous/particle-bound deposition of these chemicals, i.e. in cases of compounds occurring mainly in the gas phase, the deposition was also assumed to be mainly in gaseous form. In this study, we apply a multi-media fate model to point out that gas-particle partitioning of SVOCs in air and gaseous/particle-bound deposition of SVOCs are driven by different mechanism and, thus, cannot be deduced from each other. We apply our calculations to polychlorinated biphenyls (PCBs), as model SVOCs. We show that the fraction of particle-bound deposition to deciduous forest is 1.5–190 times higher in winter and between 5 and 1000 times higher in summer than the particle-bound fraction of these chemicals in air. The fraction of particle-bound deposition to coniferous forest is 1.5–172 times higher in winter and between 5 and 1000 times higher in summer than the particle-bound fraction of PCBs in air. In addition to the fractions of particle-bound SVOCs in air and particle-bound deposition, we recalculated particle-bound and gaseous deposition velocities to coniferous and deciduous forest for PCBs. The deposition velocities obtained for dry gaseous deposition (<1 m/h) are much lower than the existing values in the literature (10–200 m/h) because earlier studies assumed that for PCBs occurring predominantly in the gas phase, interception was also completely due to dry gaseous deposition.