Partitioning Of Semivolatile Organic Compounds Research Articles

The impact of gaseous degradation on the gas–particle partitioning of methylated polycyclic aromatic hydrocarbons

Abstract. The partitioning of semi-volatile organic compounds (SVOCs) between gas and particle phases plays a crucial role in their long-range transport and health risk assessment. However, the accurate prediction of the gas–particle (G–P) partitioning quotient (KP′) remains a challenge, especially for the light-molecular-weight (LMW) SVOCs due to their upward deviation from equilibrium state. In this study, the phenomenon with the influence of gaseous degradation on G–P partitioning was observed. Based on the diurnal study of concentrations and KP′ values for methylated polycyclic aromatic hydrocarbons (Me-PAHs), it was found that the KP′ values of methylated naphthalenes (Me-Naps; one type of LMW SVOC) during the daytime were higher than during the nighttime, and the regression lines of log KP′ versus log KOA (octanol–air partitioning coefficient) for daytime and nighttime were non-overlapping, which were different from other Me-PAHs. Compared with other diurnal influencing factors, the higher gaseous degradation of Me-Naps in the daytime than in the nighttime should partially explain their special diurnal variation in KP′, which provided a new explanation for the non-equilibrium behavior of KP′ for LMW SVOCs. Moreover, the influence of gaseous degradation on the deviation of KP′ from equilibrium state was deeply studied based on the steady-state G–P partitioning model considering particulate proportion in emission (ϕ0). The increasing times of KP′ influenced by the gaseous degradation deviated from equilibrium state can be calculated by 1 + 13.2ϕ0 × kdeg (kdeg, gaseous degradation rate). The increase in KP′ along with the increase in kdeg proved that higher gaseous degradation in the daytime could increase the KP′ value. Furthermore, an amplification in KP′ ranging from 1.11 to 5.58 times (90 % confidence interval: 1.01 to 14.4) under different ϕ0 values (0 to 1) in the temperature range of −50 to 50 °C was estimated by the Monte Carlo analysis. In summary, it can be concluded that the influence of gaseous degradation should also be considered in the G–P partitioning models of SVOCs, especially for the LMW SVOCs, which provided new insights into the related fields.

Modelling the dynamic gas/particle partitioning process of semi-volatile organic compounds emitted from point sources: Quantitative analysis and impact assessment

The deleterious impact of pollution point sources on the surrounding environment and human has long been a focal point of environmental research. When considering the local atmospheric dispersion of semi-volatile organic compounds (SVOCs) around the emission sites, it is essential to account the dynamic process for the gas/particle (G/P) partitioning, which involves the transition from an initial state to a steady state. In this study, we have developed a model that enables the prediction of the dynamic process for G/P partitioning of SVOCs, particularly considering the influence from emission. It is important to note that the dynamic processes of the concentrations of SVOCs in particle phase (CP) and in gas phase (CG) differ significantly. These differences arise due to the influence of two critical factors: particulate proportion of SVOCs in the emissions (ϕ0) and octanol-air partitioning coefficient (KOA). The validity of our model was assessed by comparing its predictions of the extremum value of the G/P partitioning quotient (KP) with the results obtained from the steady-state model. Remarkably, the characteristic time (tC), used to evaluate the timescale required for SVOCs to reach steady state, demonstrated different variations with KOA for CP and CG. Additionally, the values of tC were quite different for CP and CG, which were markedly influenced by ϕ0. For some SVOCs with high KOA values, it took approximately 35 h to reach steady state. Furthermore, it was found that the time to achieve 95 % of steady state (t95 ≈ 3tC) could reach approximately 105 h. This duration is sufficient for chemicals to disperse from their emission site to the surrounding areas. Therefore, it is crucial to consider the dynamic process of G/P partitioning in local atmospheric transport studies. Moreover, the influence of ϕ0 should be incorporated into future investigations examining the dynamic process of G/P partitioning.

Impact of pH on Gas-Particle Partitioning of Semi-Volatile Organics in Multicomponent Aerosol.

The partitioning of semivolatile organic compounds (SVOCs) between the condensed and gas phases can have significant implications for the properties of aerosol particles. In addition to affecting size and composition, this partitioning can alter radiative properties and impact cloud activation processes. We present measurements and model predictions on how activity and pH influence the evaporation of SVOCs from particles to the gas phase, specifically investigating aqueous inorganic particles containing dicarboxylic acids (DCAs). The aerosols are studied at the single-particle level by using optical trapping and cavity-enhanced Raman spectroscopy. Optical resonances in the spectra enable precise size tracking, while vibrational bands allow real-time monitoring of pH. Results are compared to a Maxwell-type model that accounts for volatile and nonvolatile solutes in aqueous droplets that are held at a constant relative humidity. The aerosol inorganic-organic mixture functional group activity coefficients thermodynamic model and Debye-Hückel theory are both used to calculate the activities of the species present in the droplet. For DCAs, we find that the evaporation rate is highly sensitive to the particle pH. For acidity changes of approximately 1.5 pH units, we observe a shift from a volatile system to one that is completely nonvolatile. We also observe that the pH itself is not constant during evaporation; it increases as DCAs evaporate, slowing the rate of evaporation until it eventually ceases. Whether a DCA evaporates or remains a stable component of the droplet is determined by the difference between the lowest pKa of the DCA and the pH of the droplet.

Gas–particle partitioning of semivolatile organic compounds when wildfire smoke comes to town

Abstract. Wildfires have become an increasingly important source of organic gases and particulate matter in the western USA. A large fraction of organic particulate matter emitted in wildfires is semivolatile, and the oxidation of organic gases in smoke can form lower-volatility products that then condense on smoke particulates. In this research, we measured the gas- and particle-phase concentrations of semivolatile organic compounds (SVOCs) during the 2017 northern California wildfires in a downwind urban area, using semivolatile thermal desorption aerosol gas chromatography (SV-TAG), and measured SVOCs in a rural site affected by biomass burning using cTAG (comprehensive thermal desorption aerosol gas chromatography mass spectrometry) in Idaho in 2018. Commonly used biomass burning markers such as levoglucosan, mannosan, and nitrocatechols were found to stay predominantly in the particle phase, even when the ambient organic aerosol (OA) was relatively low. The phase partitioning of SVOCs is observed to be dependent on their saturation vapor pressure, while the equilibrium absorption model underpredicts the particle-phase fraction of most of the compounds measured. Wildfire organic aerosol enhanced the condensation of polar compounds into the particle phase but not some nonpolar compounds, such as polycyclic aromatic hydrocarbons.

Nonequilibrium Behavior in Isoprene Secondary Organic Aerosol.

Recent studies have shown that instantaneous gas-particle equilibrium partitioning assumptions fail to predict SOA formation, even at high relative humidity (∼85%), and photochemical aging seems to be one driving factor. In this study, we probe the minimum aging time scale required to observe nonequilibrium partitioning of semivolatile organic compounds (SVOCs) between the gas and aerosol phase at ∼50% RH. Seed isoprene SOA is generated by photo-oxidation in the presence of effloresced ammonium sulfate seeds at <1 ppbv NOx, aged photochemically or in the dark for 0.3-6 h, and subsequently exposed to fresh isoprene SVOCs. Our results show that the equilibrium partitioning assumption is accurate for fresh isoprene SOA but breaks down after isoprene SOA has been aged for as short as 20 min even in the dark. Modeling results show that a semisolid SOA phase state is necessary to reproduce the observed particle size distribution evolution. The observed nonequilibrium partitioning behavior and inferred semisolid phase state are corroborated by offline mass spectrometric analysis on the bulk aerosol particles showing the formation of organosulfates and oligomers. The unexpected short time scale for the phase transition within isoprene SOA has important implications for the growth of atmospheric ultrafine particles to climate-relevant sizes.

Ten questions concerning indoor ultrafine particles

Ultrafine particles (≤100 nm in diameter) are the smallest condensed-phase materials in air. By number, they are the most abundant particles both outdoors and indoors. Because of their small size, they contribute little to mass concentrations of fine particles, a regulated air pollutant with large associated health risks. Inhaling ultrafine particles raises health concerns, in part owing to their ability to migrate from the site of deposition in the respiratory tract. Buildings provide partial protection against ultrafine particles of outdoor origin. The degree of that protection is broadly variable, influenced by particle size and by building design and operational factors, such as ventilation rates and the efficiency of particle filters. Because of the large proportion of time spent by people indoors, much exposure to ultrafine particles occurs in buildings, even for particles of outdoor origin. Diverse indoor sources, including cooking and the use of candles, contribute materially to indoor ultrafine particle concentrations. Indoor sourced ultrafine particle concentrations are also influenced by building design and operational factors. Whether of indoor or outdoor origin, dynamic processes influence the concentrations, sizes, and chemical composition of ultrafine particles. Such processes include deposition to indoor surfaces, coagulation, and sorptive partitioning of semivolatile organic compounds. Advancing scientific and technical knowledge about building factors and dynamic processes that influence indoor ultrafine particle concentrations can contribute (a) to better understanding of associated health risks and (b) to the more effective design and implementation of mitigation strategies and technologies.

Evaluating Neutral PFAS for Potential Dermal Absorption from the Gas Phase.

Exposures to per- and polyfluoroalkyl substances (PFAS) are of increasing concern. Assessments typically focus only on ingestion and inhalation exposure due to a lack of generally accepted approaches for estimating dermal absorption. Prior work indicates limited dermal absorption of ionic PFAS, but absorption of neutral PFAS has not been examined from the liquid vehicle or from vapor. Partitioning of semivolatile organic compounds from the gas phase to the skin surface (i.e., stratum corneum) is well known, but the potential for partitioning of neutral PFAS from the gas phase to the stratum corneum has yet to be estimated. The SPARC-estimated physicochemical properties were used to calculate transdermal permeability coefficients (kp_g) and dermal-to-inhalation (D/I) exposure ratios for two groups of neutral PFAS, including those on a U.S. Environmental Protection Agency PFAS list. 11 neutral PFAS gave calculated D/I ratios >5, indicating that direct transdermal absorption may be an important exposure pathway compared to inhalation. Data on consumer products or indoor air is needed for the 11 neutral PFAS, followed by possible biomonitoring to experimentally verify dermal absorption from air. Additional PFAS should be estimated by the protocol used here as they are identified in commercial products.

Gas-Particle Partitioning of Semivolatile Organic Compounds in a Residence: Influence of Particles from Candles, Cooking, and Outdoors.

Semivolatile organic compounds (SVOCs) represent an important class of indoor pollutants. The partitioning of SVOCs between airborne particles and the adjacent air influences human exposure and uptake. Presently, little direct experimental evidence exists about the influence of indoor particle pollution on the gas-particle phase partitioning of indoor SVOCs. In this study, we present time-resolved gas- and particle-phase distribution data for indoor SVOCs in a normally occupied residence using semivolatile thermal desorption aerosol gas chromatography. Although SVOCs in indoor air are found mostly in the gas phase, we show that indoor particles from cooking, candle use, and outdoor particle infiltration strongly affect the gas-particle phase distribution of specific indoor SVOCs. From gas- and particle-phase measurements of SVOCs spanning a range of chemical functionalities (alkanes, alcohols, alkanoic acids, and phthalates) and volatilities (vapor pressures from 10-13 to 10-4 atm), we find that the chemical composition of the airborne particles influences the partitioning of individual SVOC species. During candle burning, the enhanced partitioning of gas-phase SVOCs to indoor particles not only affects the particle composition but also enhances surface off-gassing, thereby increasing the total airborne concentration of specific SVOCs, including diethylhexyl phthalate.

Size-resolved gas-particle partitioning characteristics of typical semi-volatile organic compounds in urban atmosphere

Understanding particle size distribution and size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) is important for characterizing their fate in atmosphere. However, the size-resolved gas-particle partitioning characteristics of SVOCs has not been adequately considered. To address this issue, the present study collected gaseous and size-fractioned particulate samples both in and outside of schools, offices, and residences in three districts of different urbanization levels in a megacity, Guangzhou, South China during two seasons. Typical SVOCs, including 15 polycyclic aromatic hydrocarbons (PAHs), six organophosphate esters and seven phthalic acid esters were measured. Emission sources, physicochemical properties, and environmental conditions at the sampling sites considerably impacted the spatiotemporal distribution patterns and particle size distribution of target SVOCs. Not all observed gas-particle partition coefficients (Kp) of target SVOCs were negatively correlated with subcooled liquid-vapor pressures (PL0), probably because certain factors, such as the non-exchangeable part of the particle-bound SVOCs, were not considered in traditional gas-particle partition theories. Particle size was an important factor affecting gas-particle partitioning. Adsorption was the dominant mechanism for PAHs with high molecular weight in different particle modes. A new model was established to predict size-resolved Kp of PAHs with high molecular weight based on PL0 and particle size.

Steady-state model for predicting size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) in indoor environments

Steady-state model for predicting size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) in indoor environments

Steady-State Based Model of Airborne Particle/Gas and Settled Dust/Gas Partitioning for Semivolatile Organic Compounds in the Indoor Environment.

Indoor semivolatile organic compounds (SVOCs), present in the air, airborne particles, settled dust, and other indoor surfaces, can enter the human body through several pathways. Knowing the partitioning between gaseous and particulate phases is important in identifying specific pathway contributions and thereby accurately assessing human exposure. Numerous studies have developed equilibrium equations to predict airborne particle/gas (P/G) partitioning in air (KP) and dust/gas (D/G) partitioning in settled dust (KD). The assumption that P/G and D/G equilibria are instantaneous for airborne and settled dust phases, commonly adopted by current indoor fate models, is not likely valid for compounds with high octanol-air partition coefficients (KOA). Here, we develop steady-state based equations to predict KP and KD in the indoor environment. Results show that these equations perform well and are verified by worldwide monitoring data. It is suggested that instantaneous steady state could work for P/G and D/G partitioning of SVOCs in indoor environments, and the equilibrium is just a special case of the steady state when log KOA < 11.38 for P/G partitioning and log KOA < 10.38 for D/G partitioning. These newly developed equations and methods provide a tool for more accurate assessment for human exposure to SVOCs in the indoor environment.

Modelling aerosol molecular markers in a 3D air quality model: Focus on anthropogenic organic markers

We developed and implemented in the 3D air quality model CHIMERE the formation of several key anthropogenic aerosol markers including one primary anthropogenic marker (levoglucosan) and 4 secondary anthropogenic markers (nitrophenols, nitroguaiacols, methylnitrocatechols and phthalic acid). Modelled concentrations have been compared to measurements performed at 12 locations in France for levoglucosan in winter 2014–15, and at a sub-urban station in the Paris region over the whole year 2015 for secondary molecular markers. While a good estimation of levoglucosan concentrations by the model has been obtained for a few sites, a strong underestimation was simulated for most of the stations especially for western locations due to a probable underestimation of residential wood burning emissions. The simulated ratio between wood burning organic matter and particulate phase levoglucosan is constant only at high OM values (>10 μg m−3) indicating that using marker contribution ratio may be valid only under certain conditions. Concentrations of secondary markers were well reproduced by the model for nitrophenols and nitroguaiacols but were underestimated for methylnitrocatechols and phthalic acid highlighting missing formation pathways and/or precursor emissions. By comparing modelled to measured Gas/Particle Partitioning (GPP) of markers, the simulated partitioning of Semi-Volatile Organic Compounds (SVOCs) was evaluated. Except for nitroguaiacols and nitrophenols when ideality was assumed, the GPP for all the markers was underestimated and mainly driven by the hydrophilic partitioning. SVOCs GPP, and more generally of all SVOC contributing to the formation of SOA, could therefore be significantly underestimated by air quality models, especially when only the partitioning on the organic phase is considered. Our results show that marker modelling can give insights on some processes (such as precursor emissions or missing mechanisms) involved in SOA formation and could prove especially useful to evaluate the GPP in 3D air quality models.

Soil-air partitioning of semivolatile organic compounds in the Lesser Himalaya region: Influence of soil organic matter, atmospheric transport processes and secondary emissions

After decades of imposed regulations about reducing the primary emissions of persistent organic pollutants (POPs), these pollutants are still present in the environment. Soils are important repositories of such persistent semivolatile organic contaminants (SVOCs), and it is assumed that SVOCs sequestered in these reservoirs are being re-mobilized due to anthropogenic influence. In this study, concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in soil and air, their fugacities, fluxes and the soil-air partition coefficient (KSA) were determined for three different land cover types (glacial, remote/mountainous and urban) of the Lesser Himalayan Region (LHR). The concentrations of OCPs, PCBs and PBDEs in soils and air ranged between 0.01 and 2.8, 0.81–4.8, 0.089–0.75 ng g−1; 0.2–106, 0.027–182, and 0.011–7.26 pg m−3, respectively. The levels of SVOCs in the soil were correlated with soil organic matter (SOM) indicating that SOM is a substrate for the organic pollutants in soils. The Clausius-Clapeyron plots between ln P and inverse of temperature (1000/T) suggested that long range atmospheric transport was the major input source of PBDEs and higher chlorinated PCBs over the LHR. The uneven and wide distribution of local sources in LHR and up-slope enrichment of SVOCs explained the spatial variability and altitudinal patterns. The soils near mountain and urban lakes act as local sinks of SVOCs such as β-HCH, pp΄-DDT, CB-28, -118, −153, BDE-47, -99, and −154, with soil-air exchange fluxes tending more toward deposition. However, the soils near glacial lakes acted as local sources of more volatile congeners of α-HCH, γ-HCH, op′-DDT, pp′-DDE and lower to medium chlorinated PCBs such as CB-18, -28, −53, −42 and BDE-47, -99, with soil-air exchange tending more toward volatilization flux.

Particle/gas partitioning for semi-volatile organic compounds (SVOCs) in Level III multimedia fugacity models: Gaseous emissions

Atmospheric transport is a global-scale process that moves semi-volatile organic compounds (SVOCs) rapidly from source regions to remote locations, where these chemicals have never been produced or used. Particle/gas (P/G) partitioning of SVOCs during atmospheric transport governs wet and dry deposition, and thereby controls the efficiency and scope of long-range atmospheric transport and fate for these sorts of compounds. Previous work has shown that the assumption of steady state between particulate and gaseous phases in the atmosphere leads to model results that more closely match observations especially for compounds that strongly favor the particulate phase. Here, the practical application of steady-state P/G partitioning in the atmosphere in multimedia fugacity models is presented in greater detail. A method is developed whereby the fugacity of a chemical in the particle-phase is set equal to that in the gaseous phase (a pseudo equilibrium) but still maintains steady state of the chemical between air and aerosols in the atmosphere. This procedure greatly simplifies the application of multimedia fugacity models. Using this approach, a condition of steady state between air and aerosols is developed and applied in a Level III six-compartment six-fugacity model, which becomes a much simpler Level III six-compartment four-fugacity model. This newly-developed model is then applied to data observed during a monitoring program.

Role of ecosystem-atmosphere exchanges of semi-volatile organic compounds in organic aerosol formation

Deposition of the gas fraction of Semi-Volatile Organic Compounds (SVOC) may be an important removal pathway and may strongly influence concentrations of organic aerosols due to the gas-particle partitioning of SVOC. All the studies on this process are based on the classic Wesely resistance approach that uses Henry's law constants to calculate a deposition rate scaled on the deposition rate of SO2. However, even highly hydrophobic SVOC could be efficiently removed by the vegetation and soils as shown by numerous studies on Persistent Organic Pollutant (POP) modeling. Moreover, the re-volatilization of deposited SVOC is possible and could influence organic aerosol concentrations.An atmosphere-soil-vegetation module was developed and implemented in the 3D air quality model CHIMERE 2017β to represent the accumulation of compounds in the different compartments of the biosphere and the exchanges between them. The soil compartment was represented with a multi-layer approach (the layers corresponding to different in-soil depths) to simulate the multiphase diffusion of compounds inside the soil. Exchanges of SVOC between the air, soil and vegetation compartments were simulated using bi-directional approaches based on Rg (the gas-phase partitioning in the soil compartment) and Kva the vegetation-air partitioning coefficient. Parameters were estimated based on the physical properties of the compounds and their molecular structure.Simulations performed over Europe show that air-vegetation-soil exchanges may be a more efficient removal pathway than dry deposition of particles for SVOC with a gas-phase fraction above 10%. Considering air-vegetation-soil exchanges in the simulations lead to a decrease of organic aerosol concentrations by 15% and primary SVOC (considered as hydrophobic compounds) may be efficiently removed by those pathways (contrary to what is calculated with the Wesely approach). This decrease of concentrations is mainly due to air-vegetation exchanges. During summer, the use of the Wesely approach may lead to a slight overestimation of deposition fluxes (leading to an underestimation of concentration by 1%).Re-volatilization may limit the amount of deposited SVOC. Depending on assumptions, simulations showed that re-emissions (inversion of exchanges toward the emissions) in summer of SVOC accumulated during winter is theoretically possible and may be a minor source of organic aerosol.

Global–regional nested simulation of particle number concentration by combing microphysical processes with an evolving organic aerosol module

Abstract. Aerosol microphysical processes are essential for the next generation of global and regional climate and air quality models to determine particle size distribution. The contribution of organic aerosols (OAs) to particle formation, mass, and number concentration is one of the major uncertainties in current models. A new global–regional nested aerosol model was developed to simulate detailed microphysical processes. The model combines an advanced particle microphysics (APM) module and a volatility basis set (VBS) OA module to calculate the kinetic condensation of low-volatility organic compounds and equilibrium partitioning of semi-volatile organic compounds in a 3-D framework using global–regional nested domain. In addition to the condensation of sulfuric acid, the equilibrium partitioning of nitrate and ammonium, and the coagulation process of particles, the microphysical processes of the OAs are realistically represented in our new model. The model uses high-resolution size bins to calculate the size distribution of new particles formed through nucleation and subsequent growth. The multi-scale nesting enables the model to perform high-resolution simulations of the particle formation processes in the urban atmosphere in the background of regional and global environments. By using the nested domains, the model reasonably reproduced the OA components obtained from the analysis of aerosol mass spectrometry measurements through positive matrix factorization and the particle number size distribution in the megacity of Beijing during a period of approximately a month. Anthropogenic organic species accounted for 67 % of the OAs of secondary particles formed by nucleation and subsequent growth, which is considerably larger than that of biogenic OAs. On the global scale, the model well predicted the particle number concentration in various environments. The microphysical module combined with the VBS simulated the universal distribution of organic components among the different aerosol populations. The model results strongly suggest the importance of anthropogenic organic species in aerosol particle formation and growth at polluted urban sites and over the whole globe.

Emerging investigator series: chemical and physical properties of organic mixtures on indoor surfaces during HOMEChem.

Organic films on indoor surfaces serve as a medium for reactions and for partitioning of semi-volatile organic compounds and thus play an important role in indoor chemistry. However, the chemical and physical properties of these films are poorly characterized. Here, we investigate the chemical composition of an organic film collected during the HOMEChem campaign, over three cumulative weeks in the kitchen, using both Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) and offline Aerosol Mass Spectrometry (AMS). We also characterize the viscosity of this film using a model based on molecular formulas as well as poke-flow measurements. We find that the film contains organic material similar to cooking organic aerosol (COA) measured during the campaign using on-line AMS. However, the average molecular formula observed using FT-ICR MS is ∼C50H90O11, which is larger and more oxidized than fresh COA. Solvent extracted film material is a low viscous semisolid, with a measured viscosity <104 Pa s. This is much lower than the viscosity model predicts, which is parametrized with atmospherically relevant organic molecules, but sensitivity tests demonstrate that including unsaturation can explain the differences. The presence of unsaturation is supported by reactions of film material with ozone. In contrast to the solvent extract, manually removed material appears to be highly viscous, highlighting the need for continued work understanding both viscosity measurements as well as parameterizations for modeled viscosity of indoor organic films.

Determining Activity Coefficients of SOA from Isothermal Evaporation in a Laboratory Chamber

Nonideal molecular interactions in aerosol particles influence the partitioning of semivolatile organic compounds (SVOCs). However, few direct measurements exist that determine activity coefficient...

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.