Condensable Organic Vapors Research Articles

Impacts of α-pinene ozonolysis products on the morphology and optical properties of black carbon

Black carbon (BC) is known to absorb solar radiation and thus have a warming impact on climate. The atmospheric aging of fresh BC has been suggested to enhance BC's light absorption, but the extent of variation observed varies largely in field and laboratory measurements. Biogenic VOCs with much higher abundance than anthropogenic emissions are reactive towards atmospheric oxidants, and act as major sources of secondary organic aerosol (SOA) in the atmosphere. In this study, we performed experiments of BC aging in the presence of condensable organic vapors generated from the ozonolysis of α-pinene. Significant changes in the particle size, mass, effective density, morphology as well as optical properties are observed upon coating of BC by α-pinene ozonolysis products. While the BC aging rate depends on the initial concentrations of precursors forming condensable materials and the particle size, the extent of transformation of BC at a given size is mainly controlled by the volume equivalent coating thickness. The highly fractal BC core is converted to a more compact morphology for a coating thickness of ∼25–30 nm depending on the initial particle size. The absorption and scattering of light by BC also increase by more than 1.29- and 5.30- fold during the coating process. The enhancement of optical properties can be attributed to both formation of coatings and restructuring of the BC core, with the latter accounting for a large fraction of optical enhancement. Our results indicate that the ozonolysis of α-pinene has profound effects on the morphology and optical properties of BC, with a magnitude comparable to sulfuric acid and ammonium nitrate, but much higher than other reported anthropogenic hydrocarbons. Although present in relatively low concentrations, α-pinene oxidation reactions can considerably enhance the impacts of BC on air quality and climate forcing.

Modeling the Formation of Organic Compounds across Full Volatility Ranges and Their Contribution to Nanoparticle Growth in a Polluted Atmosphere.

Nanoparticle growth influences atmospheric particles' climatic effects, and it is largely driven by low-volatility organic vapors. However, the magnitude and mechanism of organics' contribution to nanoparticle growth in polluted environments remain unclear because current observations and models cannot capture organics across full volatility ranges or track their formation chemistry. Here, we develop a mechanistic model that characterizes the full volatility spectrum of organic vapors and their contributions to nanoparticle growth by coupling advanced organic oxidation modeling and kinetic gas-particle partitioning. The model is applied to Nanjing, a typical polluted city, and it effectively captures the volatility distribution of low-volatility organics (with saturation vapor concentrations <0.3 μg/m3), thus accurately reproducing growth rates (GRs), with a 4.91% normalized mean bias. Simulations indicate that as particles grow from 4 to 40 nm, the relative fractions of GRs attributable to organics increase from 59 to 86%, with the remaining contribution from H2SO4 and its clusters. Aromatics contribute much to condensable organic vapors (∼37%), especially low-volatility vapors (∼61%), thus contributing the most to GRs (32-46%) as 4-40 nm particles grow. Alkanes also contribute 19-35% of GRs, while biogenic volatile organic compounds contribute minimally (<13%). Our model helps assess the climatic impacts of particles and predict future changes.

Exploring condensable organic vapors and their co-occurrence with PM2.5and O3in winter in Eastern China

The strongest formation of oxygenated organic molecules occurs when PM2.5and O3are co-enhanced.

Insufficient Condensable Organic Vapors Lead to Slow Growth of New Particles in an Urban Environment.

Atmospheric new particle formation significantly affects global climate and air quality after newly formed particles grow above ∼50 nm. In polluted urban atmospheres with 1-3 orders of magnitude higher new particle formation rates than those in clean atmospheres, particle growth rates are comparable or even lower for reasons that were previously unclear. Here, we address the slow growth in urban Beijing with advanced measurements of the size-resolved molecular composition of nanoparticles using the thermal desorption chemical ionization mass spectrometer and the gas precursors using the nitrate CI-APi-ToF. A particle growth model combining condensational growth and particle-phase acid-base chemistry was developed to explore the growth mechanisms. The composition of 8-40 nm particles during new particle formation events in urban Beijing is dominated by organics (∼80%) and sulfate (∼13%), and the remainder is from base compounds, nitrate, and chloride. With the increase in particle sizes, the fraction of sulfate decreases, while that of the slow-desorbed organics, organic acids, and nitrate increases. The simulated size-resolved composition and growth rates are consistent with the measured results in most cases, and they both indicate that the condensational growth of organic vapors and H2SO4 is the major growth pathway and the particle-phase acid-base reactions play a minor role. In comparison to the high concentrations of gaseous sulfuric acid and amines that cause high formation rates, the concentration of condensable organic vapors is comparably lower under the high NOx levels, while those of the relatively high-volatility nitrogen-containing oxidation products are higher. The insufficient condensable organic vapors lead to slow growth, which further causes low survival of the newly formed particles in urban environments. Thus, the low growth rates, to some extent, counteract the impact of the high formation rates on air quality and global climate in urban environments.

Separation of isoprene from biologically-derived gas streams

ABSTRACT Renewable organic precursors, including olefinic compounds such as isoprene, have attracted interest from the polymer and pharmaceutical industries. Biologically-derived processes can generate these target compounds; however, their gaseous product streams are complex mixtures of condensable organic vapors (COVs), water vapor, carbon dioxide (CO2), and/or nitrogen (N2). Because COVs, CO2 and water vapor are known to alter polymer membranes, mixed gas separations data at ambient and elevated temperatures are limited. This study focused on two classes of polymer membranes, glassy [polyetherimide (Ultem®)] and a rubbery [polydimethylsiloxane (PDMS)] with results indicating that isoprene separation is possible in humidified gas environment (2–4 vol% water). Gas permeabilities of these membranes did not noticeably change in the presence of humidity; however, the selectivity of these membranes was significantly lower compared to their performance under dry conditions. The role of water vapor in gas transport was derived from the energy of activation of permeation (Ep) for PDMS and Ultem® from 30–80°C in humidified mixed gas streams. For both polymers, Ep data shows a slight decrease in selectivity with the other gases (hydrogen, N2, CO2, and methane) at elevated temperatures in the presence of water vapor. Thus, these COVs separations are feasible with polymer membranes in the presence of humidified gas streams, even in the case of glassy and rubbery membranes in series.

Wall effects in smog chamber experiments: A model study

Wall losses of condensable organic vapors are a significant complication for smog-chamber experiments designed to constrain production of Secondary Organic Aerosols (SOA). Here we develop a dynamical mass-balance model based on the Volatility Basis Set (VBS) to explore various pathways for mass transfer between the bulk of a smog-chamber volume (the vapors and suspended particles) and reservoirs near the chamber walls (deposited and/or nucleated particles on the walls, adsorption to the walls, and sorption into Teflon walls). We consider various limiting cases and explore the sensitivity of inferred SOA yields to assumptions about the actual parameters in a given SOA experiment. We also present data suggesting that adsorptive uptake to Teflon for typical SOA is modest. Broadly, we find that walls become a sink for condensable vapors when those vapors interact with either deposited particles of the Teflon walls, with qualitatively similar effects on the suspended particles. Finally, we show that having a relatively high seed condensation sink is vital to reliable chamber mass balances.Copyright © 2016 American Association for Aerosol Research

Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols

AbstractThe water solubility of oxidation intermediates of volatile organic compounds that can condense to form secondary organic aerosol (SOA) is largely unconstrained in current chemistry‐climate models. We apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere to calculate Henry's law constants for these intermediate species. Results show a strong negative correlation between Henry's law constants and saturation vapor pressures. Details depend on precursor species, extent of photochemical processing, and NOx levels. Henry's law constants as a function of volatility are made available over a wide range of vapor pressures for use in 3‐D models. In an application using the Weather Research and Forecasting model coupled with Chemistry (WRF‐Chem) over the U.S. in summer, we find that dry (and wet) deposition of condensable organic vapors leads to major reductions in SOA, decreasing surface concentrations by ~50% (10%) for biogenic and ~40% (6%) for short chain anthropogenic precursors under the considered volatility conditions.

Reduction of gaseous and particulate emissions from small-scale wood combustion with a catalytic combustor

Abstract In this study, a catalytic combustor was used on a wood stove as a secondary emission reduction measure. An experimental comparison of emissions was done from combustion experiments with and without the catalyst. Samples were collected from gasification and burn out phases and from the whole combustion cycle (from start-up to burn out). Concentrations of carbon monoxide (CO), carbon dioxide (CO 2 ), oxygen (O 2 ) and organic gaseous carbon (OGC), temperature and pressure were measured online directly from the flue gas stack. With the catalyst, the O 2 concentration in the flue gas was lower and the temperature higher than without the catalyst, due to the large amount of unburnt compounds which were oxidized by the catalyst. Reductions of 21% for CO and 14% for OGC were achieved during the whole combustion cycle. During the burn out phase, a reduction as high as 80% was achieved for CO. PM 1 (particle mass below aerodynamic size of 1 μm) was reduced by 30% during the whole combustion cycle. During gasification, a 44% reduction of PM 1 was achieved but there was no reduction during burn out. The organic and elemental carbon analyzed from PM 1 had reduced also only during gasification by 56% and 37%, respectively. The particle emission reductions were notable and it can be concluded that the catalyst affects the particles through oxidation of condensable organic vapors and oxidation of soot particles. The catalyst has potential as a secondary emission reduction method but in order to achieve low emissions, also improved combustion technology for emission reduction needs to be developed.

A study of new particle formation in the marine boundary layer over the central Arctic Ocean using a flexible multicomponent aerosol dynamic model

ABSTRACTEnhancement of number concentrations of particles with sizes less than 25 nm diameter has been frequently observed in the boundary layer over the central Arctic Ocean during summer. The sectional aerosol dynamics model for Marine Aerosol Formation (MAFOR) was applied to evaluate the capability of different nucleation mechanisms to reproduce nucleation events observed during three expeditions (1996, 2001 and 2008) onboard the Swedish icebreaker Oden. Model calculations suggest that a source rate of a condensable organic vapour (OV) of about 2×105 cm−3 s−1 is required to reproduce observed growth of nucleation mode particles. Nucleation rates predicted by the newly proposed combined sulphuric acid nucleation mechanism, which best described new particle formation in the Arctic, ranged from 0.04 to 0.1 cm−3 s−1. This mechanism additively combines ion-mediated nucleation and cluster activation, and treats condensation of OV without correction of the Kelvin effect. In several events, the simultaneous number enhancement of particles in the 20–50 nm size range remained unexplained by the nucleation mechanisms. This lends support to alternative theories such as the fragmentation of marine gels (≈200–500 nm diameter in size) by physical or chemical processes.

Simulating Marine New Particle Formation and Growth Using the M7 Modal Aerosol Dynamics Modal

A modal atmospheric aerosol model (M7) is evaluated in terms of predicting marine new particle formation and growth. Simulations were carried out for three different nucleation schemes involving (1) kinetic self‐nucleation of OIO (2) nucleation via OIO activation by H2SO4 and (3) nucleation via OIO activation by H2SO4 plus condensation of a low‐volatility organic vapour. Peak OIO and H2SO4 vapour concentrations were both limited to 6 × 106 molecules cm-3 at noontime while the peak organic vapour concentration was limited to 12 × 106 molecules cm-3. All simulations produced significant concentrations of new particles in the Aitken mode. From a base case particle concentration of 222 cm-3 at radii &gt;15 nm, increases in concentrations to 366 cm-3 were predicted from the OIO‐OIO case, 722 cm-3 for the OIO‐H2SO4 case, and 1584 cm-3 for the OIO‐H2SO4 case with additional condensing organic vapours. The results indicate that open ocean new particle production is feasible for clean conditions; however, new particle production becomes most significant when an additional condensable organic vapour is available to grow the newly formed particles to larger sizes. Comparison to sectional model for a typical case study demonstrated good agreement and the validity of using the modal model.

Aerosol dynamics simulations on the connection of sulphuric acid and new particle formation

Abstract. We have performed a series of simulations with an aerosol dynamics box model to study the connection between new particle formation and sulphuric acid concentration. For nucleation either activation mechanism with a linear dependence on the sulphuric acid concentration, kinetic mechanism with a squared dependence on the sulphuric acid concentration or ternary H2O-H2SO4-NH3 nucleation was assumed. The aim was to study the factors that affect the sulphuric acid dependence during the early stages of particle growth, and specifically to find conditions which would yield the linear dependence between the particle number concentration at 3–6 nm and sulphuric acid, as observed in field experiments. The simulations showed that the correlation with sulphuric acid may change during the growth from nucleation size to 3–6 nm size range, the main reason being the size dependent growth rate between 1 and 3 nm. In addition, the assumed size for the nucleated clusters had a crucial impact on the sulphuric acid dependence at 3 nm. A linear dependence between the particle number concentration at 3 nm and sulphuric acid was achieved, when activation nucleation mechanism was used with a low saturation vapour pressure for the condensable organic vapour, or with nucleation taking place at ~2 nm instead of ~1 nm. Simulations with activation, kinetic and ternary nucleation showed that ternary nucleation reproduces too steep dependence on sulphuric acid as compared to the linear or square dependence observed in field measurements.

Pure- and mixed-gas permeation properties of a microporous spirobisindane-based ladder polymer (PIM-1)

PIM-1, a glassy, spirobisindane-based ladder polymer is a novel intrinsically microporous membrane material. The pure- and mixed-gas permeation properties of PIM-1 are compared to those of highly permeable, microporous, linear chain, acetylene-based polymers, such as poly(1-trimethylsilyl-1-propyne) (PTMSP). PIM-1 exhibits very high permanent gas permeabilities coupled with moderate selectivities. For example, the oxygen permeability of PIM-1 at 25 °C is 1300 × 10 −10 cm 3 (STP) cm/cm 2 s cmHg combined with an oxygen/nitrogen selectivity of 3.8. Those values place PIM-1 above the Robeson trade-off curve for oxygen/nitrogen separation. Like microporous linear chain PTMSP, ladder-type PIM-1 is more permeable to large, condensable organic vapors, such as n-butane, than to small, permanent gases, such as methane. PIM-1 exhibits a mixed-gas n-butane/methane selectivity of up to 25, which is similar to that of PTMSP, the most permeable and selective polymer known for this separation. Because PIM-1 has significantly better solvent resistance than PTMSP, it could find applications as an advanced membrane material for the separation of organic vapor/permanent gas mixtures.

Evaluation and modelling of the size fractionated aerosol particle number concentration measurements nearby a major road in Helsinki – Part I: Modelling results within the LIPIKA project

Abstract. A field measurement campaign was conducted near a major road "Itäväylä" in an urban area in Helsinki in 17–20 February 2003. Aerosol measurements were conducted using a mobile laboratory "Sniffer" at various distances from the road, and at an urban background location. Measurements included particle size distribution in the size range of 7 nm–10 μm (aerodynamic diameter) by the Electrical Low Pressure Impactor (ELPI) and in the size range of 3–50 nm (mobility diameter) by Scanning Mobility Particle Sizer (SMPS), total number concentration of particles larger than 3 nm detected by an ultrafine condensation particle counter (UCPC), temperature, relative humidity, wind speed and direction, driving route of the mobile laboratory, and traffic density on the studied road. In this study, we have compared measured concentration data with the predictions of the road network dispersion model CAR-FMI used in combination with an aerosol process model MONO32. For model comparison purposes, one of the cases was additionally computed using the aerosol process model UHMA, combined with the CAR-FMI model. The vehicular exhaust emissions, and atmospheric dispersion and transformation of fine and ultrafine particles was evaluated within the distance scale of 200 m (corresponding to a time scale of a couple of minutes). We computed the temporal evolution of the number concentrations, size distributions and chemical compositions of various particle size classes. The atmospheric dilution rate of particles is obtained from the roadside dispersion model CAR-FMI. Considering the evolution of total number concentration, dilution was shown to be the most important process. The influence of coagulation and condensation on the number concentrations of particle size modes was found to be negligible on this distance scale. Condensation was found to affect the evolution of particle diameter in the two smallest particle modes. The assumed value of the concentration of condensable organic vapour of 1012 molecules cm−3 was shown to be in a disagreement with the measured particle size evolution, while the modelling runs with the concentration of condensable organic vapour of 109–1010 molecules cm−3 resulted in particle sizes that were closest to the measured values.

Investigations on the peculiar permeation properties of volatile organic compounds and permanent gases through PTMSP

In contrast to common glassy polymers, poly(1-trimethylsilyl-1-propyne) (PTMSP), a high free volume glassy polymer, shows a preferable permeation of large condensable organic vapors in comparison to permanent gases. In order to investigate this phenomenon, a systematic permeability study over a large activity range has been performed on PTMSP with three types of volatile organic compounds (VOCs) as diffusing probes: toluene, dimethylketone and dichloromethane. PTMSP was synthesized with different catalytic systems (Nb or Ta based) able to induce controlled sub-molecular cis– trans structures. Whereas dimethylketone and dichloromethane permeability can be correctly described by a classical dual-mode equation, a peculiar bell shaped pattern was obtained for toluene, with a minimum permeability located at an activity value around a=0.3–0.4. In that case, only a dual-mode expression taking into account a concentration dependent diffusion coefficient can account for the results. On the other hand some apparent conflicting data recorded from PTMSP brand new films were related to the microstructure of the polymer main chain thanks to 13 C NMR spectroscopy analysis showing importance of cis- and trans-forms of the main chain of PTMSP. cis-Structure is more flexible and can be responsible for the creation of a higher density physical network (HDN) in polymeric matrix; conversely, trans-structure is more rigid and can provide lower density physical network (LDN). The higher permeability recorded for several probes through PTMSP synthesized with TaCl 5/Al( i-Bu) 3 catalytic system compared to those of NbCl 5 based polymer can be explained by the geometric difference of the macromolecule networks.

Development of particle size and composition distributions with a novel aerosol dynamics model

An aerosol dynamics model, AEROFOR2, is developed in the context of the BIOFOR project focussing on boreal forest aerosol. It is the second version of a Lagrangian type box model AEROFOR for investigating the formation and growth of particles under clear sky atmospheric conditions. Particles can consist of soluble and insoluble material and the particle population can be externally or internally mixed. AEROFOR2 includes gas phase chemistry and aerosol dynamics, and calculates the number and composition distributions of particles as functions of time. Observed growth rates of the nucleation mode particles after a typical nucleation event are 2–3 nm/h. The model simulations predict that 3·107 molecules cm−3 of insoluble organic vapour and less than 6·106 molecules cm−3 of soluble vapour condensing onto particles are enough to make them grow in good agreement with the observed growth rates. Then the source rate of the organic vapour must be an order of 105 molecules cm−3 s−1, and its saturation vapour density should be below 106 molecules cm−3. If the aerosol was initially an internal mixture of soluble (70%) and insoluble (30%) constituents it transformed to an externally mixed aerosol during the simulation. By applying the externally-mixed aerosol based on measured soluble volume fractions, it was concluded that the modelled soluble fraction of the nucleation mode was too low in comparison with the measurements, and thus, a part of the condensable organic vapour must be water soluble.

Development of particle size and composition distributions with a novel aerosol dynamics model

An aerosol dynamics model, AEROFOR2, is developed in the context of the BIOFOR project focussing on boreal forest aerosol. It is the second version of a Lagrangian type box model AEROFOR for investigating the formation and growth of particles under clear sky atmospheric conditions. Particles can consist of soluble and insoluble material and the particle population can be externally or internally mixed. AEROFOR2 includes gas phase chemistry and aerosol dynamics, and calculates the number and composition distributions of particles as functions of time. Observed growth rates of the nucleation mode particles after a typical nucleation event are 2–3 nm/h. The model simulations predict that 3·107 molecules cm−3 of insoluble organic vapour and less than 6·106 molecules cm−3 of soluble vapour condensing onto particles are enough to make them grow in good agreement with the observed growth rates. Then the source rate of the organic vapour must be an order of 105 molecules cm−3 s−1, and its saturation vapour density should be below 106 molecules cm−3. If the aerosol was initially an internal mixture of soluble (70%) and insoluble (30%) constituents it transformed to an externally mixed aerosol during the simulation. By applying the externally-mixed aerosol based on measured soluble volume fractions, it was concluded that the modelled soluble fraction of the nucleation mode was too low in comparison with the measurements, and thus, a part of the condensable organic vapour must be water soluble.

Transport of organic vapors through poly(1-trimethylsilyl-1-propyne)

Poly(1-trimethylsilyl-1-propyne) [PTMSP], a high-free-volume glassy polymer, has the highest gas permeability of any known synthetic polymer. In contrast to conventional, low-free-volume, glassy polymers, PTMSP is more permeable to large, condensable organic vapors than to permanent gases. The organic-vapor/permanent-gas selectivity of PTMSP based on pure gas measurements is low. In organic-vapor/permanent-gas mixtures, however, the selectivity of PTMSP is much higher because the permeability of the permanent gas is reduced dramatically by the presence of the organic vapor. For example, in n-butane/methane mixtures, as little as 2 mol% n-butane (relative n-butane pressure 0.16) lowers the methane permeability 10-fold from the pure methane permeability. The result is that PTMSP shows a mixed-gas n-butane/methane selectivity of 30. This selectivity is the highest ever observed for this mixture and is completely unexpected for a glassy polymer. In addition, the gas mixture n-butane permeability of PTMSP is considerably higher than that of any known polymer, including polydimethylsiloxane, the most vapor-permeable rubber known. PTMSP also shows high mixed-gas selectivities and vapor permeabilities for the separation of chlorofluorocarbons from nitrogen. The unusual vapor permeation properties of PTMSP result from its very high free volume - more than 20% of the total volume of the material. The free volume elements appear to be connected, forming the equivalent of a finely microporous material. The large amount of condensable organic vapor sorbed into this finely porous structure causes partial blocking of the small free-volume elements, reducing the permeabilities of the noncondensable permanent gases from their pure gas values.

Simultaneous multi-instrumental monitoring of vapors in sewer headspaces by several direct-reading instruments

Simultaneous monitoring of the vapors in several sewer headspaces by three direct-reading instruments, the Century OVA flame ionization detector, a 10.2 eV H-Nu Photoionization Detector, and a Hydrogen Sulfide Ecolyzer revealed that the majority of condensable organic vapors in areas of the Metropolitan Sewer District of Cincinnati appeared to be saturated aliphatic organics, except during short, unpredictable episodes. The monitoring was performed in the wet well of a sewage treatment plant, in sewers near two chemical plants, and in three other different sewers. The approach outlined in this paper does not require the use of gas chromatography-mass spectrometry (GC-MS) analysis.