scholarly journals Development of an In Situ Dual-Channel Thermal Desorption Gas Chromatography Instrument for Consistent Quantification of Volatile, Intermediate Volatility and Semivolatile Organic Compounds

2021 ◽  
Author(s):  
Rebecca A. Wernis ◽  
Nathan M. Kreisberg ◽  
Robert J. Weber ◽  
Yutong Liang ◽  
John Jayne ◽  
...  
Keyword(s):  
Gas Phase ◽  
Organic Compounds ◽  
Thermal Desorption ◽  
Radiative Forcing ◽  
Large Fraction ◽  
Organic Aerosol ◽  
Semivolatile Organic Compounds ◽  
Secondary Products ◽  
Instrument Performance ◽  
Dual Channel

Abstract. Aerosols are a source of great uncertainty in radiative forcing predictions and have poorly understood health impacts. Most aerosol mass is formed in the atmosphere from reactive gas phase organic precursors, forming secondary organic aerosol (SOA). Semivolatile organic compounds (SVOCs) (effective saturation concentration, C*, of 10−1–103 μg m−3) comprise a large fraction of organic aerosol, while intermediate volatility organic compounds (IVOCs) (C* of 103–106 μg m−3) and volatile organic compounds (VOCs) (C* ≥ 106 μg m−3) are gas phase precursors to SOA and ozone. The Comprehensive Thermal Desorption Aerosol Gas Chromatograph (cTAG) is the first single instrument simultaneously quantitative for a broad range of compound-specific VOCs, IVOCs and SVOCs. cTAG is a two-channel instrument which measures concentrations of C5–C16 alkane equivalent volatility VOCs and IVOCs on one channel and C14–C32 SVOCs on the other coupled to a single High Resolution Time of Flight Mass Spectrometer, achieving consistent quantification across 15 orders of magnitude of vapor pressure. cTAG obtains concentrations hourly and gas–particle partitioning for SVOCs bihourly, enabling observation of the evolution of these species through oxidation and partitioning into the particle phase. Online derivatization for the SVOC channel enables detection of more polar and oxidized species. In this work we present design details and data evaluating key parameters of instrument performance such as I/VOC collector design optimization, linearity and reproducibility of calibration curves obtained using a custom liquid evaporation system for I/VOCs and the effect of an ozone removal filter on instrument performance. Example timelines of precursors with secondary products are shown and analysis of a subset of compounds detectable by cTAG demonstrates some of the analytical possibilities with this instrument.

scholarly journals Development of an in situ dual-channel thermal desorption gas chromatography instrument for consistent quantification of volatile, intermediate-volatility and semivolatile organic compounds

2021 ◽  
Vol 14 (10) ◽  
pp. 6533-6550
Author(s):  
Rebecca A. Wernis ◽  
Nathan M. Kreisberg ◽  
Robert J. Weber ◽  
Yutong Liang ◽  
John Jayne ◽  
...  
Keyword(s):  
Gas Phase ◽  
Organic Compounds ◽  
Thermal Desorption ◽  
Radiative Forcing ◽  
Large Fraction ◽  
Organic Aerosol ◽  
Semivolatile Organic Compounds ◽  
Secondary Products ◽  
Instrument Performance ◽  
Dual Channel

Abstract. Aerosols are a source of great uncertainty in radiative forcing predictions and have poorly understood health impacts. Most aerosol mass is formed in the atmosphere from reactive gas-phase organic precursors, forming secondary organic aerosol (SOA). Semivolatile organic compounds (SVOCs) (effective saturation concentration, C*, of 10−1–103 µg m−3) comprise a large fraction of organic aerosol, while intermediate-volatility organic compounds (IVOCs) (C* of 103–106 µg m−3) and volatile organic compounds (VOCs) (C* ≥ 106 µg m−3) are gas-phase precursors to SOA and ozone. The Comprehensive Thermal Desorption Aerosol Gas Chromatograph (cTAG) is the first single instrument simultaneously quantitative for a broad range of compound-specific VOCs, IVOCs and SVOCs. cTAG is a two-channel instrument which measures concentrations of C5–C16 alkane-equivalent-volatility VOCs and IVOCs on one channel and C14–C32 SVOCs on the other coupled to a single high-resolution time-of-flight mass spectrometer, achieving consistent quantification across 15 orders of magnitude of vapor pressure. cTAG obtains concentrations hourly and gas–particle partitioning for SVOCs every other hour, enabling observation of the evolution of these species through oxidation and partitioning into the particle phase. Online derivatization for the SVOC channel enables detection of more polar and oxidized species. In this work we present design details and data evaluating key parameters of instrument performance such as I/VOC collector design optimization, linearity and reproducibility of calibration curves obtained using a custom liquid evaporation system for I/VOCs and the effect of an ozone removal filter on instrument performance. Example timelines of precursors with secondary products are shown, and analysis of a subset of compounds detectable by cTAG demonstrates some of the analytical possibilities with this instrument.

scholarly journals Size-resolved characterization of organic aerosol in the North China Plain: new insights from high resolution spectral analysis

2021 ◽  
Author(s):  
Weiqi Xu ◽  
Chun Chen ◽  
Yanmei Qiu ◽  
Conghui Xie ◽  
Yunle Chen ◽  
...  
Keyword(s):  
Radiative Forcing ◽  
North China Plain ◽  
North China ◽  
Fine Particles ◽  
Large Fraction ◽  
Organic Aerosol ◽  
Size Distributions ◽  
The North ◽  
The Impact

Organic aerosol (OA), a large fraction of fine particles, has a large impact on climate radiative forcing and human health, and the impact depends strongly on size distributions. Here we...

scholarly journals Characterization of secondary organic aerosol from heated-cooking-oil emissions: evolution in composition and volatility

2021 ◽  
Vol 21 (6) ◽  
pp. 5137-5149 ◽  
Author(s):  
Manpreet Takhar ◽  
Yunchun Li ◽  
Arthur W. H. Chan
Keyword(s):  
Gas Phase ◽  
Organic Compounds ◽  
Secondary Organic Aerosol ◽  
Carbon Number ◽  
Complex Mixture ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Atmospheric Evolution ◽  
Oxidative Aging ◽  
Cooking Oil

Abstract. Cooking emissions account for a major fraction of urban organic aerosol. It is therefore important to understand the atmospheric evolution in the physical and chemical properties of organic compounds emitted from cooking activities. In this work, we investigate the formation of secondary organic aerosol (SOA) from oxidation of gas-phase organic compounds from heated cooking oil. The chemical composition of cooking SOA is analyzed using thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). While the particle-phase composition of SOA is a highly complex mixture, we adopt a new method to achieve molecular speciation of the SOA. All the GC-elutable material is classified by the constituent functional groups, allowing us to provide a molecular description of its chemical evolution upon oxidative aging. Our results demonstrate an increase in average oxidation state (from −0.6 to −0.24) and decrease in average carbon number (from 5.2 to 4.9) with increasing photochemical aging of cooking oil, suggesting that fragmentation reactions are key processes in the oxidative aging of cooking emissions within 2 d equivalent of ambient oxidant exposure. Moreover, we estimate that aldehyde precursors from cooking emissions account for a majority of the SOA formation and oxidation products. Overall, our results provide insights into the atmospheric evolution of cooking SOA, a majority of which is derived from gas-phase oxidation of aldehydes.

Temporally resolved thermal desorption of volatile organics from nanoporous silica preconcentrator

The Analyst ◽  
2021 ◽  
Vol 146 (1) ◽  
pp. 109-117
Author(s):  
William Winter ◽  
Coco Day ◽  
Joshua Prestage ◽  
Tanya Hutter
Keyword(s):  
Volatile Organic Compounds ◽  
Gas Phase ◽  
Organic Compounds ◽  
Thermal Desorption ◽  
Nanoporous Silica ◽  
Volatile Organics ◽  
Desorption Temperature ◽  
Volatile Organic

Gas-phase volatile organic compounds (VOCs) are collected in a nanoporous silica preconcentrator, then released slowly by heating onto a detector. Desorption temperature depends on VOC properties, allowing potential discrimination.

scholarly journals The role of low volatile organics on secondary organic aerosol formation

2014 ◽  
Vol 14 (3) ◽  
pp. 1689-1700 ◽  
Author(s):  
H. Kokkola ◽  
P. Yli-Pirilä ◽  
M. Vesterinen ◽  
H. Korhonen ◽  
H. Keskinen ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Atmospheric Aerosol ◽  
Radiative Forcing ◽  
Large Scale ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Wall Losses ◽  
Rapid Formation ◽  
New Particles

Abstract. Large-scale atmospheric models, which typically describe secondary organic aerosol (SOA) formation based on chamber experiments, tend to systematically underestimate observed organic aerosol burdens. Since SOA constitutes a significant fraction of atmospheric aerosol, this discrepancy translates into an underestimation of SOA contribution to radiative forcing of atmospheric aerosol. Here we show that the underestimation of SOA yields can be partly explained by wall losses of SOA forming compounds during chamber experiments. We present a chamber experiment where α-pinene and ozone are injected into a Teflon chamber. When these two compounds react, we observe rapid formation and growth of new particles. Theoretical analysis of this formation and growth event indicates rapid formation of oxidized volatile organic compounds (OVOC) of very low volatility in the chamber. If these oxidized organic compounds form in the gas phase, their wall losses will have significant implications on their partitioning between the gas and particle phase. Although these OVOCs of very low volatility contribute to the growth of new particles, their mass will almost completely be depleted to the chamber walls during the experiment, while the depletion of OVOCs of higher volatilities is less efficient. According to our model simulations, the volatilities of OVOC contributing to the new particle formation event can be of the order of 10−5 μg m−3.

Adsorption/thermal desorption with small cartridges for the determination of trace aqueous semivolatile organic compounds

1988 ◽  
Vol 60 (1) ◽  
pp. 40-47 ◽  
Author(s):  
James F. Pankow ◽  
Mary P. Ligocki ◽  
Michael E. Rosen ◽  
Lorne M. Isabelle ◽  
Kenneth M. Hart
Keyword(s):  
Organic Compounds ◽  
Thermal Desorption ◽  
Semivolatile Organic Compounds

scholarly journals Comparing secondary organic aerosol (SOA) volatility distributions derived from isothermal SOA particle evaporation data and FIGAERO–CIMS measurements

2020 ◽  
Vol 20 (17) ◽  
pp. 10441-10458 ◽  
Author(s):  
Olli-Pekka Tikkanen ◽  
Angela Buchholz ◽  
Arttu Ylisirniö ◽  
Siegfried Schobesberger ◽  
Annele Virtanen ◽  
...  
Keyword(s):  
Particle Size ◽  
Organic Compounds ◽  
Thermal Desorption ◽  
Process Modeling ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Condition ◽  
Size Change ◽  
Modeling Techniques ◽  
Dry Conditions

Abstract. The volatility distribution of the organic compounds present in secondary organic aerosol (SOA) at different conditions is a key quantity that has to be captured in order to describe SOA dynamics accurately. The development of the Filter Inlet for Gases and AEROsols (FIGAERO) and its coupling to a chemical ionization mass spectrometer (CIMS; collectively FIGAERO–CIMS) has enabled near-simultaneous sampling of the gas and particle phases of SOA through thermal desorption of the particles. The thermal desorption data have been recently shown to be interpretable as a volatility distribution with the use of the positive matrix factorization (PMF) method. Similarly, volatility distributions can be inferred from isothermal particle evaporation experiments when the particle size change measurements are analyzed with process-modeling techniques. In this study, we compare the volatility distributions that are retrieved from FIGAERO–CIMS and particle size change measurements during isothermal particle evaporation with process-modeling techniques. We compare the volatility distributions at two different relative humidities (RHs) and two oxidation conditions. In high-RH conditions, where particles are in a liquid state, we show that the volatility distributions derived via the two ways are similar within a reasonable assumption of uncertainty in the effective saturation mass concentrations that are derived from FIGAERO–CIMS data. In dry conditions, we demonstrate that the volatility distributions are comparable in one oxidation condition, and in the other oxidation condition, the volatility distribution derived from the PMF analysis shows considerably more high-volatility matter than the volatility distribution inferred from particle size change measurements. We also show that the Vogel–Tammann–Fulcher equation together with a recent glass transition temperature parametrization for organic compounds and PMF-derived volatility distribution estimates are consistent with the observed isothermal evaporation under dry conditions within the reported uncertainties. We conclude that the FIGAERO–CIMS measurements analyzed with the PMF method are a promising method for inferring the volatility distribution of organic compounds, but care has to be taken when the PMF factors are analyzed. Future process-modeling studies about SOA dynamics and properties could benefit from simultaneous FIGAERO–CIMS measurements.

scholarly journals Photochemical degradation of iron(III) citrate/citric acid aerosol quantified with the combination of three complementary experimental techniques and a kinetic process model

2021 ◽  
Vol 21 (1) ◽  
pp. 315-338
Author(s):  
Jing Dou ◽  
Peter A. Alpert ◽  
Pablo Corral Arroyo ◽  
Beiping Luo ◽  
Frederic Schneider ◽  
...  
Keyword(s):  
Citric Acid ◽  
Mass Loss ◽  
Gas Phase ◽  
Organic Compounds ◽  
Chemical Reactions ◽  
Loss Rate ◽  
Mass Loss Rate ◽  
Organic Aerosol ◽  
Photochemical Degradation ◽  
Aerosol Aging

Abstract. Iron(III) carboxylate photochemistry plays an important role in aerosol aging, especially in the lower troposphere. These complexes can absorb light over a broad wavelength range, inducing the reduction of iron(III) and the oxidation of carboxylate ligands. In the presence of O2, the ensuing radical chemistry leads to further decarboxylation, and the production of .OH, HO2., peroxides, and oxygenated volatile organic compounds, contributing to particle mass loss. The .OH, HO2., and peroxides in turn reoxidize iron(II) back to iron(III), closing a photocatalytic cycle. This cycle is repeated, resulting in continual mass loss due to the release of CO2 and other volatile compounds. In a cold and/or dry atmosphere, organic aerosol particles tend to attain highly viscous states. While the impact of reduced mobility of aerosol constituents on dark chemical reactions has received substantial attention, studies on the effect of high viscosity on photochemical processes are scarce. Here, we choose iron(III) citrate (FeIII(Cit)) as a model light-absorbing iron carboxylate complex that induces citric acid (CA) degradation to investigate how transport limitations influence photochemical processes. Three complementary experimental approaches were used to investigate kinetic transport limitations. The mass loss of single, levitated particles was measured with an electrodynamic balance, the oxidation state of deposited particles was measured with X-ray spectromicroscopy, and HO2. radical production and release into the gas phase was observed in coated-wall flow-tube experiments. We observed significant photochemical degradation with up to 80 % mass loss within 24 h of light exposure. Interestingly, we also observed that mass loss always accelerated during irradiation, resulting in an increase of the mass loss rate by about a factor of 10. When we increased relative humidity (RH), the observed particle mass loss rate also increased. This is consistent with strong kinetic transport limitations for highly viscous particles. To quantitatively compare these experiments and determine important physical and chemical parameters, a numerical multilayered photochemical reaction and diffusion (PRAD) model was developed that treats chemical reactions and the transport of various species. The PRAD model was tuned to simultaneously reproduce all experimental results as closely as possible and captured the essential chemistry and transport during irradiation. In particular, the photolysis rate of FeIII, the reoxidation rate of FeII, HO2. production, and the diffusivity of O2 in aqueous FeIII(Cit) ∕ CA system as function of RH and FeIII(Cit) ∕ CA molar ratio could be constrained. This led to satisfactory agreement within model uncertainty for most but not all experiments performed. Photochemical degradation under atmospheric conditions predicted by the PRAD model shows that release of CO2 and repartitioning of organic compounds to the gas phase may be very important when attempting to accurately predict organic aerosol aging processes.

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