Proton-transfer-reaction Time-of-flight Mass Spectrometer Research Articles

Multiple effects of relative humidity on heterogeneous ozonolysis of cooking organic aerosol proxies from heated peanut oil emissions

The exposure to cooking organic aerosols (COA) is closely related to people's daily lives. Despite extensive investigations into COA's model compounds like oleic acid, the intricacies of heterogeneous ozonolysis of real COA and the effects of ambient conditions like humidity remain elusive. In this work, the ozonolysis of COA proxies from heated peanut oil emissions was investigated using diffuse reflectance infrared Fourier transform (DRIFTS) spectroscopy, and proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). We found that humidity hinders the reaction between ozone and CC double bonds due to the competitive adsorption of water and ozone on COA. Although visible light has little influence on the ozonolysis of COA in the absence of humidity, the ozonolytic CO production is significantly promoted by visible light in the presence of humidity. It may be attributed to the formation of water-derived reactive oxygen species (ROS, mainly HO•) from the photosensitization of polycyclic aromatic hydrocarbons (PAHs) in COA. We also found that humidity can enhance the depolymerization of carboxylic acid dimers and hydrolysis of intrinsic acetals in the COA. Moreover, humidity promotes the release of VOCs during both the dark and light ozonolysis of COA. This work reveals the important roles of humidity-responsive and photo-responsive components in COA during its ozonolysis, and the change in VOC release may guide the control of human VOC exposure in indoor air.

Response of protonated, adduct, and fragmented ions in Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS)

Abstract. Volatile organic compounds (VOCs) affect secondary pollutant formation via active chemistry. Proton-transfer-reaction mass spectrometry (PTR-MS) is one of the most important techniques to study the highly variable spatial and temporal characteristics of VOCs. The response of protonated, adduct, and fragmented ions in PTR-MS in changing instrument settings and varying relative humidity (RH) requires rigorous characterization. Herein, we present dedicatedly designed laboratory experiments conducted to investigate the response of these ions for 21 VOCs, including 12 oxygenated VOCs and 2 nitriles, using the recently developed Vocus PTR-MS. Our results show that the focusing ion–molecule reactor (FIMR) axial voltage increases sensitivity by 3 to 4 orders of magnitude but does not significantly change the fractions of protonated ions. Reducing the FIMR pressure, however, substantially increases fragmentation. Applying a high radio frequency (RF) amplitude radially to the FIMR can enhance sensitivity by 1 to 2 orders of magnitude without affecting the protonated ion fractions. The change in big segmented quadrupole (BSQ) amplitude mainly affects sensitivity and protonated ion fraction by modifying ion transmission. The relationship between sensitivity and proton-transfer reaction rate constant is complicated by the influences from both ion transmission and protonated ion fraction. The protonated ions of most VOCs studied (19 out of 21) show less than 15 % variations in sensitivity as RH increases from ∼ 5% to ∼ 85 %, except for some long-chain aldehydes which show a positive RH variation of up to 30 %. Our results suggest that the Vocus PTR-MS can reliably quantify the majority of VOCs under ambient conditions with varying RH. However, caution is advised for small oxygenates such as formaldehyde and methanol due to their low sensitivity and for long-chain aldehydes due to their slight RH dependence and fragmentation.

Contribution of cooking emissions to the urban volatile organic compounds in Las Vegas, NV

Abstract. Cooking is a source of volatile organic compounds (VOCs), which degrade air quality. Cooking VOCs have been investigated in laboratory and indoor studies, but the contribution of cooking to the spatial and temporal variability in urban VOCs is uncertain. In this study, a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) is used to identify and quantify cooking emission in Las Vegas, NV, with supplemental data from Los Angeles, CA, and Boulder, CO. Mobile laboratory data show that long-chain aldehydes, such as octanal and nonanal, are significantly enhanced in restaurant plumes and regionally enhanced in areas of Las Vegas with high restaurant densities. Correlation analyses show that long-chain fatty acids are also associated with cooking emissions and that the relative VOC enhancements observed in regions with dense restaurant activity are very similar to the distribution of VOCs observed in laboratory cooking studies. Positive matrix factorization (PMF) is used to quantify cooking emissions from ground site measurements and to compare the magnitude of cooking with other important urban sources, such as volatile chemical products and fossil fuel emissions. PMF shows that cooking may account for as much as 20 % of the total anthropogenic VOC emissions observed by PTR-ToF-MS. In contrast, emissions estimated from county-level inventories report that cooking accounts for less than 1 % of urban VOCs. Current emissions inventories do not fully account for the emission rates of long-chain aldehydes reported here; thus, further work is likely needed to improve model representations of important aldehyde sources, such as commercial and residential cooking.

Characteristics of Volatile Organic Compounds Distribution in Downtown Ansan Near Industrial Complexes

There are four industrial complexes located around Ansan City, which is one of the areas with the highest VOCs emissions in Gyeonggi region based on the emissions provided by the clean policy support system (CAPSS), Korea. In this study, proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) was used to determine the distribution of volatile organic compounds (VOCs) in urban areas near industrial complexes in Ansan City in 2023 (May to June). The PTR-TOF-MS was operated over the mass range of 10-400amu at a drift tube pressure of 2.3mbar and temperature 80<sup>o</sup>C (E/N ~ 130Td) that enabled the collection of VOC data at 0.1Hz resolution. The mixing ratio calculations for methanol, acetaldehyde, acetonitrile, acetone, acetic acid, dimethyl sulfide, isoprene, methyl vinyl ketone (MVK), methyl ethyl ketone (MEK), benzene, toluene, styrene, xylene, trimethylbenzene and pinene reported in this study were done using the sensitivity factors obtained from the PTR-TOF-MS calibrations. As a result of the intensive measurement in springtime, among the substances constituting VOCs, methanol was the most abundant with 16.27±7.13 ppb, followed by acetone, acetaldehyde, acetic acid, methyl ethyl ketone (MEK), toluene, and xylene. VOCs compositions were dominated by oxidized VOCs, with CxHyO1 at 74%, CxHyO2 at 11%, aromatic CxHy at 10.5%, and CxHyN at 3.1%, respectively. As a result of the diurnal variations and conditional probability function (CPF) analysis, it was found that toluene and MEK were locally greatly influenced by industrial complexes distributed around Ansan City. Related with the ozone creating contribution, the ratio of VOCs to nitrogen oxide (NOx) was 6.5 (1.4 to 18.2), which appeared in the NOx-limited (4:1) and the VOCs-limited (15:1). Therefore it is suggested that the management of emission source NOx and VOCs are very important for the reduction of ozone in Ansan.

Secondary organic aerosol formed by Euro 5 gasoline vehicle emissions: chemical composition and gas-to-particle phase partitioning

Abstract. In this study we investigated the photo-oxidation of Euro 5 gasoline vehicle emissions during cold urban, hot urban and motorway Artemis cycles. The experiments were conducted in an environmental chamber with average OH concentrations ranging between 6.6 × 105–2.3 × 106 molec. cm−3, relative humidity (RH) between 40 %–55 % and temperatures between 22–26 °C. A proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) and the CHemical Analysis of aeRosol ON-line (CHARON) inlet coupled with a PTR-ToF-MS were used for the gas- and particle-phase measurements respectively. This is the first time that the CHARON inlet has been used for the identification of the secondary organic aerosol (SOA) produced from vehicle emissions. The secondary organic gas-phase products ranged between C1 and C9 with one to four atoms of oxygen and were mainly composed of small oxygenated C1–C3 species. The SOA formed contained compounds from C1 to C14, having one to six atoms of oxygen, and the products' distribution was centered at C5. Organonitrites and organonitrates contributed 6 %–7 % of the SOA concentration. Relatively high concentrations of ammonium nitrate (35–160 µg m−3) were formed. The nitrate fraction related to organic nitrate compounds was 0.12–0.20, while ammonium linked to organic ammonium compounds was estimated only during one experiment, reaching a fraction of 0.19. The SOA produced exhibited log C∗ values between 2 and 5. Comparing our results to theoretical estimations for saturation concentrations, we observed differences of 1–3 orders of magnitude, indicating that additional parameters such as RH, particulate water content, aerosol hygroscopicity, and possible reactions in the particulate phase may affect the gas-to-particle partitioning.

Study of secondary organic aerosol formation and aging using ambient air in an oxidation flow reactor during high pollution events over Delhi

Secondary aerosols constitute a significant fraction of atmospheric aerosols, yet our understanding of their formation mechanism and fate is very limited. In this work, the secondary organic aerosol (SOA) formation and aging of ambient air of Delhi are studied using a potential aerosol mass (PAM) reactor, an oxidation flow reactor (OFR), coupled with aerosol chemical speciation monitor (ACSM), proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS), and scanning mobility particle sizer with counter (SMPS + C). The setup mimics atmospheric aging of up to several days with the generation of OH radicals. Variations in primary volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) as a function of photochemical age were investigated. Primary VOCs such as benzene, toluene, xylene, trimethyl benzene, etc. decrease and OVOCs like formic acid, formaldehyde, acetone, ethanol, etc. increase substantially upon oxidation in OFR. The highest organic aerosol (OA) enhancement was observed for the 4.2 equivalent photochemical days of aging i.e., 1.84 times the ambient concentration, and net OA loss was observed at very high OH exposure, typically after 8.4 days of photochemical aging due to heterogeneous oxidation followed by fragmentation/evaporation. In ambient air, OA enhancement is highest during nighttime due to the high concentrations of precursor VOCs in the atmosphere. SMPS + C results demonstrated substantial new particle formation upon aging and decrement in preexisting aerosol mass. This is the first experimental study conducting an in-situ evaluation of potential SOA mass generated from the ambient aerosols in India.

Real-time evaluation of terpene emissions and exposures during the use of scented wax products in residential buildings with PTR-TOF-MS

Scented wax products, such as candles and wax warmers/melts, are popular fragranced consumer products that are commonly used in residential buildings. As scented wax products are intentionally fragranced to produce pleasant smellscapes for occupants, they may represent an important source of volatile organic compounds (VOCs) to indoor atmospheres. The aim of this study is to evaluate terpene emission factors (EFs) and inhalation intake fractions (iFs) for scented wax products to better understand their impact on indoor chemistry and chemical exposures. Full-scale emission experiments were conducted in the Purdue zEDGE Test House using a variety of scented candles (n = 5) and wax warmers/melts (n = 14) under different outdoor air exchange rates (AERs). Terpene concentrations were measured in real-time using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). PTR-TOF-MS measurements revealed that scented candle and wax warmer/melt products emit a variety of monoterpenes (C10H16) and oxygen-containing monoterpenoids (C10H14O, C10H16O, C10H18O, C10H20O), with peak concentrations in the range of 10−1 to 102 ppb. Monoterpene EFs were much greater for scented wax warmers/melts (C10H16 EFs ∼ 102 mg per g wax consumed) compared to scented candles (C10H16 EFs ∼ 10−1 to 100 mg per g wax consumed). Significant emissions of reactive terpenes from both products, along with nitrogen oxides (NO, NO2) from candles, depleted indoor ozone (O3) concentrations. Terpene iFs were similar between the two products (iFs ∼ 103 ppm) and increased with decreasing outdoor AER. Terpene iFs during concentration decay periods were similar to, or greater than, iFs during active emission periods for outdoor AERs ≤ 3.0 h−1. Overall, scented wax warmers/melts were found to release greater quantities of monoterpenes compared to other fragranced consumer products used in the home, including botanical disinfectants, hair care products, air fresheners, and scented sprays.

Identification of Volatile Molecules and Bioactivity of Gruyt Craft Beer Enriched with Citrus aurantium var. dulcis L. Essential Oil.

In this work, for the first time, a gruyt beer and the same one after the addition of Citrus aurantium essential oil (AEO), were investigated to determine the composition of the volatile fraction. The applied analytical techniques, such as Head Space/Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS/SPME-GC-MS) and Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS), allowed us to identify the content of volatile organic compounds (VOCs). From the comparison between the two beer samples, it showed that the one after the addition of AEO was particularly richened in limonene and a series of minor terpene compounds. AEO was also characterized by GC/MS analysis and the results showed that limonene reached 95%. Confocal microscopy was used to look at riboflavin autofluorescence in yeast cells. It was found that beer with AEO had twice as much fluorescence intensity as the control. A spectrophotometric analysis of total polyphenols, tannins, and flavonoids, and a bioactivity screening, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-Azinobis-(3-Ethylbenzthiazolin-6-Sulfonic Acid) (ABTS) radical scavenger, chelating, reducing, antiglycative ones, were also carried out. Moreover, the tolerability of the tested samples in human H69 cholangiocytes and the cytoprotection towards the tert-butyl hydroperoxide (tBOOH)-induced oxidative damage were evaluated. Under our experimental conditions, the beers were found to be able to scavenge DPPH and ABTS radicals and chelate iron ions, despite weak antiglycative and reducing properties. The tested samples did not affect the viability of H69 cholangiocytes up to the highest concentrations; moreover, no signs of cytoprotection against the damage induced by tBOOH were highlighted. Adding AEO to beer resulted in a moderate enhancement of its DPPH scavenging and chelating abilities, without improvements in the other assays. Conversely, AEO and its major compound limonene were ineffective when assessed at the concentrations added to beer. This evidence suggests that the addition of AEO may enhance the organoleptic features of the beer and slightly potentiate some of its bioactivities.

Gas–particle partitioning of toluene oxidation products: an experimental and modeling study

Abstract. Toluene represents a large fraction of anthropogenic emissions and significantly contributes to tropospheric ozone and secondary organic aerosol (SOA) formation. Despite the fact that toluene is one of the most studied aromatic compounds, detailed chemical mechanisms still fail to correctly reproduce the speciation of toluene gaseous and condensed oxidation products. This study aims to elucidate the role of initial experimental conditions in toluene SOA mass loadings and to investigate gas–particle partitioning of its reaction products at different relevant temperatures. Gaseous and particulate reaction products were identified and quantified using a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) coupled to a CHemical Analysis of aeRosol ONline (CHARON) inlet. The chemical system exhibited a volatility distribution mostly in the semi-volatile regime. Temperature decrease caused a shift of saturation concentration towards lower values. The CHARON–PTR-ToF-MS instrument identified and quantified approximately 60 %–80 % of the total organic mass measured by an aerosol mass spectrometer. A detailed mechanism for toluene gaseous oxidation was developed based on the Master Chemical Mechanism (MCM) and Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) deterministic mechanisms, modified following the literature. The new mechanism showed improvements in modeling oxidation product speciation with more observed species represented and more representative concentrations compared to the MCM–GECKO-A reference. Tests on partitioning processes, nonideality, and wall losses highlighted the high dependency of SOA formation on the considered processes. Our results underline the fact that volatility is not sufficient to explain the gas–particle partitioning: the organic and the aqueous phases need to be considered as well as the interactions between compounds in the particle phase.

Real-time indoor sensing of volatile organic compounds during building disinfection events via photoionization detection and proton transfer reaction mass spectrometry

Photoionization detectors (PIDs) are low-cost sensors that are widely used for real-time volatile organic compound (VOC) monitoring in buildings. Performance assessment of PIDs is often based on reference VOC measurements derived from offline, time-integrated sample analysis. Such assessment techniques lack valuable real-time information that is needed to evaluate how PIDs track transient VOC emission events. The objective of this study is to evaluate the real-time performance of a PID in sensing indoor VOC mixtures during building disinfection events through co-location measurements with a state-of-the-art proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). Field measurements were conducted in a tiny house laboratory using an isobutylene-calibrated PID and a PTR-TOF-MS during the use of spray-based disinfectants. The PID and PTR-TOF-MS measurements demonstrated that chemical disinfectants are a major source of VOCs in buildings, with the latter revealing the presence of a large diversity of VOCs. In general, the PID was successful in identifying VOC emission events during the application of the disinfectants. Thus, PIDs may be suitable for integration with building automation systems for ventilation control. The PID response was much less than the PTR-TOF-MS response, suggesting that the PID is not efficiently detecting many components of the emitted VOC mixtures. The PID performed best for alcohol-based disinfectants, moderately well for lactic acid- and botanical-based disinfectants, and poorly for disinfectants featuring peracetic and acetic acid. Detailed correlation analysis between the PID and PTR-TOF-MS responses provides a basis for improving the reliability of PIDs in estimating VOC concentrations through application of product-specific correction factors.

Fuel-Type Independent Parameterization of Volatile Organic Compound Emissions from Western US Wildfires.

Volatile organic compounds (VOCs) emitted from biomass burning impact air quality and climate. Laboratory studies have shown that the variability in VOC speciation is largely driven by changes in combustion conditions and is only modestly impacted by fuel type. Here, we report that emissions of VOCs measured in ambient smoke emitted from western US wildfires can be parameterized by high- and low-temperature pyrolysis VOC profiles and are consistent with previous observations from laboratory simulated fires. This is demonstrated using positive matrix factorization (PMF) constrained by high- and low-temperature factors using VOC measurements obtained with a proton-transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) on board the NASA DC-8 during the FIREX-AQ (Fire Influence on Regional and Global Environments and Air Quality) project in 2019. A linear combination of high- and low-temperature factors described more than 70% of the variability of VOC emissions of long-lived VOCs in all sampled wildfire plumes. An additional factor attributable to atmospheric aging was required to parameterize short-lived and secondarily produced VOCs. The relative contribution of the PMF-derived high-temperature factor for a given fire plume was strongly correlated with the fire radiative power (FRP) at the estimated time of emission detected by satellite measurements. By combining the FRP with the fraction of the high-temperature PMF factor, the emission ratios (ERs) of VOCs to carbon monoxide (CO) in fresh wildfires were estimated and agree well with measured ERs (r2 = 0.80-0.93).

Application of Cluster Analysis to Examine the Performance of Low-Cost Volatile Organic Compound Sensors

Airtight energy-efficient buildings of today need efficient ventilation to secure high indoor air quality. There is a need for affordable and reliable sensors to make demand control available in a broad range of ventilation systems. Low-cost metal oxide semiconductor (MOS) volatile organic compound (VOC) sensors offer such a possibility, but they are usually non-selective and react to broad range of compounds. The objective of the present paper was to use cluster analysis to assess the ability of five commercially available MOS VOC sensors to detect pollutants in a residential setting. We studied three scenarios: emissions from people (human bioeffluents), furnishing materials (linoleum), and human activity (surface cleaning with spray detergent). We monitored each scenario with five MOS VOC sensors and a proton-transfer-reaction–time-of-flight mass spectrometer (PTR-ToF-MS). We applied an agglomerative hierarchical clustering algorithm to evaluate the dissimilarity between clusters. Four of the five tested sensors produced signals in agreement with the concentration patterns measured with the PTR-ToF-MS; one sensor underperformed in all cases. Three sensors showed a very similar performance under all emission scenarios. The results showed that the clustering could help in understanding whether a particular sensor matched the intended emission scenario.

Field Verification of Vehicle-Mounted All-Fiber Coherent Wind Measurement Lidar Based on Four-Beam Vertical Azimuth Display Scanning

Wind parameters play a vital role in studying atmospheric dynamics and climate change. In this study, a vehicle-mounted coherent wind measurement Lidar (CWML) with a wavelength of 1.55 µm is demonstrated based on a four-beam vertical azimuth display (VAD) scanning mode, and a method to estimate wind vector from power spectrum is proposed. The feasibility of the application of wind profile Lidar in vehicles is verified by calibration tests, comparison experiments, and continuous observation experiments, successively. The effective detection height of Lidar can reach 3 km. In contrasting experiments, the correlation coefficients of the magnitude and direction of horizontal wind speed measured by vehicle-mounted Lidar and fixed Lidar are 0.94 and 0.91, respectively. The experimental results reveal that the accuracies of wind speed and direction measurements with the vehicle-mounted CWML are better than 0.58 m/s and 4.20°, respectively. Furthermore, to understand the role of the wind field in the process of energy and material transport further, a proton-transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) is utilized to measure the concentration of volatile organic compounds (VOCs). Relevant experimental results indicate that the local meteorological conditions, including wind speed and humidity, influence the VOC concentrations.

Removal of volatile organic compounds by mobile air cleaners: Dynamics, limitations, and possible side effects

Air cleaners are becoming increasingly popular as a response to the increased focus on the impact of indoor air quality on human health, comfort and performance. In this study, the removal of particulate matter (PM) and volatile organic compounds (VOCs) by mobile air cleaners is investigated in an unoccupied university classroom. From time-resolved measurements by proton-transfer-reaction time of flight mass spectrometer (PTR-TOF-MS) the study reports on VOC removal and by-product formation from different air cleaning technologies. Results revealed an inconsistency between expected and experimentally obtained clean air delivery rates (CADRs). For seven out of eight air cleaners examined, the CADRs for all VOCs tested (methanol, acetaldehyde, acetone, acetic acid, isoprene, butanone, toluene, benzaldehyde and limonene) were significantly lower than the corresponding CADRs for PM. In general, single pass removal efficiencies (REs) for VOCs were found to decrease as a function of time. The VOCs demonstrated very distinctive dynamic behavior. Results indicated adsorption as the main removal mechanism of VOCs for all air cleaners for which a significant removal (RE ≥ 5%) was observed. Formation of by-products (incl. CH2O and C4H6O) was associated with technologies containing an UV lamp. Reemission of specific VOCs was observed for adsorption-based air cleaners during operation in a newly vented room. The results highlight the inadequacy of how we currently report air cleaner performance.

Improved monitoring of cryptogam gas-exchange and volatile emissions during desiccation-rehydration cycles with a within-chamber hydration method

Desiccation-rehydration studies in cryptogams constitute an important tool to understand the relation of key physiological traits with species stress tolerance and environmental adaptability. Real-time monitoring of responses has been limited by the design of commercial or custom measuring cuvettes and difficulties in experimental manipulation. We developed a within-chamber rehydration method that allows to rewater the samples rapidly, without the need to open the chamber and take out the sample for manual rehydration by the investigator. Data is collected in real-time and simultaneously with an infrared gas-analyzer (LICOR-7000), a chlorophyll fluorometer (Maxi Imaging-PAM) and a proton transfer reaction time-of-flight mass-spectrometer (PTR-TOF-MS) for volatile organic compound emissions. The system was tested on four cryptogam species with contrasting ecological distributions. No major errors or kinetics disruptions were found during system testing and measurements. Our within-chamber rehydration method improved accuracy, as measurement periods were not lacking, and repeatability of the protocol by reducing error variance in sample manipulation. This method provides an improved technique to conduct desiccation-rehydration measurements, contributing to the standardization and accuracy of current existing methodologies. A close real-time and simultaneous monitoring of photosynthesis, chlorophyll fluorescence and volatile organic compound emission data, offers a novel perspective in the analysis of the cryptogam stress responses that is yet to be fully explored.

Temperature driven variations in VOC emissions from plastic products and their fate indoors: A chamber experiment and modelling study

Plastic products are ubiquitous in our homes, but we know very little about emissions from these products and their subsequent impact on indoor air quality. This is the first study to systematically determine temperature-dependent emissions of volatile organic compounds from commonly used plastic consumer products found in the home. The plastic types included high-density polyethylene (HDPE), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS) and polyester rubber. Plastic samples were exposed to increasing temperatures (between 18 and 28 °C) in controlled environmental chambers, connected to a proton-transfer-reaction time-of-flight mass-spectrometer (PTR-ToF-MS), where real-time emissions were detected. Average emission rates were determined and used to initialise an indoor air chemistry model (INCHEM-Py) at the highest and lowest experimental temperatures, to explore the impact these product emissions have on the indoor air chemistry. The PS tubing plastic proved to be the highest emitting polymer per surface area. Almost all selected VOC emissions were found to have a linear relationship with temperature. Upon observing the impacts of primary VOC emissions from plastics in modelled simulations, the hydroxyl radical concentration decreased by an average of 1.6 and 10 % relative to the baseline (with no plastics included) at 18 °C and 28 °C respectively. On the other hand, formaldehyde concentrations increased by 29 and 31.6 % relative to the baseline conditions at 18 °C and 28 °C respectively. The presence of plastic products indoors, therefore, has the potential to impact the indoor air quality.

Real-time measurements of non-methane volatile organic compounds in the central Indo-Gangetic basin, Lucknow, India: source characterisation and their role in O3 and secondary organic aerosol formation

Abstract. Lucknow is the capital of India's largest state, Uttar Pradesh, one of South Asia's most polluted urban cities. Tropospheric photochemistry relies on non-methane volatile organic compounds (NMVOCs), which are ozone and secondary organic aerosol precursors. Using the proton-transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) at an urban background site in Lucknow, the chemical characterisation of NMVOCs was performed in real time from December 2020 to May 2021. About ∼ 173 NMVOCs from m/z 31.018 to 197.216 were measured during the study period, including aromatics, non-aromatics, oxygenates, and nitrogen-containing compounds. The campaign daily mean concentrations of the NMVOCs were 125.5 ± 37.5 ppbv. The NMVOC daily average concentrations were about ∼ 30 % higher during the winter months (December–February) than in summer (March–May). The oxygenated volatile organic compounds and aromatics were the dominant VOC families, accounting for ∼ 57 %–80 % of the total NMVOC concentrations. Acetaldehyde, acetone, and acetic acid were the major NMVOC species, 5–15 times higher than the other species. An advanced multi-linear engine (ME-2) model was used to perform the NMVOC source apportionment using positive matrix factorisation (PMF). It resolves the five main sources contributing to these organic compounds in the atmosphere. They include traffic (23.5 %), two solid fuel combustion factors, SFC 1 (28.1 %) and SFC 2 (13.2 %), secondary volatile organic compounds (SVOCs) (18.6 %), and volatile chemical products (VCPs) (16.6 %). Aged and fresh emissions from solid fuel combustion (SFCs 1 and 2) were the dominant contributors to the total NMVOCs, and compounds related to these factors had a high secondary organic aerosol (SOA) formation potential. Interestingly, the traffic factor was the second-highest contributor to the total NMVOCs, and compounds related to this factor had a high ozone formation potential. Significant differences in the composition of the two solid fuel combustions indicate the influence of local emissions and transport of regional pollution to the city. The high temperature during summer leads to more volatilisation of oxygenated VOCs, related to the VCP factor. The study is the first attempt to highlight the sources of NMVOCs and their contribution to secondary pollutant (SOA and O3) formation in the city of Lucknow during winter and summer. The insights from the study would help various stakeholders to manage primary and secondary pollutants within the city.

Measurement report: Emission factors of NH3 and NHx for wildfires and agricultural fires in the United States

Abstract. During the 2019 Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) study, the NASA DC-8 carried out in situ chemical measurements in smoke plumes emitted from wildfires and agricultural fires in the contiguous United States. The DC-8 payload included a modified proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) for the fast measurement of gaseous ammonia (NH3) and a high-resolution time-of-flight aerosol mass spectrometer (AMS) for the fast measurement of submicron particulate ammonium (NH4+). We herein report data collected in smoke plumes emitted from 6 wildfires in the Western United States, 2 prescribed grassland fires in the Central United States, 1 prescribed forest fire in the Southern United States, and 66 small agricultural fires in the Southeastern United States. Smoke plumes contained double to triple digit ppb levels of NH3. In the wildfire plumes, a significant fraction of NH3 had already been converted to NH4+ at the time of sampling (≥2 h after emission). Substantial amounts of NH4+ were also detected in freshly emitted smoke from corn and rice field fires. We herein present a comprehensive set of emission factors of NH3 and NHx, with NHx=NH3+NH4+. Average NH3 and NHx emission factors for wildfires in the Western United States were 1.86±0.75 g kg−1 and 2.47±0.80 g kg−1 of fuel burned, respectively. Average NH3 and NHx emission factors for agricultural fires in the Southeastern United States were 0.89±0.58 and 1.74±0.92 g kg−1, respectively. Our data show no clear inverse correlation between modified combustion efficiency (MCE) and NH3 emissions. The observed NH3 emissions were significantly higher than measured in previous laboratory experiments in the FIREX FireLab 2016 study.

Photolysis frequency of nitrophenols derived from ambient measurements

Nitrophenols, a class of important intermediate products from the oxidation of aromatics, can participate in photochemistry and influence the atmospheric oxidative capacity. However, the reported photolysis frequencies of nitrophenols show considerable discrepancies. Here, measurements of nitrophenol, and methyl nitrophenol using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) at both urban and regional sites in southern China are used to constrain photolysis frequencies of nitrophenols. Considerable concentrations with a campaign average of 58 ± 32 ppt for nitrophenol and 97 ± 59 ppt for methyl nitrophenol were observed at the regional site. Based on the in-situ measurement dataset, a steady-state calculation was performed along with a zero-dimensional box model to analyze the budgets of nitrophenols. The result indicates that both primary emission and photolysis have significant impacts on nitrophenols. Primary emission contributes up to 88 % of the total nitrophenols production while photolysis accounts for up to 98 % of the total removal rate. The dominant sink of nitrophenols is photolysis with a rate of about 3.5 % ± 1.3 % of jNO2 for nitrophenol and 2.4 % ± 1.0 % of jNO2 for methyl nitrophenol. The results of this study suggest that using advanced mass spectrometry to accurately measure ambient nitrophenols, supplemented by an observation-based box model for budget analysis, provides an important indication for determining photolysis rate constants of nitrophenols.

Real-time measurement of phase partitioning of organic compounds using a proton-transfer-reaction time-of-flight mass spectrometer coupled to a CHARON inlet

Abstract. Understanding the gas–particle partitioning of semivolatile organic compounds (SVOCs) is of crucial importance in the accurate representation of the global budget of atmospheric organic aerosols. In this study, we quantified the gas- vs. particle-phase fractions of a large number of SVOCs in real time in an urban area of East China with the use of a CHemical Analysis of aeRosols ONline (CHARON) inlet coupled to a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). We demonstrated the use of the CHARON inlet for highly efficient collection of particulate SVOCs while maintaining the intact molecular structures of these compounds. The collected month-long dataset with hourly resolution allows us to examine the gas–particle partitioning of a variety of SVOCs under ambient conditions. By comparing the measurements with model predictions using instantaneous equilibrium partitioning theory, we found that the dissociation of large parent molecules during the PTR ionization process likely introduces large uncertainties to the measured gas- vs. particle-phase fractions of less oxidized SVOCs, and therefore, caution should be taken when linking the molecular composition to the particle volatility when interpreting the PTR-ToF-MS data. Our analysis suggests that understanding the fragmentation mechanism of SVOCs and accounting for the neutral losses of small moieties during the molecular feature extraction from the raw PTR mass spectra could reduce, to a large extent, the uncertainties associated with the gas–particle partitioning measurement of SVOCs in the ambient atmosphere.