Search

Electronic cigarette smoking (or vaping) is on the rise, presenting questions about the effects of secondhand exposure. The chemical composition of vape emissions was examined in the exhaled breath of eight human volunteers with the high chemical specificity of complementary online and offline techniques. Our study is the first to take multiple exhaled puff measurements from human participants and compare volatile organic compound (VOC) concentrations between two commonly used methods, proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and gas chromatography (GC). Five flavor profile groups were selected for this study, but flavor compounds were not observed as the main contributors to the PTR-ToF-MS signal. Instead, the PTR-ToF-MS mass spectra were overwhelmed by e-liquid thermal decomposition and fragmentation products, which masked other observations regarding flavorings and other potentially toxic species associated with secondhand vape exposure. Compared to the PTR-ToF-MS, GC measurements reported significantly different VOC concentrations, usually below those from PTR-ToF-MS. Consequently, PTR-ToF-MS mass spectra should be interpreted with caution when reporting quantitative results in vaping studies, such as doses of inhaled VOCs. Nevertheless, the online PTR-ToF-MS analysis can provide valuable qualitative information by comparing relative VOCs in back-to-back trials. For example, by comparing the mass spectra of exhaled air with those of direct puffs, we can conclude that harmful VOCs present in the vape emissions are largely absorbed by the participants, including large fractions of nicotine.

The role of anthropogenic NO x emissions in secondary organic aerosol (SOA) production is not fully understood but is important for understanding the contribution of emissions to air quality. Here, we examine the role of organic nitrates (RONO 2 ) in SOA formation over the Korean Peninsula during the Korea-United States Air Quality field study in Spring 2016 as a model for RONO 2 aerosol in cities worldwide. We use aircraft-based measurements of the particle phase and total (gas + particle) RONO 2 to explore RONO 2 phase partitioning. These measurements show that, on average, one-fourth of RONO 2 are in the condensed phase, and we estimate that ≈15% of the organic aerosol (OA) mass can be attributed to RONO 2 . Furthermore, we observe that the fraction of RONO 2 in the condensed phase increases with OA concentration, evidencing that equilibrium absorptive partitioning controls the RONO 2 phase distribution. Lastly, we model RONO 2 chemistry and phase partitioning in the Community Multiscale Air Quality modeling system. We find that known chemistry can account for one-third of the observed RONO 2 , but there is a large missing source of semivolatile, anthropogenically derived RONO 2 . We propose that this missing source may result from the oxidation of semi- and intermediate-volatility organic compounds and/or from anthropogenic molecules that undergo autoxidation or multiple generations of OH-initiated oxidation.

In the efforts at controlling automobile emissions, it is important to know in what extent air pollutants from on-road vehicles could be truly reduced. In 2014 we conducted tests in a heavily trafficked tunnel in south China to characterize emissions of volatile organic compounds (VOC) from on-road vehicle fleet and compared our results with those obtained in the same tunnel in 2004. Alkanes, aromatics, and alkenes had average emission factors (EFs) of 338, 63, and 42 mg km -1 in 2014 against that of 194, 129, and 160 mg km -1 in 2004, respectively. In 2014, LPG-related propane, n-butane and i-butane were the top three non-methane hydrocarbons (NMHCs) with EFs of 184 ± 21, 53 ± 6 and 31 ± 3 mg km -1 ; the gasoline evaporation marker i-pentane had an average EF of 17 ± 3 mg km -1 ; ethylene and propene were the top two alkenes with average EFs of 16 ± 1 and 9.7 ± 0.9 mg km -1 , respectively; isoprene had no direct emission from vehicles; toluene showed the highest EF of 11 ± 2 mg km -1 among the aromatics; and acetylene had an average EF of 7 ± 1 mg km -1 . While EFs of total NMHCs decreased only 9% from 493 ± 120 mg km -1 in 2004 to 449 ± 40 mg km -1 in 2014, their total ozone formation potential (OFP) decreased by 57% from 2.50 × 10 3  mg km -1 in 2004 to 1.10 × 10 3  mg km -1 in 2014, and their total secondary organic aerosol formation potential (SOAFP) decreased by 50% from 50 mg km -1 in 2004 to 25 mg km -1 in 2014. The large drop in ozone and SOA formation potentials could be explained by reduced emissions of reactive alkenes and aromatics, due largely to fuel transition from gasoline/diesel to LPG for taxis/buses and upgraded vehicle emission standards., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Volatile organic compounds (VOCs) measured from exhaled breath have great promise for the diagnosis of bacterial infections. However, determining human or microbial origin of VOCs detected in breath remains a great challenge. For example, the microbial fermentation product 2,3-butanedione was recently found in the breath of Cystic Fibrosis (CF) patients; parallel culture-independent metagenomic sequencing of the same samples revealed that Streptococcus and Rothia spp. have the genetic capacity to produce 2,3-butanedione. To investigate whether the genetic capacity found in metagenomes translates to bacterial production of a VOC of interest such as 2,3-butanedione, we fed stable isotopes to three bacterial strains isolated from patients: two gram-positive bacteria, Rothia mucilaginosa and Streptococcus salivarius, and a dominant opportunistic gram-negative pathogen, Pseudomonas aeruginosa. Culture headspaces were collected and analyzed using a gas chromatographic system to quantify the abundance of VOCs of interest; mass spectroscopy was used to determine whether the stable isotope label had been incorporated. Our results show that R. mucilaginosa and S. salivarius consumed D-Glucose- 13 C 6 to produce labeled 2,3-butanedione. R. mucilaginosa and S. salivarius also produced labeled acetaldehyde and ethanol when grown with 2 H 2 O. Additionally, we find that P. aeruginosa growth and dimethyl sulfide production are increased when exposed to lactic acid in culture. These results highlight the importance VOCs produced by P. aeruginosa, R. mucilaginosa, and S. salivarius as nutrients and signals in microbial communities, and as potential biomarkers in a CF infection.

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model--Master Chemical Mechanism (MCM) model--to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The Arabian Peninsula experiences severe air pollution, the extent and sources of which are poorly documented. Each year in Saudi Arabia this situation is intensified during Hajj, the Holy Pilgrimage of Islam that draws millions of pilgrims to Mecca. An initial study of air quality in Mecca and surrounding holy sites during the 2012 Hajj (October 24-27) revealed strongly elevated levels of the combustion tracer carbon monoxide (CO, up to 57 ppmv) and volatile organic compounds (VOCs) along the pilgrimage route-especially in the tunnels of Mecca-that are a concern for human health. The most abundant VOC was the gasoline evaporation tracer i-pentane, which exceeded 1200 ppbv in the tunnels. Even though VOC concentrations were generally lower during a follow-up non-Hajj sampling period (April 2013), many were still comparable to other large cities suffering from poor air quality. Major VOC sources during the 2012 Hajj study included vehicular exhaust, gasoline evaporation, liquefied petroleum gas, and air conditioners. Of the measured compounds, reactive alkenes and CO showed the strongest potential to form ground-level ozone. Because the number of pilgrims is expected to increase in the future, we present emission reduction strategies to target both combustive and evaporative fossil fuel sources.

Background: While much is known about the effect of chronic kidney disease (CKD) on composition of body fluids little is known regarding its impact on the gases found in exhaled breath or produced by intestinal microbiome. We have recently shown significant changes in the composition of intestinal microbiome in humans and animals with CKD. This study tested the hypothesis that uremia-induced changes in cellular metabolism and intestinal microbiome may modify the volatile organic metabolites found in the exhaled breath or generated by intestinal flora., Methods: SD rats were randomized to CKD (5/6 nephrectomy) or control (sham operation) groups. Exhaled breath was collected by enclosing each animal in a glass chamber flushed with clean air, then sealed for 45 min and the trapped air collected. Feces were collected, dissolved in pure water, incubated at 37 degrees C in glass reactors for 24 h and the trapped air collected. Collected gases were analyzed by gas chromatography., Results: Over 50 gases were detected in the exhaled breath and 36 in cultured feces. Four gases in exhaled breath and 4 generated by cultured feces were significantly different in the two groups. The exhaled breath in CKD rats showed an early rise in isoprene and a late fall in linear aldehydes. The CKD animals' cultured feces released larger amounts of dimethyldisulfide, dimethyltrisulfide, and two thioesters., Conclusions: CKD significantly changes the composition of exhaled breath and gaseous products of intestinal flora., General Significance: Analysis of breath and bowel gases may provide useful biomarkers for detection and progression of CKD and its complications.

Laser printers are one of the common indoor equipment in schools, offices, and various other places. Laser printers have recently been identified as a potential source of indoor air pollution. This study examines the characteristics of ultrafine particles (UFPs, diameter <100 nm) and volatile organic compounds (VOCs) emitted from laser printers housed in a commercial printing center. The results indicated that apart from the printer type, the age of printers, and the number of pages printed, the characteristics of UFPs emitted from printers also depend on indoor ventilation conditions. It was found that at reduced ventilation rates of indoor air, there was a rise in the number concentration of UFPs in the printing center. Interestingly, the contribution of UFPs to the total number of submicrometer-sized particles was observed to be higher at a sampling point far away from the printer than the one in the immediate vicinity of the printer. Black carbon (BC) measurements showed a good correlation (rs = 0.82) with particles in the size range of 100-560 nm than those with diameters less than 100 nm (rs = 0.33 for 50-100 nm, and rs = -0.19 for 5.6-50 nm particles). Measurements of VOCs in the printing center showed high levels of m-, o-, and p-xylene, styrene, and ethylbenzenes during peak hours of printing. Although toluene was found in higher levels, its concentration decreased during peak hours compared to those during nonoperating hours of the printing center.

In the efforts at controlling automobile emissions, it is important to know in what extent air pollutants from on-road vehicles could be truly reduced. In 2014 we conducted tests in a heavily trafficked tunnel in south China to characterize emissions of volatile organic compounds (VOC) from on-road vehicle fleet and compared our results with those obtained in the same tunnel in 2004. Alkanes, aromatics, and alkenes had average emission factors (EFs) of 338, 63, and 42 mg km-1 in 2014 against that of 194, 129, and 160 mg km-1 in 2004, respectively. In 2014, LPG-related propane, n-butane and i-butane were the top three non-methane hydrocarbons (NMHCs) with EFs of 184 ± 21, 53 ± 6 and 31 ± 3 mg km-1; the gasoline evaporation marker i-pentane had an average EF of 17 ± 3 mg km-1; ethylene and propene were the top two alkenes with average EFs of 16 ± 1 and 9.7 ± 0.9 mg km-1, respectively; isoprene had no direct emission from vehicles; toluene showed the highest EF of 11 ± 2 mg km-1 among the aromatics; and acetylene had an average EF of 7 ± 1 mg km-1. While EFs of total NMHCs decreased only 9% from 493 ± 120 mg km-1 in 2004 to 449 ± 40 mg km-1 in 2014, their total ozone formation potential (OFP) decreased by 57% from 2.50 × 103 mg km-1 in 2004 to 1.10 × 103 mg km-1 in 2014, and their total secondary organic aerosol formation potential (SOAFP) decreased by 50% from 50 mg km-1 in 2004 to 25 mg km-1 in 2014. The large drop in ozone and SOA formation potentials could be explained by reduced emissions of reactive alkenes and aromatics, due largely to fuel transition from gasoline/diesel to LPG for taxis/buses and upgraded vehicle emission standards.

Oil and natural gas operations have continued to expand and move closer to densely populated areas, contributing to growing public concerns regarding exposure to hazardous air pollutants. During the Barnett Shale Coordinated Campaign in October, 2013, ground-based whole air samples collected downwind of oil and gas sites revealed enhancements in several potentially toxic volatile organic compounds (VOCs) when compared to background values. Molar emissions ratios relative to methane were determined for hexane, benzene, toluene, ethylbenzene, and xylene (BTEX compounds). Using methane leak rates measured from the Picarro mobile flux plane (MFP) system and a Barnett Shale regional methane emissions inventory, the rates of emission of these toxic gases were calculated. Benzene emissions ranged between 51 ± 4 and 60 ± 4 kg h-1. Hexane, the most abundantly emitted pollutant, ranged from 642 ± 45 to 1070 ± 340 kg h-1. While observed hydrocarbon enhancements fall below federal workplace standards, results may indicate a link between emissions from oil and natural gas operations and concerns about exposure to hazardous air pollutants. The larger public health risks associated with the production and distribution of natural gas are of particular importance and warrant further investigation, particularly as the use of natural gas increases in the United States and internationally.

High time resolution measurements of volatile organic compounds (VOCs) were collected using a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the Platteville Atmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (O&NG) development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA’s “Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality” (DISCOVER-AQ) field campaign. The PTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO.

The fraction of urban volatile organic compounds (VOC) emissions attributable to fossil fuel combustion has been declining in many parts of the world, resulting in a need to better constrain other anthropogenic sources of these emissions. During the National Institute of Environmental Research (NIER) and National Aeronautics and Space Administration (NASA) Korea-United States Air Quality (KORUS-AQ) field study in Seoul, South Korea during May–June 2016, air quality models underestimated ozone, formaldehyde, and peroxyacetyl nitrate (PAN) indicating an underestimate of VOCs in the emissions inventory. Here, we use aircraft observations interpreted with the GEOS-Chem chemical transport model to assess the need for increases in VOC emissions. We find that the largest increases are attributable to compounds associated with volatile chemical products, liquefied petroleum gas (LPG) and natural gas emissions, and long-range transport. Revising model chemistry to better match observed VOC speciation together with increasing model emissions of underestimated VOC species increased calculated OH reactivity by +2 s-1 and ozone production by 2 ppb hr-1. Ozone increased by 6 ppb below 2 km and 9 ppb at the surface, and formaldehyde and acetaldehyde increased by 30 % and 120 % aloft, respectively, all in better agreement with observations. The larger increase in acetaldehyde was attributed to ethanol emissions which we found to be as important for ozone production as isoprene or alkenes. The increased acetaldehyde largely resolved the model PAN bias. The need for additional unmeasured VOCs however was indicated by a remaining model bias of -1 ppb in formaldehyde and 57 % and 52 % underestimate in higher peroxynitrates (PNs) and alkyl nitrates (ANs), respectively. We added additional chemistry to the model to represent an additional six PNs from observed VOCs but were unable to account for the majority of missing PNs. However, four of these PNs were modeled at concentrations similar to other commonly measured PNs (>2 % of PAN) indicating that these should be measured in future campaigns. We hypothesize that emissions of oxygenated VOCs (OVOCs) such as >C5 aldehydes from cooking and/or alkenes associated with volatile chemical products could produce both PNs and ANs and improve remaining model biases. Emerging research on the emissions and chemistry of these species will soon allow for modeling of their impact on local and regional photochemistry. [ABSTRACT FROM AUTHOR]

Ozone (O3) is an important secondary pollutant that impacts air quality and human health. Eastern Asia has high regional O3 background due to the numerous sources and increasing and rapid industrial growth, which impacts the Seoul Metropolitan Area (SMA). However, SMA has also been experiencing increasing O3 driven by decreasing NOx emissions, highlighting the role of local, in-situ O3 production on SMA. Here, comprehensive gas-phase measurements collected on the NASA DC-8 during the NIER/NASA Korea United States-Air Quality (KORUS-AQ) study are used to constrain the instantaneous O3 production rate over the SMA. The observed NOx oxidized products support the importance of non-measured peroxy nitrates (PNs) in the O3 chemistry in SMA, as they accounted for ~49 % of the total PNs. Using the total measured PNs (ΣPNs) and alkyl and multifunctional nitrates (ΣANs), unmeasured volatile organic compound (VOC) reactivity (R(VOC)) is constrained and found to range from 1.4 – 2.1 s-1. Combining the observationally constrained R(VOC) with the other measurements on the DC-8, the instantaneous net O3 production rate, which is as high as ~10 ppbv hr-1, along with the important sinks of O3 and radical chemistry, are constrained. This analysis shows that ΣPNs play an important role in both the sinks of O3 and radical chemistry. Since ΣPNs are assumed to be in steady-state, the results here highlight the role ΣPNs play in urban environments in reducing net O3 production, but ΣPNs can potentially lead to increased net O3 production downwind due to their short lifetime (~1 hr). The results provide guidance for future measurements to identify the missing R(VOCs) and ΣPNs production. [ABSTRACT FROM AUTHOR]

In this study, the WRF-Chem v4.4 model was utilized to evaluate the sensitivity of O 3 simulations with three bottom-up emission inventories (EDGAR-HTAP v2 and v3 and KORUS v5) using surface and aircraft data in East Asia during the Korea-United States Air Quality (KORUS-AQ) campaign period in 2016. All emission inventories were found to reproduce the diurnal variations of O 3 and its main precursor NO 2 as compared to the surface monitor data. However, the spatial distributions of the daily maximum 8 h average (MDA8) O 3 in the model do not completely align with the observations. The model MDA8 O 3 had a negative (positive) bias north (south) of 30° N over China. All simulations underestimated the observed CO by 50 %–60 % over China and South Korea. In the Seoul Metropolitan Area (SMA), EDGAR-HTAP v2 and v3 and KORUS v5 simulated the vertical shapes and diurnal patterns of O 3 and other precursors effectively, but the model underestimated the observed O 3 , CO, and HCHO concentrations. Notably, the model aromatic volatile organic compounds (VOCs) were significantly underestimated with the three bottom-up emission inventories, although the KORUS v5 shows improvements. The model isoprene estimations had a positive bias relative to the observations, suggesting that the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.04 overestimated isoprene emissions. Additional model simulations were conducted by doubling CO and VOC emissions over China and South Korea to investigate the causes of the model O 3 biases and the effects of the long-range transport on the O 3 over South Korea. The doubled CO and VOC emission simulations improved the model O 3 simulations for the local-emission-dominant case but led to the model O 3 overestimations for the transport-dominant case, which emphasizes the need for accurate representations of the local VOC emissions over South Korea. [ABSTRACT FROM AUTHOR]

Vehicular emission is one of the important anthropogenic pollution sources for volatile organic compounds (VOCs). Four characterization campaigns were conducted at a representative urban roadside environment in Hong Kong between May 2011 and February 2012. Carbon monoxide (CO) and VOCs including methane (CH4), non-methane hydrocarbons (NMHCs), halocarbons, and alkyl nitrates were quantified. Both mixing ratios and compositions of the target VOCs show ignorable seasonal variations. Except CO, liquefied petroleum gas (LPG) tracers of propane, i-butane and n-butane are the three most abundant VOCs, which increased significantly as compared with the data measured at the same location in 2003. Meanwhile, the mixing ratios of diesel- and gasoline tracers such as ethyne, alkenes, aromatics, halogenated, and nitrated hydrocarbons decreased by at least of 37%. The application of advanced multivariate receptor modeling technique of positive matrix factorization (PMF) evidenced that the LPG fuel consumption is the largest pollution source, accounting for 60 ± 5% of the total quantified VOCs at the roadside location. The sum of ozone formation potential (OFP) for the target VOCs was 300.9 μg-O3 m-3, which was 47% lower than the value of 567.3 μg-O3 m-3 measured in 2003. The utilization of LPG as fuel in public transport (i.e., taxis and mini-buses) contributed 51% of the sum of OFP, significantly higher than the contributions from gasoline- (16%) and diesel-fueled (12%) engine emissions. Our results demonstrated the effectiveness of the switch from diesel to LPG-fueled engine for taxis and mini-buses implemented by the Hong Kong Special Administrative Region (HKSAR) Government between the recent ten years, in additional to the execution of substitution to LPG-fueled engine and restrictions of the vehicular emissions in compliance with the updated European emission standards.

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model--Master Chemical Mechanism (MCM) model--to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities.

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C 5 H 8 H +), acetaldehyde (m/z 45, CH 3 CHO +), and benzene (m/z 79, C 6 H 6 H +). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O 2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

The "Industrial Heartland" of Alberta is Canada's largest hydrocarbon processing center, with more than 40 major chemical, petrochemical, and oil and gas facilities. Emissions from these industries affect local air quality and human health. This paper characterizes ambient levels of 77 volatile organic compounds (VOCs) in the region using high-precision measurements collected in summer 2010. Remarkably strong enhancements of 43 VOCs were detected, and concentrations in the industrial plumes were often similar to or even higher than levels measured in some of the world's largest cities and industrial regions. For example maximum levels of propene and i-pentane exceeded 100 ppbv, and 1,3-butadiene, a known carcinogen, reached 27 ppbv. Major VOC sources included propene fractionation, diluent separation and bitumen processing. Emissions of the measured VOCs increased the hydroxyl radical reactivity (kOH), a measure of the potential to form downwind ozone, from 3.4 s-1 in background air to 62 s-1 in the most concentrated plumes. The plume value was comparable to polluted megacity values, and acetaldehyde, propene and 1,3-butadiene contributed over half of the plume kOH. Based on a 13-year record (1994-2006) at the county level, the incidence of male hematopoietic cancers (leukemia and non-Hodgkin lymphoma) was higher in communities closest to the Industrial Heartland compared to neighboring counties. While a causal association between these cancers and exposure to industrial emissions cannot be confirmed, this pattern and the elevated VOC levels warrant actions to reduce emissions of known carcinogens, including benzene and 1,3-butadiene.

BackgroundThe gaseous headspace above naïve Escherichia Coli (E. coli) cultures and whole human blood inoculated with E. coli were collected and analyzed for the presence of trace gases that may have the potential to be used as novel, non-invasive markers of infectious disease.MethodsThe naïve E. coli culture, LB broth, and human whole blood or E. coli inoculated whole blood were incubated in hermetically sealable glass bioreactors at 37°C for 24 hrs. LB broth and whole human blood were used as controls for background volatile organic compounds (VOCs). The headspace gases were collected after incubation and analyzed using a gas chromatographic system with multiple column/detector combinations.ResultsSix VOCs were observed to be produced by E. coli-infected whole blood while there existed nearly zero to relatively negligible amounts of these gases in the whole blood alone, LB broth, or E. coli-inoculated LB broth. These VOCs included dimethyl sulfide (DMS), carbon disulfide (CS2), ethanol, acetaldehyde, methyl butanoate, and an unidentified gas S. In contrast, there were several VOCs significantly elevated in the headspace above the E. coli in LB broth, but not present in the E. coli/blood mixture. These VOCs included dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), methyl propanoate, 1-propanol, methylcyclohexane, and unidentified gases R2 and Q.ConclusionsThis study demonstrates 1) that cultivated E. coli in LB broth produce distinct gas profiles, 2) for the first time, the ability to modify E. coli-specific gas profiles by the addition of whole human blood, and 3) that E. coli-human whole blood interactions present different gas emission profiles that have the potential to be used as non-invasive volatile biomarkers of E. coli infection.

Ambient air measurements of volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) were conducted and characterised during a two-year grid study in the Pearl River Delta (PRD) region of southern China. The present grid study pioneered the systematic investigation of the nature and characteristics of complex VOC and OVOC sources at a regional scale. The largest contributing VOCs, accounting over 80% of the total VOCs mixing ratio, were toluene, ethane, ethyne, propane, ethene, butane, benzene, pentane, ethylbenzene, and xylenes. Sub-regional VOC spatial characteristics were identified, namely: i) relatively fresh pollutants, consistent with elevated vehicular and industrial activities, around the PRD estuary; and ii) a concentration gradient with higher mixing ratios of VOCs in the west as compared with the eastern part of PRD. Based on alkyl nitrate aging determination, a high hydroxyl radical (OH) concentration favoured fast hydrocarbon reactions and formation of locally produced ozone. The photochemical reactivity analysis showed aromatic hydrocarbons and alkenes together consisted of around 80% of the ozone formation potential (OFP) among the key VOCs. We also found that the OFP from OVOCs should not be neglected since their OFP contribution was more than one-third of that from VOCs alone. These findings support the choice of current air pollution control policy which focuses on vehicular sources but warrants further controls. Industrial emissions and VOCs emitted by solvents should be the next targets for ground-level ozone abatement. © 2012 Elsevier Ltd.

Aromatic hydrocarbons (AHs) are both hazardous air pollutants and important precursors to ozone and secondary organic aerosols. Here we investigated 14 C6-C9 AHs at one urban, one suburban and two rural sites in the Pearl River Delta region during November-December 2009. The ratios of individual aromatics to acetylene were compared among these contrasting sites to indicate their difference in source contributions from solvent use and vehicle emissions. Ratios of toluene to benzene (T/B) in urban (1.8) and suburban (1.6) were near that of vehicle emissions. Higher T/B of 2.5 at the rural site downwind the industry zones reflected substantial contribution of solvent use while T/B of 0.8 at the upwind rural site reflected the impact of biomass burning. Source apportionment by positive matrix factorization (PMF) revealed that solvent use, vehicle exhaust and biomass burning altogether accounted for 89-94% of observed AHs. Vehicle exhaust was the major source for benzene with a share of 43-70% and biomass burning in particular contributed 30% to benzene in the upwind rural site; toluene, C8-aromatics and C9-aromatics, however, were mainly from solvent use, with contribution percentages of 47-59%, 52-59% and 41-64%, respectively.

Blood is the specimen of choice for most laboratory tests for diagnosis and disease monitoring. Sampling exhaled breath is a noninvasive alternative to phlebotomy and has the potential for real-time monitoring at the bedside. Improved instrumentation has advanced breath analysis for several gaseous compounds from humans. However, application to small animal models of diseases and physiology has been limited. To extend breath analysis to mice, we crafted a means for collecting nose-only breath samples from groups and individual animals who were awake. Samples were subjected to gas chromatography and mass spectrometry procedures developed for highly sensitive analysis of trace volatile organic compounds (VOCs) in the atmosphere. We evaluated the system with experimental systemic infections of severe combined immunodeficiency Mus musculus with the bacterium Borrelia hermsii. Infected mice developed bacterial densities of ∼10(7) per ml of blood by day 4 or 5 and in comparison to uninfected controls had hepatosplenomegaly and elevations of both inflammatory and anti-inflammatory cytokines. While 12 samples from individual infected mice on days 4 and 5 and 6 samples from uninfected mice did not significantly differ for 72 different VOCs, carbon monoxide (CO) was elevated in samples from infected mice, with a mean (95% confidence limits) effect size of 4.2 (2.8-5.6), when differences in CO2 in the breath were taken into account. Normalized CO values declined to the uninfected range after one day of treatment with the antibiotic ceftriaxone. Strongly correlated with CO in the breath were levels of heme oxygenase-1 protein in serum and HMOX1 transcripts in whole blood. These results (i) provide further evidence of the informativeness of CO concentration in the exhaled breath during systemic infection and inflammation, and (ii) encourage evaluation of this noninvasive analytic approach in other various other rodent models of infection and for utility in clinical management.

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impacts urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas-chromatography (GC) pre-separation and the impact of these interferences are quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to the fragmentation and secondary ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico was conducted in May 2019 by NASA and the Bureau of Ocean Energy Management to determine the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns over the outer continental shelf. Featured were nitrogen dioxide (NO2) instruments (Pandora, Teledyne API analyzer) at Cocodrie, LA (29.26°, −90.66°), and on the Research Vessel Point Sur operating off the Louisiana coast with measurements of ozone, carbon monoxide, and volatile organic compounds (VOCs). The findings: (a) all NO2 observations revealed two atmospheric regimes over the Gulf, the first influenced by tropical air in 10–14 May, the second influenced by flow from urban areas on 15–17 May; (b) comparisons of OMI v4 and TROPOMI v1.3 TC (total column) NO2 data with shipboard Pandora NO2 column observations averaged 13% agreement with the largest difference during 15–17 May (∼20%). At Cocodrie, the satellite–Pandora agreement was ∼5%. (c) Three new‐model Pandora instruments displayed a TC NO2 precision of 0.01 Dobson Units (∼5%); (d) regions of smaller, older natural gas operations showed high methane readings from leakage; elevated VOCs were also detected. Neither satellite nor spectrometer captured the magnitude of ambient NO2 variability near ONG platforms. Given an absence of regular air quality monitoring over the Gulf of Mexico, SCOAPE data constitute a baseline against which future observations can be compared. Plain Language Summary: The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico (GOM) conducted on the Research Vessel Point Sur in May 2019 investigated the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns in a prototypical coastal environment. The results are as follows. First, measurements from SCOAPE demonstrated that satellite NO2 data can be used to monitor ONG activity over the GOM. Second, during SCOAPE both OMI and TROPOMI TC (total column) NO2 amounts were higher over land and sometimes the near‐shore ONG‐rich Gulf, than over deepwater regions farther offshore. This was confirmed by Pandora spectrometer "ground truth" TC NO2 data measured throughout SCOAPE on shore and on ship. Third, SCOAPE established the reliability and precision of a new generation of Pandora spectrometers. Fourth, comparisons of satellite and Pandora TC NO2 data in SCOAPE confirm previous land–water interface studies that point to limitations in satellite NO2 in coastal regions. Finally, neither satellite nor spectrometer captures the magnitude of ambient ("nose‐level") NO2 variability in a region dotted with hundreds of ONG platforms. Key Points: Shipboard Pandora NO2 columns and surface O3, NO2, CO, and volatile organic compounds (VOCs) over the Gulf of Mexico (GOM), May 2019, displayed two air quality (AQ) regimesGOM AQ was dominated by continental NO2 sources and near‐shore VOC; deepwater oil platforms were in a clean marine regimePandora and satellite total column NO2 over GOM agreed overall within 5% in clean, clear‐sky conditions along the coast and 13% over water [ABSTRACT FROM AUTHOR]

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LROx) to the chemical loss of NO x (LNOx). Subsequently, we challenge the predictive power of HCHO/NO2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LROx/LNOx. FNRs show a strongly linear (R2=0.94) relationship with LROx/LNOx , but only on the logarithmic scale. Following the baseline (i.e., ln(LROx/LNOx) = - 1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NOx -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the ROx – HOx cycle. We calculate high ozone production rates (PO 3) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NOx -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm -2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric. [ABSTRACT FROM AUTHOR]

Trichlorofluoromethane (CFC-11) is an ozone-depleting substance whose production and consumption are regulated under the Montreal Protocol. Global atmospheric CFC-11 levels declined less quickly than expected during 2012-2018, largely because of ongoing emissions from eastern Asia. Satellite measurements suggest additional CFC-11 hotspots in the Arabian Peninsula and north India/Nepal. Here we present CFC-11 levels measured in dozens of Asian cities during 1998-2018, including China and Pakistan before the 2010 phaseout of CFC-11, and China, Nepal, Pakistan, Saudi Arabia and South Korea after the phaseout. Surface measurements of CFCs in Nepal, Pakistan and Saudi Arabia are very rare, and these surveys provide important observational constraints from understudied regions. During pre-phaseout campaigns, higher CFC-11 levels were measured in Beijing than Karachi, despite much higher overall volatile organic compound (VOC) levels in Karachi. During post-phaseout campaigns, average CFC-11 levels were higher in inland Shandong Province and Seoul (1.11-1.23× background) than in western Saudi Arabia, Lahore and Kathmandu (1.02-1.11× background), despite higher levels of other VOCs in the latter regions. While China is known to emit excess CFC-11, elevated CFC-11 levels in Seoul, especially during stagnant meteorological conditions, suggest local emissions in 2015-2016. Rough emission estimates suggest that South Korea is likely a relatively minor global source of excess CFC-11. Hotspot CFC-11 levels were measured from a landfill fire in Mecca (average of 1.8× background) and from garbage burning in Nepal (1.5× background). Because garbage burning and open burning in dumps are common practices, further investigation of CFC-11 emissions at dumps and landfills worldwide is encouraged to determine their global impact. [ABSTRACT FROM AUTHOR]

Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenic emissions of organic compounds, constitutes a substantial fraction of the mass of submicron aerosol in populated areas around the world and contributes to poor air quality and premature mortality. However, the precursor sources of ASOA are poorly understood, and there are large uncertainties in the health benefits that might accrue from reducing anthropogenic organic emissions. We show that the production of ASOA in 11 urban areas on three continents is strongly correlated with the reactivity of specific anthropogenic volatile organic compounds. The differences in ASOA production across different cities can be explained by differences in the emissions of aromatics and intermediate- and semi-volatile organic compounds, indicating the importance of controlling these ASOA precursors. With an improved model representation of ASOA driven by the observations, we attribute 340 000 PM 2.5 -related premature deaths per year to ASOA, which is over an order of magnitude higher than prior studies. A sensitivity case with a more recently proposed model for attributing mortality to PM 2.5 (the Global Exposure Mortality Model) results in up to 900 000 deaths. A limitation of this study is the extrapolation from cities with detailed studies and regions where detailed emission inventories are available to other regions where uncertainties in emissions are larger. In addition to further development of institutional air quality management infrastructure, comprehensive air quality campaigns in the countries in South and Central America, Africa, South Asia, and the Middle East are needed for further progress in this area. [ABSTRACT FROM AUTHOR]

Since 2012, studies in mice, rats, and humans have suggested that abnormalities in purinergic signaling may be a final common pathway for many genetic and environmental causes of autism spectrum disorder (ASD). The current study in mice was conducted to characterize the bioenergetic, metabolomic, breathomic, and behavioral features of acute hyperpurinergia triggered by systemic injection of the purinergic agonist and danger signal, extracellular ATP (eATP). Responses were studied in C57BL/6J mice in the maternal immune activation (MIA) model and controls. Basal metabolic rates and locomotor activity were measured in CLAMS cages. Plasma metabolomics measured 401 metabolites. Breathomics measured 98 volatile organic compounds. Intraperitoneal eATP dropped basal metabolic rate measured by whole body oxygen consumption by 74% ± 6% (mean ± SEM) and rectal temperature by 6.2˚ ± 0.3˚C in 30 minutes. Over 200 metabolites from 37 different biochemical pathways where changed. Breathomics showed an increase in exhaled carbon monoxide, dimethylsulfide, and isoprene. Metabolomics revealed an acute increase in lactate, citrate, purines, urea, dopamine, eicosanoids, microbiome metabolites, oxidized glutathione, thiamine, niacinamide, and pyridoxic acid, and decreased folate-methylation-1-carbon intermediates, amino acids, short and medium chain acyl-carnitines, phospholipids, ceramides, sphingomyelins, cholesterol, bile acids, and vitamin D similar to some children with ASD. MIA animals were hypersensitive to postnatal exposure to eATP or poly(IC), which produced a rebound increase in body temperature that lasted several weeks before returning to baseline. Acute hyperpurinergia produced metabolic and behavioral changes in mice. The behaviors and metabolic changes produced by ATP injection were associated with mitochondrial functional changes that were profound but reversible. [ABSTRACT FROM AUTHOR]

Global coupled chemistry–climate models underestimate carbon monoxide (CO) in the Northern Hemisphere, exhibiting a pervasive negative bias against measurements peaking in late winter and early spring. While this bias has been commonly attributed to underestimation of direct anthropogenic and biomass burning emissions, chemical production and loss via OH reaction from emissions of anthropogenic and biogenic volatile organic compounds (VOCs) play an important role. Here we investigate the reasons for this underestimation using aircraft measurements taken in May and June 2016 from the Korea–United States Air Quality (KORUS-AQ) experiment in South Korea and the Air Chemistry Research in Asia (ARIAs) in the North China Plain (NCP). For reference, multispectral CO retrievals (V8J) from the Measurements of Pollution in the Troposphere (MOPITT) are jointly assimilated with meteorological observations using an ensemble adjustment Kalman filter (EAKF) within the global Community Atmosphere Model with Chemistry (CAM-Chem) and the Data Assimilation Research Testbed (DART). With regard to KORUS-AQ data, CO is underestimated by 42 % in the control run and by 12 % with the MOPITT assimilation run. The inversion suggests an underestimation of anthropogenic CO sources in many regions, by up to 80 % for northern China, with large increments over the Liaoning Province and the North China Plain (NCP). Yet, an often-overlooked aspect of these inversions is that correcting the underestimation in anthropogenic CO emissions also improves the comparison with observational O 3 datasets and observationally constrained box model simulations of OH and HO 2. Running a CAM-Chem simulation with the updated emissions of anthropogenic CO reduces the bias by 29 % for CO, 18 % for ozone, 11 % for HO 2 , and 27 % for OH. Longer-lived anthropogenic VOCs whose model errors are correlated with CO are also improved, while short-lived VOCs, including formaldehyde, are difficult to constrain solely by assimilating satellite retrievals of CO. During an anticyclonic episode, better simulation of O 3 , with an average underestimation of 5.5 ppbv, and a reduction in the bias of surface formaldehyde and oxygenated VOCs can be achieved by separately increasing by a factor of 2 the modeled biogenic emissions for the plant functional types found in Korea. Results also suggest that controlling VOC and CO emissions, in addition to widespread NO x controls, can improve ozone pollution over East Asia. [ABSTRACT FROM AUTHOR]

The absence of up-to-date emissions has been a major impediment to accurately simulating aspects of atmospheric chemistry and to precisely quantifying the impact of changes in emissions on air pollution. Hence, a nonlinear joint analytical inversion (Gauss–Newton method) of both volatile organic compounds (VOCs) and nitrogen oxide (NOx) emissions is made by exploiting the Smithsonian Astrophysical Observatory (SAO) Ozone Mapping and Profiler Suite Nadir Mapper (OMPS-NM) formaldehyde (HCHO) and the National Aeronautics and Space Administration (NASA) Ozone Monitoring Instrument (OMI) tropospheric nitrogen dioxide (NO2) columns during the Korea–United States Air Quality (KORUS-AQ) campaign over East Asia in May–June 2016. Effects of the chemical feedback of NOx and VOCs on both NO2 and HCHO are implicitly included by iteratively optimizing the inversion. Emission uncertainties are greatly narrowed (averaging kernels >0.8 , which is the mathematical presentation of the partition of information gained from the satellite observations with respect to the prior knowledge) over medium- to high-emitting areas such as cities and dense vegetation. The prior amount of total NOx emissions is mainly dictated by values reported in the MIX-Asia 2010 inventory. After the inversion we conclude that there is a decline in emissions (before, after, change) for China (87.94±44.09 Gg d -1 , 68.00±15.94 Gg d -1 , -23 %), North China Plain (NCP) (27.96±13.49 Gg d -1 , 19.05±2.50 Gg d -1 , -32 %), Pearl River Delta (PRD) (4.23±1.78 Gg d -1 , 2.70±0.32 Gg d -1 , -36 %), Yangtze River Delta (YRD) (9.84±4.68 Gg d -1 , 5.77±0.51 Gg d -1 , -41 %), Taiwan (1.26±0.57 Gg d -1 , 0.97±0.33 Gg d -1 , -23 %), and Malaysia (2.89±2.77 Gg d -1 , 2.25±1.34 Gg d -1 , -22 %), all of which have effectively implemented various stringent regulations. In contrast, South Korea (2.71±1.34 Gg d -1 , 2.95±0.58 Gg d -1 , + 9 %) and Japan (3.53±1.71 Gg d -1 , 3.96±1.04 Gg d -1 , +12 %) are experiencing an increase in NOx emissions, potentially due to an increased number of diesel vehicles and new thermal power plants. We revisit the well-documented positive bias (by a factor of 2 to 3) of MEGAN v2.1 (Model of Emissions of Gases and Aerosols from Nature) in terms of biogenic VOC emissions in the tropics. The inversion, however, suggests a larger growth of VOCs (mainly anthropogenic) over NCP (25 %) than previously reported (6 %) relative to 2010. The spatial variation in both the magnitude and sign of NOx and VOC emissions results in nonlinear responses of ozone production and loss. Due to a simultaneous decrease and increase in NOx/VOC over NCP and YRD, we observe a ∼53 % reduction in the ratio of the chemical loss of NOx (LNOx) to the chemical loss of ROx (RO2+HO2) over the surface transitioning toward NOx -sensitive regimes, which in turn reduces and increases the afternoon chemical loss and production of ozone through NO2+OH (-0.42 ppbv h -1) /HO2 (and RO2) +NO (+0.31 ppbv h -1). Conversely, a combined decrease in NOx and VOC emissions in Taiwan, Malaysia, and southern China suppresses the formation of ozone. Simulations using the updated emissions indicate increases in maximum daily 8 h average (MDA8) surface ozone over China (0.62 ppbv), NCP (4.56 ppbv), and YRD (5.25 ppbv), suggesting that emission control strategies on VOCs should be prioritized to curb ozone production rates in these regions. Taiwan, Malaysia, and PRD stand out as regions undergoing lower MDA8 ozone levels resulting from the NOx reductions occurring predominantly in NOx -sensitive regimes. [ABSTRACT FROM AUTHOR]

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NOy. The severe model overestimate of NOy during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NOy partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHR obs) or by the model (cOHR mod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHR obs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHR mod by 3 % to 9 % and improves model–measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr -1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land. [ABSTRACT FROM AUTHOR]

The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime, influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although the calculated OH reactivity was below the limit of detection for the ATom instrument used to measure OH reactivity throughout much of the free troposphere, the instrument was able to measure the OH reactivity in and just above the marine boundary layer. The mean measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom deployments was 1.9 s -1 , which is 0.5 s -1 larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 and 3.5 s -1 , with the highest values over the Northern Hemisphere Pacific Ocean. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions. [ABSTRACT FROM AUTHOR]

The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM 2.5 and PM 10 , respectively), online PM 1 , inorganic trace gases (NH3 , HNO3 , SO2 , and HCl), and carbon-containing gases (CO2 , CO, CH4 , and 93 non-methane volatile organic compounds; NMVOCs) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated origins primarily from poorly maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those 2 weeks, daily average PM 2.5 concentrations ranged from 30 to 207 µ g m -3 , which exceeded the World Health Organization 24 h guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM 2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas–aerosol phase partitioning of NH3 , HNO3 , and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (averaging 1230±1154 ng m -3), 1,3,5-triphenylbenzene (0.8±0.6 ng m -3), cholesterol (2.9±6.6 ng m -3), stigmastanol (1.0 ±0.8 ng m -3), and cis-pinonic acid (4.5±1.9 ng m -3) indicate contributions from biomass burning, garbage burning, food cooking, cow dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18±5 %), biomass burning (17±10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18±9 %). Model sensitivity tests with newly developed source profiles indicated contributions from biomass burning within a factor of 2 of previous estimates but greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM 2.5 OC included those originating from anthropogenic precursors such as naphthalene (10±4 %) and methylnaphthalene (0.3±0.1 %) and biogenic precursors for monoterpenes (0.13±0.07 %) and sesquiterpenes (5±2 %). An average of 25 % of the PM 2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) and/or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil fuel combustion) were the greatest contributors to PM 2.5 and, as such, should be considered primary targets for controlling ambient PM pollution. [ABSTRACT FROM AUTHOR]

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2 × larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R2=0.36) and reactivity (R2=0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (∼ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL : FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation. [ABSTRACT FROM AUTHOR]

We investigate regional sources contributing to CO during the Korea United States Air Quality (KORUS‐AQ) campaign conducted over Korea (1 May to 10 June 2016) using 17 tagged CO simulations from the Community Atmosphere Model with chemistry (CAM‐chem). The simulations use three spatial resolutions, three anthropogenic emission inventories, two meteorological fields, and nine emission scenarios. These simulations are evaluated against measurements from the DC‐8 aircraft and Measurements Of Pollution In The Troposphere (MOPITT). Results show that simulations using bottom‐up emissions are consistently lower (bias: −34 to −39%) and poorer performing (Taylor skill: 0.38–0.61) than simulations using alternative anthropogenic emissions (bias: −6 to −33%; Taylor skill: 0.48–0.86), particularly for enhanced Asian CO and volatile organic compound (VOC) emission scenarios, suggesting underestimation in modeled CO background and emissions in the region. The ranges of source contributions to modeled CO along DC‐8 aircraft from Korea and southern (90°E to 123°E, 20°N to 29°N), middle (90°E to 123°E, 29°N to 38.5°N), and northern (90°E to 131.5°E, 38.5°N to 45°N) East Asia (EA) are 6–13%, ~5%, 16–28%, and 9–18%, respectively. CO emissions from middle and northern EA can reach Korea via transport within the boundary layer, whereas those from southern EA are transported to Korea mainly through the free troposphere. Emission contributions from middle EA dominate during continental outflow events (29–51%), while Korean emissions play an overall more important role for ground sites (up to 25–49%) and plumes within the boundary layer (up to 25–44%) in Korea. Finally, comparisons with four other source contribution approaches (FLEXPART 9.1 back trajectory calculations driven by Weather Research and Forecasting (WRF) WRF inert tracer, China signature VOCs, and CO to CO2 enhancement ratios) show general consistency with CAM‐chem. Key Points: Korean sources contribute 6‐13% to CO along DC‐8 flight tracks, while contributions of different East Asian subregions vary from 5% to 28%Middle East Asian sources dominate (up to 64%) continental outflows to Korea, but Korean emissions are more important for CO near surfaceContributions using CAM‐chem tags agree with FLEXPART‐WRF back trajectories, WRF NO2 inert tracers, China signature VOCs, and CO/CO2 [ABSTRACT FROM AUTHOR]

Air quality in rural India is impacted by residential cooking and heating with biomass fuels. In this study, emissions of CO, CO2, and 76 volatile organic compounds (VOCs) and fine particulate matter (PM2.5) were quanti- fied to better understand the relationship between cook fire emissions and ambient ozone and secondary organic aerosol (SOA) formation. Cooking was carried out by a local cook, and traditional dishes were prepared on locally built chulha or angithi cookstoves using brushwood or dung fuels. Cook fire emissions were collected throughout the cooking event in a Kynar bag (VOCs) and on polytetrafluoroethylene (PTFE) filters (PM2.5). Gas samples were transferred from a Kynar bag to previously evacuated stainless-steel canisters and analyzed using gas chromatography coupled to flame ionization, electron capture, and mass spectrometry detectors. VOC emission factors were calculated from the measured mixing ratios using the carbon-balance method, which assumes that all carbon in the fuel is converted to CO2, CO, VOCs, and PM2.5 when the fuel is burned. Filter samples were weighed to calculate PM2.5 emission factors. Dung fuels and angithi cookstoves resulted in significantly higher emissions of most VOCs (p < 0:05). Utilizing dung--angithi cook fires resulted in twice as much of the measured VOCs compared to dung--chulha and 4 times as much as brushwood--chulha, with 84.0, 43.2, and 17.2 g measured VOCkg-1 fuel carbon, respectively. This matches expectations, as the use of dung fuels and angithi cookstoves results in lower modified combustion efficiencies compared to brushwood fuels and chulha cookstoves. Alkynes and benzene were exceptions and had significantly higher emissions when cooking using a chulha as opposed to an angithi with dung fuel (for example, benzene emission factors were 3.18 g kg-1 fuel carbon for dung--chulha and 2.38 g kg-1 fuel carbon for dung--angithi). This study estimated that 3 times as much SOA and ozone in the maximum incremental reactivity (MIR) regime may be produced from dung--chulha as opposed to brushwood--chulha cook fires. Aromatic compounds dominated as SOA precursors from all types of cook fires, but benzene was responsible for the majority of SOA formation potential from all chulha cook fire VOCs, while substituted aromatics were more important for dung--angithi. Future studies should investigate benzene exposures from different stove and fuel combinations and model SOA formation from cook fire VOCs to verify public health and air quality impacts from cook fires. [ABSTRACT FROM AUTHOR]

Multiple trace-gas instruments were deployed during the fourth Fire Lab at Missoula Experiment (FLAME-4), including the first application of proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) and comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC-TOFMS) for laboratory biomass burning (BB) measurements. Open-path Fourier transform infrared spectroscopy (OP-FTIR) was also deployed, as well as whole-air sampling (WAS) with one-dimensional gas chromatography–mass spectrometry (GC-MS) analysis. This combination of instruments provided an unprecedented level of detection and chemical speciation. The chemical composition and emission factors (EFs) determined by these four analytical techniques were compared for four representative fuels. The results demonstrate that the instruments are highly complementary, with each covering some unique and important ranges of compositional space, thus demonstrating the need for multi-instrument approaches to adequately characterize BB smoke emissions. Emission factors for overlapping compounds generally compared within experimental uncertainty, despite some outliers, including monoterpenes. Data from all measurements were synthesized into a single EF database that includes over 500 non-methane organic gases (NMOGs) to provide a comprehensive picture of speciated, gaseous BB emissions. The identified compounds were assessed as a function of volatility; 6–11 % of the total NMOG EF was associated with intermediate-volatility organic compounds (IVOCs). These atmospherically relevant compounds historically have been unresolved in BB smoke measurements and thus are largely missing from emission inventories. Additionally, the identified compounds were screened for published secondary organic aerosol (SOA) yields. Of the total reactive carbon (defined as EF scaled by the OH rate constant and carbon number of each compound) in the BB emissions, 55–77 % was associated with compounds for which SOA yields are unknown or understudied. The best candidates for future smog chamber experiments were identified based on the relative abundance and ubiquity of the understudied compounds, and they included furfural, 2-methyl furan, 2-furan methanol, and 1,3-cyclopentadiene. Laboratory study of these compounds will facilitate future modeling efforts. [ABSTRACT FROM AUTHOR]

Effective management of diabetes mellitus, affecting tens of millions of patients, requires frequent assessment of plasma glucose. Patient compliance for sufficient testing is often reduced by the unpleasantness of current methodologies, which require blood samples and often cause pain and skin callusing. We propose that the analysis of volatile organic compounds (VOCs) in exhaled breath can be used as a novel, alternative, noninvasive means to monitor glycemia in these patients. Seventeen healthy (9 females and 8 males, 28.0 ± 1.0 yr) and eight type 1 diabetic (T1DM) volunteers (5 females and 3 males, 25.8 ± 1.7 yr) were enrolled in a 240-min triphasic intravenous dextrose infusion protocol (baseline, hyperglycemia, euglycemia-hyperinsulinemia). In T1DM patients, insulin was also administered (using differing protocols on 2 repeated visits to separate the effects of insulinemia on breath composition). Exhaled breath and room air samples were collected at 12 time points, and concentrations of ∼100 VOCs were determined by gas chromatography and matched with direct plasma glucose measurements. Standard least squares regression was used on several subsets of exhaled gases to generate multilinear models to predict plasma glucose for each subject. Plasma glucose estimates based on two groups of four gases each (cluster A: acetone, methyl nitrate, ethanol, and ethyl benzene; cluster B: 2-pentyl nitrate, propane, methanol, and acetone) displayed very strong correlations with glucose concentrations (0.883 and 0.869 for clusters A and B, respectively) across nearly 300 measurements. Our study demonstrates the feasibility to accurately predict glycemia through exhaled breath analysis over a broad range of clinically relevant concentrations in both healthy and T1DM subjects. [ABSTRACT FROM AUTHOR]

The Lotts Creek coal mine fire is burning in abandoned works of the Pennsylvanian Hazard No. 9 coal, Perry County, Kentucky. Over the few months separating sampling trips, the fire showed a definite migration to the south. Several vents sampled on the first trip were extinct on the second trip. The flux of major gases varies from 1100 to 440,000 mg/s/m 2 CO 2 and < 100 to 12,000 mg/s/m 2 CO, with the gas temperature being one of the principal drivers of the emissions variations; the higher the temperature, the more CO 2 produced. Mercury, also showing wide variation, from 45 to 740 ng/s/m 2 , could not be measured at all vents due to temperature limitations inherent in the instrument. In addition to CO 2 , CO, and Hg, a number of gases among the volatile aliphatic and volatile aromatic compounds are emitted in potentially dangerous amounts. [ABSTRACT FROM AUTHOR]

Abstract: Vent emissions of the Old Smokey coal fire, Floyd County, Kentucky, were studied in May and July, 2010. Vent emissions were generally lower in July, perhaps due to a shift in the fire front, change in vent structure, or another unidentified factor. Volatile organics in the vent gasses contain dangerous levels of toxic, carcinogenic, and other hazardous compounds. Benzene ranges to nearly 400 parts per billion (volume) at one vent. Toluene exceeds 104 parts per billion (volume) at the same vent. Flux rates for CO2 and CO range to 85,000mg/s/m2 and 89mg/s/m2, respectively, for various vents for the two measuring times. Estimates of total CO2 emissions, possibly less than 1000t/year, are within the range of other eastern Kentucky coal fires. [Copyright &y& Elsevier]

A sampling campaign was conducted in the city of Milan, Italy before and during a transportation strike in January 2004. This strike provided a unique opportunity to investigate the influence of public transportation on the air quality in a major metropolitan area. Twenty-four air samples were collected each day around the city on January 2nd, 7th and 9th. The samples were analyzed for methane, carbon monoxide, non-methane hydrocarbons (NMHCs), halocarbons and alkyl nitrates. Significant differences in the mixing ratios were observed among the three days of sampling, with January 2nd showing the lowest concentrations as a result of decreased activity in the city during the holiday season. January 9th showed the highest NMHC concentrations because of increased vehicular activity in the city due to a public transportation strike. This paper investigates the correlation between the increased number of vehicles and decreased air quality because of a reduction in public transportation. Computer simulations were able to reproduce measurements of ozone production during the January 2004 strike and a July 2005 strike. The measurements and simulations suggest that reduced VOC emissions due to the existence of public transportation lowers peak ozone by 11–33% during the summer months. [Copyright &y& Elsevier]

Abstract: Whole air samples were collected in 43 Chinese cities in January and February 2001, and methane and nonmethane hydrocarbon (NMHC) concentrations for those samples are here discussed. In order to identify the main sources of the hydrocarbons in these cities, cross-correlations with the general combustion tracer ethyne and the gasoline marker i-pentane were investigated. Most of the identified NMHCs correlated with ethyne or i-pentane suggesting that their primary source is combustion or gasoline evaporation. To differentiate between vehicular and other combustion sources, the benzene to toluene ratio characteristic of the Chinese vehicular fleet was calculated using roadside samples (collected in 25 cities). Cities where the main source of the NMHCs was traffic related were identified. The slope resulting from the correlation of selected gases was used to identify the likely sources of the NMHCs measured. Vehicular emissions were found to be an important source of isoprene in some cities. Different VOC mixing ratio distributions throughout the country were also investigated. This paper gives a general overview of urban VOCs in many Chinese cities. Future more rigorous studies will be necessary to further characterize VOC sources in China. [Copyright &y& Elsevier]

Mixing ratios of carbon monoxide (CO), methane (CH[sub 4]), non-methane hydrocarbons, halocarbons and alkyl nitrates (a total of 72 species) were determined for 78 whole air samples collected during the winter of 1998-1999 in Karachi, Pakistan. This is the first time that volatile organic compound (VOC) levels in Karachi have been extensively characterized. The overall air quality of the urban environment was determined using air samples collected at six locations throughout Karachi. Methane (6.3 ppmv) and ethane (93 ppbv) levels in Karachi were found to be much higher than in other cities that have been studied. The very high CH[sub 4] levels highlight the importance of natural gas leakage in Karachi. The leakage of liquefied petroleum gas contributes to elevated propane and butane levels in Karachi, although the propane and butane burdens were lower than in other cities (e.g., Mexico City, Santiago). High levels of benzene (0.3-19 ppbv) also appear to be of concern in the Karachi urban area. Vehicular emissions were characterized using air samples collected along the busiest thoroughfare of the city (M.A. Jinnah Road). Emissions from vehicular exhaust were found to be the main source of many of the hydrocarbons reported here. Significant levels of isoprene (1.2 ppbv) were detected at the roadside, and vehicular exhaust is estimated to account for about 20% of the isoprene observed in Karachi. 1,2-Dichloroethane, a lead scavenger added to leaded fuel, was also emitted by cars. The photochemical production of ozone (O[sub 3]) was calculated for CO and the various VOCs using the Maximum Incremental Reactivity (MIR) scale. Based on the MIR scale, the leading contributors to O[sub 3] production in Karachi are ethene, CO, propene, m-xylene and toluene. [ABSTRACT FROM AUTHOR]

The nonlinear chemical processes involved in ozone production (P(O 3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O 3) on volatile organic compounds (VOCs) or nitrogen oxides (NO x). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO 2) has been widely used for studying O 3 sensitivity. Previous studies found that the errors in retrievals and the incoherent relationship between the column and the near-surface concentrations are a barrier in applying the ratio in a robust way. In addition to these obstacles, we provide calculational-observational evidence, using an ensemble of 0-D photochemical box models constrained by DC-8 aircraft measurements on an ozone event during the Korea-United States Air Quality (KORUS-AQ) campaign over Seoul, to demonstrate the chemical feedback of NO 2 on the formation of HCHO is a controlling factor for the transition line between NO x -sensitive and NO x -saturated regimes. A fixed value (~2.7) of the ratio of the chemical loss of NO x (LNO x) to the chemical loss of HO 2 +RO 2 (LRO x) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/NO 2 less than 1 can be safely classified as NO x -saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO 2 chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO 2 ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNO x /LRO x ~2.7 that accounts for the HCHO-NO 2 chemical relationship leading to HCHO = 3.7 × (NO 2 – 1.14 × 1016 molec.cm-2). Although the revised formula is locally calibrated (i.e., requires for readjustment for other regions), its mathematical format removes the need for having a wide range of thresholds used in HCHO/NO 2 ratios that is a result of the chemical feedback. Therefore, to be able to properly take the chemical feedback into consideration, the use of HCHO = a × (NO 2 – b) formula should be preferred to the ratio in future works. We then use the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument to study O 3 sensitivity in Seoul. The unprecedented spatial (250 × 250 m2) and temporal (~every 2 h) resolutions of HCHO and NO 2 observations form the sensor enhance our understanding of P(O 3) in Seoul; rather than providing a crude label for the entire city, more in-depth variabilities in chemical regimes are observed that should be able to inform mitigation strategies correspondingly. • Ozone sensitivity over Seoul on an exceptionally degraded air quality day. • Various thresholds for HCHO/NO 2 should be defined to label chemical regimes. • The inherent dependence of HCHO production on NO x levels complicates the ratio. • We redesign the formula to reflect the chemical feedback of NO x on HCHO. • GeoTASO provides in-depth variabilities in chemical regimes over Seoul. [ABSTRACT FROM AUTHOR]