Publications

Long term O ₃ -precursor relationships in Hong Kong: Fieldobservation and model simulation

Abstract. Over the past ten years (2005–2014), ground-level O3 in Hong Kong has consistently increased in all seasons except winter, despite the yearly reduction of its precursors, i.e., nitrogen oxides (NOx = O + NO2), total volatile organic compounds (TVOCs) and carbon monoxide (CO). To explain the contradictory phenomenon, an observation-based box model (OBM) coupled with CB05 mechanism was applied in order to understand the influence of both locally-produced O3 and regional transport. The simulation of locally-produced O3 showed an increasing trend in spring, a decreasing trend in autumn and no changes in summer and winter. The O3 increase in spring was caused by the net effect of more rapid decrease of NO titration and unchanged TVOC reactivity despite decreased TVOC mixing ratios, while the decreased local O3 formation in autumn was mainly due to the reduction of aromatic VOC mixing ratios and the TVOC reactivity and much slower decrease of NO titration. However, the decreased in-situ O3 formation in autumn was overridden by the regional contribution, resulting in elevated O3 observations. Furthermore, the OBM-derived relative incremental reactivity indicated that the O3 formation was VOC-limited in all seasons, and the long-term O3 formation was more sensitive to VOCs and less to NOx and CO in the past 10 years. In addition, the OBM results found that the contributions of aromatics to O3 formation decreased in all seasons of these years, particularly in autumn, likely due to effective control of solvent-related sources. In contrast, the contributions of alkenes increased, suggesting a continuing need to reduce traffic emissions. The findings provided updated information on photochemical pollution and its impact in Hong Kong.

Transport and Chemistry of Short-Lived Bromocarbons in the Tropics

We have developed a detailed chemical scheme for the degradation of the short-lived source gases bromoform (CHBr3) and dibromomethane (CH2Br2) and implemented it in the TOMCAT/SLIMCAT three-dimensional (3D) chemical transport model (CTM). The CTM has been used to predict the distribution of the two source gases (SGs) and 11 of their organic product gases (PGs). These first global calculations of the organic PGs show that their abundance is small. The longest lived organic PGs are CBr2O and CHBrO, but their peak tropospheric abundance relative to the surface volume mixing ratio (vmr) of the SGs is less than 5%. We calculate their mean local tropospheric lifetimes in the tropics to be ∼7 and ∼2 days (due to photolysis), respectively. Therefore, the assumption in previous modelling studies that SG degradation leads immediately to inorganic bromine seems reasonable.

Aromatic hydrocarbons as ozone precursors before and after outbreak of the 2008 financial crisis in the Pearl River Delta region, south China

In the second half of 2008 China's highly industrialized Pearl River Delta (PRD) region was hard‐hit by the financial crisis (FC). This study reports volatile organic compounds measured in the PRD during November–December in both 2007 before the FC and 2008 after the FC. While total mixing ratios of non‐methane hydrocarbons (NMHCs) on average were only about 7% lower from 40.2 ppbv in 2007 to 37.5 ppbv in 2008, their ozone formation potentials (OFPs) dropped about 30%, resulting from about 55% plummet of aromatic hydrocarbons (AHs) against a greater than 20% increase of total alkanes/alkenes. The elevated alkanes and alkenes in 2008 could be explained by greater emissions from vehicle exhausts and LPG combustion due to rapid increase of vehicle numbers and LPG consumption; the drop of AHs could be explained by reduced emissions from industries using AH‐containing solvents due to the influence of the FC, as indicated by much lower ratios of toluene to benzene and of xylenes/trichloroethylene/tetrachloroethylene to carbon monoxide (CO) in 2008. Source apportionment by positive matrix factorization (PMF) also revealed much less contribution of industry solvents to total anthropogenic NMHCs and particularly to toluene and xylenes in 2008 than in 2007. Based on PMF reconstructed source contributions, calculated OFPs by industrial emissions were responsible for 40.8% in 2007 in contrast to 18.4% in 2008. Further investigation into local industry output statistics suggested that the plummet of AHs in 2008 should be attributed to small enterprises, which contributed largely to ambient AHs due to their huge numbers and non‐existent emission treatment, but were much more influenced by the FC.

Limitations of Global models in Representing Arctic Tropospheric Ozone and its Precursors

Vertical transport of sulfur dioxide and dimethyl sulfide in deep convection and its role in new particle formation

The NASA Pacific Exploratory Mission‐West experiment in 1991 and 1994 covered large portions of the western Pacific Ocean troposphere and transects of the troposphere of the equatorial and subtropical North Pacific Ocean. Sulfur dioxide and dimethyl sulfide were concurrently measured from the surface to 12 km. In 1991, sulfur dioxide had significant anthropogenic and volcanic sources. In 1994, sulfur dioxide aloft was significantly lower than in 1991. During both periods, deep convection was responsible for the distribution of sulfur dioxide and dimethyl sulfide. An assessment is made of the proportion of sulfur dioxide that could be made from dimethyl sulfide convected to high altitude. The subsequent formation of new aerosol particles from sulfur dioxide at high altitude is evaluated.

Exploring dimethyl sulfide (DMS) oxidation and implications for global aerosol radiative forcing

Abstract. Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway and the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and, hence, alter the spatial distribution of sulfate aerosol and radiative impacts. The expanded scheme improves the agreement between modeled and observed concentrations of DMS, MSA, HPMTF, and sulfate over most marine regions, based on the NASA Atmospheric Tomography (ATom), the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA), and the Variability of the American Monsoon Systems (VAMOS) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) measurements. We find that the global HPMTF burden and the burden of sulfate produced from DMS oxidation are relatively insensitive to the assumed isomerization rate, but the burden of HPMTF is very sensitive to a potential additional cloud loss. We find that global sulfate burden under PI and PD emissions increase to 412 Gg S (+29 %) and 582 Gg S (+8.8 %), respectively, compared to the standard simplified DMS oxidation scheme. The resulting annual mean global PD direct radiative effect of DMS-derived sulfate alone is −0.11 W m−2. The enhanced PI sulfate produced via the gas-phase chemistry updates alone dampens the aerosol IRF as anticipated (−2.2 W m−2 in standard versus −1.7 W m−2, with updated gas-phase chemistry). However, high clouds in the tropics and low clouds in the Southern Ocean appear particularly sensitive to the additional aqueous-phase pathways, counteracting this change (−2.3 W m−2). This study confirms the sensitivity of aerosol IRF to the PI aerosol loading and the need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes.

Large hemispheric difference in ultrafine aerosol concentrations inthe lowermost stratosphere at mid and high latitudes

Abstract. The details of aerosol processes and size distributions in the stratosphere are important for both heterogeneous chemistry and aerosol-radiation interactions. Using in-situ, global-scale measurements of the size distribution of particles with diameters > 3 nm from the NASA Atmospheric Tomography Mission (ATom), we identify a mode of ultrafine aerosol in the lowermost stratosphere (LMS) at mid and high latitudes. This mode is substantial only in the northern hemisphere (NH), and was observed in all four seasons. We also observe elevated SO2, an important precursor for new particle formation (NPF) and growth, in the NH LMS. We use box modelling and thermodynamic calculations to show that NPF can occur in the LMS conditions observed on ATom. Aircraft emissions are shown as likely sources of this SO2, as well as a potential source of ultrafine particles directly emitted by, or formed in the plume of the engines. These ultra-fine particles have the potential to grow to larger sizes, and to coagulate with larger aerosol, affecting heterogeneous chemistry and aerosol-radiation interactions. Understanding all sources and characteristics of stratospheric aerosol is important in the context of anthropogenic climate change as well as proposals for climate intervention via stratospheric sulphur injection. This analysis not only adds to the, currently sparse, observations of the global impact of aviation, but also introduces another aspect of climate influence, namely a size distribution shift of the background aerosol distribution in the LMS.

Erratum: A Winogradsky-based culture system shows an association between microbial fermentation and cystic fibrosis exacerbation

Abstract Correction to: The ISME Journal advance online publication, 16 December 2014; doi:10.1038/ismej.2014.234 Since the publication of this article, the authors have identified an error concerning the acknowledgements, namely that ‘Cystic Fibrosis Research Inc.’ was incorrectly listed as ‘Cystic FibrosisResearch Foundation’.

Breath gas metabolites and bacterial metagenomes from cystic fibrosis airways indicate active pH neutral 2,3-butanedione fermentation

The airways of cystic fibrosis (CF) patients are chronically colonized by patient-specific polymicrobial communities. The conditions and nutrients available in CF lungs affect the physiology and composition of the colonizing microbes. Recent work in bioreactors has shown that the fermentation product 2,3-butanediol mediates cross-feeding between some fermenting bacteria and Pseudomonas aeruginosa, and that this mechanism increases bacterial current production. To examine bacterial fermentation in the respiratory tract, breath gas metabolites were measured and several metagenomes were sequenced from CF and non-CF volunteers. 2,3-butanedione was produced in nearly all respiratory tracts. Elevated levels in one patient decreased during antibiotic treatment, and breath concentrations varied between CF patients at the same time point. Some patients had high enough levels of 2,3-butanedione to irreversibly damage lung tissue. Antibiotic therapy likely dictates the activities of 2,3-butanedione-producing microbes, which suggests a need for further study with larger sample size. Sputum microbiomes were dominated by P. aeruginosa, Streptococcus spp. and Rothia mucilaginosa, and revealed the potential for 2,3-butanedione biosynthesis. Genes encoding 2,3-butanedione biosynthesis were disproportionately abundant in Streptococcus spp, whereas genes for consumption of butanedione pathway products were encoded by P. aeruginosa and R. mucilaginosa. We propose a model where low oxygen conditions in CF lung lead to fermentation and a decrease in pH, triggering 2,3-butanedione fermentation to avoid lethal acidification. We hypothesize that this may also increase phenazine production by P. aeruginosa, increasing reactive oxygen species and providing additional electron acceptors to CF microbes.

Biogenic and Anthropogenic VOC Emissions over the Central and Southern U.S.: Results from Recent Airborne Field Campaigns (Invited)

Sources and Characteristics of Summertime Organic Aerosol inthe Colorado Front Range: Perspective from Measurements andWRF-Chem Modeling

Abstract. Evolution of organic aerosol (OA) and their precursors in the boundary layer of Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July–August 2014) was analyzed by in-situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.068 ± 0.004 μg m−3 ppbv−1. At background mixing ratios of CO, up to ~ 2 μg m−3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&G) emissions was ~ 40 % higher than in urban-influenced plumes. Positive matrix factorization confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&G sector were used in the Weather Research and Forecasting model, coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including a top-down modified O&G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high O&G-influenced plumes. By including emissions from the O&G sector using the top-down approach, it was estimated that the O&G sector contributed to

Comment on acp-2022-399

<strong class="journal-contentHeaderColor">Abstract.</strong> Comprehensive aircraft measurements of volatile organic compounds (VOCs) covering the South Coast Air Basin (SoCAB) and San Joaquin Valley (SJV) of California were obtained in the summer of 2019. Combined with the CO, CH<span class="inline-formula">₄</span>, and NO<span class="inline-formula">_<i>x</i></span> data, the total calculated gas-phase hydroxyl radical reactivity (cOHR<span class="inline-formula">_TOTAL</span>) was quantified to be 6.1 and 4.6 s<span class="inline-formula">⁻¹</span> for the SoCAB and SJV, respectively. VOCs accounted for <span class="inline-formula">∼</span> 60 %–70 % of the cOHR<span class="inline-formula">_TOTAL</span> in both basins. In particular, oxygenated VOCs (OVOCs) contributed <span class="inline-formula"><i>&gt;</i>60</span> % of the cOHR of total VOCs (cOHR<span class="inline-formula">_VOC</span>) and the total observed VOC mixing ratio. Primary biogenic VOCs (BVOCs) represented a minor fraction (<span class="inline-formula"><i>&lt;</i>2</span> %) of the total VOC mixing ratio but accounted for 21 % and 6 % of the cOHR<span class="inline-formula">_VOC</span> in the SoCAB and SJV, respectively. Furthermore, the contribution of BVOCs to the cOHR<span class="inline-formula">_VOC</span> increased with increasing cOHR<span class="inline-formula">_VOC</span> in the SoCAB, suggesting that BVOCs were important ozone precursors during high ozone episodes. Spatially, the trace gases were heterogeneously distributed in the SoCAB, with their mixing ratios and cOHR being significantly greater over the inland regions than the coast, while their levels were more evenly distributed in SJV. The results highlight that a better grasp of the emission rates and sources of OVOCs and BVOCs is essential for a predictive understanding of the ozone abundance and distribution in California.

Kai, Tyler, Randerson &amp; Blake reply

Sulfate Mineralogy from Acid-Alteration of Pyrite: Leadville, Colorado

Factors controlling tropospheric O₃, OH, NO_<i>x</i> and SO₂ over the tropical Pacific during PEM‐Tropics B

Observations over the tropical Pacific during the Pacific Exploratory Mission (PEM)‐Tropics B experiment (March‐April 1999) are analyzed. Concentrations of CO and long‐lived nonmethane hydrocarbons in the region are significantly enhanced due to transport of pollutants from northern industrial continents. This pollutant import also enhances moderately O 3 concentrations but not NO x concentrations. It therefore tends to depress OH concentrations over the tropical Pacific. These effects contrast to the large enhancements of O 3 and NO x concentrations and the moderate increase of OH concentrations due to biomass burning outflow during the PEM‐Tropics A experiment (September‐October 1996). Observed CH 3 I concentrations, as in PEM‐Tropics A, indicate that convective mass outflux in the middle and upper troposphere is largely independent of altitude over the tropical Pacific. Constraining a one‐dimensional model with CH 3 I observations yields a 10‐day timescale for convective turnover of the free troposphere, a factor of 2 faster than during PEM‐Tropics A. Model simulated HO 2 , CH 2 O, H 2 O 2 , and CH 3 OOH concentrations are generally in agreement with observations. However, simulated OH concentrations are lower (∼25%) than observations above 6 km. Whereas models tend to overestimate previous field measurements, simulated HNO 3 concentrations during PEM‐Tropics B are too low (a factor of 2–4 below 6 km) compared to observations. Budget analyses indicate that chemical production of O 3 accounts for only 50% of chemical loss; significant transport of O 3 into the region appears to take place within the tropics. Convective transport Of CH 3 OOH enhances the production of HO x and O 3 in the upper troposphere, but this effect is offset by HO x loss due to the scavenging of H 2 O 2 . Convective transport and scavenging of reactive nitrogen species imply a necessary source of 0.4–1 Tg yr −1 of NO x in the free troposphere (above 4 km) over the tropics. A large fraction of the source could be from marine lightning. Oxidation of DMS transported by convection from the boundary layer could explain the observed free tropospheric SO 2 concentrations over the tropical Pacific. This source of DMS due to convection, however, would imply in the model free tropospheric concentrations much higher than observed. The model overestimate cannot be reconciled using recent kinetics measurements of the DMS‐OH adduct reaction at low pressures and temperatures and may reflect enhanced OH oxidation of DMS during convection.

The glyoxal budget and its contribution to organic aerosol for Los Angeles, California during CalNex 2010

Recent laboratory and field studies have indicated that glyoxal is a potentially large contributor to secondary organic aerosol mass. We present in situ glyoxal measurements acquired with a recently developed, high sensitivity spectroscopic instrument during the CalNex 2010 field campaign in Pasadena, California. We use three methods to quantify the production and loss of glyoxal in Los Angeles and its contribution to organic aerosol. First, we calculate the difference between steady state sources and sinks of glyoxal at the Pasadena site, assuming that the remainder is available for aerosol uptake. Second, we use the Master Chemical Mechanism to construct a two-dimensional model for gas-phase glyoxal chemistry in Los Angeles, assuming that the difference between the modeled and measured glyoxal concentration is available for aerosol uptake. Third, we examine the nighttime loss of glyoxal in the absence of its photochemical sources and sinks. Using these methods we constrain the glyoxal loss to aerosol to be 0-5 × 10-5 s-1 during clear days and (1 ± 0.3) × 10-5 s-1 at night. Between 07:00-15:00 local time, the diurnally averaged secondary organic aerosol mass increases from 3.2 μg m-3 to a maximum of 8.8 μg m -3. The constraints on the glyoxal budget from this analysis indicate that it contributes 0-0.2 μg m-3 or 0-4% of the secondary organic aerosol mass. Copyright 2011 by the American Geophysical Union.

Microphysical and Chemical Processes Affecting Wet Removal of Soluble Trace Gases in Deep Convection Observed over the Central U.S.

Molecular Composition of Particulate Matter Emissions from Dung and Brushwood Burning Household Cookstoves in Haryana, India

Abstract. Emissions of airborne particles from biomass-burning are a significant source of black carbon (BC) and brown carbon (BrC) in rural areas of developing countries where biomass is the predominant energy source for cooking and heating. This study explores the molecular composition of organic particles from household cooking emissions, with a focus on identifying fuel-specific compounds and BrC chromophores. Traditional meals were prepared by a local cook with dung and brushwood-fueled cookstoves in a village of Palwal district, Haryana, India. The cooking events were carried out in a village kitchen while controlling for variables including stove type, fuel moisture content, and meal. The particulate matter (PM2.5) emissions were collected on filters, and then analyzed via nanospray desorption electrospray ionization/high resolution mass spectrometry (nano-DESI-HRMS) and high performance liquid chromatography/photodiode array/high resolution mass spectrometry (HPLC-PDA-HRMS) techniques. The nano-DESI-HRMS analysis provided an inventory of compounds present in the particle phase. Although several compounds observed in this study have been previously characterized using gas chromatography methods, a majority of species in nano-DESI spectra were newly observed biomass-burning compounds. Both the stove (chulha or angithi) and the fuel (brushwood or dung) affected the composition of organic particles. The geometric mean PM2.5 emissions factor and the molecular complexity of PM2.5 emissions increased in the following order: brushwood/chulha (4.9 ± 1.7 g kg-1 dry fuel, 93 compounds), dung/chulha (12.3 ± 2.5 g kg-1 dry fuel, 212 compounds), and dung/angithi (16.7 ± 6.7 g kg-1 dry fuel, 262 compounds). The lower limit for the mass absorption coefficient (MAC) at 365 nm and 405 nm for brushwood PM2.5 was 3.4 m2 g-1 and 1.8 m2 g-1, respectively, which was approximately a factor of two higher than that for dung PM2.5. The HPLC-PDA-HRMS analysis showed that, regardless of fuel type, the main chromophores were CxHyOz lignin fragments. The main chromophores accounting for the higher MAC values of brushwood PM2.5 were C8H10O3 (tentatively assigned syringol), possible nitrophenol species C8H9NO4, and C10H10O3 (tentatively assigned methoxycinnamic acid).